Supported hybrid catalyst

1. A supported hybrid catalyst, comprising at least one first transition metal compound selected from compounds represented by the following Chemical Formula 1;

at least one second transition metal compound selected from compounds represented by the following Chemical Formula 2; and

a support on which the first and second transition metal compounds are supported,

wherein, in Chemical Formula 1,

M 1 is a Group 4 transition metal;

X 1 and X 2 are the same as or different from each other, and are each independently any one of a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 sulfonate group, and a C1 to C30 sulfone group;

R 1 and R 3 to R 10 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;

R 2 is selected from the group consisting of a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;

Q 1 and Q 2 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 hydrocarbyl group substituted with a halogen, and —NR a R b ; and

R a and R b are the same as or different from each other, and are each independently any one of hydrogen and a C1 to C30 hydrocarbyl group, or may be connected with each other to form an aliphatic or aromatic ring,

wherein, in Chemical Formula 2,

M2 is a Group 4 transition metal;

X 3 and X 4 are the same as or different from each other, and are each independently any one of a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 sulfonate group, and a C1 to C30 sulfone group;

R 11 to R 24 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;

Q 3 and Q 4 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 hydrocarbyl group substituted with a halogen, and —NR a′ R b′ ; and

R a′ and R b′ are the same as or different from each other, and are each independently any one of hydrogen and a C1 to C30 hydrocarbyl group, or may be connected with each other to form an aliphatic or aromatic ring.

2. The supported hybrid catalyst of claim 1 ,

wherein R 1 and R 3 to R 6 are each hydrogen, and

R 2 each are any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

3. The supported hybrid catalyst of claim 1 ,

wherein M 1 is Ti, Zr, or Hf,

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

R 1 and R 3 to R 6 are each hydrogen,

R 2 is a C1 to C20 alkyl group, or a C6 to C20 aryl group,

R 7 to R 10 are the same as or different from each other, and are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, and

Q 1 and Q 2 are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

4. The supported hybrid catalyst of claim 1 , wherein the first transition metal compound is any one of compounds represented by the following structural formulae:

5. The supported hybrid catalyst of claim 1 ,

wherein M 2 is Ti, Zr, or Hf,

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

R 11 and R 12 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group,

R 13 to R 20 are each independently any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, or one or more pairs of neighboring substituents of R 13 to R 20 may be connected with each other to form a substituted or unsubstituted aliphatic ring,

R 21 to R 24 are the same as or different from each other, and are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, and

Q 3 and Q 4 are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

6. The supported hybrid catalyst of claim 1 , wherein the second transition metal compound is any one of compounds represented by the following structural formulae:

7. The supported hybrid catalyst of claim 1 , wherein the first transition metal compound and the second transition metal compound are contained in a molar mixing ratio of 1:1 to 1:15.

8. The supported hybrid catalyst of claim 1 , wherein the support comprises any one or a mixture of two or more selected from the group consisting of silica, alumina, and magnesia.

9. The supported hybrid catalyst of claim 1 , further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulae 3 to 5:

R 26 —[Al(R 25 )—O] n —R 27   [Chemical Formula 3]

wherein, in Chemical Formula 3,

R 25 , R 26 , and R 27 are each independently any one of hydrogen, a halogen, a C1 to C20 hydrocarbyl group, and a halogen-substituted C1 to C20 hydrocarbyl group; and

n is an integer of 2 or more,

D(R 28 ) 3   [Chemical Formula 4]

wherein, in Chemical Formula 4,

D is aluminum or boron; and

R 28 are each independently any one of a halogen, a C1 to C20 hydrocarbyl group, a C1 to C20 hydrocarbyloxy group, and a halogen-substituted C1 to C20 hydrocarbyl group;

[L-H] + [W(A) 4 ] − or [L] + [W(A) 4 ] −   [Chemical Formula 5]

wherein, in Chemical Formula 5,

L is a neutral or cationic Lewis base; H is a hydrogen atom;

W is a Group 13 element; and

A are each independently any one of a C1 to C20 hydrocarbyl group; a C1 to C20 hydrocarbyloxy group; and a substituent in which at least one hydrogen atom of these substituents is substituted with at least one selected from a halogen, a C1 to C20 hydrocarbyloxy group, and a C1 to C20 hydrocarbyl(oxy)silyl group.

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

11. The method for preparing a polyolefin of claim 10 , wherein the olefinic monomer comprises 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.