Supported hybrid catalyst and method for preparing olefin-based polymer using the same
The present invention relates to a supported hybrid catalyst and a method for preparing an olefin based polymer using the same. The supported hybrid catalyst according to the present invention can be used in the preparation of an olefin-based polymer, and the olefin-based polymer prepared using the supported hybrid catalyst has excellent processability and mechanical properties and thus can be effectively used for the application of films or the like.
1. A supported hybrid catalyst comprising: i) a first catalyst represented by the following Chemical Formula 1; and
ii) one or more catalysts selected from the group consisting of a second catalyst represented by the following Chemical Formula 2 and a third catalyst represented by the following Chemical Formula 3:
in the above Formula 1,
M is a Group 4 transition metal;
B is silicon;
Q 1 and Q 2 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 3-20 heterocycloalkyl, or C 5-20 heteroaryl; with the proviso that at least one of Q 1 and Q 2 is C 2-20 alkoxyalkyl;
X 1 and X 2 are each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, nitro, amido, C 1-20 alkylsilyl, C 1-20 alkoxy, or C 1-20 sulfonate;
C 1 is the following Chemical Formula 2a,
C 2 is the following Chemical Formula 2a, or the following Chemical Formula 2b:
in the above Formulas 2a and 2b,
R 1 to R 13 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkylsilyl, C 1-20 silylalkyl, C 1-20 alkoxysilyl, C 1-20 ether, C 1-20 silylether, C 1-20 alkoxy, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
R′ 1 to R′ 3 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, or C 6-20 aryl,
in the above Formula 2,
R 10 to R 13 and R′ 10 to R′ 13 are each independently hydrogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 7-20 alkoxyalkyl, or C 1-20 amine, or adjacent two or more of R 10 to R 13 and R′ 10 to R′ 13 are connected to each other to form at least one aliphatic, aromatic, or heterocyclic ring, wherein the aliphatic, aromatic, or heterocyclic ring is unsubstituted or substituted with C 1-20 alkyl;
Q is —Si(Z 1 )(Z 2 )—;
Z 1 and Z 2 are each independently hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 6-10 aryloxy, C 2-20 alkenyl, C 7-40 alkylaryl, or C 7-40 arylalkyl;
M 2 is a Group 4 transition metal;
X 3 and X 4 are each independently halogen, C 1-20 alkyl, C 1-20 alkenyl, C 6-20 aryl, nitro, amido, C 1-20 alkylsilyl, C 1-20 alkoxy, or C 1-20 sulfonate;
in the above Formula 3,
M 3 is a Group 4 transition metal;
X 5 and X 6 are each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, nitro, amido, C 1-20 alkylsilyl, C 1-20 alkoxy, or C 1-20 sulfonate;
R 14 to R 19 are each independently hydrogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkoxy, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 1-20 alkylsilyl, C 6-20 arylsilyl, or C 1-20 amine; or adjacent two or more of R 14 to R 17 are connected to each other to form at least one aliphatic, aromatic, or heterocyclic ring;
L 2 is C 1-10 linear or branched alkylene;
D 2 is —O—;
A 2 is hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 2-20 heterocycloalkyl alkyl, or C 5-20 heteroaryl;
B is silicon and is a bridge which binds to cyclopentadienyl ligand and J(R 19 ) z-y by a covalent bond;
J is a nitrogen atom;
z is 3; and
y is 2.
2. The supported hybrid catalyst according to claim 1 wherein,
in the Chemical Formula 1,
M is zirconium,
B is silicon,
Q 1 and Q 2 are each independently C 1-20 alkyl, or C 2-20 alkoxyalkyl, with the proviso that at least one of Q 1 and Q 2 is C 2-20 alkoxyalky, and
X 1 and X 2 are halogen.
3. The supported hybrid catalyst according to claim 2 wherein
Q 1 is methyl, and Q 2 is 6-tert-butoxy-hexyl.
4. The supported hybrid catalyst according to claim 1 wherein,
in Chemical Formulas 2a and 2b,
R 1 to R 13 are hydrogen and
R′ 1 to R′ 3 are C 1-20 alkyl.
5. The supported hybrid catalyst according to claim 4 wherein
R′ 1 to R′ 3 are methyl.
6. The supported hybrid catalyst according to claim 1 wherein,
in Chemical Formula 2,
R 10 to R 13 and R′ 10 to R′ 13 are each independently hydrogen, C 1-20 alkyl, or C 2-20 alkoxyalkyl, or adjacent two or more of R 10 to R 13 and R′ 10 to R′ 13 are connected to each other to form at least one aliphatic or aromatic ring, wherein the aliphatic or aromatic ring is unsubstituted or substituted with by C 1-20 alkyl;
Q is —Si(Z 1 )(Z 2 )—;
Z 1 and Z 2 are each independently C 1-20 alkyl, or C 2-20 alkoxyalkyl;
M 2 is zirconium; and
X 3 and X 4 are halogen.
7. The supported hybrid catalyst according to claim 6 wherein
R 10 to R 13 and R′ 10 to R′ 13 are each independently hydrogen, methyl or6-tert-butoxy-hexyl, or adjacent two or more of R 10 to R 13 and R′ 10 to R′ 13 are connected to each other to form at least one benzene ring or cyclohexane ring, wherein the benzene ring is unsubstituted or substituted with tert-butoxy;
Q is —Si(Z 1 )(Z 2 )—;
Z 1 and Z 2 are each independently methyl, or 6-tert-butoxy-hexyl;
M 2 is zirconium; and
X 3 and X 4 is chloro.
8. The supported hybrid catalyst according to claim 1 wherein,
in Chemical Formula 3,
M 3 is titanium;
X 5 and X 6 are halogen;
R 14 to R 19 are C 1-20 alkyl,
L 2 is C 1-10 linear or branched alkylene;
D 2 is —O—;
A 2 is C 1-20 alkyl;
B is silicone;
J is nitrogen;
z is the oxidation number of the element J; and
y is the number of bond of the element J.