Process for preparing a hybrid catalyst for olefin polymerization, hybrid catalyst for olefin polymerization, and polyolefin

Patent metadata

Field	Value
Publication number	US-12534545-B2
Application number	US-202017768221-A
Country	US
Kind code	B2
Filing date	Oct 8, 2020
Priority date	Oct 16, 2019
Publication date	Jan 27, 2026
Grant date	Jan 27, 2026

Abstract

The present invention relates to a process for preparing a hybrid catalyst for olefin polymerization, to a hybrid catalyst for olefin polymerization, and to a polyolefin. The supported hybrid metallocene catalyst for olefin polymerization prepared by the process for preparing a supported hybrid metallocene catalyst for olefin polymerization according to an embodiment of the present invention is capable of preparing a polyolefin having a broad molecular weight distribution of bimodal characteristics and being excellent in mechanical strength and processability.

First claim

The invention claimed is:

1 . A process for preparing a supported hybrid metallocene catalyst for olefin polymerization, which comprises (1) mixing a first transition metal compound represented by Formula 1 with a first cocatalyst compound; (2) supporting the mixture of the first transition metal compound and the first cocatalyst compound obtained in step (1) on a carrier; and (3) mixing the supported catalyst obtained in step (2) with (3a) a mixture of a second transition metal compound represented by Formula 2 and a second cocatalyst compound, or (3b) a second transition metal compound represented by Formula 2, which is then mixed with a second cocatalyst compound, or (3c) a second cocatalyst compound, which is then mixed with a second transition metal compound represented by Formula 2:

in Formulae 1 and 2, M is each independently 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,
l and m are each an integer from 0 to 5,
R 1 and R 2 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, wherein R 1 and R 2 are each independently capable of being linked to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring,
Q is an anionic leaving group and is each independently hydrogen, hydrocarbyl, heteroatom or halogen, a straight or branched chain alkyl radical, or an alkenyl radical, an alkynyl radical, a cycloalkyl radical or an aryl radical, an acyl radical, an aroyl radical, an alkoxy radical, an aryloxy radical, an alkylthio radical, a dialkylamino radical, an alkoxycarbonyl radical, an aryloxycarbonyl radical, a carbomoyl radical, an alkyl- or dialkyl-carbamoyl radical, an acyloxy radical, an acylamino radical, an aroylamino radical, a straight-chain, branched-chain or cyclic alkylene radical, or a combination thereof,
n is the oxidation state of M and is +3, +4, or +5,
o is the formal charge of the YZL ligand and is 0, −1, −2, or −3,
L is nitrogen,
Y is nitrogen or phosphorus,
Z is nitrogen or phosphorus,
R 3 and R 4 are each independently a C 1-20 hydrocarbon group or a heteroatom-containing group, wherein the hetero atom is silicon, germanium, tin, lead, or phosphorus, or R 3 and R 4 are capable of being linked to each other,
R 5 is absent or is hydrogen, C 1-20 alkyl, halogen, or a heteroatom-containing group,
R 6 and R 7 are each independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a multiple ring system, and
R 8 and R 9 are each independently absent or hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom-containing group.

2 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 1 , wherein, in Formula 1, M is zirconium or hafnium, X is each independently halogen, and 1 and m are each an integer of 1 to 3, and in Formula 2, M is zirconium or hafnium, Q is each independently hydrogen, a halogen, or a hydrocarbyl group, R 3 and R 4 are each independently a C 1-6 hydrocarbon group, R 5 is hydrogen or methyl, and R 6 and R 7 are each independently a substituted aryl group.

3 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 2 , wherein, in Formula 2, R 6 and R 7 are each independently a group represented by Formula 3:

in Formula 3, R 10 to R 14 are each independently hydrogen, a C 1-20 alkyl group, a hetero atom, or a heteroatom-containing group having up to 40 carbon atoms, and two groups of R 10 to R 14 are capable of being fused to form a cyclic group or a heterocyclic group.

4 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 3 , wherein R 11 , R 12 , and R 14 are methyl, and R 10 and R 13 are hydrogen.

5 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 2 , wherein the first transition metal compound and the second transition metal compound are compounds represented by Formula 1a and Formula 2a, respectively:

in Formula 2a, Ph is a phenyl group.

6 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 1 , wherein the first cocatalyst compound and the second cocatalyst compound each comprise at least one selected from the group consisting of a compound represented by Formula 4, a compound represented by Formula 5, and a compound represented by Formula 6:
[L-H] + [Z(A) 4 ] −
or
[L] + [Z(A) 4 ] −   [Formul 6]

in Formula 4, n is an integer of 2 or more, and R a may each independently be a halogen atom, a hydrocarbon group having 1-20 carbon atoms, or a hydrocarbon group having 1-20 carbon atoms substituted with halogen,
in Formula 5, D is aluminum (Al) or boron, and R b , R c , and R a are each independently a halogen atom, a hydrocarbon group having 1-20 carbon atoms, a hydrocarbon group having 1-20 carbon atoms substituted with halogen, or an alkoxy group having 1-20 carbon atoms, and
in Formula 6, L is a neutral or cationic Lewis acid, [L-H] + and [L] + a Brönsted acid, Z is a group 13 element, and A is each independently a substituted or unsubstituted aryl group having 6-20 carbon atoms or a substituted or unsubstituted alkyl group having 1-20 carbon atoms.

7 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 6 , wherein the compound represented by Formula 4 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

8 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 6 , wherein the compound represented by Formula 5 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.

9 . The process for preparing a supported hybrid metallocene catalyst for olefin polymerization of claim 6 , wherein the compound represented by Formula 6 is at least one selected from the group consisting of triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimet

Assignees

• Hanwha Solutions Corp

Inventors

• Park Hye Ran
• Kim Sung Dong
• Seo Junho
• Lee Munhee
• Joung Ui Gap
• Jeong Tae Uk
• Lim Seongjae

Classifications

• C08F210/16 Primary

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

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65904

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

• C08F4/65916 Primary

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