Method for preparing hybrid supported metallocene catalyst

A method for preparing a hybrid supported metallocene catalyst which comprises the steps of

• supporting a first cocatalyst compound on a support;
• supporting one or more first metallocene compounds represented by the following Chemical Formula 1 and one or more second metallocene compounds selected among the compounds represented by the following Chemical Formula 3 to 5 on the support on which the first cocatalyst compound has been supported;
• and
• supporting a second cocatalyst compound on the support on which the first cocatalyst compound, the first metallocene compound and the second metallocene compound have been supported:
• in Chemical Formula 1,
• A is hydrogen, halogen, C1-C20 alkyl group, C2-C20 alkenyl group, C6-C20 aryl group, C7-C20 alkylaryl group, C7-C20 arylalkyl group, C1-C20 alkoxy group, C2-C20 alkoxyalkyl group, C3-C20 heterocycloalkyl group, or C5-C20 heteroaryl group;
• D is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are same as or different from each other and each are independently hydrogen, halogen, C1-C20 alkyl group, C2-C20 alkenyl group, or C6-C20 aryl group;
• L is C1-C10 linear or branched alkylene group;
• B is carbon, silicon, or germanium;
• Q is hydrogen, halogen, C1-C20 alkyl group, C2-C20 alkenyl group, C6-C20 aryl group, C7-C20 alkylaryl group, or C7-C20 arylalkyl group;
• M is a Group 4 transition metal;
• X1 and X2 are same as or different from each other, and each are independently halogen, C1-C20 alkyl group, C2-C20 alkenyl group, C6-C20 aryl group, nitro group, amido group, C1-C20 alkylsilyl group, C1-C20 alkoxy group, or C1-C20 sulfonate group;
• C1 and C2 are same as or different from each other, and each is independently represented by any one of the following Chemical Formula 2a, Chemical Formula 2b or Chemical Formula 2c, provided that both C1 and C2 are not represented by Chemical Formula 2c:
• in Chemical Formulae 2a, 2b and 2c, R1 to R17 and R1′ to R9′ are same as or different from each other, and each independently hydrogen, halogen, C1-C20 alkyl group, C2-C20 alkenyl group, C1-C20 alkylsilyl group, C1-C20 silylalkyl group, C1-C20 alkoxysilyl group, C1-C20 alkoxy group, C6-C20 aryl group, C7-C20 alkylaryl group, or C7-C20 arylalkyl group, wherein two or more adjacent groups among R10 to R17 may be connected together to form 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 same as or different from each other, and each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
• Ra and Rb are same as or different from each other, and each independently hydrogen, C1-C20 alkyl, C1-C10 alkoxy, C2-C20 alkoxyalkyl, C6-C20 aryl, C6-C10 aryloxy, C2-C20 alkenyl, C7-C40 alkylaryl, C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkinyl;
• Z1 is halogen atom, C1-C20 alkyl, C2-C10 alkenyl, C7-C40 alkylaryl, C7-C40 arylalkyl, C6-C20 aryl, substituted or unsubstituted C1-C20 alkylidene, substituted or unsubstituted amino group, C2-C20 alkylalkoxy, or C7-C40 arylalkoxy;
• and
• n is 1 or 0;
• (Cp3Rc)mB1(Cp4Rd)M2Z23-m [Chemical Formula 4]
• in Chemical Formula 4,
• M2 is a Group 4 transition metal;
• Cp3 and Cp4 are same as or different from each other, and each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
• Rc and Rd are same as or different from each other, and each independently hydrogen, C1-C20 alkyl, C1-C10 alkoxy, C2-C20 alkoxyalkyl, C6-C20 aryl, C6-C10 aryloxy, C2-C20 alkenyl, C7-C40 alkylaryl, C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkinyl;
• Z2 is halogen atom, C1-C20 alkyl, C2-C10 alkenyl, C7-C40 alkylaryl, C7-C40 arylalkyl, C6-C20 aryl, substituted or unsubstituted C1-C20 alkylidene, substituted or unsubstituted amino group, C2-C20 alkylalkoxy, or C7-C40 arylalkoxy;
• B1 is one or more selected among the radicals containing carbon, germanium, silicon, phosphorous or nitrogen atom, which crosslink Cp3Rc ring to Cp4Rd ring or crosslink one Cp4Rd ring to M2, combinations thereof;
• and
• m is 1 or 0;
• (Cp5Re)B2(J)M3Z32 [Chemical Formula 5]
• in Chemical Formula 5,
• M3 is a Group 4 transition metal;
• Cp5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
• Re is hydrogen, C1-C20 alkyl, C1-C10 alkoxy, C2-C20 alkoxyalkyl, C6-C20 aryl, C6-C10 aryloxy, C2-C20 alkenyl, C7-C40 alkylaryl, C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkinyl;
• Z3 is halogen atom, C1-C20 alkyl, C2-C10 alkenyl, C7-C40 alkylaryl, C7-C40 arylalkyl, C6-C20 aryl, substituted or unsubstituted C1-C20 alkylidene, substituted or unsubstituted amino group, C2-C20 alkylalkoxy, or C7-C40 arylalkoxy;
• B2 is one or more selected among the radicals containing carbon, germanium, silicon, phosphorous or nitrogen atom, which crosslink Cp5Re ring to J, or combinations thereof, and
• J is any one selected from the group consisting of NRf, O, PRf and S, wherein Rf is C1-C20 alkyl, aryl, substituted alkyl or substituted aryl.