Metallocene compound, a catalyst composition comprising the same, and a method of preparing an olefinic polymer by using the same

1. A metallocene compound represented by Chemical Formula 1:

wherein in Chemical Formula 1:

A is hydrogen, a halogen, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 20 arylalkyl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkoxyalkyl group, a C 3 -C 20 heterocycloalkyl group, or a C 5 -C 20 heteroaryl group;

D is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are, the same or different from each other, and are independently hydrogen, a halogen, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, or a C 6 -C 20 aryl group;

L is a C 1 -C 10 linear or branched alkylene group;

B is carbon, silicon, or germanium;

Q is hydrogen, a halogen, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl group, a C 7 -C 20 alkylaryl group, or a C 7 -C 20 arylalkyl group;

M is a group 4 transition metal;

X 1 and X 2 are the same or different from each other, and are independently hydrogen, a halogen, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl group, a nitro group, an amido group, a C 1 -C 20 alkylsilyl group, a C 1 -C 20 alkoxy group, or a C 1 -C 20 sulfonate group;

C 1 is represented by one of Chemical Formula 2a and Chemical Formula 2b:

and C 2 is represented by Chemical Formula 3:

wherein in Chemical Formulae 2a, 2b and 3, R 1 to R 17 and R 1 ′ to R 9 ′ are the same or different from each other, and are independently hydrogen, a halogen, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 1 -C 20 alkylsilyl group, a C 1 -C 20 silylalkyl group, a C 1 -C 20 alkoxysilyl group, a C 1 -C 20 alkoxy group, a C 6 -C 20 aryl group, a C 7 -C 20 alkylaryl group, or a C 7 -C 20 arylalkyl group, wherein 2 or more adjacent groups among R 10 to R 17 may form a substituted or unsubstituted aliphatic or aromatic ring by being connected together; and

wherein B and M of Chemical Formula 1 are bonded to the cyclopentadienyl groups of C 1 and C 2 of Chemical Formula 1.

2. The metallocene compound according to claim 1 , wherein R 1 to R 17 and R 1 ′ to R 9 ′ in Chemical Formulae 2a, 2b and 3 are independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a halogen group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a methoxy group, or an ethoxy group.

3. The metallocene compound according to claim 1 , wherein L in Chemical Formula 1 is a C 4 -C 8 linear or branched alkylene group.

4. The metallocene compound according to claim 1 , wherein A in Chemical Formula 1 is hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, a tert-butoxybutyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.

5. The metallocene compound according to claim 1 , wherein the structure represented by Chemical Formula 2a is one of the following structures:

6. The metallocene compound according to claim 1 , wherein the structure represented by Chemical Formula 2b is one of the following structures:

7. The metallocene compound according to claim 1 , wherein the structure represented by Chemical Formula 3 is one of the following structures:

8. The metallocene compound according to claim 1 , wherein the structure represented by Chemical Formula 1 is one of the following structures:

9. A catalyst composition, including the metallocene compound of claim 1 and a cocatalyst.

10. The catalyst composition according to claim 9 , wherein the cocatalyst includes one or more of the compounds represented by Chemical Formulae 4 to 6:

[Al(R 18 )—O] n —  [Chemical Formula 4]

in Chemical Formula 4,

each R 18 is the same or different, and is independently a halogen; a C 1 -C 20 hydrocarbon; or a halogen-substituted C 1 -C 20 hydrocarbon; and

n is an integer of 2 or more;

J(R 18 ) 3   [Chemical Formula 5]

in Chemical Formula 5,

R 18 is same as that in Chemical Formula 4; and

J is aluminum or boron;

[E-H] + [ZA′ 4 ] − or [E] + [ZA′ 4 ] −   [Chemical Formula 6]

in Chemical Formula 6,

E is a neutral or cationic Lewis acid;

H is hydrogen atom;

Z is group 13 element; and

each A′ is the same or different, and is independently a C 6 -C 20 aryl group or a C 1 -C 20 alkyl group of which at least one hydrogen atom is unsubstituted or substituted with a halogen, a C 1 -C 20 hydrocarbon, an alkoxy, or phenoxy.

11. The catalyst composition according to claim 10 , wherein the catalyst is supported on a carrier.

12. The catalyst composition according to claim 11 , wherein the carrier is one or more carriers selected from the group consisting of silica, silica-alumina, and silica-magnesia.

13. A method of preparing an olefinic polymer, including the step of polymerizing olefinic monomers in the presence of the catalyst composition according to claim 9 .

14. The method of preparing an olefinic polymer according to claim 13 , wherein the polymerization reaction is carried out according to a solution polymerization process, slurry process, or a gas phase process.

15. The method of preparing an olefinic polymer according to claim 13 , wherein the olefinic monomer is one or more monomers 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, and 1-eicosene.