Method of preparing supported metallocene catalyst

A method of preparing a supported metallocene catalyst, comprising:

• preparing a molecular weight modifier composition by mixing a cyclopentadienyl metal compound of the following Chemical Formula 1 and an organic aluminum compound of the following Chemical Formula 2 and stirring a resulting mixture at room temperature for 50 hours to 108 hours;
• and
• supporting one or more metallocene compounds represented by any one of the following Chemical Formulae 3 to 6 and the molecular weight modifier composition on a support,
• wherein the molecular weight modifier composition is supported in an amount of about 1 mol % to 85 mol %, based on the total weight of the metallocene compound:
• (R1—Cp1)(R2-Cp2)M4X2 Chemical Formula 1
• in Chemical Formula 1,
• Cp1 and Cp2 are each independently a ligand comprising a cyclopentadienyl group, an indenyl group, or a fluorenyl group;
• R1 and R2 are substituents of Cp1 and Cp2, and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms, a heteroalkylaryl group having 6 to 20 carbon atoms, a heteroarylalkyl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms;
• M4 is a Group 4 transition metal element;
• and X is a halogen,
• R3R4R5Al Chemical Formula 2
• in Chemical Formula 2,
• R3, R4, and R5 are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R3, R4, and R5 is an alkyl group having 4 to 20 carbon atoms,
• (Cp5Ra)n(Cp6Rb)M1Z13-n Chemical Formula 3
• in Chemical Formula 3,
• M1 is a Group 4 transition metal;
• Cp5 and Cp6 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 radicals-which are optionally substituted with a hydrocarbon 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;
• and
• n is 1 or 0,
• (Cp7Rc)mB1(Cp8Rd)M2Z23-m Chemical Formula 4
• in Chemical Formula 4,
• M2 is a Group 4 transition metal;
• Cp7 and Cp8 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 radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms;
• Rc and Rd 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;
• Z2 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;
• B1 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp3Rc ring and a Cp4Rd ring or crosslink one Cp4Rd ring to M2, or a combination thereof;
• and
• m is 1 or 0,
• (Cp9Re)B2(J)M3Z32 Chemical Formula 5
• in Chemical Formula 5,
• M3 is a Group 4 transition metal;
• Cp9 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms;
• Re is 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;
• Z3 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;
• B2 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp5Re ring to J, or a combination thereof;
• J is any one selected from the group consisting of NRf, O, PRf and S;
• and Rf is a C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl,
• in Chemical Formula 6,
• 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′)—, in which 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 straight 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;
• C1 and C2 are the same as or different from each other, and are each independently represented by any one of the following Chemical Formula 7a, Chemical Formula 7b, and Chemical Formula 7c, excluding that both C1 and C2 are Chemical Formula 7c,
• in Chemical Formulae 7a, 7b, and 7c,
• 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 alkoxysilyl 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 two or more neighboring groups of R10 to R17 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.