HYBRID SUPPORTED METALLOCENE CATALYST AND POLYOLEFIN PREPARATION METHOD USING SAME (As Amended)

A hybrid supported metallocene catalyst comprising:

• one or more of a first metallocene compound represented by the following Chemical Formula 1;
• one or more of a second metallocene compound represented by the following Chemical Formula 3;
• one or more of a third metallocene compound represented by the following Chemical Formula 4;
• a cocatalyst compound;
• and a support:
• in Chemical Formula 1,
• A is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
• D is —O—, —S—, —N(R)— or —Si(R)(R′)—, wherein R and R′ are the same as or different from each other and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
• L is a C1 to C10 linear or branched alkylene group;
• B is carbon, silicon or germanium;
• Q is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
• M is a Group 4 transition metal;
• X1 and X2 are the same as or different from each other and are each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
• and
• C1 and C2 are the same as or different from each other and are each independently one of the following Chemical Formulas 2a, 2b or 2c, provided that the case where both C1 and C2 are Chemical Formula 2c is excluded;
• in Chemical Formulas 2a, 2b and 2c, R1 to R17 and R1′ to R9′ are the same as or different from each other and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysily group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group or a C7 to C20 arylalkyl group, and adjacent two or more substituents of R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
• (Cp1Ra)n(Cp2Rb)M1Z13-n [Chemical Formula 3]
• in Chemical Formula 3,
• M1 is a Group 4 transition metal;
• Cp1 and Cp2 are the same as or different from each other and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical, which may be substituted with hydrocarbons having 1 to 20 carbon atoms;
• Ra and Rb are the same as or different from each other and are each independently hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
• Z1 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
• n is 1 or 0;
• in Chemical Formula 4,
• M2 is a Group 4 transition metal;
• B is carbon, silicon or germanium;
• Q1 and Q2 are the same as or different from each other and are each independently hydrogen, a C1 to C20 alkyl, or an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms;
• X3 and X4 are the same as or different from each other and are each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
• C3 and C4 are the same or different and each independently represents one of the following Chemical Formula 4a or 4b:
• in Chemical Formulas 4a and 4b, R18 to R2 are the same as or different from each other and are each independently hydrogen, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group containing a hetero atom of N or O, a C6 to C20 aryl group, or an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, and
• at least one of Q1, Q2, and R18 to R27 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms.