Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-02-16
2003-06-24
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S012000, C556S019000, C556S020000, C556S043000, C556S053000, C556S058000, C526S127000, C526S348600, C526S351000, C526S352000, C526S943000, C502S103000, C502S117000
Reexamination Certificate
active
06583304
ABSTRACT:
BACKGROUND OF THE INVENTION
(a). Field of the Invention
The present invention relates to metallocene compounds, metallocene catalysts including the compounds and methods of polymerizing olefins with the catalysts.
(b). Description of the Related Art
Catalysts including transition metals have been widely used for olefin polymerization. Lately, German Patent Nos. 2,608,933 and 3,007,725 have disclosed that metallocene compound consisting of Group 4B transition metal such as zirconium, titanium or hafnium, and ligand having cyclopentadienyl structure can be used as catalyst for olefin polymerization in the presence of an activator such as methylaluminoxane. The examples of the ligands having the cyclopentadienyl structures include cyclopentadiene, indene, fluorene, and substituted varieties of such compounds.
Various metallocene compounds having cyclopentadienyl-type ligands have been used to prepare the catalyst systems for the olefin polymerization. It has also been known that changes of chemical structures of the cyclopentadienyl ligands may produce significant effects on the suitabilities of metallocene compounds as the catalysts. For example, activities, stereospecificities, and stabilities of the catalysts, and physical properties of the polymers obtained by the polymerization depend on the sizes and positions of substituents bonded to cyclopentadienyl ligands.
In various documents such as European patent No. 129,368, U.S. Pat. Nos. 4,874,880 and 5,324,800 and Makromol. Chem. Rapid Commun., 4, 417(1983) et al., it have also been disclosed that the catalyst systems including of metallocene compounds, which consists of substituted-cyclopentadienyl ligands and zirconium as the transition metal, and methylaluminoxane have high activities in the olefin polymerization. In addition, the metallocene compounds consisting of zirconium and cyclopentadienyl ligands substituted with hydrocarbyl group are also known. For examples, bis(alkylcyclopentadienyl) zirconium dichloride (wherein, alkyl represents methyl, ethyl, isopropyl, tert-butyl or trimethylsilyl.) [J. Chem. Soc. Dalton Trans.,805(1981)], bis(pentamethylcyclopentadienyl)zirconium dichloride [J. Amer. Chem. Soc., 100, 3078(1978)], (pentamethylcyclopentadienyl) (cyclopentadienyl)zirconium dichloride [J. Amer. Chem. Soc., 106, 6355(1984)], bis(di, tri, or tetra alkyl-cyclopentadienyl)zirconium dichloride [U.S. Pat. No. 4,874,880], non-bridged metallocene compounds having substituted indenyl ligands [U.S. Pat. No. 5,780,659], metallocene compounds having mono substituted cyclopentadienyl ligand [German patent No. 4,312,270] are known.
Even though the activities of the metallocene catalysts have been progressively increased by changing the structures of the metallocene compounds, there exists a need for the better metallocene catalysts having sufficient activities to prepare polyolefin of high molecular weight and better physical properties.
SUMMARY OF THE INVENTION
Thus, the present invention is directed to the preparation of polyolefin with novel catalyst systems, which include metallocene compounds consisting of cyclopentadienyl-type ligands having silacycloalkyl substituents and transition metal such as zirconium, titanium or hafnium.
It is, therefore, an object of the present invention to provide novel metallocene compounds, which forms metallocene catalysts for olefin polymerization.
It is another object of the present invention to provide new metallocene catalysts prepared from the metallocene compounds.
It is also another object of the present invention to provide methods of polymerizing olefins with the metallocene catalysts.
In accordance with an embodiment of the present invention, there is provided metallocene compounds of the following formula 1 or 2, which can be used to prepare metallocene catalysts for olefin polymerization.
(CpR
1
a
R
s
b
)(Cp′R
2
a′
R
s
b′
)MX
2
[Formula 1]
In formula 1 and 2, Cp and Cp′, which can be the same or different, represent a radical selected from the group consisting of cyclopentadienyl radical, indenyl radical, 4,5,6,7-tetrahydro-1-indenyl radical and fluorenyl radical;
R
1
and R
2
, which can be the same or different, represent phosphine, amino, alkyl having 1 to 20 carbon atoms, alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, alkylaryl or arylalkyl radical;
R
s
represents 1-alkyl-1-silacyclohydrocarbyl radical of the following formula 3,
wherein, R
3
and R
4
, which can be the same or different, represent hydrogen or alkyl radical having 1 to 5 carbon atoms, R
5
is alkyl radical having 1 to 8 carbon atoms, and n is an integer of 4 to 8;
Cp′R
2
a′
, R
s
b′
in the formula 2 can be displaced with divalent NR″ radical, wherein R″ represents R
s
, alkyl radical having 1 to 12 carbon atoms, or aryl radical having 6 to 10 carbon atoms;
M represents a Group 4B, 5B, 6B transition metal, and preferably represents titanium, zirconium or hafnium;
X, which can be the same or different, represents one radical selected from the group consisting of halogen, alkyl radical having 1 to 20 carbon atoms, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy and aryloxy radicals; and
Q represents alkylene radical having 1 to 4 carbon atoms, dialkyl germanium or silicon, alkyl phosphine or amine radical, bis-dialkylsilyl or bis-dialkylgermanyl having hydrocarbyl radical of 1 to 4 carbon atoms.
In formula 1, a is an integer of 0 to 4, a′ is an integer of 0 to 5, b is an integer of 1 to 3, and b′ is an integer of 0 to 3, wherein 1≦a+b≦5, 0≦a′+b′≦5; and in formula 2, a is an integer of 0 to 3, a′ is an integer of 0 to 4, b is an integer of 1 to 2, and b′ is an integer of 0 to 3, wherein 1≦a+b≦4, 0≦a′+b′≦4.
In accordance with another embodiment of the present invention, there is provided metallocene catalysts comprising:
at least one metallocene compound selected from the compounds represented by formula 1 or 2; and
at least one activator selected from the group consisting of aluminoxanes represented by the following formula 4 or 5, aromatic boron compounds substituted with fluoride, and modified clays.
In the formula 4 and 5, R′, which can be the same or different, represent hydrocarbyl radical having 1 to 10 carbon atoms, x is an integer of 1 to 50, and y is an integer of 3 to 50.
In accordance with another embodiment of the present invention, there is provided methods of polymerizing olefins with the metallocene catalysts comprising:
at least one metallocene compound selected from the compounds represented by formula 1 or 2; and
at least one activator selected from the group consisting of aluminoxanes represented by the following formula 4 or 5, aromatic boron compounds substituted with fluoride, and modified clays.
The methods of polymerizing olefins preferably include liquid phase polymerization, slurry phase polymerization or gas phase polymerization.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be illustrated in detail by the following preferred embodiments.
The present invention is to provide methods of polymerizing olefins in the presence of the metallocene catalysts comprising at least one metallocene compounds of the formula 1 or 2, which consist of cyclopentadienyl-type ligands substituted with silacycloalkyl radical and a Group 4B, 5B, 6B transition metal. Hereinafter, the method for preparing the metallocene compounds of the present invention will be described step by step in detail, and then the preferable examples of metallocene compounds of the present invention will be provided.
The metallocene compounds, (CpR
1
a
R
S
b
)
2
MX
2
, which is a compound of formula 1 when CpR
1
a
R
S
b
is the same with Cp′R
2
a′
R
s
b′
, can be prepared by the following 7 steps.
Step 1 is to produce a compound represented by R
s
X′ by reacting X′(CR
3
R
4
)
n
Si(R
5
)X′
2
with magnesium
Hong Sah Mun
Hwang Tae Soo
Jun Young Jae
Kang Sung Woo
Sohn Byoung Keel
Daelim Industrial Co., Ltd.
Nazario-Gonzalez Porfirio
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