Olefin polymerization catalyst and olefin polymerization process using the same

1. An olefin polymerization catalyst for the polymerization of α-olelins and cycloolefins which comprises:

an organometallic compound of the following Formula 1;

aluminoxane;

and an organic transition metal compound of the following Formula 2:

M 1 R 1 1 R 2 m R 3 n or R 2 m R 3 n M 1 1 -Q-R 1 1 M 1 R 2 m R 3 n   [Formula 1]

in Formula 1, M 1 is selected from the group consisting of Group 2A, 2B and 3A of the Periodic Table, R 1 is selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, azulenyl, substituted azulenyl, fluorenyl, substituted fluorenyl group and mixtures thereof, R 2 and R 3 are independently hydrocarbyl group of 1 to 24 carbon atoms, l is an integer of more than 1 and an integer of less than a valence of M 1 , m and n are independently an integer of 0 to 2, l+m+n is equal to the valence of M 1 , Q is a divalent group selected from the group consisting of(CR 5 2 ) b , (SiR 5 2 ) b , (GeR 5 2 ) b , NR 5 and PR 5 for bridging R 1 , where R 5 substituent is independently hydrogen atom, alkyl radical of 1 to 20 carbon atoms, cycloalkyl radical of 3 to 20 carbon atoms, alkenyl radical of 1 to 20 carbon atoms, aryl radical of 6 to 20 carbon atoms, alkyl radical of 7 to 20 carbon atoms or arylalkyl radical of 7 to 20 carbon atoms, b is an integer of 1 to 4.

M 2 R 4 p X q   [Formula 2]

in Formula 2, M 2 is zirconium(Zr) or hafnium(Hf), R 4 is selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, azulenyl, substituted azulenyl, fluorenyl, substituted fluorenyl groups and mixtures thereof, X is halogen atom, p is an integer of 1, q is an integer of 3, p+q is equal to the valence of metal M 2 .

2. The olefin polymerization catalyst according to claim 1 , wherein M 1 is selected from magnesium(Mg) or aluminum(Al); cyclopentadienyl, indenyl, azulenyl or fluorenyl of R 1 is partially substituted with 1 to 6 substituents, which are selected from the group consisting of alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, haloalkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, arylalkyl of 6 to 20 carbon atoms, arylsilyl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkylsiloxy of 1 to 20 carbon atoms, aryloxy of 6 to 20 carbon atoms; halogen atom, amino group and mixtures thereof.

3. The olefin polymerization catalyst according to claim 1 , wherein the amount of the organoinetallic compound of Formula 1 is 0.2 to 20 mole and the amount of aluminum of the aluminoxane is 1 to 100,000 mole per 1 mole of the organic transition metal compound of the above Formula 2.

4. The olefin polymerization catalyst according to claim 1 , wherein the olefin polymerization catalyst is supported on an organic or inorganic earner.

5. The olefin polymerization catalyst according to claim 1 , wherein the α-olefin is selected from the group consisting of ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1,4-methylpentene- 1,3-methylpentene-1, heptene-1, octene-1, decene-1,4,4-dimethyl-1-pentene, 4,4-diethyl- 1-hexene and 3,4-dimethyl- 1-hexene, and the cycloolefin is selected from the group consisting of cyclopentene, cyclobutene, cyclohexenc, 3-methylcyclohexene, cyclooctene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbonene, 5-methyl-2-norbonene, 5-ethyl-2-norbonene, 5-isobutyl-2-norbonene, 5,6-dimethyl -2-norbonene, 5,5,6-trimethyl-2-norbonene and ethylene norbonene.

6. A process for the polymerization of α-olefins and cycloolefins which comprises conducting the poymerization in the presence of a catalyst which is prepared by mixing an organometallic compound of the following Formula 1; aluminoxane; and an organic transition metal compound of the following Formula 2:

M 1 R 1 1 R 2 m R 3 n or R 2 m R 3 n M 1 R 1 1 -Q-R 1 1 M 1 R 2 m R 3 n   [Formula 1]

in Formula 1, M 1 is selected from the group consisting of Group 2A, 2B and 3A of the Periodic Table. R 1 is selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, azulenyl, substituted azulenyl, fluorenyl, substituted fluorenyl group and mixtures thereof, R 2 and R 3 are independently hydrocarbyl group of 1 to 24 carbon atoms, l is an integer of more than 1 and an integer of less than a valence of M 1 , m and n are independently an integer of 0 to 2, l+m+n is equal to the valence of M 1 , Q is a divalent group selected from the group consisting of (CR 5 2 ) b , (SiR 5 2 ) b , (GeR 5 2 ) b , NR 5 and PR 5 for bridging R 1 , where R 5 substituent is independently hydrogen atom, alkyl radical of 1 to 20 carbon atoms, cycloalkyl radical of 3 to 20 carbon atoms, alkenyl radical of 1 to 20 carbon atoms, aryl radical of 6 to 20 carbon atoms, alkyl radical of 7 to 20 carbon atoms or arylalkyl radical of 7 to 20 carbon atoms, b is an integer of 1 to 4;

M 2 R 4 p X q   [Formula 2]

in Formula 2, M 2 is zirconium(Zr) or hafnium(Hf), R 4 is selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, azulenyl, substituted azulenyl, fluorenyl, substituted fluorenyl group and mixtures thereof, X is halogen atom, p is an integer of 1, q is an integer of 3, p+q is equal to the valence of metal M 2 .

7. The olefin polymerization process according to claim 6 , wherein the olefin polymerization catalyst is supported on an organic or inorganic carrier.

8. The olefin polymerization process according to claim 6 , wherein the α-olefin is selected from the group consisting of ethylene, propylene, butene-1, pentene-1,3-methylbutene-1, hexene- 1,4-methylpentene- 1,3-methylpentene-1, heptene-1, octene-1, decene-1,4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene and 3,4-dimethyl-1-hexene, and the cycloolefin is selected from the group of consisting of cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbonene, 5-methyl-2-norbonene, 5-ethyl-2-norbonene, 5-isobutyl-2-norbonene, 5,6-dimethyl-2-norbonene, 5,5,6-trimethyl-2-norbonene and ethylene norbonene.