# US 10,865,260 B2 · Supported hybrid catalyst

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- Number: US 10,865,260 B2
- Document ID: US10865260B2
- Status: Granted
- Kind: B2
- Application number: 16/090,763
- Filed: 2018-01-25
- Published: 2020-01-09
- Granted: 2020-12-15
- Earliest claimed: 2017-01-25
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Jin Young Lee; Sung Ho Park; Heon Yong Kwon; Hyun Jee Kwon; Sol Cho; Oh Joo Kwon; Ki Soo Lee; Dae Sik Hong
- Web page: https://patentgrep.com/patent/US10865260B2

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08J 5/18: Manufacture of films or sheets
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2420/01: Cp or analog bridged to a non-Cp X neutral 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
- C08J 2323/08: Copolymers of ethene (C08J2323/16 takes precedence)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

The present disclosure provides a supported hybrid catalyst which facilitates the preparation of polyolefins having improved bubble stability and exhibiting excellent processability for a blown film while maintaining high transparent haze and improved melt strength, and a method for preparing the same.

## Claims

### Claim 1

A supported hybrid catalyst, comprising at least one first transition metal compound selected from compounds represented by the following Chemical Formula 1;
at least one second transition metal compound selected from compounds represented by the following Chemical Formula 2; and
a support on which the first and second transition metal compounds are supported,
wherein, in Chemical Formula 1,
M1 is a Group 4 transition metal;
X1 and X2 are the same as or different from each other, and are each independently any one of a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 sulfonate group, and a C1 to C30 sulfone group;
R1 and R3 to R10 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;
R2 is selected from the group consisting of a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;
Q1 and Q2 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 hydrocarbyl group substituted with a halogen, and —NRaRb; and
Ra and Rb are the same as or different from each other, and are each independently any one of hydrogen and a C1 to C30 hydrocarbyl group, or may be connected with each other to form an aliphatic or aromatic ring,
wherein, in Chemical Formula 2,
M2 is a Group 4 transition metal;
X3 and X4 are the same as or different from each other, and are each independently any one of a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 sulfonate group, and a C1 to C30 sulfone group;
R11 to R24 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;
Q3 and Q4 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH3, a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 hydrocarbyl group substituted with a halogen, and —NRa′Rb′; and
Ra′ and Rb′ are the same as or different from each other, and are each independently any one of hydrogen and a C1 to C30 hydrocarbyl group, or may be connected with each other to form an aliphatic or aromatic ring.

### Claim 2 (depends on 1)

The supported hybrid catalyst of claim 1,
wherein R1 and R3 to R6 are each hydrogen, and
R2 each are any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

### Claim 3 (depends on 1)

The supported hybrid catalyst of claim 1,
wherein M1 is Ti, Zr, or Hf,
X1 and X2 are the same as or different from each other, and are each independently any one of a halogen, a C1 to C20 alkyl group, and a C1 to C20 alkoxy group,
R1 and R3 to R6 are each hydrogen,
R2 is a C1 to C20 alkyl group, or a C6 to C20 aryl group,
R7 to R10 are the same as or different from each other, and are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, and
Q1 and Q2 are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

### Claim 4 (depends on 1)

The supported hybrid catalyst of claim 1, wherein the first transition metal compound is any one of compounds represented by the following structural formulae:

### Claim 5 (depends on 1)

The supported hybrid catalyst of claim 1,
wherein M2 is Ti, Zr, or Hf,
X3 and X4 are the same as or different from each other, and are each independently any one of a halogen, a C1 to C20 alkyl group, and a C1 to C20 alkoxy group,
R11 and R12 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group,
R13 to R20 are each independently any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, or one or more pairs of neighboring substituents of R13 to R20 may be connected with each other to form a substituted or unsubstituted aliphatic ring,
R21 to R24 are the same as or different from each other, and are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, and
Q3 and Q4 are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

### Claim 6 (depends on 1)

The supported hybrid catalyst of claim 1, wherein the second transition metal compound is any one of compounds represented by the following structural formulae:

### Claim 7 (depends on 1)

The supported hybrid catalyst of claim 1, wherein the first transition metal compound and the second transition metal compound are contained in a molar mixing ratio of 1:1 to 1:15.

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 1)

The supported hybrid catalyst of claim 1, further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulae 3 to 5:
R26—[Al(R25)—O]n—R27 [Chemical Formula 3]
wherein, in Chemical Formula 3,
R25, R26, and R27 are each independently any one of hydrogen, a halogen, a C1 to C20 hydrocarbyl group, and a halogen-substituted C1 to C20 hydrocarbyl group; and
n is an integer of 2 or more,
D(R28)3 [Chemical Formula 4]
wherein, in Chemical Formula 4,
D is aluminum or boron; and
R28 are each independently any one of a halogen, a C1 to C20 hydrocarbyl group, a C1 to C20 hydrocarbyloxy group, and a halogen-substituted C1 to C20 hydrocarbyl group;
[L-H]+[W(A)4]− or [L]+[W(A)4]− [Chemical Formula 5]
wherein, in Chemical Formula 5,
L is a neutral or cationic Lewis base; H is a hydrogen atom;
W is a Group 13 element; and
A are each independently any one of a C1 to C20 hydrocarbyl group; a C1 to C20 hydrocarbyloxy group; and a substituent in which at least one hydrogen atom of these substituents is substituted with at least one selected from a halogen, a C1 to C20 hydrocarbyloxy group, and a C1 to C20 hydrocarbyl(oxy)silyl group.

### Claim 10 (depends on 1)

A method for preparing a polyolefin, comprising the step of polymerizing olefinic monomers in the presence of the supported hybrid catalyst of claim 1.

### Claim 11 (depends on 10)

The method for preparing a polyolefin of claim 10, wherein the olefinic monomer comprises 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-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.