Supported hybrid metallocene catalyst, and method for preparing polyolefin using the same

1. A supported hybrid metallocene catalyst, comprising:

a first metallocene compound represented by the following Chemical Formula 1;

a second metallocene compound which is represented by the following Chemical Formula 2 and one of C 1 and C 2 of Chemical Formula 2 is represented by the following Chemical Formula 3a;

a third metallocene compound which is represented by the following Chemical Formula 2 and one of C 1 and C 2 of Chemical Formula 2 is represented by the following Chemical Formula 3b;

a cocatalyst; and

a support:

in Chemical Formula 1,

at least one of R 1 to R 8 is —(CH 2 ) n —OR, wherein R is a C1 to C6 linear or branched alkyl group, and n is an integer of 2 to 10, and the others are the same as or different from each other, and are each independently hydrogen, 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 1 is a Group 4 transition metal, and

X 1 and X 2 are the same as or different from each other, and are each independently a halogen or a C1 to C20 alkyl group,

in Chemical Formula 2,

M 2 is a Group 4 transition metal,

X 3 and X 4 are the same as or different from each other, and are each independently a halogen or a C1 to C20 alkyl group,

B is carbon, silicon, or germanium,

at least one of Q 1 and Q 2 is —(CH 2 ) m —OR′, wherein R′ is a C1 to C6 linear or branched alkyl group, and m is an integer of 2 to 10, and the others 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 C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and

one of C 1 and C 2 is represented by the following Chemical Formula 3a or 3b, and the other is represented by the following Chemical Formula 3c,

in Chemical Formulae 3a to 3c,

R 9 to R 27 are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

2. The supported hybrid metallocene catalyst of claim 1 ,

wherein at least one of R 1 and R 5 of Chemical Formula 1 is —(CH 2 ) n —OR, wherein R is a C1 to C6 linear or branched alkyl group, and n is an integer of 2 to 10.

3. The supported hybrid metallocene catalyst of claim 1 ,

wherein R 10 of Chemical Formula 3a is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

4. The supported hybrid metallocene catalyst of claim 1 ,

wherein at least one of R 24 and R 27 of Chemical Formula 3c is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

5. The supported hybrid metallocene catalyst of claim 1 ,

wherein the first metallocene compound is selected from the group consisting of the following structural formulae:

6. The supported hybrid metallocene catalyst of claim 1 ,

wherein the second metallocene compound is selected from the group consisting of the following structural formulae:

7. The supported hybrid metallocene catalyst of claim 1 ,

wherein the third metallocene compound is represented by the following structural formula:

8. The supported hybrid metallocene catalyst of claim 1 ,

wherein a molar mixing ratio of the first metallocene compound to the second metallocene compound to the third metallocene compound is 1:0.1 to 5:0.1 to 5.

9. The supported hybrid metallocene catalyst of claim 1 ,

wherein the cocatalyst comprises at least one selected from the group consisting of a first cocatalyst represented by the following Chemical Formula 4 and a second cocatalyst represented by the following Chemical Formula 5:

—[Al(R 28 )—O—] k —  [CHEMICAL FORMULA 4]

in Chemical Formula 4, each R 28 is the same as or different from each other, and each is independently a halogen, or a C1 to C20 hydrocarbyl group substituted or unsubstituted with a halogen, and k is an integer of 2 or more,

T + [BG 4 ] −   [CHEMICAL FORMULA 5]

in Chemical Formula 5, T + is a polyatomic ion having a valence of +1, B is boron in a +3 oxidation state, and each G is independently selected from the group consisting of hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, and halo-substituted hydrocarbyl, and G has 20 or fewer carbons, provided that G is a halide in one or fewer positions.

10. A method for preparing a polyolefin, comprising the step of polymerizing olefinic monomers in the presence of the supported hybrid metallocene catalyst of claim 1 .

11. The method of claim 10 , wherein the olefinic monomers include at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.