JPH11228588A - New metallocene compound and polymerization of olefin by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound consisting of a specific metallocene compound in which a substituent is introduced at a specific site of fluorenyl group and capable of producing a highly stereoregular polyolefin having a high melting point as a homogeneous catalyst component, etc., for olefin polymerization. SOLUTION: This new metallocene compound is a new metallocene compound expressed by formula I [R<1> , R<2> are each H, an alkyl or an aryl ; R<3> to R<7> are each H, an alkyl, an aryl or an alkyl containing silicon; R<8> is an alkyl; Y is a divalent carbon or silicon; X is a halogen, an alkyl or an anionic ligand; (m) is 1-3 integer] and useful as a catalytic component, etc., for an olefin polymerization capable of producing a highly stereoregular polyolefin having a high melting point. The compound is obtained by reacting a cyclopentadiene derivative expressed by formula II with a fluorenyl-alkali metal compound expressed by formula III (L is an alkali metal) to form a ligand expressed by formula IV, and then reacting the ligand with a compound of the formula: M(X)n in the presence of methyllithium, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel metallocene compound and a method for polymerizing an olefin using the same. More specifically, the present invention relates to a metallocene compound having a specific structure and a method for polymerizing an olefin 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 C2 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, and isotactic compounds obtained with these metallocene compounds have been reported. Attempts to improve the tacticity of polymers are common (Yamazaki et al., Chemistry Letters, 1853 (19
89), JP-A-4-268307). Many similar attempts have been reported to improve the stereoregularity of olefin polymers by metallocene compounds having an ethylenebisindenyl derivative having a C2 target structure as a ligand (see, for example, Organometallics, 13,
954 (1994), J. Organmet.Chem., 288, 63 (1985).
etc).

On the other hand, JA Ewen has found that a metallocene compound obtained by crosslinking cyclopentadienyl and fluorenyl having a Cs target structure with dimethylmethane polymerizes an α-olefin with syndiotactic stereoregularity (J. Am. Chem. Soc., 110, 6255 (1988)). As an improvement of this metallocene, 2,7-di-te
Attempts have been made to further control the stereoregularity by introducing rt-butylfluorenyl (Japanese Patent Laid-Open Publication No.
69394).

[0004]

However, this C
s having a structure in which a substituent is introduced at the 4-position or 4- and 5-positions of fluorenyl of a metallocene compound having a target structure;
No metallocene compound for synthesizing an olefin polymer has been found.

[0005]

Means for Solving the Problems The present inventors have solved the above-mentioned problems, and have intensively studied a metallocene compound having a novel structure for synthesizing an α-olefin polymer and a polymerization method using the same. Was completed.

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

[0007]

Embedded image(Where R¹, R^TwoIs selected from hydrogen, alkyl and aryl
Bar, R^Three, R^Four, R^Five, R⁶, R⁷Is hydrogen, alkyl,
Selected from aryl and silicon-containing alkyl; ⁸Is that
At least one of which is alkyl, aryl, silicon-containing
Chosen from kills. M is a metal selected from Group 4 of the periodic table
Y is divalent carbon or silicon, and X is halo
Gen, alkyl or anionic ligands;
Among them, the same or different combinations may be selected.
It is an integer of 3. ).

Further, the present invention is a method for polymerizing an olefin, comprising polymerizing an olefin using a metallocene compound represented by the general formula [1].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, R of the general formula [1]
¹ and R ² are selected from hydrogen, alkyl and aryl, wherein alkyl is preferably alkyl having 1 to 20 carbons, and specific examples include methyl, ethyl or isopropyl or tert-butyl or cyclohexyl, and menthyl. The aryl is preferably an aryl having 6 to 20 carbon atoms, and specific examples include phenyl,
Tolyl, naphthyl and the like. Y is divalent carbon or silicon, and R ¹ and R ² are bonded to Y, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, diphenylmethylene, It constitutes dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl tert-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, diphenylsilylene, dinaphthylsilylene and the like.

In the present invention, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula [1] are selected from hydrogen, alkyl, aryl and silicon-containing alkyl. 1 to 20 alkyl, and specific examples include methyl, ethyl, propyl or isopropyl, 2-methylpropyl or tert-butyl or cyclohexyl, norbornyl, menthyl and the like.
The aryl is preferably an aryl having 6 to 20 carbon atoms, and specific examples include phenyl, tolyl, and naphthyl. The silicon-containing alkyl is preferably a silicon-containing alkyl having 1 to 20 carbon atoms, and specific examples include trimethylsilyl and dimethylethylsilyl.

R ⁸ is at least one selected from the group consisting of alkyl, aryl and silicon-containing alkyl. Alkyl is preferably alkyl having 1 to 20 carbon atoms. Specific examples include methyl, ethyl or isopropyl or tert-butyl and the like; and the aryl is preferably an aryl having 6 to 20 carbon atoms. Specific examples include phenyl, tolyl, and naphthyl. The silicon-containing alkyl is preferably a silicon-containing alkyl having 1 to 20 carbon atoms, and specific examples include trimethylsilyl, dimethylethylsilyl, and cyclohexyldimethylsilyl. When one of R ⁸ is selected from alkyl, aryl and silicon-containing alkyl, the other is not particularly limited. Other specific examples include hydrogen, alkyl, aryl, silicon-containing alkyl and the like. Alkyl is preferably alkyl having 1 to 20 carbon atoms, and specific examples include methyl, ethyl or isopropyl or tert-alkyl. Butyl and the like, and the aryl is preferably a group having 6 carbon atoms.
To 20 aryls, and specific examples include phenyl, tolyl, and naphthyl. The silicon-containing alkyl is preferably a silicon-containing alkyl having 1 to 20 carbon atoms, and specific examples thereof include trimethylsilyl,
Examples thereof include dimethylethylsilyl and cyclohexyldimethylsilyl.

In the present invention, M in the general formula [1] is a metal selected from Group 4 of the periodic table. Examples of M include titanium, zirconium and hafnium. X is a halogen, an alkyl or an anionic ligand, selected from the same or different combinations thereof, and specific examples of the halogen include fluorine, chlorine, bromine, and iodine. 20 alkyl, specific examples include methyl, ethyl, butyl or isopropyl or tert-butyl, and specific examples of the anion ligand include trimethylphosphine, triethylphosphine or triphenylphosphine or diphenylmethylphosphine. Organic phosphorus compounds such as
Or alkoxy such as methoxy or tert-butoxy or phenoxy, or tetrahydrofuran (hereinafter, THF) diethyl ether, dioxane, 1,2-
Examples include ethers such as dimethoxyethane, wherein X may be the same or a different combination.

In the present invention, for example, R ^{8 at} the 4-position of the ligand which is a precursor of the metallocene compound of the general formula [1]
2,7-diethyl-4-methylfluorene, 2,7-diisopropyl-4-methylfluorene, 2,7-ditert
Butyl-4-methylfluorene, 2,4,7-trimethylfluorene and the like can be synthesized as in the general formula [2], and the substituent of R ^{8 at} the 4-position or 4-position and 5-position is methyl. 4-methylfluorene, 4,5-dimethylfluorene, 2,4,
Methyl-substituted fluorenes such as 7-trimethylfluorene, 2,4,5,7-tetramethylfluorene can be synthesized as in the general formula [3].

[0014]

Embedded image (In the formula, R ⁹ is an alkyl group such as methyl, ethyl, isopropyl, and tertbutyl.)

[0015]

Embedded image (The carboxylic acid in the formula may be in any of the 1- to 8-positions of fluorene, and may be in any number.)

In the present invention, a ligand which is a precursor of the metallocene compound represented by the general formula [1], for example, 9-
(Dimethyl (cyclopentadienyl) methyl) -4-methylfluorene, 9- (diphenyl (cyclopentadienyl) methyl) -4-methylfluorene, 9- (dimethyl (3,4-dimethylcyclopentadienyl) methyl )
-4-methylfluorene, 9- (diphenyl (3,4-
Dimethylcyclopentadienyl) methyl) -4-methylfluorene, 9- (dimethyl (2,3,4,5-tetramethylcyclopentadienyl) methyl) -4-methylfluorene, 9- (diphenyl (2,3 4,4,5-tetramethylcyclopentadienyl) methyl) -4-methylfluorene, 9- (dimethyl (cyclopentadienyl) methyl) -4,5-dimethylfluorene, 9- (diphenyl (cyclopentadienyl) Methyl) -4,5-dimethylfluorene, 9- (dimethyl (3,4-dimethylcyclopentadienyl) methyl) -4,5-dimethylfluorene, 9- (diphenyl (3,4-dimethylcyclopentadienyl) Methyl) -4,5-dimethylfluorene,
9- (dimethyl (2,3,4,5-tetramethylcyclopentadienyl) methyl) -4,5-dimethylfluorene, 9- (diphenyl (2,3,4,5-tetramethylcyclopentadienyl) Methyl) -4,5-dimethylfluorene, 9- (dimethyl (cyclopentadienyl) silyl) -4-methylfluorene, 9- (diphenyl (cyclopentadienyl) silyl) -4-methylfluorene, 9- (dimethyl (3,4-dimethylcyclopentadienyl) silyl) -4-methylfluorene, 9- (diphenyl (3,4-dimethylcyclopentadienyl) silyl) -4-methylfluorene, 9- (dimethyl (2,
3,4,5-tetramethylcyclopentadienyl) silyl) -4-methylfluorene, 9- (diphenyl (2,
3,4,5-tetramethylcyclopentadienyl) silyl) -4-methylfluorene, 9- (dimethyl (cyclopentadienyl) silyl) -4,5-dimethylfluorene, 9- (diphenyl (cyclopentadienyl) ) Silyl) -4,5-dimethylfluorene, 9- (dimethyl (3,4-dimethylcyclopentadienyl) silyl)-
4,5-dimethylfluorene, 9- (diphenyl (3,
4-dimethylcyclopentadienyl) silyl) -4,5
-Dimethylfluorene, 9- (dimethyl (2, 3, 4,
5-tetramethylcyclopentadienyl) silyl)-
4,5-dimethylfluorene, 9- (diphenyl (2,
3,4,5-Tetramethylcyclopentadienyl) silyl) -4,5-dimethylfluorene can be synthesized as represented by the general formula [4] or the general formula [5].

[0017]

Embedded image(Where R¹, R^TwoIs selected from hydrogen, alkyl and aryl
Bar, R^Three, R^Four, R^Five, R⁶, R⁷Is hydrogen, alk
R, aryl, silicon-containing alkyl, ⁸Is
At least one of which is alkyl, aryl or silicon-containing
Selected from alkyl. Y is divalent carbon or silicon
And L is an alkali metal. ).

[0018]

Embedded image(Where R¹, R^TwoIs selected from hydrogen, alkyl and aryl
Bar, R^Three, R^Four, R^Five, R⁶, R⁷Is hydrogen, alk
R, aryl, silicon-containing alkyl, ⁸Is
At least one of which is alkyl, aryl or silicon-containing
Selected from alkyl. Y is divalent carbon or silicon
Where L is an alkali metal and Z is a halogen.
You. ).

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
In an organic solvent of an aliphatic hydrocarbon such as pentane, hexane, heptane, cyclohexane and decalin or an aromatic hydrocarbon such as benzene, toluene and xylene or an ether such as THF, diethyl ether, dioxane and 1,2-dimethoxyethane, It can be performed in a temperature range of -80C to 200C.

The ligand, which is a precursor of the metallocene compound of the general formula [1] obtained by the reaction of the general formula [4] or [5], may be an alkali metal such as lithium, sodium, potassium or the like, or a hydride. In an alkali metal hydride such as sodium or potassium hydride or an organic alkali metal such as methyllithium, butyllithium or phenyllithium and the above-mentioned aliphatic hydrocarbon, aromatic hydrocarbon or an organic solvent such as ether, the reaction temperature is − A dialkali metal salt is formed by contacting at a temperature in the range of 80 ° C to 200 ° C, and the dialkali metal salt and a halide of a metal selected from Group 4 of the periodic table, specifically, trivalent or tetravalent titanium fluoride , Chloride, bromide or iodide or their THF, diethyl ether, dioxane or 1,2-
Complexes with ethers such as dimethoxyethane, or zirconium tetrafluoride, chloride, bromide and iodide or their ether complexes, or hafnium tetrafluoride, chloride, bromide and iodide or their ether complexes By reacting, the metallocene compound of the general formula [1] can be synthesized. The reaction between the dialkali metal salt and the metal halide of Group 4 of the periodic table is preferably carried out by an equimolar reaction, and in an organic solvent, the reaction temperature is -80 ° C to 2 ° C.
It can be performed in the range of 00 ° C. As the organic solvent used, pentane, hexane, heptane, cyclohexane, aliphatic hydrocarbons such as decalin, or benzene,
Aromatic hydrocarbons such as toluene and xylene, or TH
Preferred are ethers such as F, diethyl ether, dioxane and dimethoxyethane, and halogenated hydrocarbons such as dichloromethane and chloroform.

Specific examples of the metallocene compound represented by the general formula [1] in the present invention are shown below, but the invention is not particularly limited thereto.

Dimethylmethylene (cyclopentadienyl) (4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(2,4,7-trimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,4,5,7-tetramethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) ( 3,4,6-trimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,4,5,6-tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4 -Methylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4,5-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,4,7-trimethylfluorenyl) Jill Pyridinium dichloride, diphenylmethylene (cyclopentadienyl) (2,4,5,7
Tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(3,4,6-trimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4,5,6-tetramethylfluorenyl)
Zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-diisopropyl-4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-diisopropyl-4,5-dimethylfluoride) Nil) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diisopropyl-4-methylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diisopropyl-
4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(3,6-diisopropyl-4-methylfluorenyl)
Zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-diisopropyl-4,5-
Dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butyl-4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-di ter-butyl-4,5-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dite
rt-butyl-4-methylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butyl-4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) Enyl) (3,6-diter
t-butyl-4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butyl-4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) Enyl) (2,7-dicyclohexyl-4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(2,7-dicyclohexyl-4,5-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dicyclohexyl-4-methylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) Enil)
(2,7-dicyclohexyl-4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-dicyclohexyl-4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) Enil) (3,
6-dicyclohexyl-4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-diphenyl-4-methylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2 , 7-diphenyl-4,5-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-4-methylfluorenyl)
Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-diphenyl-4-methylfluorenyl) Zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(3,6-diphenyl-4,5-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) [2,7-di (trimethylsilyl) -4-methylfluorenyl] zirconium dichloride, dimethylmethylene ( Cyclopentadienyl)
[2,7-di (trimethylsilyl) -4,5-dimethylfluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) [2,7-di (trimethylsilyl) -4-methylfluorenyl] zirconium dichloride, Diphenylmethylene (cyclopentadienyl) [2,7-di (trimethylsilyl) -4,5-
Dimethylfluorenyl] zirconium dichloride, dimethylmethylene (cyclopentadienyl) [3,6-di (trimethylsilyl) -4-methylfluorenyl] zirconium dichloride, dimethylmethylene (cyclopentadienyl) [3,6-di (Trimethylsilyl) -4,
5-dimethylfluorenyl] zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,
4,5,7-tetraisopropylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,4,5,7-tetraisopropylfluorenyl) zirconium dichloride.

Alternatively, dimethylmethylene (3,4-dimethylcyclopentadienyl) (4-methylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (4,5-
Dimethylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (2,4,7-trimethylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) ( 2,4,5,7-tetramethylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl)
(3,4,6-trimethylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (3,4,5,6-tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (3 , 4-dimethylcyclopentadienyl)
(4-methylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (4,5-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (2,4,7-trimethylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl)
(2,4,5,7-tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (3,4,6-trimethylfluorenyl) zirconium dichloride, diphenylmethylene (3 , 4-dimethylcyclopentadienyl)
(3,4,5,6-tetramethylfluorenyl) zirconium dichloride or the like obtained by converting cyclopentadienyl of the above metallocene compound into 3,4-dimethylcyclopentadienyl.

Alternatively, dimethylmethylene (2, 3,
4,5-tetramethylcyclopentadienyl) (4-methylfluorenyl) zirconium dichloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (4,5-dimethylfluorenyl) Zirconium dichloride, dimethyl methylene (2, 3, 4,
5-tetramethylcyclopentadienyl) (2,4,7
-Trimethylfluorenyl) zirconium dichloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2,4,5,7-tetramethylfluorenyl) zirconium dichloride, dimethylmethylene (2, 3,4,5-tetramethylcyclopentadienyl) (3,4,6-trimethylfluorenyl) zirconium dichloride, dimethylmethylene (2,3,
4,5-tetramethylcyclopentadienyl) (3,
4,5,6-tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-
Tetramethylcyclopentadienyl) (4-methylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (4,5-dimethylfluorenyl) zirconium dichloride, diphenyl Methylene (2, 3, 4, 5-
Tetramethylcyclopentadienyl) (2,4,7-trimethylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2,4,5,7-tetra Methylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3,4,6-trimethylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,
4,5-tetramethylcyclopentadienyl) (3,
(4,5,6-Tetramethylfluorenyl) zirconium dichloride and the like, in which cyclopentadienyl of the above metallocene compound is converted into 2,3,4,5-tetramethylcyclopentadienyl.

Alternatively, the metallocene compound in which chloride is converted to methyl such as dimethylmethylene (cyclopentadienyl) (4-methylfluorenyl) zirconium dimethyl, or dimethylmethylene (cyclopentadienyl) (4-methyl The above metallocene compound in which chloride is converted to trimethylphosphine such as fluorenyl) zirconiumbis (trimethylphosphine),
Or dimethylmethylene (cyclopentadienyl)
The above metallocene compound in which chloride is converted to methoxy such as (4-methylfluorenyl) dimethoxyzirconium, or THF such as dimethylmethylene (cyclopentadienyl) (4-methylfluorenyl) zirconium dichloride / THF. The above-mentioned coordinated metallocene compounds are exemplified. Further, a metallocene compound comprising titanium or hafnium in place of zirconium of the above metallocene compounds may be used.

In the present invention, the olefin polymerized using the metallocene compound represented by the general formula [1] is an α-olefin having 2 to 20 carbon atoms (including ethylene), preferably an α-olefin having 2 to 10 carbon atoms. It is an olefin. 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, a diene having 4 to 20 carbon atoms such as butadiene, 1,4-pentadiene, 1,5-hexadiene and 1,4-hexadiene, or dicyclopentadiene, norbornene, methylnorbornene, tetracyclododecene, methyltetra Examples include cyclic olefins such as cyclododecene, and silicon-containing olefins such as allyltrimethylsilane and vinyltrimethylsilane. These olefins 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 metallocene compound represented by the general formula [1] includes the following general formula [6]:

[0028]

Embedded image Alternatively, a compound represented by the general formula [7] is used.

[0029]

Embedded image (Wherein R ¹⁰ may be the same or different and is alkyl having 1 to 6 carbons, aryl having 6 to 18 carbons or hydrogen, and m is an integer of 2 to 50, preferably 10 to 35. ).

The ratio of the aluminoxane represented by the general formulas [6] and [7] to the metallocene compound represented by the general formula [1] is generally from 1 to 10,000 mol times as aluminum / metallocene. It is a target. In using the above aluminoxane, carbon number 1 to 1
It is also possible to use 20 organic aluminum compounds in combination, in which case good performance can be obtained with a relatively small amount of aluminoxane. Examples of such organoaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum Chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, disec
-Butylaluminum chloride and the like.

Further, in the present invention, in the polymerization of an olefin using the metallocene compound represented by the general formula [1], the olefin is supported on a support insoluble in an inert organic solvent of a hydrocarbon such as pentane, hexane, heptane, benzene or toluene. Aluminoxane may be used. As the support, an inorganic oxide or an organic polymer compound having a functional group insoluble in an inert organic solvent is used. Examples of the inorganic oxide include silica, alumina, magnesium silicate, talc, smectite and the like. Examples of the organic polymer compound having a functional group include organic compounds obtained by (co) polymerizing monomers such as acrylic acids such as methacrylic acid and acrylic acid, or acrylic esters such as methyl methacrylate and methyl acrylate. Examples thereof include a polymer compound or an organic polymer compound obtained by grafting an acrylic acid such as methacrylic acid or acrylic acid, or a carboxylic anhydride such as methyl methacrylate or maleic anhydride to an inert polyolefin.

In the present invention, when an olefin is polymerized using the metallocene compound represented by the general formula [1], the metallocene compound used in combination is converted into a cationic compound to form a stable ionic species. In the compound and the organoaluminum compound, specific examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, N
, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetratetrakis (phenyl) borate, tri-n-butylammonium tetra (phenyl)
Examples thereof include carbenium borane such as borate, metalabran, and ammonium borane.
Nos. 01950 and 1-502036.

The ratio of the ionic compound to the metallocene compound used is 0.1 to 10 times as much as the ionic compound / metallocene. As the organic aluminum compound, an organic aluminum compound having 1 to 20 carbon atoms is used in combination. For example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, triisobutylaluminum,
sec-butylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, disec-butylaluminumchloride and the like. The ratio of the organoaluminum compound to the metallocene compound is 1 to 100 as organoaluminum compound / metallocene.
It is 00 mole times.

In the present invention, the polymerization of the olefin can be carried out by any of a bulk polymerization method and a gas phase polymerization method in addition to the ordinary solvent polymerization method.
The temperature is from 0 to 200C, preferably from -20 to 100C. The polymerization pressure is not particularly limited, but is preferably normal pressure to 5 M
Pa.

[0035]

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

Example 1 [Synthesis of ligand] (1) 4-methylfluorene Under a nitrogen atmosphere, fluorene-4-carboxylic acid (4.97 g, 23.8 m
mol) was dissolved in acetonitrile (40 ml), and trichlorosilane (24 g, 177 mmol) was added thereto.
Heated. After cooling to room temperature, isopropylamine (12
ml, 62 mmol) was added slowly, and the mixture was heated under reflux for 16 hours. After cooling to room temperature, diethyl ether was added, the precipitate was filtered off under a nitrogen atmosphere, the solvent was removed under reduced pressure, methanol (20 ml) was slowly added to the obtained orange liquid, and the mixture was heated under reflux for 2 hours. After cooling the reaction mixture to room temperature, potassium hydroxide (13.3 g) in methanol (20 ml) and water (10
ml) solution was added slowly and heated to reflux for a further 24 hours. The reaction mixture was cooled to room temperature, added with 100 ml of water, extracted with hexane, dried over magnesium sulfate, and filtered.The solvent was removed from the filtrate under reduced pressure, and further developed with hexane on a short silica gel column. The solvent was removed under reduced pressure to obtain 3.53 g of a colorless solid. ¹ H-NMR spectrum (90 MHz, CDCl ₃ ) δ 7.94 (1H), 7.15 | 7.62 (6
H), 3.91 (2H), 2.74 (3H)

(2) 9- (Dimethyl (cyclopentadienyl) methyl) -4-methylfluorene 4-methylfluorene (3.24 g, 18 mmol) in THF (30
hexane solution of n-butyl lithium (20 ml,
32 mmol) was added dropwise at -78 ° C under nitrogen, and the mixture was further stirred at room temperature for 16 hours. Subsequently, the solvent was removed from this reaction solution under reduced pressure under a nitrogen atmosphere, and the orange solid obtained by washing with pentane was dried under reduced pressure and then dissolved in THF. The solution was cooled to −78 ° C. under a nitrogen atmosphere, a THF solution of 6,6-dimethylfulvene (2.87 g, 27 mmol) was added, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was decomposed with cold water, extracted with ether, dried over magnesium sulfate, and filtered.The solvent was removed from the filtrate under reduced pressure, further developed with hexane on a silica gel short column, and the solvent was removed under reduced pressure. This gave 5.05 g of a pale yellow liquid. ¹ H-NMR
Spectrum (90MHz, CDCl ₃ ) δ 7.86 (1H), 7.45 | 6.90
(6H), 6.66 | 5.87 (3H), 4.15 (1H), 3.19 | 3.08 (2H), 2.69
(3H), 1.02 (6H)

(3) 9- (Diphenyl (cyclopentadienyl) methyl) -4-methylfluorene 4-methylfluorene (3.24 g, 18 mmol) in THF (30
ml) solution in n-butyllithium hexane solution (20m
l, 32 mmol) were added dropwise at -78 ° C under nitrogen, and 1
Stir for 6 hours. Subsequently, the solvent was removed from this reaction solution under reduced pressure under a nitrogen atmosphere, and the orange solid obtained by washing with pentane was dried under reduced pressure and then dissolved in THF. The solution was cooled to −78 ° C. under a nitrogen atmosphere, a THF solution of 6,6-diphenylfulvene (4.14 g, 18 mmol) was added, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was decomposed with cold water, extracted with ether, dried over magnesium sulfate and filtered.The solvent was removed from the filtrate under reduced pressure, recrystallized from hot methanol, and developed with hexane on a silica gel short column. The solvent was removed under reduced pressure to obtain 4.43 g of a pale red solid. A pale yellow solid was obtained. ¹ H-
NMR spectrum (90 MHz, CDCl ₃ ) δ 7.78 (1H), 7.3
0 | 6.88 (16H), 6.57 | 5.50 (4H), 3.00 (1H), 2.90 (1H), 2.
56 (3H)

Example 2 [Synthesis of dimethylmethylene (cyclopentadienyl) -4-methylfluorenyltitanium dichloride] 9-dimethyl (cyclopentadienyl) methyl-4-methyl synthesized in (2) of Example 1 Fluorene (1.43g, 5mmo
To a solution of l) in THF (20 ml) was added dropwise a solution of methyllithium in diethyl ether (13 ml, 13 mmol) under ice cooling under nitrogen, and the mixture was further stirred at room temperature for 16 hours. The THF was then distilled under nitrogen and the solid was washed with diethyl ether,
Dissolved in dichloromethane cooled to -78 ° C. Titanium tetrachloride 2THF complex (1.88 g, 5 mmol) dissolved in dichloromethane was added to this solution at -78 ° C, and the mixture was stirred for 24 hours and then slowly returned to room temperature. Further, this solution was filtered through celite, the solvent was concentrated from the filtrate, and the solution was cooled at −30 ° C., and the precipitated solid was washed with pentane and dried under reduced pressure to obtain 603 mg of a red-purple solid. ¹ H-NMR spectrum (90 MHz, CDCl ₃ ) δ 8.00 | 7.05 (7H), 6.41 | 6.05 (4
H), 2.66 (3H), 1.31 (6H)

Example 3 [Synthesis of dimethylmethylene (cyclopentadienyl) -4-methylfluorenylzirconium dichloride] 9- (dimethyl (cyclopentadienyl) methyl) -synthesized in Example 1 (2) 4-methylfluorene (1.43g
, 5 mmol) in THF (20 ml) was added dropwise under nitrogen with a solution of methyllithium in diethyl ether (13 ml, 13 mmol) under ice cooling, and the mixture was further stirred at room temperature for 16 hours. Then, T
HF was distilled under nitrogen, and the solid was washed with diethyl ether and then dissolved in dichloromethane cooled to -78 ° C.
To this solution, zirconium tetrachloride 2THF complex (1.88 g, 5 mmol) dissolved in dichloromethane was added at -78 ° C, and the mixture was stirred for 24 hours and then slowly returned to room temperature. Further, this solution was filtered through celite, the solvent was concentrated from the filtrate, the solution was cooled at −30 ° C., and the precipitated solid was washed with pentane and dried under reduced pressure to obtain 458 mg of a red-brown solid. ¹ H-
NMR spectrum (90 MHz, CDCl ₃ ) δ 8.21 | 6.98 (17
H), 6.38 | 5.79 (4H), 2.64 (3H)

Example 4 [Diphenylmethylene (cyclopentadienyl) -4-
Synthesis of methylfluorenyl zirconium dichloride)
9- (Diphenyl (cyclopentadienyl) methyl) -4-methylfluorene synthesized in (3) of Example 1 (1.
To a solution of 43 g (5 mmol) in THF (20 ml) was added dropwise a solution of methyllithium in diethyl ether (13 ml, 13 mmol) under ice-cooling under nitrogen, and the mixture was further stirred at room temperature for 16 hours. Then
THF was distilled under nitrogen, and the solid was washed with diethyl ether and then dissolved in dichloromethane cooled to -78 ° C. To this solution was added zirconium tetrachloride 2THF complex (1.88 g, 5 mmol) dissolved in dichloromethane at −78.
C. and stirred for 24 hours, then slowly returned to room temperature. Further, this solution was filtered through celite, the solvent was concentrated from the filtrate, cooled at −30 ° C., the precipitated solid was washed with pentane, and dried under reduced pressure to obtain 745 mg of a red solid. ¹ H
-NMR spectrum _{(90MHz, CDCl 3) δ 8.30} | 7.08 (1
7H), 6.34 | 5.76 (4H), 2.84 (3H), 2.41 (6H)

Example 5 In a 5 L autoclave sufficiently purged with nitrogen, Example 2 was added.
To a toluene solution of 10 mg of the red-purple solid obtained in the above was added 25 mmol of methylaluminoxane (manufactured by Albemarle) in terms of aluminum, and polymerized at 70 ° C. for 1 hour in the presence of 3.25 Nl of hydrogen and 1.5 kg of propylene. After the polymerization, propylene was purged, and the obtained polymer was dried at 80 ° C. under reduced pressure for 6 hours. The obtained polymer was 17 g, the intrinsic viscosity ([η]) at 135 ° C. tetralin was 1.44 dl / g, the polymer melting point (Tm) at DSC was 156 ° C., and infrared spectroscopy (IR) analysis was performed. The result was isotactic PP.

Example 6 10 mg of the reddish purple solid obtained in Example 5 in Example 5
Propylene was polymerized in the same manner as in Example 5 except that 5.3 mg of the reddish brown solid obtained in Example 3 was used in place of the above. The obtained polymer weighed 120 g and [η] = 0.
It was 65 dl / g, Tm = 129 ° C., and was a syndiotactic PP according to the result of IR analysis.

Example 7 The magenta solid obtained in Example 6 in Example 3 5.3
Polymerization of propylene was carried out in the same manner as in Example 6, except that 6.8 mg of the red solid obtained in Example 4 was used instead of mg. The obtained polymer weighed 179 g and [η] = 1.
It was 27 dl / g, Tm = 130 ° C., and was found to be syndiotactic PP from the result of IR analysis.

Example 8 The procedure of Example 6 was repeated, except that 11 mg of triphenylcarbenium tetrakis (pentafluorophenyl) borate and 128 mg of triisobutylaluminum were used instead of 25 mmol of methylaluminoxane in terms of aluminum in Example 6. Propylene was polymerized in the same manner. The obtained polymer was 105.0 g, [η] = 0.74 dl / g, Tm = 12
9 ° C.

Example 9 In Example 6, 0.65 g of methylaluminoxane was contacted at 120 ° C. with 1 g of a 10 wt% maleic anhydride graft PP dissolved in xylene in place of methylaluminoxane of 25 mmol in terms of aluminum at 120 ° C., and heptane was added to precipitate the mixture. Then, the solid component obtained by filtering and drying was carried out in the same manner as in Example 6 except that 3.6 mg of the reddish-brown solid obtained in Example 3 was carried in 120 mg of the solid component, and 128 mg of triisobutylaluminum was used. Was polymerized with propylene. The resulting polymer was 83.0
g, [η] = 0.70 dl / g and Tm = 125 ° C.

[0047]

According to the present invention, a polyolefin having a high stereoregularity and a high melting point can be produced by the method of the present invention, which is extremely valuable industrially.

[Brief description of the drawings]

FIG. 1 shows the ¹ H-NMR spectrum of the metallocene compound of the present invention obtained in Example 3.

Claims (6)

[Claims] 1. A novel metallocene represented by the following general formula [1]:
Compound. Embedded image(Where R¹, R^TwoIs selected from hydrogen, alkyl and aryl
Bar, R^Three, R^Four, R^Five, R⁶, R⁷Is hydrogen, alk
R, aryl, silicon-containing alkyl, ⁸Is
At least one of which is alkyl, aryl or silicon-containing
Selected from alkyl. M was chosen from group 4 of the periodic table
A metal, Y is divalent carbon or silicon, and X is
A halogen, alkyl or anionic ligand,
They may be selected in the same or different combinations, and m is
It is an integer of 1 to 3. ) 2. A method for polymerizing an olefin, comprising polymerizing an olefin using a metallocene compound represented by the general formula [1]. 3. The olefin polymerization method according to claim 2, wherein the metallocene compound represented by the general formula [1] and an aluminoxane are used in combination. 4. The method according to claim 2, wherein the metallocene compound represented by the general formula [1] and the ionic compound which converts the compound into a cationic compound and generates a stable counter anion species are used in combination with an organoaluminum compound. Olefin polymerization method. 5. The method according to claim 2, wherein the metallocene compound represented by the general formula [1] is used in combination with an aluminoxane supported on a support insoluble in an inert organic solvent. 6. R ¹ and R ² are methyl or phenyl,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are hydrogen, at least one of R ⁸ is methyl, M is zirconium or titanium,
The novel metallocene compound according to claim 1, wherein Y is carbon, X is chlorine, and m is 2.