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

Patent metadata

Field	Value
Publication number	US-9718907-B2
Application number	US-201615194622-A
Country	US
Kind code	B2
Filing date	Jun 28, 2016
Priority date	Jul 8, 2015
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

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 ;
less than or about 0.01 long chain branches per 1000 total carbon atoms; and
a ratio of Mw/Mn in a range from about 2.5 to about 8;
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 10 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.

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

3. The copolymer of claim 1 , 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 8 wt. % of the polymer eluted between 76 and 86° C.;
from about 28 to about 48 wt. % of the polymer eluted above a temperature of 86° C.;
and the remaining percentage of the polymer eluted between 40 and 76° C.

4. The copolymer of claim 1 , wherein the copolymer has a high load melt index in a range from about 2 to about 40 g/10 min.

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

6. The copolymer of claim 1 , wherein the copolymer has a substantially constant short chain branch distribution.

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

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

9. 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.

10. 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 300,000 g/mol; and
a ratio of Mw/Mn in a range from about 2.5 to about 8;
and having 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 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.

11. The copolymer of claim 10 , wherein the ethylene copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

12. The copolymer of claim 11 , wherein the copolymer is characterized by:
a melt index of less than or equal to about 2 g/10 min;
a density in a range from about 0.91 g/cm 3 to about 0.93 g/cm 3 ; and
a ratio of Mw/Mn in a range from about 2.5 to about 7.

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

14. The copolymer of claim 10 , 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 28 to about 48 wt. % of the polymer eluted above a temperature of 86° C.;
and the remaining percentage of the polymer eluted between 40 and 76° C.

15. The copolymer of claim 14 , wherein the copolymer has a high load melt index in a range from about 2 to about 40 g/10 min.

16. The copolymer of claim 15 , wherein the ethylene copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

17. The copolymer of claim 16 , wherein the ethylene copolymer is characterized by a Mw in a range from about 120,000 to about 260,000 g/mol, and from about 1 to about 8 wt. % of the polymer is eluted between 76 and 86° C.

18. The copolymer of claim 10 , wherein the copolymer has less than about 0.008 long chain branches per 1000 total carbon atoms.

19. The copolymer of claim 10 , wherein the copolymer has a substantially constant short chain branch distribution.

20. The copolymer of claim 10 , wherein a number of short chain branches per 1000 total carbon atoms of the copolymer at Mz is less than at Mn.

21. The copolymer of claim 10 , 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. The copolymer of claim 21 , wherein from about 1 to about 8 wt. % of the polymer is eluted between 76 and 86° C.

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F2/01

  characterised by special features of the polymerisation apparatus used · CPC title

• C08F210/02 Primary

  Ethene · CPC title