Metallocene compound, catalyst composition including the same, and method of preparing olefin-based polymer using the same

Patent metadata

Field	Value
Publication number	US-9994653-B2
Application number	US-201515317038-A
Country	US
Kind code	B2
Filing date	Jan 28, 2015
Priority date	Jan 28, 2015
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Provided are a novel metallocene compound, a catalyst composition including the same, and a method of preparing an olefin-based polymer using the same. The metallocene compound according to the present invention or the catalyst composition including the same may be used for the preparation of an olefin-based polymer, may have excellent polymerization ability, and may produce an olefin-based polymer having a high molecular weight. In particular, when the metallocene compound according to the present invention is employed, an olefin-based polymer having a high molecular weight may be polymerized because the metallocene compound shows high polymerization activity even when it is supported on a support and maintains high activity even in the presence of hydrogen because of its low hydrogen reactivity.

First claim

The invention claimed is:

1. A metallocene compound represented by the following Chemical Formula 1:

wherein A is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is —O—, —S—, —N(R)—, or —Si(R)(R′)—, wherein R and R′ are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L is a C1 to C10 linear or branched alkylene group;
B is carbon, silicon, or germanium;
Q is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
M is a Group 4 transition metal;
X 1 and X 2 are the same as or different from each other, and are each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group; and
C 1 and C 2 are the same as or different from each other, at least one of C 1 and C 2 is represented by the following Chemical Formula 2, and the other is cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, fluorenyl, or indenoindolyl, and they are substituted with a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group,

wherein n is an integer of 0 to 5; and
R 1 to R 13 are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and at least one of R 9 to R 13 is a halogen.

2. The metallocene compound of claim 1 , wherein R 1 to R 13 in Chemical Formula 2 are each independently hydrogen, a halogen, 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 of claim 1 , wherein at least one of R 9 to R 13 in Chemical Formula 2 is fluorine (F).

4. The metallocene compound of claim 1 , wherein L in Chemical Formula 1 is a C4 to C8 linear or branched alkylene group.

5. The metallocene compound of 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-butoxymethyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.

6. The metallocene compound of claim 1 , wherein the compound represented by Chemical Formula 2 is any one of the following structural formulae:

7. The metallocene compound of claim 1 , wherein the compound represented by Chemical Formula 1 is any one of the following structural formulae:

8. A catalyst composition comprising the metallocene compound of claim 1 and a cocatalyst.

9. The catalyst composition of claim 8 , wherein the cocatalyst comprises one or more of compounds represented by the following Chemical Formula 3, Chemical Formula 4, and Chemical Formula 5:
—[Al(R 14 )—O] m —  [Chemical Formula 3]

wherein, in Chemical Formula 3,
R 14 's are the same as or different from each other, and are each independently a halogen;
hydrocarbon having 1 to 20 carbon atoms; or halogen-substituted hydrocarbon having 1 to 20 carbon atoms; and
m is an integer of 2 or more,
J(R 14 ) 3   [Chemical Formula 4]

wherein, in Chemical Formula 4,
R 14 's are the same as defined in Chemical Formula 3; and
J is aluminum or boron,
[E-H] + [ZA′ 4 ] − or [E] + [ZA′ 4 ] −   [Chemical Formula 5]

wherein, in Chemical Formula 5,
E is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element; and
A's are the same as or different from each other, and are each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, of which one or more hydrogen atoms are unsubstituted or substituted with a halogen, a hydrocarbon having 1 to 20 carbon atoms, alkoxy, or phenoxy.

10. The catalyst composition of claim 8 , wherein the catalyst composition is in the form of being supported on a support.

11. The catalyst composition of claim 10 , wherein the support is one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia.

12. A method of preparing an olefin-based polymer, comprising the step of polymerizing olefin-based monomers in the presence of the catalyst composition of claim 8 .

13. The method of claim 12 , wherein the polymerizing is carried out by a solution polymerization process, a slurry process, or a gas phase process.

14. The method of claim 12 , wherein the olefin-based monomer is one or more 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.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Yong Ho
• Cho Kyung Jin
• Park Jin Young
• Lee Ki Soo
• Cho Min Seok
• Kim Se Young
• Lee Sung Min
• Han Chang Woan

Classifications

• C08F2420/10

  Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom · CPC title

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title

• C08F2420/06

  Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom · CPC title

• C08F110/02

  Ethene · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title