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- Nachgewiesen in: USPTO Patent Applications
- Sprachen: English
- Document Number: 20230192914
- Publication Date: June 22, 2023
- Appl. No: 17/552451
- Application Filed: December 16, 2021
- Claim: 1. A polymerization process comprising: (a) contacting a metallocene compound, an organoaluminum compound, a first activator-support, and a second activator-support to form a catalyst composition; (b) contacting the catalyst composition with ethylene and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer having a long chain branch (LCB) content; and (c) controlling a relative amount of the first activator-support and the second activator-support in the catalyst composition in step (a) to adjust the LCB content of the ethylene polymer.
- Claim: 2. The process of claim 1, wherein: the first activator-support comprises a fluorided solid oxide; and the second activator-support comprises a sulfated solid oxide.
- Claim: 3. The process of claim 1, wherein: the first activator-support comprises fluorided silica-coated alumina; and the second activator-support comprises sulfated bentonite and/or sulfated alumina.
- Claim: 4. The process of claim 1, wherein: step (a) comprises pre-contacting the organoaluminum compound, the first activator-support, and the second activator-support, and then contacting the metallocene compound, to form the catalyst composition; or step (a) comprises contacting the organoaluminum compound, the first activator-support, the second activator-support, and the metallocene compound substantially contemporaneously to form the catalyst composition.
- Claim: 5. The process of claim 1, wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or any combination thereof.
- Claim: 6. The process of claim 1, wherein the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof.
- Claim: 7. The process of claim 1, wherein the metallocene compound comprises: a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; a bridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; or any combination thereof.
- Claim: 8. The process of claim 1, wherein the metallocene compound comprises: (1) rac-ethylene-bis(1-indenyl) zirconium dichloride; (2) methyl(buten-3-yl)methylidene(η5-cyclopentadien-1-ylidene)(η5-2,7-di-tert-butylfluoren-9-ylidene) zirconium dichloride; (3) diphenylmethylidene[η5-[3-(pent-4-enyl)cyclopentadien-1-ylidene]][η5-(2,7-di-tert-butylfluoren-9-ylidene)] hafnium dichloride; (4) (n-butylcyclopentadienyl)(1-allylindenyl)zirconium dichloride; (5) rac-dimethylsilylbis(1-indenyl)zirconium dichloride; (6) 1-ethylpropylidene[(η5-cyclopentadien-1-ylidene)(η5-(3-propyl)inden-1-ylidene]] zirconium dichloride; or any combination thereof.
- Claim: 9. The process of claim 1, wherein: a weight ratio of the first activator-support to the second activator-support is in a range from 10:1 to 1:10; and the ethylene polymer has from 1 to 150 LCBs per million total carbon atoms.
- Claim: 10. The process of claim 1, further comprising the steps of: measuring the LCB content of the ethylene polymer; and adjusting the relative amount of the first activator-support and the second activator-support in the catalyst composition based on the difference between the measured LCB content and a target LCB content.
- Claim: 11. The process of claim 1, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.
- Claim: 12. A catalyst composition comprising: (i) a first activator-support comprising a fluorided solid oxide; (ii) a second activator-support comprising a sulfated solid oxide; (iii) a metallocene compound; and (iv) an organoaluminum compound.
- Claim: 13. The composition of claim 12, wherein: a weight ratio of the metallocene compound to the activator-supports is in a range from 1:1 to 1:100,000; and a molar ratio of the organoaluminum compound to the metallocene compound is in a range from 1:1 to 1000:1.
- Claim: 14. The composition of claim 12, wherein a weight ratio of the first activator-support to the second activator-support is in a range from 10:1 to 1:10.
- Claim: 15. The composition of claim 12, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.
- Claim: 16. The composition of claim 12, wherein the catalyst composition contains two or more metallocene compounds.
- Claim: 17. The composition of claim 12, wherein the metallocene compound comprises: (1) rac-ethylene-bis(1-indenyl) zirconium dichloride; (2) methyl(buten-3-yl)methylidene(η5-cyclopentadien-1-ylidene)(η5-2,7-di-tert-butylfluoren-9-ylidene) zirconium dichloride; (3) diphenylmethylidene[η5-[3-(pent-4-enyl)cyclopentadien-1-ylidene]][η5-(2,7-di-tert-butylfluoren-9-ylidene)] hafnium dichloride; (4) (n-butylcyclopentadienyl)(1-allylindenyl)zirconium dichloride; (5) rac-dimethylsilylbis(1-indenyl)zirconium dichloride; (6) 1-ethylpropylidene[(η5-cyclopentadien-1-ylidene)(η5-(3-propyl)inden-1-ylidene]] zirconium dichloride; or any combination thereof.
- Claim: 18. A catalyst composition comprising: (i) a first activator-support comprising fluorided silica-coated alumina; (ii) a second activator-support comprising sulfated bentonite and/or sulfated alumina; (iii) a metallocene compound; and (iv) an organoaluminum compound.
- Claim: 19. The composition of claim 18, wherein the second activator-support comprises sulfated bentonite.
- Claim: 20. The composition of claim 18, wherein the metallocene compound comprises: a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; a bridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; or any combination thereof.
- Current International Class: 08; 08; 07
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