# US 11,993,665 B2 · Hybrid supported catalyst and method of preparing polyolefin using the same

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- Number: US 11,993,665 B2
- Document ID: US11993665B2
- Status: Granted
- Kind: B2
- Application number: 17/294,743
- Filed: 2020-09-25
- Published: 2022-01-20
- Granted: 2024-05-28
- Earliest claimed: 2019-09-27
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Sun Mi Kim; Ue Ryung Seo; Bog Ki Hong; Eun Kyoung Song; Daesik Hong; Si Jung Lee; Cheolhwan Jeong; Kiju Um
- Web page: https://patentgrep.com/patent/US11993665B2

## CPC

- C08F 110/02: Ethene
- C08F 4/02: Carriers therefor
- C08F 4/65922: {containing at least two cyclopentadienyl rings, fused or not}
- C08F 8/20: Halogenation
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2410/02: Anti-static agent incorporated into the catalyst
- C08F 2420/00: Metallocene catalysts
- C08F 2420/02: Cp or analog bridged to a non-Cp X anionic donor
- C08F 2420/07: Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Provided are a hybrid supported catalyst which includes two or more kinds of transition metal compounds having the following Chemical Formulas 1 and 2, thereby preparing a polyolefin, particularly, a high-density polyethylene having a molecular structure which is optimized to improve tensile strength of a chlorinated polyolefin compound, and a method of preparing a polyolefin using the same: wherein all the variables are described herein.

## Claims

### Claim 1

A hybrid supported catalyst comprising:
one or more of a first transition metal compound represented by Chemical Formula 1;
one or more of a second transition metal compound represented by Chemical Formula 2; and
a support on which the first and second transition metal compounds are supported:
(Cp1R11)m(Cp2R12)M1(Z1)3-m [Chemical Formula 1]
in Chemical Formula 1,
M1 is a transition metal of Group 4;
Cp1 and Cp2 are the same as or different from each other, and each independently, any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which are unsubstituted or substituted with C1-20 hydrocarbon;
R11 and R12 are the same as or different from each other, and each independently, hydrogen, C1-20 alkyl, C1-20 alkoxy, C2-20 alkoxyalkyl, C6-20 aryl, C6-20 aryloxy, C2-20 alkenyl, C7-40 alkylaryl, C7-40 arylalkyl, C8-40 arylalkenyl, C2-20 alkynyl, or C2-20 heteroaryl comprising one or more heteroatoms of N, O, or S;
Z1 is halogen, C1-20 alkyl, C2-20 alkenyl, C7-40 alkylaryl, C7-40 arylalkyl, C6-20 aryl, an amino group, C2-20 alkylalkoxy, or C7-40 arylalkoxy; and
m is 1 or 0;
in Chemical Formula 2,
A is carbon or silicon,
M2 is a transition metal of Group 4,
R21 is C6-20 aryl substituted with C1-20 alkyl,
R22 is C3-20 branched alkyl,
R23 to R25 are each independently C1-20 alkyl,
Z21 and Z22 are each independently halogen or C1-10 alkyl, and
n is an integer of 1 to 10.

### Claim 2 (depends on 1)

The hybrid supported catalyst of claim 1, wherein M1 is Ti, Zr, or Hf;
Cp1 and Cp2 are the same as or different from each other, and each independently, any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which are unsubstituted or substituted with C1-10 alkyl;
R11 and R12 are each independently hydrogen, C1-20 alkyl, C2-20 alkoxyalkyl, C6-20 aryl, C7-20 arylalkyl, furanyl, or thiophenyl, wherein at least one of R11 or R12 is C2-20 alkoxyalkyl; and
Z1 is halogen.

### Claim 3 (depends on 1)

The hybrid supported catalyst of claim 1, wherein the first transition metal compound is selected from the group consisting of compounds having the following structures:

### Claim 4 (depends on 1)

The hybrid supported catalyst of claim 1, wherein M2 is titanium, and
Z21 and Z22 are each independently C1-4 alkyl.

### Claim 5 (depends on 1)

The hybrid supported catalyst of claim 1, wherein R21 is phenyl substituted with one or two of C3-6 branched alkyl, and
R22 and R23 are each independently C3-6 branched alkyl.

### Claim 6 (depends on 1)

The hybrid supported catalyst of claim 1, wherein A is silicon,
R25 is C3-6 branched alkyl, and
n is an integer of 4 to 6.

### Claim 7 (depends on 1)

The hybrid supported catalyst of claim 1, wherein R22 is isopropyl.

### Claim 8 (depends on 1)

The hybrid supported catalyst of claim 1, wherein the second transition metal compound is selected from the group consisting of compounds having the following structures:

### Claim 9 (depends on 1)

The hybrid supported catalyst of claim 1, wherein the first and second transition metal compounds are comprised at a molar ratio of 1:3 to 3:1.

### Claim 10 (depends on 1)

The hybrid supported catalyst of claim 1, wherein the support comprises at least one of silica, alumina, or magnesia.

### Claim 11 (depends on 1)

A method for preparing a polyolefin, comprising polymerizing an olefin monomer in the presence of a catalyst composition comprising the hybrid supported catalyst of claim 1.

### Claim 12 (depends on 11)

The method of claim 11, wherein the catalyst composition further comprises one or more of a cocatalyst or an antistatic agent.

### Claim 13 (depends on 12)

The method of claim 12, wherein the cocatalyst comprises a compound represented by any one of Chemical Formulae 9 to 11:
—[Al(Ra)—O]m— [Chemical Formula 9]
in Chemical Formula 9,
Ra's are the same as or different from each other, and each independently, halogen; C1-20 hydrocarbon; or halogen-substituted C1-20 hydrocarbon; and
m is an integer of 2 or more;
J(Rb)3 [Chemical Formula 10]
in Chemical Formula 10,
Rb's are the same as or different from each other, and each independently, halogen; C1-20 hydrocarbon; or halogen-substituted C1-20 hydrocarbon; and
J is aluminum or boron;
[E-H]+[ZQ4]+ or [E]+[ZQ4]− [Chemical Formula 11]
in Chemical Formula 11,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is an element of Group 13; and
Q's are the same as or different from each other, and each independently, a C6-20 aryl or C1-20 alkyl group, of which is optionally substituted with halogen, C1-20 hydrocarbon, alkoxy, or phenoxy.

### Claim 14 (depends on 12)

The method of claim 12, wherein the antistatic agent is ethoxylated alkyl amine.

### Claim 15 (depends on 11)

The method of claim 11, wherein the polymerization is performed while introducing hydrogen gas of 0.1% by volume to 0.2% by volume, based on a total volume of the olefin monomer.

### Claim 16 (depends on 11)

The method of claim 11, wherein the olefin monomer is ethylene.

### Claim 17 (depends on 11)

The method of claim 11, wherein in a molecular weight distribution curve of the polyolefin by gel permeation chromatography analysis, where the molecular weight distribution curve is obtained by plotting log value (log Mw) of weight average molecular weight (Mw) on the x-axis, and molecular weight distribution (dwt/d log Mw) with respect to the log value on the y-axis, an area ratio occupied by an area of log Mw of 3.5 or less relative to the total area of the distribution curve is 1.4% or less, and a molecular weight distribution is 6 to 15.