Hybrid supported metallocene catalyst and method for preparing olefin polymer using the same

Patent metadata

Field	Value
Publication number	US-11384183-B2
Application number	US-202017043194-A
Country	US
Kind code	B2
Filing date	Jan 15, 2020
Priority date	Jan 17, 2019
Publication date	Jul 12, 2022
Grant date	Jul 12, 2022

Abstract

A catalyst composition, a method from preparing an olefin polymer using the same, and an olefin polymer prepared from the same are disclosed herein. In some embodiments, a catalyst composition includes a first metallocene compound represented by the Chemical Formula 1, a second metallocene compound represented by the Chemical Formula 2, and a support. The catalyst composition can exhibit high activity in an olefin polymerization reaction and thus contribute to reducing catalyst costs, and can also exhibit high copolymerizability which can secure excellent processability and long-term physical properties, and thus, is suitable for providing polymers for pipes.

First claim

The invention claimed is:

1. A hybrid supported metallocene catalyst, comprising:
a first metallocene compound represented by the following Chemical Formula 1;
a second metallocene compound represented by the following Chemical Formula 2; and
a support supporting the first and second metallocene compounds,
wherein a molar ratio of the first metallocene compound and the second metallocene compound is 1:1 to 15:1,

in Chemical Formula 1,
X 1 and X 2 are each independently halogen,
R 1 and R 5 are each independently C 6-20 aryl substituted with C 1-20 alkyl,
R 2 to R 4 and R 6 to R 8 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 silyl ether, C 1-20 alkoxy, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
A is carbon, silicon or germanium, and
R 9 and R 10 are each independently C 1-2 linear alkyl, or C 3-10 linear alkyl substituted with C 1-10 alkoxy, wherein at least one of R 9 and R 10 is C 3-10 linear alkyl substituted with C 1-10 alkoxy,

in Chemical Formula 2,
X 3 and X 4 are each independently halogen,
R 11 to R 20 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 silyl ether, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
wherein at least one of R 11 and R 12 is C 2-20 alkoxyalkyl, and
at least one of R 17 to R 20 is C 1-20 alkyl.

2. The hybrid supported metallocene catalyst of claim 1 , wherein the R 1 and R 5 are each independently phenyl substituted with C 3-6 branched alkyl.

3. The hybrid supported metallocene catalyst of claim 1 , wherein the R 9 and R 10 are each independently methyl, or C 5-9 linear alkyl substituted with tert-butoxy, wherein at least one of R 9 and R 10 is a C 5-9 linear alkyl substituted with tert-butoxy.

4. The hybrid supported metallocene catalyst of claim 1 , wherein the first metallocene compound represented by Chemical Formula 1 is the following Chemical Formula 1-1

5. The hybrid supported metallocene catalyst of claim 1 , wherein R 12 is a C 5-9 linear alkyl substituted with tert-butoxy.

6. The hybrid supported metallocene catalyst of claim 1 , wherein one of R 18 and R 19 is normal-butyl.

7. The hybrid supported metallocene catalyst of claim 1 , wherein the second metallocene compound represented by Chemical Formula 2 is the following Chemical Formula 2-1

8. The hybrid supported metallocene catalyst of claim 1 , wherein the support includes any one selected from the group consisting of silica, alumina and magnesia, or a mixture of two or more thereof.

9. The hybrid supported metallocene catalyst of claim 1 , further comprising:
at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5:
R 22 —[Al(R 21 )—O] n —R 23   [Chemical Formula 3]

in Chemical Formula 3,
R 21 , R 22 and R 23 are each independently hydrogen, halogen, a C 1-20 hydrocarbyl group, or a C 1-20 hydrocarbyl group substituted with halogen, and
n is an integer of 2 or more,
D(R 24 ) 3   [Chemical Formula 4]

in Chemical Formula 4,
D is aluminum or boron, and
each R 24 is independently halogen, a C 1-20 hydrocarbyl group, a C 1-20 hydrocarbyloxy group, or a C 1-20 hydrocarbyl group substituted with halogen,
[L-H] + [W(A) 4 ] − or [L] + [W(A) 4 ] −   [Chemical Formula 5]

in Chemical Formula 5,
L is neutral or cationic Lewis base,
H is a hydrogen atom,
W is a Group 13 atom, and
each A is independently one of a C 1-20 hydrocarbyl group, or a C 1-20 hydrocarbyloxy group, wherein at least one hydrogen atom of the C 1-20 hydrocarbyl group and the C 1-20 hydrocarbyloxy group is substituted with at least one substituent selected among halogen, a C 1-20 hydrocarbyloxy group and a C 1-20 hydrocarbyl(oxy)silyl group.

10. A method for preparing an olefin polymer comprising:
polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst of claim 1 .

11. The method for preparing the olefin polymer of claim 10 , wherein the polymerization is performed in a semi-batch reactor.

12. The method for preparing the olefin polymer of claim 10 , wherein the olefin monomer includes at least one 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, 1-eitocene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Ye Jin
• Song Eun Kyoung
• Hong Daesik
• Lee Hye Kyung
• Kim Joongsoo
• Shin Eunyoung
• Kwak Jinyoung

Classifications

• C07F17/00

  Metallocenes · CPC title

• C08F210/02

  Ethene · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title