JP3120601B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound having a phosphorus atom and a π-electron as a ligand.
A transition metal compound characterized by containing one VA group transition metal and Fe in a molecule is used as a main catalyst, and an organometallic compound, aluminoxane and an ionized ionic compound are used alone or in combination as a co-catalyst. And a process for polymerizing olefins in the presence of the catalyst.

[0002]

2. Description of the Related Art Various polymerization methods and catalyst systems are known for the polymerization of olefins. If a Ziegler-Natta catalyst system comprising a transition metal compound with a conventional alkylaluminum co-catalyst is used, a wide molecular weight distribution is obtained. It is known that high molecular weight polyolefins can be produced.

Recently, a catalyst system containing a transition metal compound containing a cyclopentadienyl derivative as a ligand (generally called a metallocene compound) has been developed. This catalyst system acts as a polymerization catalyst for olefins. In particular, metallocenes composed of transition metals of group IVA of titanium, zirconium or hafnium are used for producing polyethylene, ethylene copolymers or polypropylene, and aluminoxane is used as a cocatalyst. It has been found that a polyolefin can be produced with high activity by using the same (Japanese Patent Application Laid-Open No. 58-1930).
No. 9, etc.).

Many studies have been made on catalyst systems containing aluminoxane and a group IVA metallocene compound having various cyclopentadienyl derivatives as ligands, and various substituents are introduced into the cyclopentadienyl group. As a result, it was revealed that the primary structure such as the three-dimensional structure and composition distribution of the produced polymer or the production efficiency could be controlled (JP-A-61-26491 and JP-A-64-51408). JP-A-64-66216, JP-A-1-301704, J. Am.
em. Soc. 1988, 110, 6255-62).

[0005] In addition, since a large amount of aluminoxane is required, there is an industrial problem. Therefore, various organometallic compounds have been used as a co-catalyst in place of aluminoxane (JP-A-3-197513, JP-A-3-197513). 3-290408
), And polymerization of olefins using a cationic metallocene compound (eg, Japanese Patent Application Laid-Open No. 3-207704) is being studied.

According to the above specification, a polymer obtained by polymerization using a metallocene compound has a small oligomer content which is a problem in processing, and has a uniform composition when used in propylene or ethylene-α-olefin copolymerization. Although some characteristics are seen, such as showing the distribution, the molecular weight distribution is narrow and there are also problems in workability and mechanical strength. Conventionally, various studies have been made to solve these problems, but they have not been solved yet. Therefore, as a method for solving these problems, the necessity of developing a new catalyst system is increasing.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve this problem, and provides a catalyst capable of efficiently producing a polyolefin having excellent physical properties and processability, and a method for polymerizing an olefin using the same. It is to be.

[0008]

Means for Solving the Problems Mercy et al. Have reported several transition metal compounds containing as a ligand a phosphoryl group having an electronic structure similar to that of a cyclopentadienyl group. Organometallics, 198.
8,7,921, IVA having a phosphoryl group
Group transition metal compounds have been reported. Furthermore, J.I. Orga
nomet. Chemistry, 1990, 384,
271 reports that a reaction between this compound and an iron carbonyl compound produces an iron-zirconium binuclear transition metal compound in which two phosphoryl groups are crosslinked with iron.

As a result of intensive studies, the present inventors have found that the above-mentioned heteroatom-containing cyclic compound having a π-electron as a ligand has two kinds of compounds bonded through this heteroatom. Completion of the present discovery by finding that polymerization activity is exhibited for olefins by using a binuclear transition metal compound consisting of the above metals in combination with an organometallic compound, aluminoxane and an ionized ionic compound alone or in combination. I came to.

That is, the present invention provides a transition metal compound represented by the following general formula (1) containing a phosphorus compound and a π electron as a ligand and containing two or more metal atoms.

[0011]

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(Where A and B each contain a phosphorus atom,
Further, it is a compound having a π electron, and is represented by the following general formulas (2) and (3), respectively.

[0013]

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[0014]

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R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen, a silyl group , an alkyl group, an aryl group or an aralkyl group. Yes,
Fe is bonded to one or both of A and B in the general formula (1) via a phosphorus atom , M is a titanium atom,
R ⁹ is a zirconium atom or a hafnium atom, R ⁹ may be the same or different, and is hydrogen, halogen, silyl group, alkyl group, aryl group, aralkyl group, alkoxide, amide, phosphide or sulfide; A ligand or a transition metal compound that stabilizes Fe , and n is 1 to
And m is an integer of 0 to 6) and the period
A metal atom from Table IA, IIA, IIB or IIIB
An olefin polymerization catalyst comprising an organometallic compound having at least one or more alkyl groups as a constituent component, an olefin polymerization method using the same, an olefin polymerization catalyst wherein the organometallic compound is an organoaluminum compound, and The polymerization method of the olefin used and the aluminoxane wherein the organometallic compound is represented by the general formula (4) or (5)

[0016]

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[0017]

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(However, R ¹⁰ may be the same or different, and may be hydrogen, halogen, alkoxide , alkyl group, aryl,
Lumpur group, an aralkyl group, the polymerization of olefins q is using catalysts and it for the polymerization of olefins is an a) integer from 0 to 100, transition metal compound represented by the general formula (1), the periodic table IA, IIA, IIB or IIIB
Consisting of group metal atoms, at least one alkyl
Olefin polymerization catalyst comprising an organometallic compound having a group and an aluminoxane represented by general formula (4) or (5), a method for polymerizing olefin using the same, and transition of general formula (1) metal compounds, ionizing ionic compound represented by the general formula ^{(6) [C +] [} A -] (6) ( where, [C ^+] is a Bronsted acid, Karuboniumuka
Thion, oxonium cation or sulfonium click
Is on, [A ^-] is borate anion or aluminum
And the Periodic Tables IA, IIA, I
A metal atom of group IB or IIIB, at least
Provided are an olefin polymerization catalyst comprising an organometallic compound having at least one alkyl group as a component, a method for polymerizing an olefin using the catalyst, and the like.

Hereinafter, the present invention will be described in detail.

The transition metal compound as a catalyst component used in the present invention comprises at least two transition metals represented by the general formula (1), and further comprises a cyclic compound containing a phosphorus atom and having π electrons. Fe is represented by the above general formula (1)
Has A, a binding via <br/> to either one or both phosphorus atoms of B in. M is titanium, zirconium or hafnium. Ligand L for stabilizing Fe
Is a Lewis base such as an unsaturated hydrocarbon group represented by carbonyl, phosphine, amine, ethylene, etc., hydride,
A hydrocarbon group such as a halogen, a cyanide, an isocyanide, an alkoxide, an amide, a phosphide, an alkyl group, an aryl group, an aralkyl group, or a cycloalkadienyl group or a transition metal compound, and m is an integer of 0 to 6. is there. Specific examples of L include oxygen, ether, tetrahydrofuran, phosphorus, phosphine, phenylphosphine, methylphosphine, diphenylphosphine, dimethylphosphine, triphenylphosphine, trimethylphosphine,
Bis (diphenylphosphino) ethane, bis (diphenylphosphino) butane, bis (dimethylphosphino) ethane, bis (dimethylphosphino) butane, etc. crosslinked by two or more phosphorus atoms, nitrogen, amine, methylamine , Dimethylamine, trimethylamine, aniline,
Crosslinked two or more nitrogen atoms such as methylaniline, dimethylaniline, ethylenediamine, bis (dimethylamino) ethane, bipyridyl, carbon, carbonyl, ethylene, butadiene, cyclooctadiene, cyclooctatetraene, hydride, fluorine, Chlorine, bromine,
Iodine, cyanide, isocyanide, methoxy, ethoxy, butoxy, methylamide, ethylamide, propylamide, butylamide, dimethylamide, diethylamide, dipropylamide, dibutylamide, phosphide,
Methyl phosphide, ethyl phosphide, butyl phosphide, methyl, ethyl, propyl, butyl, phenyl, toluyl, phenyl, aryl, benzyl, cyclopentadienyl, substituted cyclopentadienyl, fluorenyl,
Cycloalkadienyl such as indenyl, carbon dioxide,
Examples include, but are not limited to, cluster compounds containing carbon disulfide, carborane or Fe , such as iron carbonyl compounds or inorganic salts . ^{Further, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 and R ⁸ may each be the same or different, hydrogen, a silyl group, an alkyl group, an aryl group, such aralkyl groups It is a hydrocarbon group, and examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a butylsilyl group, a phenylsilyl group, a diphenylsilyl group, and a triphenylsilyl group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a toluyl group, a cyclohexyl group, and a benzyl group.

Further, examples of the ligand include compounds having a cyclic carbon skeleton as shown below, for example, a phosphoindenyl group, a phosphofluorenyl group and the like.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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(Provided that R ′ and R ″ are each hydrogen, a silyl group or a hydrocarbon group such as an alkyl group, an aryl group, an aralkyl group, etc.)
It bonds with a phosphorus atom and / or a carbon atom and stabilizes the transition metal compound represented by the general formula (1).

R ⁹ may be the same or different,
Hydrogen, halogen, silyl group, alkyl group, aryl group,
Aralkyl groups, alkoxides, aryloxides, amides, phosphides or sulfides, such as fluorine, chlorine, bromine, iodine, trimethylsilyl,
Triethylsilyl group, butylsilyl group, phenylsilyl group, diphenylsilyl group, triphenylsilyl group, methyl group, ethyl group, propyl group, butyl group, hexyl group ,
Examples include octyl, phenyl, toluyl, cyclohexyl, benzyl, methoxy, ethoxy, dimethylamide, diethylamide, dipropylamide, dimethylphosphide, and methylsulfide groups.

Specific examples of the portion represented by the following general formula (7) in the transition metal compound of the general formula (1) include:

[0035]

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Bis (phosphoryl) titanium dimethyl,
Bis (phosphoryl) zirconium dimethyl, bis (phos
(Holyl) hafnium dimethyl, bis (phosphoryl) tita
Dichloride, bis (phosphoryl) zirconium
Dichloride, bis (phosphoryl) hafnium dichlora
Id, bis (2-methylphosphoryl) titanium dimethyl
, Bis (2-methylphosphoryl) zirconium dimethyl
, Bis (2-methylphosphoryl) hafnium dimethyl
Bis (2-methylphosphoryl) titanium dichlora
Id, bis (2-methylphosphoryl) zirconium dic
Loride, bis (2-methylphosphoryl) hafnium di
Chloride, bis (3-methylphosphoryl) titanium
Dimethyl, bis (3-methylphosphoryl) zirconium
Dimethyl, bis (3-methylphosphoryl) hafnium di
Methyl, bis (3-methylphosphoryl) titanium dic
Chloride, bis (3-methylphosphoryl) zirconium
Dichloride, bis (3-methylphosphoryl) hafnium
Mudichloride, bis (2,3-dimethylphosphoryl)
Titanium dimethyl, bis (2,3-dimethyl phosphoryl
B) zirconium dimethyl, bis (2,3-dimethylpho
Sphoryl) hafnium dimethyl, bis (2,3-dimethyl)
Ruphosphoryl) titanium dichloride, bis (2,3
-Dimethylphosphoryl) zirconium dichloride,
(2,3-dimethylphosphoryl) hafnium dichlora
Id, bis (2,4-dimethylphosphoryl) titanium
Dimethyl, bis (2,4-dimethylphosphoryl) zircon
Dimethyl, bis (2,4-dimethylphosphoryl)
Hafnium dimethyl, bis (2,4-dimethyl phosphoryl
Le) titanium dichloride, bis (2,4-dimethyl)
Phosphoryl) zirconium dichloride, bis (2,4
-Dimethylphosphoryl) hafnium dichloride, bis
(2,5-dimethylphosphoryl) titanium dimethyl,
Bis (2,5-dimethylphosphoryl) zirconium dime
Chill, bis (2,5-dimethylphosphoryl) hafnium
Dimethyl, bis (2,5-dimethylphosphoryl) titani
Um dichloride, bis (2,5-dimethyl phosphoryl
B) zirconium dichloride, bis (2,5-dimethyl)
Ruphosphoryl) hafnium dichloride, bis (3,4
-Dimethylphosphoryl) titanium dimethyl, bis
(3,4-dimethylphosphoryl) zirconium dimethyl
, Bis (3,4-dimethylphosphoryl) hafnium di
Methyl, bis (3,4-dimethylphosphoryl) titanium
Mudichloride, bis (3,4-dimethylphosphoryl)
Zirconium dichloride, bis (3,4-dimethylpho
Sphoryl) hafnium dichloride, bis (2,3,4)
-Trimethylphosphoryl) titanium dimethyl, bis
(2,3,4-trimethylphosphoryl) zirconium di
Methyl, bis (2,3,4-trimethylphosphoryl)
Funium dimethyl, bis (2,3,4-trimethylphos
(Holyl) titanium dichloride, bis (2,3,4-
Trimethylphosphoryl) zirconium dichloride,
(2,3,4-trimethylphosphoryl) hafnium di
Chloride, bis (2,3,5-trimethyl phosphoryl
Le) titanium dimethyl, bis (2,3,5-trimethyl)
Ruphosphoryl) zirconium dimethyl, bis (2,3,
5-trimethylphosphoryl) hafnium dimethyl, bis
(2,3,5-trimethylphosphoryl) titanium dic
Loride, bis (2,3,5-trimethylphosphoryl)
Zirconium dichloride, bis (2,3,5-trime
Tyl phosphoryl) hafnium dichloride, bis (2,
3,4,5-tetramethylphosphoryl) titanium dye
Chill, bis (2,3,4,5-tetramethyl phosphoryl
B) zirconium dimethyl, bis (2,3,4,5-te)
Tramethylphosphoryl) hafnium dimethyl, bis
(2,3,4,5-tetramethylphosphoryl) titanium
Mudichloride, bis (2,3,4,5-tetramethyl
Phosphoryl) zirconium dichloride, bis (2,
3,4,5-tetramethylphosphoryl) hafnium dik
Loride, bis (phosphoindenyl) titanium dimethyl
, Bis (phosphoindenyl) zirconium dimethyl,
Bis (phosphoindenyl) hafnium dimethyl, bis
(Phosphofluorenyl) titanium dichloride, bis
(Phosphofluorenyl) zirconium dichloride, bi
(Phosphofluorenyl) hafnium dichloride,
(Phosphoryl) (phosphoindenyl) titanium dimethyl
(Phosphoryl) (phosphoindenyl) zirconium
Dimethyl, (phosphoryl) (phosphoindenyl) hafni
Dimethyl, (phosphoryl) (phosphoindenyl) thio
Titanium dichloride, (phosphoryl) (phosphoinde
Nil) zirconium dichloride, (phosphoryl) (e
(Sphoindenyl) hafnium dichloride, (2-methyl
Ruphosphoryl) (phosphoindenyl) titanium dimethyl
Le, (2- Mechiruhosuhoriru) (Hosuhoinde sulfonyl) di
Ruconium dimethyl, (2-methylphosphoryl) (phos
(Hoindenyl) hafnium dimethyl, (2-methylphos
(Holyl) (phosphoindenyl) titanium dichlorai
Do, (2-methylphosphoryl) (phosphoindenyl) di
Ruconium dichloride, (2-methylphosphoryl)
(Phosphoindenyl) hafnium dichloride, (3-
Methylphosphoryl) (phosphoindenyl) titaniumdi
Methyl, (3-methylphosphoryl) (phosphoindenyl
Le) zirconium dimethyl, (3-methylphosphoryl)
(Phosphoindenyl) hafnium dimethyl, (3-methyl
Ruphosphoryl) (phosphoindenyl) titanium dichloride
Ride, (3-methylphosphoryl) (phosphoindenyl
Ru) zirconium dichloride, (3-methyl phosphoryl)
Le) (phosphoindenyl) hafnium dichloride,
(2,3-dimethylphosphoryl) (phosphoindenyl)
Titanium dimethyl, (2,3-dimethylphosphoryl)
(Phosphoindenyl) zirconium dimethyl, (2,3
-Dimethylphosphoryl) (phosphoindenyl) hafnium
Dimethyl, (2,3-dimethylphosphoryl) (phospho
Indenyl) titanium dichloride, (2,3-dimethyl)
Tylphosphoryl) (phosphoindenyl) zirconiumdi
Chloride, (2,3-dimethylphosphoryl) (phospho
Indenyl) hafnium dichloride, (2,4-dimension)
Tylphosphoryl) (phosphoindenyl) titanium
Chill, (2,4-dimethylphosphoryl) (phosphoinde
Nyl) zirconium dimethyl, (2,4-dimethylphos)
Folyl) (phosphoindenyl) hafnium dimethyl,
(2,4-dimethylphosphoryl) (phosphoindenyl)
Titanium dichloride, (2,4-dimethyl phosphoryl
Le) (phosphoindenyl) zirconium dichloride,
(2,4-dimethylphosphoryl) (phosphoindenyl)
Hafnium dichloride, (2,5-dimethyl phosphoryl
Le) (phosphoindenyl) titanium dimethyl, (2
5-dimethylphosphoryl) (phosphoindenyl) zirco
Dimethyl, (2,5-dimethylphosphoryl) (e
(Sphoindenyl) hafnium dimethyl, (2,5-dimension)
Tylphosphoryl) (phosphoindenyl) titaniumdic
Chloride, (2,5-dimethylphosphoryl) (phosphoi
Ndenyl) zirconium dichloride, (2,5-dimethyl)
Tylphosphoryl) (phosphoindenyl) hafniumdic
Chloride, (3,4-dimethylphosphoryl)
Ndeniru) titanium dimethyl, (3,4-di Mechiruho
Sphoryl) (phosphoindenyl) zirconium dimethyl
, (3,4-dimethylphosphoryl) (phosphoindenyl
Le) hafnium dimethyl, (3,4-dimethyl phosphoryl)
Le) (phosphoindenyl) titanium dichloride,
(3,4-dimethylphosphoryl) (phosphoindenyl)
Zirconium dichloride, (3,4-dimethylphospho
Ril) (phosphoindenyl) hafnium dichloride,
(2,3,4-trimethylphosphoryl) (phosphoindene
Nyl) titanium dimethyl, (2,3,4-trimethyl
Phosphoryl) (phosphoindenyl) zirconium dimethyl
, (2,3,4-trimethylphosphoryl) (phosphoi
Ndenyl) hafnium dimethyl, (2,3,4-trime
Tylphosphoryl) (phosphoindenyl) titaniumdic
Chloride, (2,3,4-trimethylphosphoryl) (e
(Sphoindenyl) zirconium dichloride, (2,
3,4-trimethylphosphoryl) (phosphoindenyl)
Hafnium dichloride, (2,3,5-trimethyl
Suphoryl) (phosphoindenyl) titanium dimethyl,
(2,3,5-trimethylphosphoryl) (phosphoindene
Nyl) zirconium dimethyl, (2,3,5-trimethyl)
Ruphosphoryl) (phosphoindenyl) hafnium dimethyl
, (2,3,5-trimethylphosphoryl) (phosphoi
Ndenyl) titanium dichloride, (2,3,5-to
Limethylphosphoryl) (phosphoindenyl) zirconium
Mudichloride, (2,3,5-trimethyl phosphoryl
Le) (phosphoindenyl) hafnium dichloride,
(2,3,4,5-tetramethylphosphoryl) (phospho
Indenyl) titanium dimethyl, (2,3,4,5-
Tetramethylphosphoryl) (phosphoindenyl) zirco
Dimethyl, (2,3,4,5-tetramethylphos
Folyl) (phosphoindenyl) hafnium dimethyl,
(2,3,4,5-tetramethylphosphoryl) (phospho
(Indenyl) titanium dichloride, (2,3,4,
5-tetramethylphosphoryl) (phosphoindenyl) di
Ruconium dichloride, (2,3,4,5-tetrame
Tylphosphoryl) (phosphoindenyl) hafniumdic
Loride, (phosphofluorenyl) (phosphoindenyl
Le) titanium dichloride, (phosphofluorenyl)
(Phosphoindenyl) zirconium dichloride, (e
Sufofluorenyl) (phosphoindenyl) hafnium di
Chloride, (phosphoryl) (phosphofluorenyl) thio
Motor bromide dimethyl, (phosphoryl) (Hosuhofuru fluorenylidenephenyl
Le) zirconium dimethyl, (phosphoryl) (phosphof
Fluorenyl) hafnium dimethyl, (phosphoryl) (e
(Shofluorenyl) titanium dichloride, (phospho
Lil) (phosphofluorenyl) zirconium dichlorai
De, (phosphoryl) (phosphofluorenyl) hafnium
Dichloride, (2-methylphosphoryl) (phosphoflur
(Oenyl) titanium dimethyl, (2-methyl phosphoryl)
Le) (phosphofluorenyl) zirconium dimethyl,
(2-Methylphosphoryl) (phosphofluorenyl) hough
Dimethyl, (2-methylphosphoryl) (phosphof
Fluorenyl) titanium dichloride, (2-methylpho
Sphoryl) (phosphofluorenyl) zirconium dichloride
Ride, (2-methylphosphoryl) (phosphofluorenyl
Le) hafnium dichloride, (3-methyl phosphoryl)
Le) (phosphofluorenyl) titanium dimethyl, (3
-Methylphosphoryl) (phosphofluorenyl) zirconi
Dimethyl, (3-methylphosphoryl) (phosphofur
(Oenyl) hafnium dimethyl, (3-methyl phosphoryl)
Le) (phosphofluorenyl) titanium dichloride,
(3-methylphosphoryl) (phosphofluorenyl) zyl
Conium dichloride, (3-methylphosphoryl) (e
(Shofluorenyl) hafnium dichloride, (2,3
-Dimethylphosphoryl) (phosphofluorenyl) titani
Dimethyl, (2,3-dimethylphosphoryl) (phos
Fluorenyl) zirconium dimethyl, (2,3-di)
Methylphosphoryl) (phosphofluorenyl) hafnium
Dimethyl, (2,3-dimethylphosphoryl) (phosphof
Fluorenyl) titanium dichloride, (2,3-dimethyl)
Tylphosphoryl) (phosphofluorenyl) zirconium
Dichloride, (2,3-dimethylphosphoryl) (phos
(Hofluorenyl) hafnium dichloride, (2,4-
Dimethylphosphoryl) (phosphofluorenyl) titanium
Dimethyl, (2,4-dimethylphosphoryl) (phospho
Fluorenyl) zirconium dimethyl, (2,4-dimethyl)
Tylphosphoryl) (phosphofluorenyl) hafniumdi
Methyl, (2,4-dimethylphosphoryl) (phosphoflur
(Oenyl) titanium dichloride, (2,4-dimethyl)
Ruphosphoryl) (phosphofluorenyl) zirconiumdi
Chloride, (2,4-dimethylphosphoryl) (phospho
Fluorenyl) hafnium dichloride, (2,5-di
Methylphosphoryl) (phosphofluorenyl) titanium
Dimethyl, (2,5-dimethyl phosphoryl) (Hosuhofu
Fluorenyl) zirconium dimethyl, (2,5-dimethyl)
Lephosphoryl) (phosphofluorenyl) hafnium dime
Chill, (2,5-dimethylphosphoryl) (phosphofluor
(Renyl) titanium dichloride, (2,5-dimethyl)
Phosphoryl) (phosphofluorenyl) zirconium dik
Chloride, (2,5-dimethylphosphoryl) (phosphof
Fluorenyl) hafnium dichloride, (3,4-dimethyl)
Tylphosphoryl) (phosphofluorenyl) titaniumdi
Methyl, (3,4-dimethylphosphoryl) (phosphoflur
(Oenyl) zirconium dimethyl, (3,4-dimethyl)
Phosphoryl) (phosphofluorenyl) hafnium dimethyl
, (3,4-dimethylphosphoryl) (phosphofluor
Nyl) titanium dichloride, (3,4-dimethylphos)
Sphoryl) (phosphofluorenyl) zirconium dichloride
Ride, (3,4-dimethylphosphoryl) (phosphoflur
(Oenyl) hafnium dichloride, (2,3,4-to)
Limethylphosphoryl) (phosphofluorenyl) titanium
Dimethyl, (2,3,4-trimethylphosphoryl)
(Phosphofluorenyl) zirconium dimethyl, (2
3,4-trimethylphosphoryl) (phosphofluorenyl
Le) hafnium dimethyl, (2,3,4-trimethylpho
Sphoryl) (phosphofluorenyl) titanium dichlora
Id, (2,3,4-trimethylphosphoryl) (phospho
Fluorenyl) zirconium dichloride, (2,3,
4-trimethylphosphoryl) (phosphofluorenyl) c
Funium dichloride, (2,3,5-trimethylphos
Folyl) (phosphofluorenyl) titanium dimethyl,
(2,3,5-trimethylphosphoryl) (phosphofluor
(Renyl) zirconium dimethyl, (2,3,5-trime
Tylphosphoryl) (phosphofluorenyl) hafniumdi
Methyl, (2,3,5-trimethylphosphoryl) (phos
(Fluorenyl) titanium dichloride, (2, 3,
5-trimethylphosphoryl) (phosphofluorenyl) di
Ruconium dichloride, (2,3,5-trimethylpho
Suphoryl) (phosphofluorenyl) hafnium dichlora
Id, (2,3,4,5-tetramethylphosphoryl)
(Phosphofluorenyl) titanium dimethyl, (2
3,4,5-tetramethylphosphoryl) (phosphofluor
(Renyl) zirconium dimethyl, (2,3,4,5-te)
Tramethylphosphoryl) (phosphofluorenyl) hafni
Dimethyl, (2,3,4,5-tetramethylphospho
Lil) (phosphonate fluorenyl) Chita Niumujikurorai
, (2,3,4,5-tetramethylphosphoryl) (e
(Shofluorenyl) zirconium dichloride, (2,
3,4,5-tetramethylphosphoryl) (phosphofluor
(Renyl) hafnium dichloride, (phosphoindeni
Le) (phosphofluorenyl) titanium dimethyl, (e
Sphoindenyl) (phosphofluorenyl) zirconium
Dimethyl, (phosphoindenyl) (phosphofluorenyl
Le) hafnium dimethyl and the like.
It is not limited. Also, ligand A and / or
Transition metal moiety that has a binding between the phosphorus atoms of the ligand B, that portion represented by the following general formula (8), specific examples of L _m Fe (8), such as tricarbonyl iron But are not limited to these.

As the organometallic compound used together with the compound of the general formula (1), there can be mentioned those comprising a metal atom belonging to Group IA, IIA, IIB or IIIB of the periodic table and having at least one alkyl group. It is preferably composed of lithium, boron, aluminum, magnesium, zinc, and may be the same or different, but may be a hydrocarbon group such as alkyl, aryl, and aralkyl bonded to a metal with hydrogen or carbon, an alkoxide bonded to a metal with oxygen, or Those having a substituent such as halogen, and having one or more alkyl groups are exemplified.

These organometallic compounds can be used according to the physical properties of the target polymer, the control of polymerization during production, and the like. Specific examples of the organometallic compounds used in the present invention are given below. Alkyl lithium such as methyl lithium and butyl lithium, alkyl borane such as triethyl borane, alkyl aluminum such as trimethyl aluminum, triethyl aluminum and triisobutyl aluminum, dimethyl aluminum fluoride, dimethyl aluminum chloride, diethyl aluminum chloride, diisobutyl aluminum chloride and the like Alkyl aluminum hydrides such as alkyl aluminum halide, diethyl aluminum hydride and diisobutyl aluminum hydride, dibutyl magnesium Alkylmagnesium, such as butylethylmagnesium, methylmagnesium chloride, methylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, etc., and alkylzinc, such as diethylzinc and diphenylzinc, but are not limited thereto. Not something.

One of the organometallic compounds having a bond between aluminum and oxygen is represented by the general formula (4):
Alternatively, an aluminoxane represented by the general formula (5) is also included. In the general formula (4) or (5), R ¹⁰ of the substituent may be the same or different and is hydrogen, halogen, alkoxide or hydrocarbon group. Specific examples include chlorine, bromine and iodine. Methoxy, ethoxy, propoxy, butoxy, phenoxy, methyl, ethyl, propyl, butyl, hexyl, phenyl, tolyl, cyclohexine and the like.

The preparation of such compounds is known.
(1) Trialkylaluminum is added to a hydrocarbon medium suspension of a compound having adsorbed water and salts containing water of crystallization (eg, magnesium sulfate hydrate, copper sulfate hydrate, and aluminum sulfate hydrate). A method of reacting or (2) a method of directly reacting water with a trialkylaluminum in a hydrocarbon medium can be exemplified.

These organometallic compounds may be used singly or in combination of two or more kinds according to the purpose. The organometallic compound when used alone is preferably one containing aluminum. And more preferably aluminoxane. When two or more of the above-described organometallic compounds are used in combination, it is preferable to include aluminoxane as a component of the organometallic compound. The method for preparing the catalyst from the organometallic compound and the transition metal compound represented by the general formula (1) is not particularly limited. Examples of the method for preparing the catalyst include a solvent which is inert with respect to both or a monomer which undergoes polymerization. And mixing. The temperature at which this processing is performed is not particularly limited, and the processing time is not particularly limited.

The ratio of the transition metal compound to the organometallic compound in the preparation of the catalyst is not particularly limited, but preferably, the molar ratio of the transition metal compound to the organometallic compound per metal atom is (metal of the transition metal compound): (Metal of organometallic compound) = 1
The range is from 00: 1 to 1: 1,000,000, particularly preferably from 1: 1 to 1: 100000.

The ionized ionic compound used as a component of the catalyst of the present invention is represented by the following general formula (6): [C ⁺ ] [A ⁻ ] (6) where [C ⁺ ] is a cation, Specifically, protons themselves or trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, N,
N-dimethylanilinium, N, N-diethylanilinium, triphenylphosphonium, tri (o-tolyl)
Examples of a Brönsted acid represented by phosphonium, tri (p-tolyl) phosphonium, tri (mesityl) phosphonium, etc., or a carbonium, oxonium or sulfonium cation containing no active proton include triphenylcarbenium and tropylium ions , Trimethyloxonium, triethyloxonium, compounds represented by triphenyloxonium, and the like, and lithium ions, magnesium ions, palladium ions, platinum ions, copper ions, and silver ions that are cations of metal atoms and organic metals. , Gold ion, mercury ion and etherate compounds having a base such as ether coordinated thereto, ferrocenium ion, dimethylferrocenium ion, and the like, but are not limited thereto. [A ⁻ ] is an anion, which is not particularly limited, but only weakly coordinates without reacting with the above-mentioned transition metal compound. For example, a metal such as magnesium or aluminum having a charge or a halogen, It is preferably bulky and non-nucleophilic, containing non-metals such as boron, phosphorus, etc., AlR ₄ ⁻ , B
R ₄ ^-, PR ₆ ^- or ClO ₄ ^- is such a compound of, specifically, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis (o-fluorophenyl) borate, tetrakis (p- fluorophenyl) borate, tetrakis (m-fluorophenyl) borate, tetrakis (3,5-difluorophenyl)
Borate, tetrakis (2,5-difluorophenyl)
Borate, tetrakis (2,6-difluorophenyl)
Borate, tetrakis (o- tolyl) borate, tetra
Kiss (p- tolyl) borate, tetrakis (3,5-dimethylphenyl) borate, tetrakis (2,5-dimethylphenyl) borate, tetraphenyl aluminate, tetrakis (pentafluorophenyl) aluminate, tetrakis ( o- fluorophenyl) aluminate, tetrakis (p- fluorophenyl) aluminate, tetrakis (m-fluorophenyl) aluminate, tetrakis (3,5-difluorophenyl) aluminate, tetrakis (2,5 difluorophenyl) aluminate, tetrakis (2,6-difluorophenyl) aluminate, tetrakis (o-tolyl) aluminate, tetrakis (p- tolyl) aluminate, tetra
Tetrakis (3,5-dimethylphenyl) aluminate, Tet <br/> La tetrakis (2,5-dimethylphenyl) aluminate, octadecanol borate, dodecaborate, 1-Cal bouncer deca borate, 1-carba dodecaborate etc. But are not limited to these.

Specific examples of the ionized ionic compound include lithium tetrakispentafluorophenyl borate, anilinium tetrakispentafluorophenyl borate, triphenylcarbenium tetrakispentafluorophenyl borate, tropinium tetrakispentafluorophenyl borate, and lithium tetrakispentafluoroborate. Examples include, but are not limited to, phenylaluminate, anilinium tetrakispentafluorophenylaluminate, triphenylcarbenium tetrakispentafluorophenylaluminate, tropinium tetrakispentafluorophenylaluminate, and the like.

The organometallic compound used herein may be any of the periodic tables IA, IIA, IIB or III described above.
Those comprising a Group B metal atom and having at least one or more alkyl groups are exemplified. Preferably lithium,
Consisting of boron, aluminum, magnesium, zinc,
They may be the same or different, but have a substituent such as a hydrogen, a hydrocarbon group such as alkyl, aryl, aralkyl and the like bonded to the metal by carbon, an alkoxide bonded to the metal by oxygen, and a substituent such as halogen. Those having an alkyl group are exemplified.

As specific examples, alkyllithiums such as methyllithium and butyllithium, alkylboranes such as triethylborane, alkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum, dimethylaluminum fluoride, dimethylaluminum chloride and diethylaluminum Alkyl aluminum halides such as chloride and diisobutyl aluminum chloride; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride;
Examples thereof include alkylmagnesium such as dibutylmagnesium and butylethylmagnesium; Grignard compounds such as methylmagnesium chloride, methylmagnesium bromide, butylmagnesium chloride and butylmagnesium bromide; and alkylzincs such as diethylzinc and diphenylzinc. It is not limited to these. Aluminoxane as described above can also be used.

There is no particular limitation on the method for preparing a catalyst from these ionized ionic compounds and the transition metal compounds and organometallic compounds listed in the general formula (1). Mixing in a solvent or using a monomer to be polymerized as a solvent can be mentioned. There is no particular limitation on the order in which these components are reacted. There is no particular limitation on the temperature at which this treatment is performed, and there is no particular limitation on the treatment time.

The ratio between the transition metal compound and the organometallic compound in the preparation of the catalyst is not particularly limited, but preferably, the molar ratio of the transition metal compound to the organometallic compound per metal atom is (metal of the transition metal compound): (Metal of organometallic compound) = 1
The range is from 00: 1 to 1: 1,000,000, particularly preferably from 1: 1 to 1: 100000. Also,
The ratio between the transition metal compound and the ionized ionic compound is not particularly limited, and preferably, the molar ratio between the transition metal compound and the ionized ionic compound is (transition metal compound) :( ionized ionic compound) = 10: 1 to 1: 1000. It is particularly preferably in the range of 1: 1 to 1: 100.

In the polymerization of olefins using a catalyst comprising the above components, an organometallic compound can be used as a cocatalyst according to the purpose. For example, when a polymer having a wide molecular weight distribution is synthesized, methylaluminoxane is used. In the case of synthesizing a polymer having a high molecular weight by using as a co-catalyst, examples of using an ionized ionic compound and an organoaluminum compound as a co-catalyst can be given, but the present invention is not limited thereto.

The polymerization of the present invention can be performed in a liquid phase or a gas phase. When the polymerization is carried out in the liquid phase, any solvent may be used as long as it is a commonly used organic solvent, and specific examples thereof include benzene, toluene, xylene, pentane, hexane, heptane, dichloromethane and the like, or propylene, 1- Butene, 1-hexene, 4-methyl-1-pen
Olefins themselves such as ten and 1-octene can also be used as the solvent.

The olefins used in the polymerization reaction include α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and styrene, and conjugated and non-conjugated such as butadiene and 1,4-hexadiene. Examples include cyclic olefins such as conjugated dienes and cyclobutenes, and a mixture of two or more of these can be polymerized.

The polymerization temperature, polymerization time, and catalyst concentration are not particularly limited, but the polymerization temperature is preferably in the range of -100 to 230 ° C.

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

All reactions are carried out under an inert gas atmosphere.
All solvents used in the reaction were purified by a known method in advance,
The dried and deoxidized one was used.

The molecular weight of the polyolefin obtained in the present invention was measured by gel permeation chromatography (GP).
C) (Waters 150C type), using a column of TSK-gel GMH, a sample volume of 350 μl, a column temperature of 140 ° C., and a flow rate of 1 ml / min.

Reference Example Synthesis of "1-phenyl-2,3,4,5-tetramethylphosphol" 17.44 g of 2-butyne in 250 ml of dichloromethane
Was dissolved, and 22.7 g of aluminum chloride was suspended in 250 ml of dichloromethane and added to the solution which had been cooled to -10 ° C. The resulting mixed solution was heated to complete the reaction. The reaction solution was cooled again, and 31.7 g of dichlorophenylphosphine was added to 250 ml of dichloromethane.
Was added. Further, a solution prepared by dissolving 39 ml of n-butylphosphine in 350 ml of dichloromethane was added to complete the reaction. After work-up and distillation under reduced pressure, 24 g of the desired product was obtained.

Synthesis of "bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride" 1-phenyl-2,3,50 ml of tetrahydrofuran was added to 50 ml of tetrahydrofuran.
2.27 g of 4,5-tetramethylphosphol was added, and 0.47 g of lithium was further added, and the mixture was reacted to remove excess lithium. Aluminum chloride was added to the reaction solution to neutralize phenyllithium generated by the reaction, and 1.17 g of zirconium chloride suspended in 10 ml of toluene was added. 2.3 g of an orange solid (target substance) was obtained from the reaction solution.

Synthesis of "bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride-tricarbonium iron" 0.44 g of the above orange solid and Fe ₂ (CO) ₉
0.46 g was stirred in methylcyclohexane and then heated to reflux, and a red powder (the target substance) was obtained from the reaction solution.
1 g was obtained and used as a catalyst.

Example 1 To a 2 l autoclave was added 500 ml of toluene.
Methylaluminoxane (Tosoh Akzo Co., Ltd.)
(Molecular weight: 1121) in terms of aluminum atom and 25 mmol thereof, and 1.4 mg of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride-tricarbonium iron. Polymerization was carried out at 60 ° C. for 1 hour while supplying ethylene to the autoclave so that the ethylene pressure became 8 kg / cm ² G. As a result, 46
g of polyethylene were obtained. Weight average molecular weight (Mw) is 7
1000, molecular weight distribution (Mw / number average molecular weight (Mn))
Was 5.6.

Example 2 The polymerization of ethylene was carried out in the same manner as in Example 1 except that 1.25 mmol of methylaluminoxane was used. As a result, 14 g of polyethylene was obtained. Mw is 22000
0 and Mw / Mn were 2.5.

Example 3 The polymerization of ethylene was carried out in the same manner as in Example 2 except that the polymerization temperature was 90 ° C. As a result, 8 g of polyethylene was obtained. Mw was 230,000 and Mw / Mn was 11.8.

Example 4 Ethylene was polymerized in the same manner as in Example 2 except that 1.25 mmol of triisobutylaluminum was used in addition to 1.25 mmol of methylaluminoxane. As a result, 24 g of powdered polyethylene was obtained. The polyethylene obtained here is probably because the molecular weight is too large.
Could not be measured. The molecular weight (Mv) determined from the viscosity average was 250,000.

Example 5 Copolymerization of ethylene was carried out in the same manner as in Example 1 except that 100 ml of hexene-1 was added. As a result, 23 g of a homogeneous ethylene-hexene-1 copolymer having a composition distribution was obtained.
Mw was 61000 and Mw / Mn was 4.2.

Example 6 To a 2 l autoclave was added 500 ml of toluene.
1.25 mmol of trimethylaluminum and the above bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride-tricarbonyliron
1.4 mg were added. 8 ethylene pressure in autoclave
kg / cm ² G while supplying ethylene.
Polymerization was carried out at 0 ° C. for 1 hour. As a result, 0.1 g of polyethylene was obtained.

Example 7 To a 2 l autoclave was added 500 ml of toluene.
To this were added 1.25 mmol of triisobutylaluminum and 1.4 mg of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride-tricarbonyliron described above. Further, a solution prepared by dissolving 10 mg of anilinium tetrakispentafluorophenyl borate synthesized by a known method in 10 ml of toluene was added to the autoclave. Polymerization was performed at 60 ° C. for 30 minutes while supplying ethylene to the autoclave so that the ethylene pressure became 8 kg / cm ² G. As a result, 54 g
Of polyethylene was obtained. Mw is 233000, Mw / M
n was 2.0.

[0066]

According to the present invention, a compound containing a hetero atom,
Also has a cyclic compound having a π electron as a ligand, binuclear transition metal compound and organometallic compound, aluminoxane and ionized ionic compound according to the purpose,
When used alone or in combination, it exhibits polymerization activity for olefins, has good polymer shape, and can produce polyolefins with excellent properties such as a wide molecular weight distribution, composition during copolymerization, and processability. Therefore, it can be utilized as an industrially valuable polymerization catalyst and an olefin polymerization method.

Claims (6)

(57) [Claims] A transition metal compound represented by the following general formula (1) containing a phosphorus compound and having a π electron as a ligand and containing two or more metal atoms: (Where A and B are compounds containing a phosphorus atom and having π electrons, and are represented by the following general formulas (2) and (3), respectively) Embedded image R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, and may be hydrogen, silyl group , alkyl
A group, an aryl group, or an aralkyl group, and Fe is phosphorus and either or both of A and B in the general formula (1).
And M is a titanium atom, a zirconium atom or a hafnium atom, and R ⁹ may be the same or different and each represents hydrogen, halogen, a silyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxide, amide, a phosphide or sulfide, L is may each be the same or different, ligand or stabilize the Fe
Other is a transition metal compound, n is an integer from 1 to 4,
m is an integer from 0 to 6) and the periodic tables IA, IIA,
Consisting of a Group IIB or IIIB metal atom, at least
An olefin polymerization catalyst comprising an organometallic compound having at least one alkyl group as a component. 2. The olefin polymerization catalyst according to claim 1, wherein the organometallic compound is an organoaluminum compound. 3. An aluminoxane wherein the organometallic compound is represented by the following general formula (4) or (5): Embedded image (Provided that R ¹⁰ may be the same or different and include hydrogen, halogen, alkoxide , alkyl group, aryl group,
An alkyl group, an olefin polymerization catalyst according to claim 1, q is characterized in that it is a an a) integer from 0 to 100. 4. The catalyst for olefin polymerization according to claim 3, wherein an organic metal compound other than aluminoxane is contained as an organic metal compound. 5. The olefin polymerization catalyst according to claim 1, which comprises an ionized ionic compound represented by the following general formula (6) as a constituent. ^{[C +] [A -]} (6) ( where, [C ^+] is a Bronsted acid, Karuboniumuka
Thion, oxonium cation or sulfonium click
Is on, [A ^-] is borate anion or aluminum
Is a nitrate anion ) 6. A method for polymerizing olefins, comprising using the catalyst for olefin polymerization according to claim 1.