Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina

Patent metadata

Field	Value
Publication number	US-9845367-B2
Application number	US-201514863698-A
Country	US
Kind code	B2
Filing date	Sep 24, 2015
Priority date	Sep 24, 2015
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

Catalyst systems containing a Ziegler-Natta catalyst component are disclosed. Such catalyst systems can contain a co-catalyst and a supported catalyst containing a fluorided silica-coated alumina, a magnesium compound, and vanadium and/or tetravalent titanium.

First claim

We claim:

1. A process to produce a supported catalyst, the process comprising:
(i) contacting:
(a) a fluorided silica-coated alumina;
(b) a magnesium compound; and
(c) a first titanium (IV) compound and/or vanadium compound to form a first solid precatalyst;

(ii) contacting the first solid precatalyst with an organoaluminum compound to form a second solid precatalyst; and
(iii) contacting the second solid precatalyst with a second titanium (IV) compound and/or vanadium compound to form the supported catalyst.

2. The process of claim 1 , wherein step (i) comprises contacting a slurry of the fluorided silica-coated alumina in a non-polar solvent with a solution of the magnesium compound and the first titanium (IV) compound and/or vanadium compound in a polar aprotic solvent.

3. The process of claim 1 , wherein step (ii) comprises contacting a slurry of the first solid precatalyst with a solution of the organoaluminum compound.

4. The process of claim 1 , wherein step (iii) comprises contacting a slurry of the second solid precatalyst in a non-polar solvent with a solution of the second titanium (IV) compound and/or vanadium compound in a polar aprotic solvent.

5. The process of claim 1 , wherein the fluorided silica-coated alumina comprises from about 20 to about 45 wt. % silica and from about 2 to about 15 wt. % fluorine.

6. The process of claim 1 , wherein the supported catalyst comprises from about 0.5 to about 7 wt. % magnesium.

7. The process of claim 1 , wherein the supported catalyst comprises from about 0.5 to about 10 wt. % titanium.

8. A catalyst composition comprising a co-catalyst and a supported catalyst comprising:
(a) a fluorided silica-coated alumina;
(b) a magnesium compound; and
(c) from about 0.5 to about 10 wt. % titanium (IV) and/or vanadium.

9. The composition of claim 8 , wherein:
the fluorided silica-coated alumina comprises from about 20 to about 45 wt. % silica and from about 3 to about 12 wt. % fluorine; and
the supported catalyst comprises from about 0.5 to about 3 wt. % magnesium, and the magnesium compound is not a reducing agent.

10. The composition of claim 8 , wherein the supported catalyst comprises a titanium (IV) compound comprising a titanium halide, a titanium alkoxide, an alkoxytitanium halide, or a combination thereof.

11. The composition of claim 8 , wherein the supported catalyst comprises a magnesium halide, a magnesium alkoxide, an alkoxymagnesium halide, or a combination thereof.

12. The composition of claim 8 , wherein the supported catalyst further comprises from about 1 to about 50 ppm THF by weight.

13. The composition of claim 8 , wherein a weight ratio of the co-catalyst to the supported catalyst is in a range from about 1:50 to about 1:600.

14. The composition of claim 8 , wherein the catalyst composition has a catalyst activity greater than about 2,000 g/g/hr, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as the diluent, at a polymerization temperature of 80° C. and a reactor pressure of 260 psig.

15. An olefin polymerization process, the process comprising contacting the catalyst composition of claim 8 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

16. The process of claim 15 , wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

17. The process of claim 15 , wherein the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof.

18. The process of claim 15 , wherein the olefin polymer is an ethylene/alpha-olefin copolymer.

19. The process of claim 18 , wherein the ethylene/alpha-olefin copolymer has less than about 0.008 long chain branches per 1000 total carbon atoms and a substantially constant short chain branch distribution (SCBD).

20. The process of claim 18 , wherein the ethylene/alpha-olefin copolymer has a Natural Draw Ratio (NDR) in a range from about 400% to about 600%.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Ding Errun
• Greco Jeffrey F
• Yang Qing
• Yu Youlu

Classifications

• C08F210/16 Primary

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

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F4/685

  Vanadium or compounds thereof in combination with titanium or compounds thereof · CPC title

• C08F4/656

  with silicon or compounds thereof · CPC title

• C08F4/6543 Primary

  halides of magnesium · CPC title