JPH10110012A - Olefin polymerization catalyst and method for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst which can catalyze the polymerization of an olefin in excellent activity and can give an olefin polymer having a high molecular weight and to provide a method for producing an olefin by using this catalyst. SOLUTION: This catalyst comprises a transition metal (of group IVB in the periodic table) compound having as the ligand a polydentate compound composed of two different cycloalkadienyl groups or substitution products thereof selected from among cyclopentadienyl, indenyl, tetrahydroindenyl and fluorenyl groups and bonded to each other through a hydrocarbon group, a silylene group or a substituted silylene group and an organoaluminumoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst. More particularly, the present invention relates to an olefin polymerization catalyst capable of polymerizing olefins with excellent polymerization activity and having a large molecular weight. The present invention relates to an olefin polymerization catalyst capable of producing a coalescence and a method for polymerizing olefins using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Heretofore, a method for producing an .alpha.-olefin polymer has been a method for producing an .alpha.-olefin in the presence of a titanium catalyst comprising a titanium compound and an organoaluminum compound or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound. A method for polymerizing is known.

On the other hand, as a new Ziegler type olefin polymerization catalyst, a catalyst comprising a zirconium compound and an aluminoxane has been recently proposed. For example, JP
No. 8-19309 discloses that the following formula (cyclopentadienyl) ₂ MeRHal (where R is cyclopentadienyl, alkyl having 1 to 6 carbon atoms, halogen, Me is a transition metal,
a is a transition metal-containing compound represented by the following formula: Al ₂ OR ₄ (Al (R) —O) _n (where R is methyl or ethyl, and n is 4 to 2)
A linear aluminoxane represented by the following formula:

[0004]

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(Wherein the definitions of R and n are the same as those described above) in the presence of a catalyst comprising a cyclic aluminoxane represented by the formula (1), wherein ethylene and / or α-olefin having 3 to 12 carbon atoms are used. A method of polymerizing at least a seed at a temperature of -50C to 200C is described. The publication discloses that to control the density of the resulting polyethylene, 10
It is stated that the polymerization of ethylene should be carried out in the presence of small amounts of up to% by weight of somewhat longer chain α-olefins or mixtures.

[0006] JP-A-59-95292 discloses the following formula:

[0007]

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Wherein n is 2 to 40, and R is alkyl having 1 to 8 carbon atoms, and a linear aluminoxane represented by the following formula:

[0009]

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(Here, the definitions of n and R are the same as described above.) This invention describes a method for producing a cyclic aluminoxane represented by the formula: The publication discloses that, for example, a mixture of methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method and polymerizing an olefin gives, per 1 g of transition metal, It is stated that over 25 million g of polyethylene are obtained per hour.

JP-A-60-35005 discloses the following formula:

[0012]

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(Wherein R ¹ is alkyl having 1 to 10 carbon atoms and R ⁰ is R ¹ or is bonded to represent -O-). And then chlorinating the reaction product and further treating it with a compound of Ti, V, Zr or Cr to produce a polymerization catalyst for olefins. According to the publication, the catalyst is composed of ethylene and carbon atoms having 3 to 1 carbon atoms.
It is stated to be particularly suitable for the copolymerization of a mixture of α-olefins of No. 2.

JP-A-60-35006 discloses, as a catalyst system for producing a reactor blend polymer, mono-, di- or tri-cyclopentadienyl of two or more different transition metals or derivatives thereof (a). And alumoxane (aluminoxane) (b). Example 1 of the publication discloses that ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and alumoxane as catalysts to obtain a number average molecular weight of 15,300, a weight average molecular weight of 36,400 and a propylene component. It is disclosed that a polyethylene containing 3.4% was obtained. In Example 2, ethylene and propylene were polymerized with bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane as catalysts, and the number average molecular weight was 2,200.
A toluene-soluble portion containing a propylene component having a weight average molecular weight of 11,900 and 30 mol% and a number average molecular weight of 3,0
A polyethylene containing a propylene component having a number average molecular weight of 2,000, a weight average molecular weight of 8,300 and 7.1 mol% comprising a toluene-insoluble portion containing a propylene component having a weight average molecular weight of 7,400 and 4.8 mol%; A blend of ethylene-propylene copolymer is obtained.
Similarly, in Example 3, the molecular weight distribution (Mw / Mn) was 4.
A blend of LLDPE and an ethylene-propylene copolymer comprising 57 and a soluble portion of 20.6 mol% of a propylene component and a molecular weight distribution of 3.04 and an insoluble portion of 2.9 mol% of a propylene component is described.

JP-A-60-35007 discloses that ethylene alone or together with an α-olefin having 3 or more carbon atoms has a metallocene and a compound represented by the following formula:

[0016]

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(Where R is an alkyl group having 1 to 5 carbon atoms and n is an integer of 1 to about 20), or a cyclic alumoxane represented by the following formula:

[0018]

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(Where the definitions of R and n are the same as described above) and a method of polymerizing in the presence of a catalyst system containing a linear alumoxane. According to the description in the publication, the polymer obtained by the same method is about 50%.
Having a weight average molecular weight of 0 to about 1.4 million, and 1.5 to
It has a molecular weight distribution of 4.0.

JP-A-60-35008 discloses that a catalyst system containing at least two kinds of metallocenes and alumoxane is used to form polyethylene or ethylene having a wide molecular weight distribution and α-α having 3 to 10 carbon atoms. It is described that an olefin copolymer is produced. The publication discloses that the copolymer has a molecular weight distribution (Mw / M
n) is described as having 2 to 50.

The catalyst formed from the transition metal compound and the aluminoxane proposed in these prior arts has a higher polymerization activity than a catalyst system formed from a conventionally known transition metal compound and an organoaluminum compound. Although these catalyst systems are remarkably excellent, most of the catalyst systems proposed in these systems are soluble in the reaction system, and often employ a solution polymerization system, which not only limits the production process but also produces a high molecular weight polymer. In this case, the solution viscosity of the polymer system becomes extremely high.

On the other hand, one or both components of the above-mentioned transition metal compound and aluminoxane are silica,
Attempts have also been made to carry out olefin polymerization in a suspension polymerization system or a gas phase polymerization system using a catalyst supported on a porous inorganic oxide carrier such as silica / alumina or alumina.

For example, Japanese Patent Application Laid-Open No. 60-35 cited above
006, JP-A-60-35007 and JP-A-60-35008 disclose that a catalyst in which a transition metal compound and an aluminoxane are supported on silica, silica-alumina, alumina or the like can be used. Have been described.

JP-A-60-106808 and JP-A-60-106809 describe that a highly active catalyst component containing titanium and / or zirconium which is soluble in a hydrocarbon solvent is brought into contact with a filler in advance. A composition comprising a polyethylene-based polymer and a filler by copolymerizing ethylene or ethylene and an α-olefin in the presence of a product obtained by the treatment and an organoaluminum compound, and a filler having a polyolefin affinity. Have been proposed.

JP-A-61-31404 discloses that in the presence of a mixed catalyst comprising a product obtained by reacting a trialkylaluminum with water in the presence of silicon dioxide or aluminum oxide and a transition metal compound. , Ethylene or a method of polymerizing or copolymerizing ethylene and an α-olefin has been proposed.

Japanese Unexamined Patent Publication (Kokai) No. 61-276805 discloses that a reaction mixture obtained by reacting a trialkylaluminum with a zirconium compound and an aluminoxane is further reacted with an inorganic oxide having a surface hydroxyl group such as silica. There has been proposed a method of polymerizing an olefin in the presence of a catalyst comprising the reaction mixture.

Further, JP-A-61-108610 and JP-A-61-296008 disclose a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a support such as an inorganic oxide. A method for polymerizing an olefin has been proposed.

However, even when the olefin is polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system using the solid catalyst component supported on a carrier proposed in the prior art, the olefin is more in comparison with the solution polymerization system described above. No polymerization activity is remarkably reduced, and none of the catalysts composed of the transition metal compound catalyst component and the aluminoxane catalyst component fully exhibit the original characteristics possessed by the catalyst.

J. Am. Chem. Soc., 110, 6255 (1988) describes that syndiotactic polypropylene can be obtained by a combination of a specific zirconium or hafnium compound and an aluminoxane. However, there is no description about copolymerization of α-olefin.

When the present invention is applied to copolymerization of two or more olefins having a narrow molecular weight distribution, the olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution, particularly a narrow molecular weight distribution, As a result of studying a catalyst capable of producing a copolymer of an α-olefin having 3 or more carbon atoms having a high tacticity with excellent polymerization activity and a polymerization method using the same, (A) a specific polydentate It has been found that the above object can be achieved by using a catalyst comprising a transition metal compound of Group IVB of the periodic table having a coordinating compound as a ligand and (B) an organoaluminum oxy compound. It was completed.

[0031]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and has a narrow molecular weight distribution, and when applied to copolymerization of two or more olefins, the molecular weight distribution and the composition distribution are low. Narrow olefin copolymer, especially for olefin polymerization capable of producing a copolymer of α-olefins having 3 or more carbon atoms with excellent polymerization activity, having a narrow molecular weight distribution and high syndiotacticity. An object of the present invention is to provide a catalyst and a method for polymerizing an olefin using the catalyst.

[0032]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
(A) two different cycloalkadienyl groups selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, or a substituted product thereof is formed through a hydrocarbon group, a silylene group or a substituted silylene group; It is characterized by being formed from a transition metal compound of Group IVB of the periodic table having a bound polydentate compound as a ligand, and (B) an organoaluminum oxy compound.

The method for polymerizing an olefin according to the present invention comprises: (A) two different cycloalkadienyl groups selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, or a substitution thereof. Formed from a transition metal compound of Group IVB of the Periodic Table having a polydentate compound bonded through a hydrocarbon group, a silylene group or a substituted silylene group as a ligand, and (B) an organoaluminumoxy compound Olefin is polymerized or copolymerized in the presence of a catalyst.

[0034]

DETAILED DESCRIPTION OF THE INVENTION The catalyst for olefin polymerization according to the present invention and the method for polymerizing olefins using this catalyst will be specifically described below.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymers. It may be used for the purpose.

The olefin polymerization catalyst according to the present invention is formed from the above two catalyst components (A) and (B). Transition metal compound of group IVB of the periodic table (A)
Is a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, two different cycloalkadienyl groups selected from the group or a substituent thereof are formed through a hydrocarbon group or a silylene group or a substituted silylene group. It is a transition metal compound of Group IVB of the periodic table having a bonded polydentate compound as a ligand. The transition metal of Group IVB of the periodic table in such a catalyst component (A) is selected from the group consisting of titanium, zirconium and hafnium. Of these, hafnium and zirconium are preferred.

The transition metal compound (A) of Group IVB of the periodic table is, for example, a compound represented by the following general formula (I).

[0038]

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(Where Me is the transition of group IVB of the periodic table)
Metal, R⁰Is a hydrocarbon or silylene group
Represents a substituted silylene group;¹And R^TwoIs different,
Cyclopentadienyl group, indenyl group, tet
Selected from lahydroindenyl and fluorenyl groups
A cycloalkadienyl group or a substituted product thereof,
^ThreeAnd R^FourIs an aryl group, alkyl group, aralkyl
Group, cycloalkyl group, halogen atom, hydrogen, OR^a,
SR^b, NR^cOr PR^dAnd R^a, R^b, R^c
And R^dIs an alkyl group, a cycloalkyl group, an aryl
Group, a hydrocarbon group such as an aralkyl group or a silyl group.
Two R^cAnd R^dAre linked to form a ring
Can also. Here, specific examples of the hydrocarbon group include methylene
Group, ethylene group, propylene group, butylene group, diphenyl
Alkylene group such as lmethylene group, isopropylidene
Group, an alkylidene group such as a cyclohexylidene group,
There are arylene groups such as a nylene group, and has 1 to 10 carbon atoms.
Examples include hydrocarbon groups, including hydrocarbon groups.
Can be.

Examples of the substituted silylene group include a dimethylsilylene group. Specific examples of the cycloalkadienyl group include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, dimethylcyclopentadienyl group, indenyl group, tetrahydroindenyl group, and fluorenyl group. Examples can be given.

Specific examples of the aryl group include a phenyl group and a tolyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, Octyl group, 2-
Examples thereof include an ethylhexyl group and a decyl group.Specific examples of the aralkyl group include a benzyl group and a neophyl group.Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloalkyl group. Examples include an octyl group, a norbornyl group, a bicyclononyl group, and an alkyl substituent of these groups.

Examples of the halogen atom include fluorine, chlorine, bromine and the like. When the transition metal is zirconium, examples of the transition metal compound include the following compounds.

Isopropylidene (cyclopentadienyl)
-Methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadiene) Enyl-tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-ethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-diethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl-triethylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl-tetraethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl- Fluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (ethylcyclopentadienyl-
Fluorenyl) zirconium dichloride, isopropylidene (diethylcyclopentadienyl-fluorenyl)
Zirconium dichloride, isopropylidene (methylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl) Zirconium dichloride, isopropylidene (ethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (diethylcyclopentadienyl-2,7-di-t-butylfluorenyl) Zirconium dichloride, isopropylidene (methylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, isopropylidene (ethylcyclopentadienyl-octahydro) Fluore Le) zirconium dichloride, isopropylidene (diethyl cyclopentadienyl - octahydrofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl -
Methylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-dimethylcyclopentadienyl) zirconium dichloride,
Cyclohexylidene (cyclopentadienyl-trimethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-tetramethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-ethylcyclopentadiene) Enyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-diethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-triethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl- Tetraethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexyl Silidene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl
-Octahydrofluorenyl) zirconium dichloride, cyclohexylidene (methylcyclopentadienyl)
-Fluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (ethylcyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (diethylcyclopentadienyl-fluorenyl) zirconium dichloride , Cyclohexylidene (methylcyclopentadienyl)
-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (ethylcyclopentane) Dienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (diethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (methyl Cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, cyclohexylidene (ethylcyclopentadienyl-octahydrofluorenyl) zirconium Dichloride, cyclohexylidene (diethyl Cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl-trimethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-tetramethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-ethylcyclopentadienyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl-diethylcyclopentadienyl) zirconium dichloride, diphenylmethylene Pentadienyl-triethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-tetraethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2) , 7-Di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (dimethyl) Cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (ethylcyclopentadienyl-fluorenyl) zyl Conium dichloride, diphenylmethylene (diethylcyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl-2,7-di-
t-butylfluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadienyl-2,7-
Di-t-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (ethylcyclopentadienyl-2,7
-Di-t-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (diethylcyclopentadienyl-
2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl)
-Octahydrofluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (ethylcyclopentadienyl)
-Octahydrofluorenyl) zirconium dichloride, diphenylmethylene (diethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentane Dienyl-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-diethylcyclyl) (Pentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-triethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-tetraethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadiene) Enyl-fluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilyl (Ethylcyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium Dichloride, dimethylsilylene (dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium Dichloride, dimethylsilylene (diethylcyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclo Pentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl-octahydrofluorenyl) zirconium dichloride.

Examples of the hafnium compound used in the present invention include compounds in which the central metal of the above-mentioned zirconium compound is changed from zirconium to hafnium.

Further, as the titanium compound used in the present invention, a compound in which the center metal of the above-mentioned zirconium compound is changed from zirconium to titanium can be exemplified.

Examples of the organoaluminum oxy compound used as the catalyst component (B) include benzene-soluble aluminoxane represented by the following general formula (II) or (III).

[0047]

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In such an aluminoxane, R
And R ₂ may be the same or different and a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, hydrocarbon groups such as isobutyl group, preferably methyl group, ethyl group, isobutyl group, particularly preferably methyl group, m is 2 or more, It is preferably an integer of 5 or more.

As a method for producing aluminoxane as described above, for example, the following method can be exemplified. (1) Compounds containing water of adsorption, salts containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate,
A method in which a trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate to cause a reaction. (2) A method in which water is allowed to directly act on trialkylaluminum in a medium such as benzene, toluene, ethyl ether, and tetrahydrofuran.

Of these methods, the method (1) is preferably employed. The aluminoxane may contain a small amount of an organic metal component. Further, as the organoaluminum oxy compound used in the present invention, a benzene-insoluble organoaluminum oxy compound can be exemplified. The benzene-insoluble organic aluminum oxy compound will be described below.

The benzene-insoluble organoaluminum oxy compound used in the present invention may be (i) a reaction between an organoaluminum compound and water, or a solution of aluminoxane such as a hydrocarbon solution and water or (ii) an active hydrogen-containing compound. Obtained by the reaction with

The benzene-insoluble organoaluminum oxy compound is

[0053]

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(Wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms), and the Al component soluble in benzene at 60 ° C. is converted to Al atoms. 10% or less, preferably 5%
% Or less, particularly preferably 2% or less, and is insoluble or hardly soluble in benzene.

The solubility of the organic aluminum oxy compound used in the present invention is 100 milligram atoms of Al.
100 m of the organoaluminum oxy compound corresponding to
1 g of benzene, mixed at 60 ° C. for 6 hours with stirring, and filtered while hot at 60 ° C. using a G-5 glass filter with a jacket. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

In the above alkyloxyaluminum unit, R ¹ is specifically a methyl group, an ethyl group, an n-
Propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl,
Examples thereof include a cyclohexyl group and a cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound used in the present invention has the formula

[0058]

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In addition to the alkyloxyaluminum unit represented by the formula,

[0060]

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May contain an oxyaluminum unit represented by the formula: Where R ¹ is the same as above,
R ² is a hydrocarbon group having 1 to 12 carbon atoms, 1 to 12 carbon atoms.
, An aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, halogen or hydrogen, and R ¹ and R ² represent different groups.

In that case, an alkyloxyaluminum unit represented by the following formula:

[0063]

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At least 30 mol%, preferably 50 mol%
As described above, an organic aluminum oxy compound containing at least 70 mol% is particularly preferable. (I) The organoaluminum compound used in producing such a benzene-insoluble organoaluminum oxy compound is:
R ¹ _n AlX _3-n (wherein, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or hydrogen And n is 2-3).

Specific examples of such (ii) organoaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, trisec-butylaluminum, and tritert-butylaluminum. Aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tridecyl aluminum, tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, dialkyl aluminum such as diethyl aluminum bromide, diisobutyl aluminum chloride Aluminum halide, diethylaluminum hydride, diisobutylaluminum Dialkylaluminum hydride such as beam hydride, dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide are used. Among these organoaluminum compounds, an organoaluminum compound in which R is an alkyl group and X is a chlorine atom in the above general formula is preferable, and a trialkylaluminum is particularly preferable.

Further, (i) As the organoaluminum compound, the general formula (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (x, y, z are positive numbers, and z ≧ 2x Isoprenylaluminum represented by the formula:

The (a) organoaluminum compound as described above is used alone or in combination. In addition, as the (ii) active hydrogen-containing compound used in producing the benzene-insoluble organic aluminum oxy compound used in the present invention, alcohols such as methyl alcohol and ethyl alcohol, and diols such as ethylene glycol and hydroquinone are used. Can be

In the present invention, when water is used in preparing the benzene-insoluble organoaluminum oxy compound, when water is used, the water is dissolved in a hydrocarbon solvent such as benzene, toluene and hexane, an ether solvent such as tetrahydrofuran, and an amine solvent such as triethylamine. It can be used by dissolving or dispersing in water or in the state of steam or ice. In addition, as water, crystallization water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, cerous chloride, etc., or inorganic compounds or polymers such as silica, alumina, aluminum hydroxide and the like are adsorbed. Adsorbed water or the like can also be used.

The benzene-insoluble organoaluminum oxy compound used in the present invention may be, as described above, (i) a reaction between an organoaluminum compound and water, or a solution of an aluminoxane, for example, a hydrocarbon solution and water or (i).
i) Obtained by reaction with an active hydrogen-containing compound.
In order to produce a benzene-insoluble organoaluminum oxy compound from (i) an organoaluminum compound and water, (i) contacting the (a) organoaluminum compound with water in a solvent, for example, a hydrocarbon solvent, Water may be added to the reaction system so that the organic aluminum atoms dissolved therein are 20% or less of the total organic aluminum atoms. In order to obtain a benzene-insoluble organoaluminum oxy compound in this manner, (i) water is contacted in a range of 1 to 5 mol, preferably 1.5 to 3 mol, per 1 mol of the organoaluminum compound. desirable.

The reaction for producing the benzene-insoluble organoaluminum oxy compound as described above is carried out in a solvent, for example, a hydrocarbon solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene. , Butane, isobutane, pentane, hexane,
Hydrocarbon solvents such as aliphatic hydrocarbons such as octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclooctane, cyclodecane and cyclododecane; petroleum fractions such as gasoline, kerosene, and light oil; Alternatively, halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, in particular, halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran can also be used. Among these hydrocarbon media, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. And the concentration of water such as water of crystallization in the reaction system is usually 1 × 10 ^{−3 to} 20 mol / mol.
Liter, preferably in the range of 1 × 10 ⁻² to 10 mol / l. At this time, the amount of the organic aluminum atoms dissolved in the reaction system is desirably 20% or less, preferably 10% or less, more preferably 0 to 5% based on all the organic aluminum atoms. (I) The contact between the organoaluminum compound and water may be specifically performed as follows. (1) (i) A method in which a hydrocarbon solution of organoaluminum is brought into contact with a hydrocarbon solvent containing water. (2) A method in which (i) the organic aluminum is brought into contact with the water vapor by, for example, blowing water vapor into a hydrocarbon solution of the organic aluminum. (3) (i) mixing a hydrocarbon solution of an organoaluminum with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and bringing (i) the organoaluminum into contact with the adsorbed water or the water of crystallization. Method. (4) (i) A method of bringing a hydrocarbon solution of an organoaluminum into contact with ice.

The above-mentioned contact reaction between (i) the organoaluminum compound and water is carried out usually at -100 to 150 ° C, preferably at -50 to 100 ° C, and more preferably at -30 to 8-8.
It is performed at a temperature of 0 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually about 1 to 200 hours, preferably about 2 to 100 hours.

To produce the benzene-insoluble organoaluminum oxy compound used in the present invention from an aluminoxane solution and water or (ii) an active hydrogen-containing compound, the aluminoxane in the aluminoxane solution is used. And water or (ii) an active hydrogen-containing compound.

The solution of aluminoxane is preferably a solvent used when aluminoxane forms the above-mentioned benzene-insoluble organic aluminum oxy compound, preferably an aromatic hydrocarbon such as benzene or toluene. It is a solution dissolved therein, but may contain other components as long as it does not adversely affect the reaction between the aluminoxane and water or the compound containing active hydrogen.

The water or (ii) active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, per 1 gram atom of aluminum in the solution of aluminoxane. Used in quantity. The concentration in the reaction system is usually 1 × 10 ^{-3 to} 5 in terms of aluminum atoms.
It is desirably in the range of gram atoms / liter, preferably 1 × 10 ^{-2 to} 3 gram atoms / liter, and the concentration of water in the reaction system is usually 2 × 10 ^{-4 to} 5 mol / liter, preferably The concentration is preferably 2 × 10 ^{−3 to} 3 mol / l.

A solution of aluminoxane as described above,
The contact of water or (ii) the active hydrogen-containing compound with the aluminoxane solution and water will be described as an example. Specifically, the contact reaction may be performed as follows. (1) A method of contacting a solution of aluminoxane with a hydrocarbon solvent containing water. (2) A method of contacting the aluminoxane in the aluminoxane solution with the steam by, for example, blowing steam into the aluminoxane solution. (3) mixing a solution of aluminoxane with a hydrocarbon suspension of a compound containing absorbed water or a compound containing water of crystallization,
A method in which aluminoxane in an aluminoxane solution is brought into contact with adsorbed water or crystal water. (4) A method of bringing a solution of aluminoxane into direct contact with water or ice. (Ii) When an active hydrogen-containing compound is used, the same can be applied as described above.

A solution of aluminoxane as described above,
The contact reaction with water or (ii) an active hydrogen-containing compound is usually carried out at a temperature of -50 to 150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually about 0.5 to 300 hours, preferably about 1 to 150 hours.

The fine particle carrier used as the catalyst component (C) has an average particle size of usually 1 to 300 μm, preferably 1 to 300 μm.
It is a fine-grained inorganic carrier or a fine-grained organic carrier in the range of 00 to 200 μm. Oxides are preferred as the particulate inorganic carrier, and specifically, SiO ₂ , Al
Examples include ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , and mixtures thereof. Among them, SiO
₂ , a carrier containing at least one component selected from the group consisting of Al ₂ O ₃ and MgO as a main component is preferable. The inorganic oxide carrier is usually 150 to 1000 ° C,
Preferably, it is used by firing at 200 to 800 ° C. for 2 to 20 hours.

Examples of the finely divided organic carrier include finely divided organic polymers, for example, polyolefin fine particles such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene, and polystyrene. Examples thereof include a particulate polymer.

The electron donor which may be optionally contained as a component of the solid catalyst for olefin polymerization of the present invention includes carboxylic acids, esters, ethers, ketones, aldehydes, alcohols, phenols, and acids. Amides, metal atoms such as aluminum and silicon -OC
Examples thereof include oxygen-containing compounds such as bond-containing compounds, nitriles, amines, and phosphines.

As described above, the catalyst for olefin polymerization of the present invention comprises (A) a transition metal compound belonging to Group IVB of the periodic table;
Such catalysts, formed from an organoaluminum oxy compound and (C) a particulate carrier, are prepared by simultaneously mixing the catalyst components (A), (B) and (C) in a hydrocarbon or olefin medium, It is also possible to adopt a method in which two catalyst components are mixed in advance and the remaining one catalyst component is mixed. When mixing the two catalyst components in advance, it is preferable to previously mix the catalyst components (B) and (C) or the catalyst components (A) and (B).

The aluminum atom constituting the organoaluminum oxy compound per 100 g of the fine particle carrier in the olefin polymerization catalyst of the present invention is 0.01 or less.
10 to 10 gram atoms, preferably 0.1 to 5 gram atoms, and the transition metal atom per 100 g of the particulate carrier is 1 × 10 ^{−5 to} 0.1 gram atom, preferably 1 to 10 gram atom.
X 10 ^{-4 to} 5 x 10 ^-2 gram atoms. The ratio of the aluminum atom constituting the organic aluminum oxy compound to the transition metal atom is usually 5 to 2000, preferably 1 to 2000.
It is in the range of 0-1000.

The specific method for preparing the olefin polymerization catalyst according to the present invention is as follows: (1) An organic aluminum oxy compound is added to a particulate carrier suspended in a hydrocarbon medium, mixed, and then the solvent is removed. A method of bringing a transition metal compound suspended or dissolved in a hydrocarbon medium into contact with a solid component obtained by removal by filtration. (2) After adding and mixing an organoaluminum oxy compound to the particulate carrier suspended in an aromatic hydrocarbon medium,
Further, an aliphatic hydrocarbon is added, and the aromatic hydrocarbon is removed under reduced pressure. By this operation, the organoaluminum oxy compound is deposited on the particulate carrier.

Next, a method in which a transition metal compound suspended or dissolved in a hydrocarbon medium is brought into contact with a solid component obtained by removing an aliphatic hydrocarbon by filtration. (3) A method in which a mixture of an organoaluminum oxy compound and a transition metal compound is added to a particulate carrier suspended in a hydrocarbon medium, mixed, and then the hydrocarbon medium is removed by filtration or an evaporator. .

In the preparation method, the concentration of the organic aluminum oxy compound is usually 0.01 to 3 g atom / liter, preferably 0.1 to 0.3 g atom / liter, in terms of aluminum atom.
And the concentration of the particulate carrier is usually 1 to 200 g / L, preferably 5 to 200 g / L.
The concentration of the transition metal compound is usually 1 × 10 ^{−5 to} 5 × 10 ⁻² g atoms / liter, preferably 5 × 10 ⁻⁵ to 1 × 10 ^−2, as transition metal atoms.
Gram atoms / liter.

The excessive mixing of the organoaluminum oxy compound and the particulate carrier is usually from -20 to 100 ° C.
The mixing time is 0.1 to 10 hours. The temperature at which the transition metal compound is supported is usually −20 to 120 ° C., and the mixing time is 0.1 to 10 hours.

Specific examples of the hydrocarbon medium used in the preparation method include aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane;
Examples include alicyclic hydrocarbons such as methylcyclopentane and cyclooctane, and aromatic hydrocarbons such as benzene, toluene, and xylene.

The olefin polymerization catalyst according to the present invention as described above is used for producing an olefin polymer, and is particularly effective for producing an olefin polymer having a high syndiotacticity. Further, prior to the polymerization, a small amount of olefin may be prepolymerized and then used in the main polymerization.

Examples of olefins that can be used in the process of the present invention include ethylene and those having 3 to 3 carbon atoms.
20 α-olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene,
Examples thereof include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Further, if necessary, a polyene such as a diene can be copolymerized.

In the method of the present invention, the olefin polymerization reaction can be carried out by a gas phase polymerization method or a liquid phase polymerization method. In each case, the polymerization reaction is carried out in the presence of a hydrocarbon medium, if necessary.For example, in the case of a gas phase polymerization method, the polymerization reaction is carried out in the presence of a diluent consisting of a hydrocarbon medium, if necessary. It is carried out in the presence of a solvent comprising a hydrocarbon medium, if necessary.

Specific examples of the hydrocarbon medium include butane,
Isobutane, pentane, hexane, octane, decane,
Aliphatic hydrocarbons such as dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, gasoline, kerosene, In addition to petroleum fractions such as gas oil, olefins as raw materials also serve as hydrocarbon media.

In the method of the present invention, the temperature during the polymerization reaction is usually -50 to 150 ° C, preferably -20 to 120 ° C.
It is in the range of ° C. The polymerization can be carried out under normal pressure, under pressure or under reduced pressure, but preferably under pressure. Normally, normal pressure to 50kg / c
m ² , preferably under a pressure of about ² to 30 kg / cm ² . When the method of the present invention is carried out, the ratio of the transition metal compound used is usually 10 ⁻⁸ to 10 ⁻² g atom / g, preferably 10 ⁻⁷ to 10 g, as the concentration of the transition metal atom in the polymerization reaction system. ^In the range of ^-3 gram atoms / g.

[0093] The molecular weight of the polymer can be controlled by hydrogen and / or the polymerization temperature. In the method of the present invention, the olefin polymer of the present invention can be obtained by treating the polymerization reaction mixture after the polymerization reaction in a conventional manner.

[0094]

When the olefin is polymerized using the olefin polymerization catalyst according to the present invention, a polymer having a narrow molecular weight distribution can be obtained with excellent polymerization activity. Moreover, when an α-olefin having 3 or more carbon atoms is polymerized,
A polymer having a high syndiotacticity can be obtained.

[0095]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

[0096]

Example 1 [Preparation of aluminoxane] 400 sufficiently substituted with nitrogen
Al ₂ (SO ₄ ) ₃ .14H ₂ O37
g and 125 ml of toluene and cooled to 0 ° C.
500 mmol of trimethylaluminum diluted with 125 mm of toluene was added dropwise. Next, the temperature is raised to 40 ° C.
The reaction was continued at that temperature for 10 hours.

After completion of the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the filtrate to obtain 13 g of aluminoxane as a white solid. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in the catalyst component [B] was 14. In the polymerization, the aluminoxane obtained as described above was redissolved in toluene and used. [Preparation of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride] 8.3 g of fluorene and 150 ml of tetrahydrofuran (THF) were charged into a 400 ml flask which had been sufficiently purged with nitrogen.
After cooling to 0 ° C., 40 ml of an n-butyllithium hexane solution (1.6 M) was added dropwise. After reacting for 5 hours,
5.0 ml of dimethylfulvene was added dropwise, and after the temperature was raised to room temperature, the reaction was continued overnight.

After completion of the reaction, the reaction mixture was extracted with toluene, and then purified by silica gel column chromatography to obtain 4 g of 2-cyclopentadienyl-2-fluorenylpropane.

Next, 4 g of 2-cyclopentadienyl-2-fluorenylpropane and 150 ml of THF were charged into a 400 ml flask which had been sufficiently purged with nitrogen, cooled to -78 ° C., and then cooled with n-butyllithium. Hexane solution (1.6
M) was added dropwise. Zirconium tetrachloride was added to the resulting dianion and allowed to react overnight. Filtration yielded 2 g of the desired catalyst, ie, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride.

[Preparation of catalyst component]
A 00 ml glass flask was charged with 6 g of silica (F952 manufactured by Devison) baked at 700 ° C. for 12 hours and 100 ml of toluene. Furthermore, after adding 23.8 ml of a toluene solution of aluminoxane (Al 2.1 mol / l) at room temperature, the mixture was stirred at 40 ° C. for 1 hour. Subsequently, the liquid part was removed from the reaction solution using a glass filter,
The remaining solid was suspended again with 100 ml of toluene. 0.2 mmol of the zirconium compound synthesized above was added to this suspension and stirred at 40 ° C. for 1 hour. Thereafter, a liquid part was removed from the suspension using a glass filter, and then washed twice with toluene to obtain a catalyst component. The supported amounts of zirconium and aluminum in the catalyst component were 0.22% by weight, 1
It was 3% by weight.

[Polymerization] 500 g of propylene and the above solid catalyst were converted into 3 zirconium atoms at 20 ° C. in a 2-liter stainless steel autoclave sufficiently purged with nitrogen.
× 10 ^-3 milligrams were charged atomically. Thereafter, the temperature was raised to 30 ° C., and polymerization was carried out at that temperature for 1 hour. After 1 hour of polymerization,
The polymerization was stopped by adding a small amount of methanol. Next, unreacted propylene was purged.
[Η] determined in decalin at 35 ° C. is 1.04 dl / g
And the syndiotactic fraction (rr) measured by ¹³ C-NMR was 92%, and Mw / Mn measured by GPC
Was 2.23, and 51 g of a spherical polymer having a bulk specific gravity of 0.45 g / cm ³ was obtained. The content of the finely divided polymer having a particle size of 100 μm or less was 0.1% by weight or less.

[0102]

[Example 2] [Preparation of catalyst component] 5 g of silica (F952 manufactured by Davison) and 100 ml of toluene calcined at 700 ° C for 5 hours were charged into a 400 ml glass flask sufficiently purged with nitrogen. Further, a toluene solution of aluminoxane (Al
(2.1 mol / l) and 0.16 mmol of the zirconium compound synthesized in Example 1 were added.
Stirred at 5 ° C for 2 hours. Thereafter, a liquid part was removed from the suspension using a glass filter, and then washed twice with toluene to obtain a catalyst component. The supported amounts of zirconium and aluminum in the catalyst component were 0.20% by weight and 13% by weight, respectively.

[Polymerization] When the polymerization was carried out in the same manner as in Example 1, [η] was 0.96 dl / g, rr was 91%, Mw / Mn was 2.30, and the bulk specific gravity was 0.1. 42g
/ Spherical polymer 48g it was obtained is cm ^3. Also,
The finely divided polymer having a particle size of 100 μm or less was 0.1% by weight or less.

[0104]

Example 3 [Preparation of isopropylidene (cyclopentadienyl-fluorenyl) hafnium dichloride] The procedure of Example 1 was repeated, except that hafnium tetrachloride was used instead of zirconium tetrachloride.

[Preparation of catalyst component] The procedure of Example 1 was repeated except that the hafnium compound was used in an amount of 0.18 mmol instead of the zirconium compound. .39% by weight and 12% by weight of a solid catalyst component were obtained.

[Polymerization] In the polymerization of Example 1, 70 ° C.
Example 2 except that the temperature was raised until the polymerization was carried out at that temperature for 1 hour.
When polymerization was carried out in the same manner as in Example 1, [η] was 2.97 d.
l / g, rr is 83%, and Mw / Mn is 2.3.
7, with a bulk specific gravity of 0.43 g / cm ^ThreeIs a spherical poly
36 g of mers were obtained. In addition, fine powder
The limer was less than 0.1% by weight.

[0107]

Example 4 [Polymerization] Ethylene polymerization was carried out using the catalyst component prepared in Example 1.

150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Thereafter, the system was cooled to 75 ° C., and 0.01 mg of the solid catalyst component prepared in Example 1 was inserted in terms of zirconium atoms. Thereafter, 50 ml of hydrogen was introduced, ethylene was further introduced at 75 ° C., and the total pressure was 8 kg /
The polymerization was started as cm ² -G. Thereafter, only ethylene was supplied, and the polymerization was carried out at 80 ° C. for 0.5 hour while maintaining the total pressure at 8 kg / cm ² -G. After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with hexane and then dried under reduced pressure at 80 ° C. overnight. 190 ° C, load 2.
MFR measured under a condition of 16 kg was 0.11 g / 10 min, Mw / Mn measured by GPC was 2.49, and 126 g of a spherical polymer having a bulk specific gravity of 0.41 g / cm ³ was obtained.

[0109]

Example 5 [Preparation of solid catalyst component (A)] In [Preparation of catalyst component] of Example 1, dimethylsilylene (cyclopentadienyl) was used instead of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride. -2,7-di
A solid catalyst component (A) was prepared in the same manner as in Example 1, except that (-tert-butylfluorenyl) zirconium dichloride was used. The supported amounts of zirconium and aluminum in the solid catalyst component (A) were 0.23, respectively.
% By weight and 13% by weight.

[Polymerization] In [Polymerization] of Example 4,
Example 4 Example 4 was repeated except that the solid catalyst component (A) obtained above was used in an amount of 0.01 mg atom in terms of zirconium atom instead of "the solid catalyst component prepared in Example 1".
The polymerization of ethylene was carried out in the same manner as described above. As a result, 19
The MFR measured under the conditions of 0 ° C. and a load of 2.16 kg is 0.07 g / 10 min, and the bulk specific gravity is 0.40 g / cm.
115 g of ³ spherical polymer was obtained.

[0111]

Example 6 [Preparation of solid catalyst component (B)] In [Preparation of catalyst component] of Example 1, dimethylsilylene (3-methylcyclohexane) was used instead of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride. A solid catalyst component (B) was prepared in the same manner as in Example 1 except that (pentadienyl-fluorenyl) zirconium dichloride was used. The supported amounts of zirconium and aluminum in the solid catalyst component (B) were 0.22% by weight and 13%, respectively.
% By weight.

[Polymerization] In [Polymerization] of Example 4,
Example 4 Example 4 was repeated except that the solid catalyst component (B) obtained above was used in an amount of 0.01 mg atom in terms of zirconium atom instead of "the solid catalyst component prepared in Example 1".
The polymerization of ethylene was carried out in the same manner as described above. As a result, 19
The MFR measured under the conditions of 0 ° C. and a load of 2.16 kg is 0.24 g / 10 min, and the bulk specific gravity is 0.41 g / cm.
78 g of ³ spherical polymer was obtained.

[0113]

Example 7 [Preparation of solid catalyst component (C)] In [Preparation of catalyst component] of Example 1, ethylene (indenyl-fluorenyl) zirconium was used instead of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride. A solid catalyst component (C) was prepared in the same manner as in Example 1 except that dichloride was used. The supported amounts of zirconium and aluminum in the solid catalyst component (C) were 0.24% by weight and 13% by weight, respectively.

[Polymerization] In [Polymerization] of Example 4,
Example 4 Example 4 was repeated except that the solid catalyst component (C) obtained above was used in an amount of 0.01 mg atom in terms of zirconium atom instead of "the solid catalyst component prepared in Example 1".
The polymerization of ethylene was carried out in the same manner as described above. As a result, 19
The MFR measured under the conditions of 0 ° C. and a load of 2.16 kg is 0.57 g / 10 min, and the bulk specific gravity is 0.41 g / cm.
73 g of ³ spherical polymer was obtained.

[0115]

Example 8 [Preparation of solid catalyst component (D)] In [Preparation of catalyst component] of Example 1, dimethylsilylene (cyclopentadienyl) was used instead of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride. A solid catalyst component (D) was prepared in the same manner as in Example 1, except that (-indenyl) zirconium dichloride was used. The supported amounts of zirconium and aluminum in the solid catalyst component (D) were 0.21% by weight and 13% by weight, respectively.

[Polymerization] In [Polymerization] of Example 4,
Example 4 Example 4 was repeated except that the solid catalyst component (D) obtained above was used in an amount of 0.01 mg atom in terms of zirconium atom instead of "the solid catalyst component prepared in Example 1".
The polymerization of ethylene was carried out in the same manner as described above. As a result, 19
The MFR measured under the conditions of 0 ° C. and a load of 2.16 kg is 1.53 g / 10 minutes, and the bulk specific gravity is 0.40 g / cm.
64 g of ³ spherical polymer was obtained.

[0117]

Example 9 [Preparation of diphenylmethylene (cyclopentadienyl-fluorenyl) zirconium dichloride] In Example 1, [Preparation of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride], 6,6-
12.1 g of cyclopentadienyldiphenylfluorenylmethane was obtained in the same manner as in Example 1 except that 10.8 g of 6,6-diphenylfulvene was used instead of 5 g of dimethylfulvene. Next, diphenylation was performed using 5.5 g of cyclopentadienyldiphenylfluorenylmethane, followed by reaction with zirconium tetrachloride in the same manner as in Example 1 to obtain diphenylmethylene (cyclopentadienyl-fluorenyl) zirconium dichloride in 3 g. .
6 g were obtained.

[Preparation of catalyst component] The procedure of Example 1 was repeated except that the diphenylmethylene (cyclopentadienyl-fluorenyl) zirconium dichloride prepared above was used as the zirconium compound in the preparation of [catalyst component]. In the same manner as in 1, the solid catalyst component (E) was prepared.

[Polymerization] Propylene was prepared in the same manner as in Example 1 except that the solid catalyst component (E) prepared above was used in an amount of 0.2 mmol in terms of zirconium atom in [Polymerization] of Example 1. [Η] is 3.00 dl / g, racemic dyad is 94%, Mw /
A spherical polymer having an Mn of 2.10 and a bulk specific gravity of 0.43
8 g were obtained.

[0120]

Example 10 [Isopropylidene (cyclopentadienyl-2,7-di-te
Preparation of rt-butyl-9-fluorenyl) zirconium dichloride In "Preparation of isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride" of Example 1, Synthesi was used instead of 8.3 g of fluorene.
s-335 (1984), except that 13.0 g of 2,7-di-tert-butyl-9-fluorene was used in the same manner as in Example 1 except that 13.0 g of 2,7-di-tert-butyl-9-fluorene was used. 2- (2 ', 7'-di-t
19.0 g of (ert-butyl-9-fluorenyl) propane were obtained. Furthermore, the 2-cyclopentadienyl-2- (2 ', 7'-di-t
Dipropylation using 5.6 g of ert-butyl-9-fluorenyl) propane followed by reaction with zirconium tetrachloride in the same manner as in Example 1 to give isopropylidene (cyclopentadienyl-2,7-di-tert. 2.4 g of (-butyl-9-fluorenyl) zirconium dichloride were obtained.

[Preparation of Catalyst Component] In the preparation of [Preparation of Catalyst Component] in Example 1, the isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-butyl) prepared above was used as the zirconium compound. A solid catalyst component (F) was prepared in the same manner as in Example 1 except that fluorenyl) zirconium dichloride was used.

[Polymerization] Propylene was prepared in the same manner as in Example 1 except that the solid catalyst component (F) prepared above was used as a solid catalyst in an amount of 0.2 mmol in terms of zirconium atoms. [Η] is 0.96 dl / g, racemic dyad is 95%, Mw /
A spherical polymer having an Mn of 2.21 and a bulk specific gravity of 0.44
0.0 g was obtained.

[Brief description of the drawings]

FIG. 1 is a flowchart illustrating a method for polymerizing an olefin according to the present invention.

Claims (6)

[Claims] (A) two different cycloalkadienyl groups selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group, or a substituted product thereof is a hydrocarbon group, a silylene group or a substituted group; An olefin polymerization catalyst characterized by being formed from a transition metal compound of Group IVB of the periodic table having a polydentate compound bonded via a silylene group as a ligand and (B) an organoaluminumoxy compound. 2. A transition metal compound of Group IVB of the periodic table
(A) is a transition metal compound represented by the following general formula (I)
2. The catalyst for olefin polymerization according to claim 1;(Where Me is a transition metal of Group IVB of the periodic table,
R⁰Is a hydrocarbon or silylene group or substituted silylene
And R represents¹And R^TwoAre different from each other
Lopentadienyl group, indenyl group, tetrahydroin
Cycloal selected from benzyl and fluorenyl groups
A carbenyl group or a substituent thereof, ^ThreeAnd R^Four
Is an aryl, alkyl, aralkyl, cycloalkyl
Kill group, halogen atom, hydrogen, OR^a, SR^b, NR^c
Or PR^dAnd R^a, R^b, R^cAnd R^dIs
Alkyl group, cycloalkyl group, aryl group, aralkyl
Or silyl group, two R^cAnd R^dIs linked
To form a ring. ) 3. In the general formula (I), the cycloalkadienyl group or a substituent thereof is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, The olefin polymerization catalyst according to claim 2, which is an indenyl group, a tetrahydroindenyl group, or a fluorenyl group. (A) two different cycloalkadienyl groups selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group or a substituted product thereof is a hydrocarbon group, a silylene group or a substituted group; In the presence of a catalyst formed from a transition metal compound of Group IVB of the Periodic Table having a polydentate compound bonded via a silylene group as a ligand and (B) an organoaluminum oxy compound, an olefin is polymerized or A method for polymerizing olefins, comprising copolymerizing. 5. A transition metal compound of Group IVB of the periodic table
(A) is a transition metal compound represented by the following general formula (I)
5. The method for polymerizing an olefin according to claim 4;(Where Me is a transition metal of Group IVB of the periodic table,
R⁰Is a hydrocarbon or silylene group or substituted silylene
And R represents¹And R^TwoAre different from each other
Lopentadienyl group, indenyl group, tetrahydroin
Cycloal selected from benzyl and fluorenyl groups
A carbenyl group or a substituent thereof, ^ThreeAnd R^Four
Is an aryl, alkyl, aralkyl, cycloalkyl
Kill group, halogen atom, hydrogen, OR^a, SR^b, NR^c
Or PR^dAnd R^a, R^b, R^cAnd R^dIs
Alkyl group, cycloalkyl group, aryl group, aralkyl
Or silyl group, two R^cAnd R^dIs linked
To form a ring. ) 6. The compound of the formula (I) wherein the cycloalkadienyl group or a substituent thereof is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, The method for polymerizing an olefin according to claim 5, which is an indenyl group, a tetrahydroindenyl group or a fluorenyl group.