Metallocene compounds, metallocene catalysts including the compounds and methods of polymerizing olefins with the catalysts

A metallocene catalyst comprising:

• at least one metallocene compound selected from the compounds represented by the following 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 clay,
• (CpR1aRSb)(Cp′R2a′RSb′)MX2 [Formula 1]
• 15
• wherein, 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;
• R1 and R2, 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;
• Rs represents 1-alkyl-1-silacyclohydrocarbyl radical of the following formula 3, 16
• wherein, R3 and R4, which can be the same or different, represent hydrogen or alkyl radical having 1 to 5 carbon atoms, R5 is alkyl radical having 1 to 8 carbon atoms, and n is an integer of 4 to 8;
• Cp′R2a′Rsb′ in formula 2 can be displaced with divalent NR″ radical, wherein R″ represents Rs, 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;
• 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;
• 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;
• and 17
• wherein, 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.

A method of polymerizing olefin with metallocene catalyst comprising:

• at least one metallocene compound selected from the compounds represented by the following 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 clay.
• (CpR1aRSb)(Cp′R2a′RSb′)MX2 [Formula 1] 18
• wherein, 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;
• R1 and R2, 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;
• Rs represents 1-alkyl-1-silacyclohydrocarbyl radical of the following formula 3, 19
• wherein, R3 and R4, which can be the same or different, represent hydrogen or alkyl radical having 1 to 5 carbon atoms, R5 is alkyl radical having 1 to 8 carbon atoms, and n is an integer of 4 to 8;
• Cp′R2a′RSb′ in formula 2 can be displaced with divalent NR″ radical, wherein R″ represents Rs, 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;
• 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;
• 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;
• and 20
• wherein, R′, which can be the same or different, represent hydrocarbyl radical having 1 to 1 0 carbon atoms, x is an integer of 1 to 50, and y is an integer of 3 to 50.