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1. A hybrid supported metallocene catalyst comprising a hybrid of a first metallocene compound represented by the following Chemical Formula 2 and a second metallocene compound represented by the following Chemical Formula 3, which hybrid is supported on a carrier surface-treated with an ionic compound represented by the following Chemical Formula 1 and a co-catalyst.
X+Y− [Chemical Formula 1] [In Chemical Formula 1, X+ is imidazolium ion, pyridinium ion, ammonium ion, phosphonium ion, sulfonium ion, pyrazolium ion, or pyrrolidium ion and substituted with (C1-C20)alkyl or (C6-C20)aryl substituted or unsubstituted with at least one functional group selected from —CN, —OH, —SO3H, —COOH, amino, —SiR11R12R13 (R11 to R13 each are independently (C1-C20)alkyl or (C6-C30)aryl), (C1-C20)alkyl, and (C1-C20)alkoxy; Y− may be BE4−, BCl4−, PF6−, AlCl4−, halogen−, CH3CO2−, CF3CO2−, CH3SO4−, CH3CH2SO4−, CF3SO3−, N(CN)2−, HCO3−, (CF3SO2)N−, SCN−, NO3−, SbF6−, Sb2F11−, MePhSO3−, (CF3SO2)2N−, (CF3SO2)3C−, (OR)2PO2− (R=(C1-C20)alkyl), Bu2PO2−, Et2PO2−, or HSO4−.]
Cp′L1M1L2m [Chemical Formula 2] [In Chemical Formula 2, M1 is a Group 4 transition metal in the Periodic Table of Elements; Cp′ is a fused ring including cyclopentadienyl or cyclopentadienyl ring capable of being η5-bonded to a central metal M1; L1 is a fused ring containing cyclopentadiene or cyclopentadienyl ring, or an anion ligand including (C1-C20)hydrocarbon substituents and O, N, or P atoms; L2 is a halogen atom, (C1-C20)alkyl, (C6-C30)aryl(C1-C20)alkyl, (C3-C20)cycloalkyl, (C1-C20)alkoxy, (C6-C30)aryloxy, (C6-C30)aryl, —SiRaRbRc, —NRdRe, —OSiRfRgRh, or —PRiRj; Ra to Rj each are independently (C1-C20)alkyl or (C6-C30)aryl; m is an integer of 1 or 2; and Cp′ and L′ are not connected to each other, or are connected via silicon or (C1-C4)alkenylene bond, the cyclopentadienyl ring or the fused ring containing the cyclopentadienyl ring of Cp′ and L1 are further substituted with at least one selected from (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C30)aryl, (C2-C20)alkenyl, and (C6-C30)aryl(C1-C20)alkyl.] [In Chemical Formula 3, M2 is a Group 4 transition metal in the Periodic Table of Elements; n is an integer of 1 or 2, and when n is 2, R1(s) are the same as or different from each other; R1 is hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C1-C20)alkyl(C6-C30)aryl, (C6-C30)aryl, (C6-C30)ar(C1-C20)alkyl, ((C1-C20)alkyl(C6-C30)aryl)(C1-C20)alkyl, —NRkRl, —SiRmRnRo, or 5- to 7-membered N-heterocycloalkyl containing at least one nitrogen atom; R2 and R3 each are independently, hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C1-C20)alkyl(C6-C30)aryl, (C6-C30)aryl, (C6-C30)aryloxy, (C1-C20)alkyl(C6-C30)aryloxy, (C6-C30)ar(C1-C20)alkyl, ((C1-C20)alkyl(C6-C30)aryl)(C1-C20)alkyl, —NRkRl, or —SiRmRnRo; R4, R5, R10, R11, and R12 each are independently (C1-C20)alkyl, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C1-C20)alkyl(C6-C30)aryl, (C6-C30)aryl, (C1-C20)alkoxy(C6-C30)aryl, (C6-C30)ar(C1-C20)alkyl, ((C1-C20)alkyl(C6-C30)aryl)(C1-C20)alkyl, —NRkRl, or —SiRmRnRo; R6, R7, R8, and R9 each are independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C1-C20)alkoxy, (C6-C30)aryl, (C1-C20)alkyl(C6-C30)aryl, (C6-C30)ar(C1-C20)alkyl, ((C1-C20)alkyl(C6-C30)aryl)(C1-C20)alkyl, (C1-C20)alkoxy(C6-C30)aryl, (C6-C30)aryloxy, (C1-C20)alkyl(C6-C30)aryloxy, N-carbazolyl, —NRkRl, or —SiRmRnRo or linked to substituent adjacent thereto via (C1-C5)alkylene to form a ring, at least one CH2— of alkylene may be substituted by a hetero atom selected from —O—, —S—, and NR′—, and alkylene may be further substituted with (C1-C20)alkyl; R′ and Rk to Ro each are independently (C1-C20)alkyl or (C6-C30)aryl; and X1, and X2 each are independently halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C3-C20)cycloalkyl, (C6-C30)aryl, (C6-C30)ar(C1-C20)alkyl, ((C1-C20)alkyl(C6-C30)aryl)(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C30)aryloxy, (C1-C20)alkyl(C6-C30)aryloxy, (C1-C20)alkoxy(C6-C30)aryloxy, (C1-C20)alkylidene, or an anion or dianion ligand consisting of 60 or less atoms containing N, P, O, S, Si, and halogen, except hydrogen, provided that one of X1, and X2 is a dianion ligand, the other is ignored.] |
