Metallocene supported catalyst and method for preparing polyolefin using the same

1. A metallocene supported catalyst comprising:

one or more kinds of metallocene compounds,

two or more kinds of cocatalyst compounds, and

a carrier,

wherein the cocatalyst compounds include a first cocatalyst compound represented by the following Chemical Formula 1 and diethyl zinc as a second cocatalyst compound, and

the diethyl zinc is included in the content of 0.1 to 3 mmol/g, based on the weight (g) of the carrier, and at least a part of the diethyl zinc is supported on the first cocatalyst compound:

—[Al(R a )—O] n —  [Chemical Formula 1]

wherein, in Chemical Formula 1,

each R a is identical to or different from each other, and are independently a halogen, a C1-20 hydrocarbon, or a C1-20 hydrocarbon substituted with a halogen; and

n is an integer of 2 or more.

2. The metallocene supported catalyst according to claim 1 , wherein the compound represented by Chemical Formula 1 is methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or butylaluminoxane.

3. The metallocene supported catalyst according to claim 1 , wherein the metallocene compound is represented by the following Chemical Formulae 2 to 5:

(Cp 5 R b ) n (Cp 6 R c )M 1 Z 1 3-n   [Chemical Formula 2]

wherein, in Chemical Formula 2,

M 1 is Group 4 transition metal;

Cp 5 and Cp 6 are identical to or different from each other, and are independently one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which are substituted with a C1-20 hydrocarbon;

R b and R c are identical to or different from each other, and are independently hydrogen, a C1-20 alkyl, a C1-10 alkoxy, a C2-20 alkoxyalkyl, a C6-20 aryl, a C6-10 aryloxy, a C2-20 alkenyl, a C7-40 alkylaryl, a C7-40 arylalkyl, a C8-40 arylalkenyl, or a C2-10 alkynyl;

Z 1 is a halogen atom, a C1-20 alkyl, a C2-10 alkenyl, a C7-40 alkylaryl, a C7-40 arylalkyl, a C6-20 aryl, a substituted or unsubstituted C1-20 alkylidene, a substituted or unsubstituted amino group, a C2-20 alkylalkoxy, or a C7-40 arylalkoxy; and

n is 1 or 0,

(Cp 7 R d ) m B 1 (Cp 8 R e )M 2 Z 2 3-m   [Chemical Formula 3]

wherein, in Chemical Formula 3,

M 2 is Group 4 transition metal;

Cp 7 and Cp 8 are identical to or different from each other, and are independently one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which are substituted with a C1-20 hydrocarbon;

R d and R e are identical to or different from each other, and are independently hydrogen, a C1-20 alkyl, a C1-10 alkoxy, a C2-20 alkoxyalkyl, a C6-20 aryl, a C6-10 aryloxy, a C2-20 alkenyl, a C7-40 alkylaryl, a C7-40 arylalkyl, a C8-40 arylalkenyl, or a C2-10 alkynyl;

Z 2 is a halogen atom, a C1-20 alkyl, a C2-10 alkenyl, a C7-40 alkylaryl, a C7-40 arylalkyl, a C6-20 aryl, a substituted or unsubstituted C1-20 alkylidene, a substituted or unsubstituted amino group, a C2-20 alkylalkoxy, or a C7-40 arylalkoxy;

B 1 is one or more selected from carbon, germanium, silicon, phosphorous, or nitrogen atom-containing radicals or a combination thereof, which crosslinks a Cp 7 R d ring with a Cp 8 R e ring, or crosslinks one Cp 8 R e ring to M 2 ; and

m is 1 or 0,

(Cp 9 R f )B 2 (J)M 3 Z 3 2   [Chemical Formula 4]

wherein, in Chemical Formula 4,

M 3 is Group 4 transition metal;

Cp 9 is one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which are substituted with a C1-20 hydrocarbon;

R f is hydrogen, a C1-20 alkyl, a C1-10 alkoxy, a C2-20 alkoxyalkyl, a C6-20 aryl, a C6-10 aryloxy, a C2-20 alkenyl, a C7-40 alkylaryl, a C7-40 arylalkyl, a C8-40 arylalkenyl, or a C2-10 alkynyl;

Z 3 is a halogen atom, a C1-20 alkyl, a C2-10 alkenyl, a C7-40 alkylaryl, a C7-40 arylalkyl, a C6-20 aryl, a substituted or unsubstituted C1-20 alkylidene, a substituted or unsubstituted amino group, a C1-20 alkylalkoxy, or a C7-40 arylalkoxy;

B 2 is one or more selected from carbon, germanium, silicon, phosphorous, or nitrogen atom-containing radicals or a combination thereof, which crosslinks a Cp 9 R f ring with J; and

J is one selected from the group consisting of NR g , O, PR g , and S, and R g is a C1-20 alkyl, aryl, substituted alkyl, or substituted aryl,

wherein, in Chemical Formula 5,

A is hydrogen, a halogen, a C1-20 alkyl, a C2-20 alkenyl, a C6-20 aryl, a C7-20 alkylaryl, a C7-20 arylalkyl, a C1-20 alkoxy, a C2-20 alkoxyalkyl, a C3-20 heterocycloalkyl, or a C5-20 heteroaryl;

D is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are identical to or different from each other, and are independently hydrogen, a halogen, a C1-20 alkyl, a C2-20 alkenyl, or a C6-20 aryl;

L is a C1-10 linear or branched alkylene group;

B is carbon, silicon, or germanium;

Q is hydrogen, a halogen, a C1-20 alkyl, a C2-20 alkenyl, a C6-20 aryl, a C7-20 alkylaryl, or a C7-20 arylalkyl;

M is a Group 4 transition metal;

X 1 and X 2 are identical to or different from each other, and are independently a halogen, a C1-20 alkyl, a C2-20 alkenyl, a C6-20 aryl, a nitro, an amido, a C1-20 alkylsilyl, a C1-20 alkoxy, or a C1-20 sulfonate group; and

C 1 and C 2 are identical to or different from each other, and are independently represented by one of the following Chemical Formula 6a, Chemical Formula 6b, or Chemical Formula 6c, provided that both C 1 and C 2 are not Chemical Formula 6c:

wherein, in Chemical Formulas 6a, 6b, and 6c, R1 to R17 and R1′ to R9′ are identical to or different from each other, and are independently hydrogen, a halogen, a C1-20 alkyl, a C2-20 alkenyl, a C1-20 alkylsilyl, a C1-20 silylalkyl, a C1-20 alkoxysilyl, a C1-20 alkoxy, a C6-20 aryl, a C7-20 alkylaryl, or a C7-20 arylalkyl group, and two or more neighboring groups of the R10 to R17 are linked to form a substituted or unsubstituted aliphatic or aromatic ring.

4. The metallocene supported catalyst according to claim 1 , wherein the cocatalyst compounds include, at least one compound represented by a compound of Chemical Formula 7 or a compound of Chemical Formula 8:

J(R 23 ) 3   [Chemical Formula 7]

wherein, in Chemical Formula 7,

each R23 is identical to or different from each other, and are is independently a halogen, a C1-20 hydrocarbon, or a C1-20 hydrocarbon substituted with a halogen; and

J is aluminum or boron,

[E-H] + [ZA′ 4 ] − or [E] + [ZA′ 4 ] −   [Chemical Formula 8]

wherein, in Chemical Formula 8,

E is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z is a Group 13 atom; and

each A is identical to or different from each other, and is independently a C6-20 aryl or a C1-20 alkyl group, in which at least one hydrogen atom is unsubstituted or substituted with a halogen, a C1-20 hydrocarbon, an alkoxy or a phenoxy group.

5. The metallocene supported catalyst according to claim 1 , wherein the carrier is silica, silica-alumina or silica-magnesia.

6. A method for preparing a metallocene supported catalyst comprising:

supporting two or more kinds of cocatalyst compounds including a first cocatalyst compound and a second cocatalyst compound on a carrier,

and then supporting one or more kinds of metallocene compounds,

wherein the first cocatalyst compound is a compound represented by the following Chemical Formula 1 and the second cocatalyst compound is diethyl zinc, and

the diethyl zinc is supported in the content of 0.1 to 3 mmol/g based on the weight (g) of the carrier, after the first cocatalyst compound is supported:

—[Al(R a )—O] n —  [Chemical Formula 1]

wherein, in Chemical Formula 1,

each R a is identical to or different from each other, and are independently a halogen, a C1-20 hydrocarbon, or a C1-20 hydrocarbon substituted with a halogen; and

n is an integer of 2 or more.

7. A method for preparing a polyolefin comprising the step of polymerizing olefin monomers in the presence of the metallocene supported catalyst of claim 1 .

8. The method for preparing a polyolefin according to claim 7 , wherein the polymerization is a solution polymerization process, a slurry process or a gas phase process.

9. The method for preparing a polyolefin according to claim 7 , wherein the olefin monomers include one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene, or 3-chloromethylstyrene.