# US 2019/0169332 A1 · Silica-Coated Alumina Activator-Supports For Metallocene Catalyst Compositions

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- Number: US 2019/0169332 A1
- Document ID: US20190169332A1
- Status: Published application
- Kind: A1
- Application number: 16/266,176
- Filed: 2019-02-04
- Published: 2019-06-06
- Earliest claimed: 2008-03-20
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Max P. McDaniel; Qing Yang; Randy S. Muninger; Elizabeth A. Benham; Kathy S. Clear
- Web page: https://patentgrep.com/patent/US20190169332A1

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 10/02: Ethene
- C08F 110/02: Ethene
- C08F 210/06: Propene
- C08F 210/08: Butenes
- B01J 27/00: Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J 27/053: Sulfates
- B01J 27/10: Chlorides
- B01J 27/12: Fluorides
- B01J 27/16: containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr}
- B01J 31/143: {of aluminium}
- B01J 31/1608: {the ligands containing silicon}
- 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 31/1805: {the ligands containing nitrogen}
- B01J 31/2226: {Anionic ligands, i.e. the overall ligand carries at least one formal negative charge}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 2531/0225: Complexes comprising pentahapto-cyclopentadienyl analogues
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 2410/06: Catalyst characterized by its size
- C08F 2410/07: Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
- C08F 2420/01: Cp or analog bridged to a non-Cp X neutral donor
- Y02P 20/52: using catalysts, e.g. selective 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Silica-coated alumina activator-supports, and catalyst compositions containing these activator-supports, are disclosed. Methods also are provided for preparing silica-coated alumina activator-supports, for preparing catalyst compositions, and for using the catalyst compositions to polymerize olefins.

## Claims

### Claim at position 1

1-20. (canceled)

### Claim 21

An activator-support comprising a silica-coated alumina treated with an electron-withdrawing anion, wherein:
the silica-coated alumina has a weight ratio of alumina to silica in a range from about 1:1 to about 2:1; and
the electron-withdrawing anion comprises fluoride.

### Claim 22 (depends on 21)

The activator-support of claim 21, wherein the weight ratio of alumina to silica is in a range from about 1.2:1 to about 1.8:1.

### Claim 23 (depends on 21)

The activator-support of claim 21, wherein the silica-coated alumina is further characterized by:
a surface area in a range from about 200 to about 600 m2/g; and
a pore volume in a range from about 0.5 to about 1.8 mL/g.

### Claim 24 (depends on 21)

The activator-support of claim 21, wherein the activator-support contains from about 2 to about 15 wt. % fluoride.

### Claim 25 (depends on 24)

The activator-support of claim 24, wherein the silica-coated alumina is further characterized by an average particle size in a range from about 5 to about 150 microns.

### Claim 26 (depends on 24)

The activator-support of claim 24, wherein the silica-coated alumina is further characterized by:
a surface area in a range from about 150 to about 750 m2/g; and
a pore volume in a range from about 0.5 to about 1.8 mL/g.

### Claim 27 (depends on 26)

The activator-support of claim 26, wherein the silica-coated alumina is further characterized by an average particle size in a range from about 30 to about 100 microns.

### Claim 28 (depends on 26)

The activator-support of claim 26, wherein the activator-support is further characterized by a surface area in a range from about 150 to about 750 m2/g.

### Claim 29 (depends on 21)

The activator-support of claim 21, wherein:
the weight ratio of alumina to silica is in a range from about 1.2:1 to about 1.8:1; and
the activator-support contains from about 3 to about 12 wt. % fluoride.

### Claim 30 (depends on 29)

The activator-support of claim 29, wherein the silica-coated alumina is further characterized by:
a surface area in a range from about 200 to about 600 m2/g; and
a pore volume in a range from about 0.5 to about 1.8 mL/g.

### Claim 31 (depends on 29)

The activator-support of claim 29, wherein the electron-withdrawing anion further comprises sulfate or phosphate.

### Claim 32 (depends on 29)

The activator-support of claim 29, wherein the activator-support is further characterized by a surface area in a range from about 150 to about 750 m2/g.

### Claim 33

A process for preparing an activator-support, the process comprising:
contacting a silica-coated alumina with a fluoriding agent to form the activator-support;
wherein the silica-coated alumina has a weight ratio of alumina to silica in a range from about 1:1 to about 2:1; and
wherein the activator-support contains from about 2 to about 15 wt. % fluoride.

### Claim 34 (depends on 33)

The process of claim 33, further comprising a step of drying and/or a step of calcining after the contacting step.

### Claim 35 (depends on 33)

The process of claim 33, further comprising a step of calcining the silica-coated alumina prior to the contacting step.

### Claim 36 (depends on 33)

The process of claim 33, wherein a slurry of the silica-coated alumina in a solvent is contacted with the fluoriding agent.

### Claim 37 (depends on 33)

The process of claim 33, wherein the silica-coated alumina is impregnated with a solution containing the fluoriding agent and a solvent.

### Claim 38 (depends on 37)

The process of claim 37, wherein the solvent comprises water or an alcohol.

### Claim 39 (depends on 33)

The process of claim 33, wherein the fluoriding agent comprises hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium hexafluorosilicate ((NH4)2SiF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4)2TiF6), hexafluorozirconic acid (H2ZrF6), AlF3, NH4AlF4, triflic acid, ammonium triflate, or any combination thereof.

### Claim 40 (depends on 33)

The process of claim 33, wherein the silica-coated alumina is calcined while being contacted with the fluoriding agent.

### Claim 41 (depends on 33)

The process of claim 33, wherein a gas stream containing the fluoriding agent fluidizes the silica-coated alumina during calcination.

### Claim 42 (depends on 33)

The process of claim 33, wherein the fluoriding agent comprises a freon, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, HF, F2, silicon tetrafluoride (SiF4), a tetrafluoroborate (BF4−) compound, or any combination thereof.

### Claim 43 (depends on 33)

The process of claim 33, wherein:
the silica-coated alumina is characterized by a surface area in a range from about 200 to about 600 m2/g and a pore volume in a range from about 0.5 to about 1.8 mL/g;
the weight ratio of alumina to silica is in a range from about 1.2:1 to about 1.8:1; and
the activator-support contains from about 3 to about 12 wt. % fluoride.