# US 2013/0253154 A1 · Method for preparing supported hybrid metallocene catalyst

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2013/0253154 A1
- Document ID: US20130253154A1
- Status: Published application
- Kind: A1
- Application number: 13/824,935
- Filed: 2011-09-28
- Published: 2013-09-26
- Earliest claimed: 2010-09-29
- Assignees: LG Chem, Ltd.
- Inventors: Hyeon-Gook Kim; Ki-Soo Lee; Dae-Sik Hong; Eun-Kyoung Song; Man-Seong Jeon
- Web page: https://patentgrep.com/patent/US20130253154A1

## CPC

- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- B01J 31/1616: {Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00)}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 2420/02: Cp or analog bridged to a non-Cp X anionic donor
- Y10S 526/943: Polymerization with metallocene catalysts
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The present invention relates to a preparation method of a metallocene catalyst. More particularly, the present invention relates to a preparation method of a supported hybrid metallocene catalyst, including the steps of treating a support having a water content of 4 to 7% by weight with trialkyl aluminum at a predetermined temperature; supporting alkyl aluminoxane on the support; and supporting a metallocene compound on the alkyl aluminoxane-supported support. According to the present invention, it is possible to prepare a supported hybrid metallocene catalyst which shows a high activity in the polymerization of olefins and enables the preparation of polyolefins having a high bulk density, by a simple process.

## Claims

### Claim 1

A preparation method of a supported hybrid metallocene catalyst, comprising the steps of:
treating a support having a water content of 4 to 7% by weight with trialkyl aluminum at a temperature of 60 to 100° C.;
supporting alkyl aluminoxane on the support; and
supporting a metallocene compound on the alkyl aluminoxane-supported support.

### Claim 2 (depends on 1)

The preparation method according to claim 1, wherein the support includes a hydroxy group of 2 to 4 mmol/g on the surface.

### Claim 3 (depends on 1)

The preparation method according to claim 1, wherein a molar ratio of trialkyl aluminium and alkyl aluminoxane is 1:10 to 1:30.

### Claim 4 (depends on 1)

The preparation method according to claim 1, wherein a loading amount of alkyl aluminoxane on the support is 6 to 20 mmol/g.

### Claim 5 (depends on 1)

The preparation method according to claim 1, wherein a loading amount of the metallocene compound on the support is 0.1 to 0.5 mmol/g.

### Claim 6 (depends on 1)

The preparation method according to claim 1, wherein the step of supporting alkyl aluminoxane is performed at a temperature of 40 to 80° C.

### Claim 7 (depends on 1)

The preparation method according to claim 1, wherein the support is one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia.

### Claim 8 (depends on 1)

preparation method according to claim 1, wherein the trialkyl aluminium is one or more selected from the group consisting of trimethyl aluminium, triethyl aluminium, and tributyl aluminium.

### Claim 9 (depends on 1)

The preparation method according to claim 1, wherein the alkyl aluminoxane is one or more selected from the group consisting of methylaluminoxane, ethylaluminoxane, butylaluminoxane, and isobutylaluminoxane.

### Claim 10 (depends on 1)

The preparation method according to claim 1, wherein the metallocene compound is one or more selected from the group consisting of the following
(C5Ra)p(C5Rb)MQ3-p [Chemical Formula 1]
wherein M is a Group 4 transition metal;
(C5Ra) and (C5Rb) are each independently a Group 14 metalloid, cyclopentadienyl ligand that is substituted with one or more selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl and hydrocarbyl, or a cyclopentadienyl ligand, in which two neighboring carbon atoms in C5 are connected to each other through hydrocarbyl to form one or more rings having 4 to 16 carbon atoms;
Q is a halogen atom, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or alkylidene;
p is 0 or 1;
wherein M is a Group 4 transition metal;
R3 and R4 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl, or t-butyl;
A is alkylene having 2 to 4 carbon atoms, alkylsilicon having 1 to 4 carbon atoms, alkylgermanium having 1 to 4 carbon atoms, alkylphosphine having 1 to 4 carbon atoms or alkylamine having 1 to 4 carbon atoms;
Q is each independently a halogen atom, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkylaryl having 7 to 40 carbon atoms, arylalkyl having 7 to 40 carbon atoms, aryl having 6 to 20 carbon atoms, substituted or unsubstituted alkylidene having 1 to 20 carbon atoms, substituted or unsubstituted amino group, alkylalkoxy having 2 to 20 carbon atoms or arylalkoxy having 7 to 40 carbon atoms;
m is an integer of 0 to 10;
wherein R1 and R2 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, silyl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms or a Group 14 metalloid substituted with hydrocarbyl; R1 and R2, or two R2s are connected to each other by alkylidine containing alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms so as to form a ring;
R3s are each independently hydrogen, a halogen atom, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms or amido; two or more of R3s are connected to each other so as to form an aliphatic or aromatic ring;
CY1 is a substituted or unsubstituted aliphatic or aromatic ring, in which the substituent in CY1 is a halogen atom, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, or amido; when a plurality of substituents are present, two or more of the substituents are connected to each other so as to form an aliphatic or aromatic ring;
M is a Group 4 transition metal; and
Q1 and Q2 are each independently halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms or alkylidene having 1 to 20 carbon atoms.

### Claim 11 (depends on 1)

A supported hybrid metallocene catalyst that is prepared according to the method of claim 1.

### Claim 12 (depends on 11)

A preparation method of polyolefins, comprising the step of polymerizing olefin-based monomers in the presence of the catalyst according to claim 11.