Processes for preparing solid metallocene-based catalyst systems

Patent metadata

Field	Value
Publication number	US-2016108145-A1
Application number	US-201414517158-A
Country	US
Kind code	A1
Filing date	Oct 17, 2014
Priority date	Oct 17, 2014
Publication date	Apr 21, 2016
Grant date	—

Abstract

Methods for preparing metallocene-based catalyst systems containing an activator-support are disclosed. These methods can include contacting a solid metallocene compound, an activator-support, and an organoaluminum compound, resulting in catalyst systems with increased catalytic activity as compared to catalyst systems utilizing a solution of the metallocene compound.

First claim

1 . A process to produce a catalyst composition, the process comprising:
(i) contacting an activator-support and a solid metallocene compound for a first period of time to form a precontacted mixture; and (ii) contacting the precontacted mixture with an organoaluminum compound for a second period of time to produce the catalyst composition; wherein an activity of the catalyst composition is from about 5% to about 100% greater than that of a catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

2 . The process of claim 1 , wherein in step (i), a slurry of the activator-support in a first diluent is contacted with a slurry of the solid metallocene compound in a second diluent.

3 . The process of claim 1 , wherein in step (i), at least one of the activator-support and the solid metallocene compound is a dry solid.

4 . The process of claim 1 , wherein:
the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or a combination thereof; and the solid metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group.

5 . The process of claim 1 , wherein:
the first period of time is at least about 15 seconds; and the activity of the catalyst composition is from about 5% to about 75% greater than that of a catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

6 . 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; and the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof.

7 . The process of claim 1 , wherein:
a weight ratio of the solid metallocene compound to the activator-support is in a range from about 1:10 to about 1:10,000; and a weight ratio of the activator-support to the organoaluminum compound is in a range from about 1:5 to about 1000:1.

8 - 9 . (canceled)

10 . A process to produce a catalyst composition, the process comprising contacting, in any order:
(a) an activator-support; (b) a solid metallocene compound; and (c) an organoaluminum compound;
to produce the catalyst composition;
wherein an activity of the catalyst composition is from about 5% to about 100% greater than that of a catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

11 . The process of claim 10 , wherein the process comprises comprising contacting a slurry of the activator-support in a first diluent, a slurry of the solid metallocene compound in a second diluent, and the organoaluminum compound.

12 . The process of claim 10 , wherein the process comprises comprising contacting a slurry of the activator-support in a first diluent, a slurry of the solid metallocene compound in a second diluent, and a solution of the organoaluminum compound.

13 . The process of claim 10 , wherein at least one of the activator-support and the solid metallocene compound is a dry solid.

14 . The process of claim 10 , wherein:
the solid metallocene compound comprises a bridged metallocene compound; and the activator-support comprises sulfated alumina.

15 . The process of claim 10 , wherein:
the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof; the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and the solid metallocene compound comprises an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group.

16 . The process of claim 10 , wherein the activity of the catalyst composition is from about 5% to about 75% greater than that of a catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

17 - 20 . (canceled)

21 . The process of claim 1 , wherein:
the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; and the solid metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent.

22 . The process of claim 21 , wherein the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof.

23 . The process of claim 1 , wherein:
the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; and the solid metallocene compound comprises an unbridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group.

24 . The process of claim 2 , wherein the first diluent and the second diluent independently comprise propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or combinations thereof.

25 . The process of claim 10 , wherein:
the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; and the solid metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent.

26 . The process of claim 25 , wherein the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof.

27 . The process of claim 11 , wherein the first diluent and the second diluent independently comprise propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or combinations thereof.

28 . The process of claim 15 , wherein:
the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof; and the solid metallocene compound comprises an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group, and with an alkenyl substituent.

Assignees

• Chevron Phillips Chemical Co

Inventors

• Clark Kensha M
• Yang Qing
• Glass Gary L

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C08F10/02

  Ethene · CPC title

• C08F2410/07

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

• C08F210/16

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