Ziegler-natta—metallocene dual catalyst systems with activator-supports

Patent metadata

Field	Value
Publication number	US-10435492-B2
Application number	US-201815890524-A
Country	US
Kind code	B2
Filing date	Feb 7, 2018
Priority date	Jul 8, 2015
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

Abstract

Catalyst systems having both a metallocene catalyst component and a Ziegler-Natta component are disclosed. Such catalyst systems can contain a metallocene compound, an activator-support, an organoaluminum compound, and a Ziegler-Natta component comprising titanium supported on magnesium chloride.

First claim

We claim:

1. An ethylene copolymer characterized by:
a melt index of less than or equal to about 10 g/10 min;
a density in a range from about 0.90 g/cm 3 to about 0.935 g/cm 3 ;
a Mw in a range from about 100,000 to about 500,000 g/mol; and
a ratio of Mw/Mn in a range from about 2.5 to about 12;
and having the following polymer fractions in an ATREF test: less than about 4 wt. % of the polymer eluted below a temperature of 40° C.; from about 40 to about 62 wt. % of the polymer eluted between 40 and 76° C.; from about 2 to about 21 wt. % of the polymer eluted between 76 and 86° C.; and from about 29 to about 40 wt. % of the polymer eluted above a temperature of 86° C.

2. An article of manufacture comprising the copolymer of claim 1 .

3. The copolymer of claim 1 , wherein from about 0.5 to about 4 wt. % of the polymer is eluted below a temperature of 40° C.

4. The copolymer of claim 1 , wherein:
the melt index is less than or equal to about 2 g/10 min;
the density is in a range from about 0.91 g/cm 3 to about 0.93 g/cm 3 ;
the Mw is in a range from about 100,000 to about 300,000 g/mol; and
the ratio of Mw/Mn is in a range from about 2.5 to about 7.

5. The copolymer of claim 4 , wherein the ethylene copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octane copolymer.

6. An article of manufacture comprising the copolymer of claim 5 .

7. The copolymer of claim 4 , wherein the copolymer has a high load melt index in a range from about 2 to about 40 g/10 min.

8. The copolymer of claim 1 , wherein the copolymer has less than about 0.008 long chain branches per 1000 total carbon atoms.

9. The copolymer of claim 8 , wherein the ethylene copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octane copolymer, and is characterized by a Mw in a range from about 120,000 to about 260,000 g/mol.

10. The copolymer of claim 1 , wherein:
a number of short chain branches per 1000 total carbon atoms of the copolymer at Mz is less than at Mn; and
the copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

11. An ethylene copolymer characterized by:
a melt index of less than or equal to about 10 g/10 min;
a density in a range from about 0.90 g/cm 3 to about 0.935 g/cm 3 ;
a Mw in a range from about 100,000 to about 500,000 g/mol; and
a ratio of Mw/Mn in a range from about 4 to about 10;
and having the following polymer fractions in an ATREF test: from about 1 to about 18 wt. % of the polymer eluted below a temperature of 40° C.; from about 1 to about 15 wt. % of the polymer eluted between 76 and 86° C.; from about 27 to about 60 wt. % of the polymer eluted above a temperature of 86° C.; and the remaining percentage of the polymer eluted between 40 and 76° C.

12. An article of manufacture comprising the copolymer of claim 11 .

13. The copolymer of claim 11 , wherein from about 1 to about 8 wt. % of the polymer is eluted below a temperature of 40° C.

14. The copolymer of claim 11 , wherein from about 1 to about 10 wt. % of the polymer is eluted between 76 and 86° C.

15. The copolymer of claim 11 , wherein the Mw is in a range from about 100,000 to about 300,000 g/mol.

16. An article of manufacture comprising the copolymer of claim 15 .

17. The copolymer of claim 15 , wherein the copolymer has a high load melt index in a range from about 2 to about 40 g/10 min.

18. The copolymer of claim 15 , wherein:
from about 1 to about 8 wt. % of the polymer is eluted below a temperature of 40° C.; and
from about 1 to about 10 wt. % of the polymer is eluted between 76 and 86° C.

19. The copolymer of claim 15 , wherein the ethylene copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octane copolymer, and is characterized by a ratio of Mw/Mn in a range from about 4 to about 8.

20. The copolymer of claim 11 , wherein:
the melt index is less than or equal to about 2 g/10 min;
the density is in a range from about 0.91 g/cm 3 to about 0.93 g/cm 3 ; and
the Mw is in a range from about 100,000 to about 300,000 g/mol.

21. The copolymer of claim 20 , wherein the copolymer has the following polymer fractions in an ATREF test:
from about 1 to about 8 wt. % of the polymer eluted below a temperature of 40° C.;
from about 1 to about 10 wt. % of the polymer eluted between 76 and 86° C.;
from about 29 to about 40 wt. % of the polymer eluted above a temperature of 86° C.;
and the remaining percentage of the polymer eluted between 40 and 76° C.

22. An article of manufacture comprising the copolymer of claim 21 .

23. The copolymer of claim 21 , wherein the copolymer has:
less than about 0.008 long chain branches per 1000 total carbon atoms; and
a number of short chain branches per 1000 total carbon atoms of the copolymer at Mz that is less than at Mn.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Ding Errun
• Tso Chung C
• Yu Youlu
• Yang Qing
• Buck Richard M

Classifications

• C08F210/16 Primary

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

• C08F210/02 Primary

  Ethene · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F4/65916

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

• C08F4/6423

  Component of C08F4/64 containing at least two different metals · CPC title