Processes for preparing metallocene-based catalyst systems for the control of long chain branch content

Patent metadata

Field	Value
Publication number	US-11945897-B2
Application number	US-202318489106-A
Country	US
Kind code	B2
Filing date	Oct 18, 2023
Priority date	Aug 26, 2021
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

Methods for preparing a metallocene-based catalyst composition that can impact the long chain branching of ethylene homopolymers and copolymers produced using the catalyst composition are described. The catalyst composition can be prepared by contacting a metallocene compound, a hydrocarbon solvent, and a first organoaluminum compound for a first period of time to form a metallocene solution, and then contacting the metallocene solution with an activator-support and a second organoaluminum compound for a second period of time to form the catalyst composition.

First claim

We claim:

1. A polymerization process comprising:
(A) contacting a metallocene compound, a hydrocarbon solvent, and a first organoaluminum compound for a first period of time to form a metallocene solution, and contacting the metallocene solution with an activator-support and a second organoaluminum compound for a second period of time to form a high LCB catalyst composition;
(B) contacting the metallocene compound, the hydrocarbon solvent, the activator-support, and the second organoaluminum compound to form a low LCB catalyst composition;
(C) contacting the high LCB catalyst composition and/or the low LCB 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
(D) controlling a relative amount of the high LCB catalyst composition and the low LCB catalyst composition in step (C) to adjust the LCB content of the ethylene polymer.

2. The process of claim 1 , wherein step (A) comprises contacting a solution of the metallocene compound in the hydrocarbon solvent with the first organoaluminum compound.

3. The process of claim 1 , wherein the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide.

4. The process of claim 1 , wherein first organoaluminum compound and the second organoaluminum compound are the same.

5. 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; and/or
a bridged zirconium based metallocene compound with two indenyl groups.

6. 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.

7. 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.

8. The process of claim 1 , wherein:
a weight ratio of the high LCB catalyst composition to the low LCB catalyst composition 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.

9. 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 high LCB catalyst composition and the low LCB catalyst composition in step (C) based on the difference between the measured LCB content and a target LCB content.

10. The process of claim 1 , wherein the hydrocarbon solvent comprises an alkane, an olefin, an aromatic, or any combination thereof.

11. The process of claim 1 , wherein the second 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.

12. The process of claim 1 , wherein:
the first organoaluminum compound comprises triisobutylaluminum and/or tri-n-octylaluminum;
the second 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; and
the first organoaluminum compound and the second organoaluminum compound are different.

13. 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;
the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; and
a weight ratio of the high LCB catalyst composition to the low LCB catalyst composition is in a range from 10:1 to 1:10.

14. The process of claim 13 , wherein:
the weight ratio of the high LCB catalyst composition to the low LCB catalyst composition is in a range from 5:1 to 1:5; and
the hydrocarbon solvent comprises an alkane, an olefin, an aromatic, or any combination thereof.

15. The process of claim 13 , wherein the ethylene polymer has from 1 to 150 LCBs per million total carbon atoms.

16. The process of claim 13 , wherein the ethylene polymer has from 1 to 10 LCBs per million total carbon atoms.

17. The process of claim 13 , further comprising the steps of:
measuring the LCB content of the ethylene polymer; and
adjusting the relative amount of the high LCB catalyst composition and the low LCB catalyst composition in step (C) based on the difference between the measured LCB content and a target LCB content.

18. The process of claim 13 , wherein:
the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or any combination thereof; and
the hydrocarbon solvent comprises 1-hexene and/or heptane.

19. The process of claim 13 , wherein the hydrocarbon solvent comprises an alkane solvent, an aromatic solvent, an olefin solvent, or any combination thereof.

20. The process of claim 19 , wherein the polymerization reactor system comprises a loop slurry reactor.

21. The process of claim 1 , wherein:
a weight ratio of the metallocene compound to the activator-support is from 1:1 to 1:100,000; and
a molar ratio of the first organoaluminum compound to the second organoaluminum compound is from 1000:1 to 1:1000.

22. The process of claim 21 , wherein:
the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or any combination thereof; and
the hydrocarbon solvent comprises toluene and/or heptane.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Yang Qing
• Mcdaniel Max P
• Crain Tony R

Classifications

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2500/09

  Long chain branches · CPC title

• C08F2410/07

  Catalyst support treated by an anion, e.g. Cl-, F-, SO42- · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title