Processes for preparing solid metallocene-based catalyst systems

Patent metadata

Field	Value
Publication number	US-10059783-B2
Application number	US-201715421510-A
Country	US
Kind code	B2
Filing date	Feb 1, 2017
Priority date	Oct 17, 2014
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

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

We claim:

1. An olefin polymerization process, the olefin polymerization process comprising:
(i) contacting an activator-support and a solid metallocene compound for a first period of time to form a precontacted mixture;
(ii) contacting the precontacted mixture with an organoaluminum compound for a second period of time to produce a catalyst composition; and
contacting the catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer;
wherein an activity of the catalyst composition is from about 5% to about 150% 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 olefin polymerization process of claim 1 , wherein:
the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, phosphated alumina, or a combination thereof;
the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; and
the olefin monomer comprises ethylene and the olefin comonomer comprises a C 3 -C 10 alpha-olefin.

3. An olefin polymerization process, the olefin polymerization process comprising contacting a catalyst composition with ethylene and an optional olefin comonomer comprising a C 3 -C 10 alpha-olefin in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises:
(a) an activator-support;
(b) a solid metallocene compound; and
(c) an organoaluminum compound;
wherein an activity of the catalyst composition is from about 5% to about 150% 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.

4. The olefin polymerization process of claim 3 , wherein:
the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; and
the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

5. The olefin polymerization 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.

6. The olefin polymerization process of claim 5 , wherein the first diluent and the second diluent independently comprise propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or combinations thereof.

7. The olefin polymerization process of claim 1 , wherein 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; or
a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group.

8. The olefin polymerization process of claim 1 , wherein the olefin polymer is an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

9. The olefin polymerization process of claim 1 , wherein the olefin polymer is a polypropylene homopolymer or a propylene-based copolymer.

10. The olefin polymerization process of claim 1 , wherein the activity of the catalyst composition is from about 5% to about 150% 100% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

11. The olefin polymerization process of claim 10 , wherein:
the catalyst composition is contacted with ethylene and an olefin comonomer comprising a C 3 -C 10 alpha-olefin;
the activator-support comprises sulfated alumina; and
the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof.

12. The olefin polymerization process of claim 1 , wherein the activity of the catalyst composition is from about 5% to about 75% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

13. The olefin polymerization process of claim 12 , wherein:
the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;
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; or
a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent.

14. The olefin polymerization process of claim 3 , wherein:
the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof; and
the activity of the catalyst composition is from about 5% to about 150% 100% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

15. The olefin polymerization process of claim 14 , wherein the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof.

16. The olefin polymerization process of claim 3 , wherein the activity of the catalyst composition is from about 5% to about 75% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions.

17. The olefin polymerization process of claim 16 , wherein the solid metallocene compound comprises an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group, and with an alkenyl substituent.

18. The olefin polymerization process of claim 16 , wherein 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.

19. The olefin polymerization process of claim 3 , 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.

20. The olefin polymerization process of claim 19 , wherein:
the activator-support comprises sulfated alumina; and
the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof.

21. The olefin polymerization process of claim 16 , wherein:
the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;
the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof; and
the soli

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Clark Kensha M
• Yang Qing
• Glass Gary L

Classifications

• C08F210/16

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

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F110/02 Primary

  Ethene · CPC title