Silica-coated alumina activator-supports for metallocene catalyst compositions

Patent metadata

Field	Value
Publication number	US-11208514-B2
Application number	US-202017124605-A
Country	US
Kind code	B2
Filing date	Dec 17, 2020
Priority date	Mar 20, 2008
Publication date	Dec 28, 2021
Grant date	Dec 28, 2021

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.

First claim

We claim:

1. An activator-support comprising a silica-coated alumina treated with a source of fluoride ion, wherein:
the silica-coated alumina has a weight ratio of alumina to silica in a range from about 1:1 to about 15:1 and a surface area in a range from about 200 to about 600 m 2 /g.

2. The activator-support of claim 1 , wherein the source of fluoride ion comprises fluorosulfate, fluoroborate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or any combination thereof.

3. The activator support of claim 1 , wherein the source of fluoride ion comprises hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium tetrafluoroborate, ammonium hexafluorosilicate, ammonium hexafluorophosphate, hexafluorotitanic acid, ammonium hexafluorotitanic acid, hexafluorozirconic acid, aluminum fluoride, ammonium aluminum fluoride, triflic acid, ammonium triflate, or any combination thereof.

4. The activator-support of claim 1 , wherein the source of fluoride ion comprises perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, hydrogen fluoride, fluorine, silicon tetrafluoride, tetrafluoroborate, or any combination thereof.

5. The activator-support of claim 1 , wherein:
the silica-coated alumina is further characterized by a pore volume in a range from about 0.5 to about 1.8 mL/g; and
the silica-coated alumina is treated with a combination of the source of fluoride ion and a source of chloride ion and/or a source of sulfate.

6. A catalyst composition comprising the activator-support of claim 1 and a metallocene compound.

7. The catalyst composition of claim 6 , wherein the catalyst composition further comprises a co-catalyst.

8. The catalyst composition of claim 7 , wherein the co-catalyst comprises an organoaluminum compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

9. 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 1.5:1 to about 15:1 and a surface area in a range from about 200 to about 600 m 2 /g; and
the electron-withdrawing anion comprises fluoride, fluorosulfate, fluoroborate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, hexafluorosilicate, or any combination thereof.

10. The activator-support of claim 9 , wherein the activator-support is characterized by:
a pore volume in a range from about 0.8 to about 1.8 mL/g; and
an average particle size in a range from about 5 microns to about 150 microns.

11. The activator-support of claim 10 , wherein the electron-withdrawing anion comprises fluoride.

12. The activator-support of claim 9 , wherein the electron-withdrawing anion comprises fluoroborate.

13. The activator-support of claim 9 , wherein the electron-withdrawing anion comprises hexafluorosilicate.

14. A catalyst composition comprising the activator-support of claim 9 and a metallocene compound.

15. The catalyst composition of claim 14 , wherein the catalyst composition further comprises a co-catalyst.

16. The catalyst composition of claim 15 , wherein the co-catalyst comprises an organoaluminum compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

17. An activator-support comprising a silica-coated alumina treated with a source of fluoride ion, wherein:
the silica-coated alumina has a weight ratio of alumina to silica in a range from about 2:1 to about 10:1 and a surface area in a range from about 200 to about 600 m 2 /g.

18. The activator-support of claim 17 , wherein the silica-coated alumina is further characterized by a pore volume in a range from about 0.5 to about 1.8 mL/g.

19. The activator-support of claim 17 , wherein the source of fluoride ion comprises fluorosulfate, fluoroborate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or any combination thereof.

20. The activator support of claim 17 , wherein the source of fluoride ion comprises hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium tetrafluoroborate, ammonium hexafluorosilicate, ammonium hexafluorophosphate, hexafluorotitanic acid, ammonium hexafluorotitanic acid, hexafluorozirconic acid, aluminum fluoride, ammonium aluminum fluoride, triflic acid, ammonium triflate, or any combination thereof.

21. The activator-support of claim 17 , wherein the source of fluoride ion comprises perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, hydrogen fluoride, fluorine, silicon tetrafluoride, tetrafluoroborate, or any combination thereof.

22. A catalyst composition comprising the activator-support of claim 17 , a metallocene compound, and a co-catalyst.

23. The activator-support of claim 17 , wherein the activator-support is characterized by:
a surface area in a range from about 200 to about 600 m 2 /g; and
a pore volume in a range from about 0.8 to about 1.8 mL/g.

24. A catalyst composition comprising the activator-support of claim 23 , a metallocene compound, and a co-catalyst.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Yang Qing
• Muninger Randy S
• Benham Elizabeth A
• Clear Kathy S

Classifications

• B01J31/2226

  Anionic ligands, i.e. the overall ligand carries at least one formal negative charge · CPC title

• B01J27/12

  Fluorides · CPC title

• C08F110/02

  Ethene · CPC title

• B01J31/1608

  the ligands containing silicon · CPC title

• C08F2420/01

  Cp or analog bridged to a non-Cp X neutral donor · CPC title