Catalyst for olefin polymerization

Patent metadata

Field	Value
Publication number	US-11859040-B2
Application number	US-201917283572-A
Country	US
Kind code	B2
Filing date	Oct 11, 2019
Priority date	Oct 19, 2018
Publication date	Jan 2, 2024
Grant date	Jan 2, 2024

Abstract

The present invention relates to a catalyst for olefin polymerization. Specifically, the present invention relates to a hybrid catalyst comprising different transition metal compounds and capable of preparing a polyolefin, particularly a linear low-density polyethylene, which has excellent processability, impact strength, and haze.

First claim

The invention claimed is:

1. A catalyst for olefin polymerization, which comprises a first transition metal compound represented by Formula A and a second transition metal compound represented by Formula B:

in Formulae A and B, n and o are each an integer of 0 to 2, provided that at least one of them is not 0, and m and l are each an integer of 0 to 4,
M is titanium (Ti), zirconium (Zr), or hafnium (Hf),
X is each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn),
R 1 , R 2 , R 6 , and R 7 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl,
R 3 to R 5 are each C 1-20 alkyl,
at least one of R 1 and R 2 is independently linked to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring, and
R 3 to R 7 are each independently optionally linked to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.

2. The catalyst for olefin polymerization of claim 1 , wherein in Formulae A and B, n and o are each 1 or 2, m and l are each 1, X is each independently halogen, M is zirconium, Q is carbon, and at least one of R 1 and R 2 is independently linked to adjacent groups to form a substituted or unsubstituted unsaturated C 4-20 ring, and R 6 and R 7 are each C 6-20 aryl.

3. The catalyst for olefin polymerization of claim 2 , the compounds represented by Foiiiiulae A and B are compounds represented by Formulae A-1 and B-1, respectively:

4. The catalyst for olefin polymerization of claim 1 , which comprises the first transition metal compound and the second transition metal compound at a weight ratio of 20:1 to 1:20.

5. The catalyst for olefin polymerization of claim 1 , which further comprises a cocatalyst compound selected from the group consisting of a compound represented by Formula 1, a compound represented by Formula 2, and a compound represented by Formula 3:

in Formula 1, n is an integer of 2 or more, and R a is each independently a halogen atom, C 1-20 hydrocarbon, or C 1-20 hydrocarbon substituted with halogen,
in Formula 2, D is aluminum (Al) or boron, and R b , R c , and R d are each independently a halogen atom, C 1-20 hydrocarbon, C 1-20 hydrocarbon substituted with halogen, or C 1-20 alkoxy, and
in Formula 3, L is a neutral or cationic Lewis acid, [L-H] + and [L] + a Bronsted acid, Z is a group 13 element, and A is each independently substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 1-20 alkyl.

6. The catalyst for olefin polymerization of claim 5 , wherein the compound represented by Formula 1 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

7. The catalyst for olefin polymerization of claim 5 , wherein the compound represented by Formula 2 is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentyaluminum, trihexyaluminum, trioctyaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminummethoxide, dimethylaluminumethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron.

8. The catalyst for olefin polymerization of claim 5 , wherein the compound represented by Formula 3 is at least one selected from the group consisting of triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(o,p-dimethylphenyl)aluminate, tributylammonium tetra(p-trifluoromethylphenyl)aluminate, trimethylammonium tetra(p-trifluoromethylphenyl)aluminate, tributylammonium tetrapentafluorophenylaluminate, N,N-diethylanilinium tetraphenylaluminate, N,N-diethylanilinium tetrapentafluorophenylaluminate, diethylammonium tetrapentatetraphenylaluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, and triphenylcarbonium tetrapentafluorophenylborate.

9. The catalyst for olefin polymerization of claim 1 , which further comprises a carrier for supporting the first transition metal compound, the second transition metal compound, or both.

10. The catalyst for olefin polymerization of claim 9 , wherein the carrier supports all of the first transition metal compound, the second transition metal compound, and the cocatalyst.

11. The catalyst for olefin polymerization of claim 10 , wherein the total amount of the first transition metal compound and the second transition metal compound supported on the carrier is 0.001 mmole to 1 mmole based on 1 g of the carrier, and the amount of the cocatalyst compound supported on the carrier is 2 mmoles to 15 mmoles based on the 1 g of the carrier.

12. The catalyst for olefin polymerization of claim 9 , wherein the carrier comprises at least one selected from the group consisting of silica, alumina, and magnesia.

13. The catalyst for olefin polymerization of claim 9 , which is a hybrid supported catalyst in which the first transition metal compound and the second transition metal compound are supported together.

14. The catalyst for olefin polymerization of claim 9 , which is a hybrid supported catalyst in which the first transition metal compound and the second transition metal compound are supported together on a single carrier.

15. The catalyst for olefin polymerization of claim 9 , which is a hybrid supported catalyst in which the first transition metal compound, the second transition me

Assignees

• Hanwha Solutions Corp

Inventors

• Seo Junho
• Kim Ahreum
• Lee Munhee

Classifications

• C08F4/65927 Primary

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65904

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

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F210/16 Primary

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title