Catalyst composition, a method for preparing the same, and a method for preparing polyolefin using the same

Patent metadata

Field	Value
Publication number	US-9725531-B2
Application number	US-201314895763-A
Country	US
Kind code	B2
Filing date	Dec 27, 2013
Priority date	Jun 25, 2013
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

This disclosure relates to a catalyst composition that can prepare polyolefin having high molecular weight, a method for preparing the same, and a method for preparing polyolefin using the same. The dinuclear metallocene compound included in the catalyst composition according to the present invention is a dinuclear metallocene compound with a new structure, and, unlike a single-site catalyst, has high accessibility to a substrate, and thus, can provide a multi-site catalyst with high activity.

First claim

What is claimed is:

1. A catalyst composition comprising
a dinuclear metallocene compound represented by Chemical Formula 1; and
at least one cocatalyst compound selected from the group consisting of a compound represented by Chemical Formula 2, a compound represented by Chemical Formula 3, and a compound represented by Chemical Formula 4:

in Chemical Formula 1,
R1 to R4 are independently hydrogen; a halogen radical; an alkyl radical having a carbon number of 1 to 20; an alkenyl radical having a carbon number of 2 to 20; a silyl radical; an aryl radical having a carbon number of 6 to 20; an alkylaryl radical having a carbon number of 7 to 20; or an arylalkyl radical having a carbon number of 7 to 20; and two or more adjacent radicals of R1 to R4 are optionally linked to each other to form an aliphatic ring, or an aromatic ring;
R5 to R7 are independently hydrogen; a halogen radical; an alkyl radical having a carbon number of 1 to 20; an alkenyl radical having a carbon number of 2 to 20; an aryl radical having a carbon number of 6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an arylalkyl radical having a carbon number of 7 to 20; an alkoxy radical having a carbon number of 1 to 20; an aryloxy radical having a carbon number of 6 to 20; or an amido radical; and two or more adjacent radicals of R5 to R7 are optionally linked to each other to form an aliphatic ring, or an aromatic ring;
CY is an aliphatic or aromatic ring containing nitrogen, and may be unsubstituted or substituted with halogen, an alkyl or aryl radical having a carbon number of 1 to 20, and when CY has multiple substituents, two or more substituents are optionally linked to each other to form an aliphatic or aromatic ring;
M is Group 4 transition metal;
X1 is a halogen radical; an alkyl radical having a carbon number of 1 to 20; an alkenyl radical having a carbon number of 2 to 20; an aryl radical having a carbon number of 6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an arylalkyl radical having a carbon number of 7 to 20; an alkylamido radical having a carbon number of 1 to 20; an arylamido radical having a carbon number of 6 to 20; or an alkylidene radical having a carbon number of 1 to 20; and
n is an integer of 0 to 10,
—[Al(R 8 )—O] c —  [Chemical Formula 2]

in Chemical Formula 2, R 8 is a halogen radical, a hydrocarbyl radical having a carbon number of 1 to 20, or a hydrocarbyl radical having a carbon number of 1 to 20 substituted with halogen, and c is an integer equal to or greater than 2,
D(R 9 ) 3   [Chemical Formula 3]

in Chemical Formula 3,
D is aluminum or boron, R 9 is hydrocarbyl having a carbon number of 1 to 20 or hydrocarbyl having a carbon number of 1 to 20 substituted with halogen,
[L-H] + [ZA 4 ] − or [L] + [ZA 4 ] −   [Chemical Formula 4]

in Chemical Formula 4,
L is neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 atom, A's are independently an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, where one or more hydrogen atoms are unsubstituted or substituted with halogen, a hydrocarbon having a carbon number of 1 to 20, alkoxy or phenoxy.

2. The catalyst composition according to claim 1 , wherein in Chemical Formula 1, R1 to R7 are independently hydrogen, an alkyl group having a carbon number of 1 to 20, or an aryl group having a carbon number of 6 to 20, and CY is a 5-membered or 6-membered aliphatic or aromatic ring containing nitrogen, unsubstituted or substituted with an alkyl group having a carbon number of 1 to 20, M is titanium(Ti), zirconium(Zr), or hafnium(Hf), and X1 is halogen or an alkyl group having a carbon number of 1 to 20.

3. The catalyst composition according to claim 1 , wherein the compound of Chemical Formula 1 is represented by the following structures:

4. A method for preparing a catalyst composition comprising the steps of:
contacting a dinuclear metallocene compound represented by Chemical Formula 1 with a compound represented by Chemical Formula 2 and/or a compound represented by Chemical Formula 3 to obtain a mixture; and
adding a compound represented by Chemical Formula 4 to the mixture:

in Chemical Formula 1,
R1 to R4 are independently hydrogen; a halogen radical; an alkyl radical having a carbon number of 1 to 20; an alkenyl radical having a carbon number of 2 to 20; a silyl radical; an aryl radical having a carbon number of 6 to 20; an alkylaryl radical having a carbon number of 7 to 20; or an arylalkyl radical having a carbon number of 7 to 20; and two or more adjacent radicals of R1 to R4 are optionally linked to each other to form an aliphatic ring, or an aromatic ring;
R5 to R7 independently hydrogen; a halogen radical; an alkyl radical having a carbon number of 1 to 20; an alkenyl radical having a carbon number of 2 to 20; an aryl radical having a carbon number of 6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an arylalkyl radical having a carbon number of 7 to 20; an alkoxy radical having a carbon number of 1 to 20; an aryloxy radical having a carbon number of 6 to 20; or an amido radical; and two or more adjacent radicals of R5 to R7 are optionally linked to each other to form an aliphatic ring, or an aromatic ring;
CY is an aliphatic or aromatic ring containing nitrogen, and may be unsubstituted or substituted with halogen, an alkyl or aryl radical having a carbon number of 1 to 20, and when CY has multiple substituents, two or more substituents are optionally linked to each other to form an aliphatic or aromatic ring;
M is Group 4 transition metal;
X1 is a halogen radical; an alkyl radical having a carbon number of 1 to 20; an alkenyl radical having a carbon number of 2 to 20; an aryl radical having a carbon number of 6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an arylalkyl radical having a carbon number of 7 to 20; an alkylamido radical having a carbon number of 1 to 20; an arylamido radical having a carbon number of 6 to 20; or an alkylidene radical having a carbon number of 1 to 20; and
n is an integer of 0 to 10,
—[Al(R 8 )—O] c —  [Chemical Formula 2]

in Chemical Formula 2, R 8 is a halogen radical, a hydrocarbyl radical having a carbon number of 1 to 20, or a hydrocarbyl radical having a carbon number of 1 to 20, substituted with halogen, and c is an integer equal to or greater than 2,
D(R 9 ) 3   [Chemical Formula 3]

in Chemical Formula 3,
D is aluminum or boron, R 9 is hydrocarbyl having a carbon number of 1 to 20 or hydrocarbyl having a carbon number of 1 to 20 substituted with halogen,
[L-H] + [ZA 4 ] − or [L] + [ZA 4 ] −   [Chemical Formula 4]

in Chemical Formula 4,
L is neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 atom, A's are independently an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, where one or more hydrogen atoms are unsubstituted or substituted with halogen, a hydrocarbon having a carbon number of 1 to 20, alkoxy or phenoxy.

5. A method for preparing a catalyst composition according to claim 4 , wherein a mole ratio of the dinuclear metallocene compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 3 is 1:2 to 1:5,000, and a mole ratio of the dinuclear metallocene compound represented

Assignees

• Lg Chemical Ltd

Inventors

• Do Young Shil
• Lee Choong Hoon
• Jung Seung Hwan
• Kum Don Ho
• Park Sang Eun
• Park Hae Woong

Classifications

• C08F210/16

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/6592 Primary

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

• C08F4/65908 Primary

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65925 Primary

  two cyclopentadienyl rings being mutually non-bridged · CPC title