Trialkylaluminum treated supports

• US 7,385,015 B2
• Filed: 09/06/2005
• Issued: 06/10/2008
• Est. Priority Date: 10/12/2004
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Holtcamp, Matthew W.
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US11/220,164
• Publication Number:
  US 20060079394A1
• Time in Patent Office: 1,008 Days
• Field of Search: 502/120, 502/232, 502/104, 502/152, 526/129, 526/160, 526/348, 526/943
• US Class Current: 526/160
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 4/02 Carriers therefor
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

This invention relates to a process to prepare a trialkylaluminum treated support comprising: 1) combining a support with first trialkylaluminum compound(s), where the alkyl groups have at least 2 carbon atoms; then 2) calcining the combination of the support and the trialkylaluminum compound(s); then 3) combining the calcined support with second trialkylaluminum compound(s), where the alkyl groups have at least 2 carbon atoms; where the first and second trialkylaluminum compound(s) may be the same or different. This invention further relates to catalyst systems comprising catalyst compounds and such supports, as well as processes to polymerize unsaturated monomers using the supports in combination with catalyst compounds.

Claims

1. A process to polymerize olefins comprising:

A) preparing a supported metallocene catalyst compound by a process comprising;

1) combining a support with first trialkylaluminum compound(s) selected from the group consisting of triethylaluminum, tri-isobutylaluminum, and tri-n-hexylaluminum;

then

2) calcining the combination of the support and the trialkylaluminum compound(s);

then

3) combining the calcined support with a solvent or diluent and second trialkylaluminum compound(s) selected from the group consisting of triethylaluminum, tri-isobutylaluminum, and tri-n-hexylaluminum;

where the first and second trialkylaluminum compound(s) may be the same or different;

then

4) optionally, drying the combination;

5) combining the combination of the calcined support and the second trialkylaluminum compound(s) with a metallocene catalyst compound and, optionally, a solvent or diluent;

then,

6) optionally, removing the solvent or diluent;

then

B) contacting the supported transition metal catalyst compound with one or more olefins.

2. The process of claim 1 wherein the support is selected from the group consisting of silica, fumed silica, alumina, silica-alumina, magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays, silica-chromium, silica-alumina, silica-titania, polymeric beads and combinations thereof.

3. The process of claim 1 wherein the support is silica.

4. The process of claim 3 wherein the support has a surface area in the range of from about 10 to about 700 m²/g, and/or a pore volume in the range of from about 0.1 to about 4.0 cc/g and/or an average particle size in the range of from about 5 to about 500 μ

m.

5. The process of claim 1 wherein the first trialkylaluminum compound comprises triethylaluminum.

6. The process of claim 1 wherein the second trialkylaluminum compound comprises triethylaluminum.

7. The process of claim 1 wherein the first and second trialkylaluminum compounds are triethylaluminum.

8. The process of claim 1 wherein the ratio of aluminum to support element (as determined by XPS) of the calcined support of step 2) to aluminum to support element of the treated support of step 3) is about 2:

1 or less.

9. The process of claim 1 wherein the support is silica and the ratio of aluminum to silicon of the calcined support of step 2) to aluminum to silicon of the treated support of step 3) is about 2:

1 or less.

10. The process of claim 1 wherein the support is silica and the ratio of aluminum to silicon of the calcined support of step 2) to aluminum to silicon of the treated support of step 3) is about 0.85:

1 or less.

11. The process of claim 1 wherein the metallocene catalyst comprises at least two metallocene compounds.

12. The process of claim 1 wherein the metallocene catalyst comprises one or more of:

rac-dimethylsilyl-bis(indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(indenyl)hafniumdichloride,

rac-dimethylsilyl-bis(indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(indenyl)zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl) hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl) zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl) zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-benzindenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-benzindenyl) hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-benzindenyl) zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-benzindenyl) zirconiumdichloride,

rac-dimethylsilyl-bis-(2-methyl-indenyl) zirconiumdimethyl,

rac-dimethylsilyl-bis-(2-methyl-indenyl) hafniumdimethyl,

rac-dimethylsilyl-bis-(2-methyl-indenyl) hafniumdichloride,

rac-dimethylsilyl-bis-(2-methyl-indenyl) zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl) zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl) hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl) zirconiumdimethyl,

rac-ethylene-bis(indenyl)hafniumdimethyl,

rac-ethylene-bis(indenyl)hafniumdichloride,

rac-ethylene-bis(indenyl)zirconiumdimethyl,

rac-ethylene-bis(indenyl)zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(2′

-methyl-phenyl)-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(2′

-methyl-phenyl)-indenyl)hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(2′

-methyl-phenyl)-indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(2′

-methyl-phenyl)-indenyl) zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-methyl-phenyl)-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-methyl-phenyl)-indenyl)hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-methyl-phenyl)-indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-methyl-phenyl)-indenyl) zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl-phenyl)-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl-phenyl)-indenyl)

zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl-phenyl)-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)hafniumdichloride,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4-(4′

-tert-butyl-phenyl)-indenyl) zirconiumdichloride,

rac-dimethylsilyl-(2-methyl-4-(4′

-tert-butyl-phenyl)-indenyl)(2-isoprpyl-4-(4′

-tert-butyl-phenyl)-indenyl)hafniumdimethyl,

rac-dimethylsilyl-(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)(2-isoprpyl-4-(4′

-tert-butyl-phenyl)-indenyl)hafniumdichloride,

rac-dimethylsilyl-(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)(2-isoprpyl-4-(4′

-tert-butyl-phenyl)-indenyl)zirconiumdichloride,

rac-dimethylsilyl-(2-methyl-4-(4′

-tert-butyl -phenyl)-indenyl)(2-isoprpyl-4-(4′

-tert-butyl-phenyl)-indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafniumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)zirconiumdimethyl,

rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)zirconiumdichloride,

rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafniumdichloride,

Bis(cyclopentadieneyl)zirconiumdichloride,

Bis(cyclopentadienyl)zirconiumdimethyl,

Bis(pentamethylcyclopentadieneyl)zirconiumdichloride,

Bis(pentamethylcyclopentadienyl)zirconiumdimethyl,

Bis(cyclopentadieneyl)(pentamethylcyclopentadienyl)zirconiumdichloride,

Bis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,

Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdichloride,

Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl,

Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethoxide,

Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl,

Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdifluoride,

Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide,

Bis(1-methyl,4-ethylcyclopentadienyl)zirconiumdichloride,

Bis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl,

Bis(1-methyl,4-benzylcyclopentadienyl)zirconiumdichloride,

Bis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl,

Bis(1-methyl,3-butylcyclopentadienyl)zirconiumdichloride,

Bis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl,

Bis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdichloride,

Bis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl,

Bis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdichloride,

Bis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdimethyl,

Bis(1,3-dimethylcyclopentadienyl)zirconiumdichloride,

Bis(1,3-dimethylcyclopentadienyl)zirconiumdimethyl,

Bis(n-propylcyclopentadienyl)zirconiumdichloride,

Bis(n-propylcyclopentadienyl)zirconiumdimethyl,

Bis(n-propylcyclopentadienyl)zirconiumdifluoride,

Bis(n-propylcyclopentadienyl)zirconiumdiamide,

Bis(n-propylcyclopentadienyl)zirconiumdibenzyl,

Bis(n-propylcyclopentadienyl)zirconiumdimethoxide,

Bis(n-propylcyclopentadienyl)hafniumdichloride,

Bis(n-propylcyclopentadienyl)hafniumdimethyl,

Bis(n-propylcyclopentadienyl)hafniumdifluoride,

Bis(n-propylcyclopentadienyl)hafniumdiamide,

Bis(n-propylcyclopentadienyl)hafniumdibenzyl,

Bis(n-propylcyclopentadienyl)hafniumdimethoxide,

Bis(n-butylcyclopentadienyl)zirconiumdichloride,

Bis(n-butylcyclopentadienyl)zirconiumdimethyl,

Bis(tert-butylcyclopentadienyl)zirconiumdichloride,

Bis(tert-butylcyclopentadienyl)zirconiumdimethyl,

Bis(benzylcyclopentadienyl)zirconiumdichloride,

Bis(benzylcyclopentadienyl)zirconiumdimethyl,

Bis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,

Bis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdichloride,

Bis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,

Bis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdichloride,

Bis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdimethyl,

Bis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,

Bis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdi methyl,

Bis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdi chloride,

Bis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)zirconiumdimethyl,

Bis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(cyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(cyclopentadienyl)zirconiumdimethoxide,

Dimethylsilylbis(cyclopentadienyl)zirconiumdiamide,

Dimethylsilylbis(cyclopentadienyl)zirconiumdifluoride,

Dimethylsilylbis(cyclopentadienyl)zirconiumdiiodide,

Dimethylsilylbis(cyclopentadienyl)zirconiumdibromide,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdifluoride,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdimethoxide,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdiamide,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdibromide,

Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdibenzyl,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdichloride,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdimethyl,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdimethoxide,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdibromide,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdiamide,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdifluoride,

Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl) zirconiumdibenzyl,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethoxide,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdibromide,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdifluoride,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethoxide,

Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl,

Dimethylsilylbis(1-methyl,4-ethylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(1-methyl,4-benzylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(1-methyl,3-butylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(1,3-dimethylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(1,3-dimethylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(n-propylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(n-propylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(tert-butylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(tert-butylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(benzylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(benzylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)-zirconiumdimethyl,

Dimethylsilylbis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)-zirconiumdichloride,

Dimethylsilylbis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)-zirconiumdimethyl,

Dimethylsilylbis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)-zirconiumdichloride,

Dimethylsilylbis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdimethyl,

Dimethylsilylbis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopenta-dienyl)zirconiumdimethyl,

Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopenta-dienyl)zirconiumdichloride,

Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)-zirconiumdimethyl, and

Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)-zirconiumdichloride.

13. The method of claim 1 where the olefins comprise ethylene.

14. The method of claim 1 where the olefins comprise propylene.

15. The method of claim 1 wherein the olefins comprise ethylene and propylene.

16. The method of claim 1 wherein the olefins comprise ethylene and a comonomer selected from the group consisting of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, hexadecene, 4-methylpentene-1, 3-methylpentene-1, 3,5,5-trimethylhexene-1, 5-ethylnonene-1, and isomers thereof.

17. The method of claim 1 wherein the olefins comprise propylene and a comonomer selected from the group consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, hexadecene, 4-methylpentene-1, 3-methylpentene-1, 3,5,5-trimethylhexene-1, 5-ethylnonene-1, and isomers thereof.

18. The method of claim 1 wherein the polymerization occurs in the gas phase.

19. The method of claim 1 wherein the polymerization occurs in the slurry phase.