Metallocene compound, metallocene-supported catalyst, and method of preparing polyolefin using the same

Patent metadata

Field	Value
Publication number	US-10450390-B2
Application number	US-201515507968-A
Country	US
Kind code	B2
Filing date	Dec 15, 2015
Priority date	Dec 15, 2014
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

Provided are a novel metallocene compound, a metallocene-supported catalyst, and a method of preparing a polyolefin using the same. The metallocene-supported catalyst according to the present disclosure exhibits a high polymerization activity even when the metallocene compound is supported on a support, thereby showing an excellent activity and preparing a polyolefin having a high molecular weight.

First claim

What is claimed is:

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

wherein M is titanium, zirconium or hafnium;
B is carbon, silicon, or germanium;
Q 1 and Q 2 are the same as or different from each other, and each independently 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 tert-butoxyhexyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group;
X 1 and X 2 are the same as or different from each other, and each is independently a halogen;
one of C 1 and C 2 is represented by the following Chemical Formula 2a, and the other is represented by the following Chemical Formula 2b:

in Chemical Formula 2a, R 1 to R 4 , R 6 , R 7 and R 9 are hydrogen, and R 5 and R 8 are the same as or different from each other, and each independently is 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, an ethylene group, a propylene group, a butenyl group, a phenyl group, a benzyl group, a naphthyl group, a methoxy group, an ethoxy group, a tert-butoxyhexyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, or a tert-butyldimethylsilylether group;
in Chemical Formula 2b, R 10 and R 12 to R 15 are hydrogen, and R 11 is 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, an ethylene group, a propylene group, a butenyl group, a phenyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a tert-butyldimethylsilylether group, a methoxy group, an ethoxy group, a tert-butoxyhexyl group, an aryl group, an alkylaryl group or an arylalkyl group.

2. The metallocene compound of claim 1 , wherein Q 1 and Q 2 of Chemical Formula 1 are a methyl group or a tert-butoxyhexyl group.

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

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

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

6. A metallocene-supported catalyst, comprising the metallocene compound of claim 1 ;
a cocatalyst compound; and
a support.

7. The metallocene-supported catalyst of claim 6 , wherein the cocatalyst compound comprises one or more of compounds represented by the following Chemical Formula 3, Chemical Formula 4, and Chemical Formula 5:
—[Al(R 16 )—O] n —  [Chemical Formula 3]

wherein R 16 s are the same as or different from each other, and each independently halogen; C1 to C20 hydrocarbon; or halogen-substituted C1 to C20 hydrocarbon; and
n is an integer of 2 or more;
J(R 17 ) 3   [Chemical Formula 4]

wherein R 17 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 E is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element; and
As are the same as or different from each other, and each independently a C6 to C20 aryl group or a C1 to C20 alkyl group, of which one or more hydrogen atoms are unsubstituted or substituted with halogen, C1 to C20 hydrocarbon, alkoxy, or phenoxy.

8. The metallocene-supported catalyst of claim 6 , wherein the support is one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia.

9. The metallocene-supported catalyst of claim 6 , wherein a weight ratio of the transition metal of the metallocene compound to the support is 1:10 to 1:1,000.

10. The metallocene-supported catalyst of claim 6 , wherein a weight ratio of the cocatalyst compound to the support is 1:1 to 1:100.

11. A method of preparing a polyolefin, the method comprising polymerizing olefinic monomers in the presence of the metallocene-supported catalyst of claim 6 .

12. The method of claim 11 , wherein the polymerization is performed by a solution polymerization process, a slurry process, or a gas phase process.

13. The method of claim 11 , wherein the olefinic monomer comprises one or more monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, norbornene, ethylidenenorbornene, styrene, alpha-methylstyrene, and 3-chloromethylstyrene.

14. A polyolefin prepared by the preparation method of claim 11 .

15. The polyolefin of claim 14 , wherein a weight average molecular weight is 200,000 g/mol to 900,000 g/mol.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Sung Min
• Hong Bog Ki
• Cho Kyung Jin
• Kim Se Young
• Han Chang Woan
• Lee Ki Soo
• Song Eun Kyoung

Classifications

• C08F4/652

  Pretreating with metals or metal-containing compounds · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F12/00

  Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring · CPC title

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C07D221/18 Primary

  Ring systems of four or more rings · CPC title