Dual catalyst systems for producing polymers with a broad molecular weight distribution and a uniform short chain branch distribution

Patent metadata

Field	Value
Publication number	US-9217049-B2
Application number	US-201414284689-A
Country	US
Kind code	B2
Filing date	May 22, 2014
Priority date	Nov 19, 2013
Publication date	Dec 22, 2015
Grant date	Dec 22, 2015

Abstract

Disclosed herein are ethylene-based polymers having a melt index less than 50 g/10 min, a ratio of Mw/Mn from 4 to 20, a density from 0.90 to 0.945 g/cm 3 , and a substantially constant short chain branch distribution. These polymers can be produced using a dual catalyst system containing a boron bridged metallocene compound with a cyclopentadienyl group and an indenyl group, and a single atom bridged metallocene compound with a fluorenyl group.

First claim

The invention claimed is:

1. An olefin polymer having a melt index of less than or equal to about 50 g/10 min, a ratio of Mw/Mn in a range from about 4 to about 20, a density in a range from about 0.90 g/cm 3 to about 0.945 g/cm 3 , and a percentage of data points deviating from the average short chain branch content, determined over the range from D15 to D85, by greater than 1 short chain branch per 1000 total carbon atoms of less than or equal to about 10%.

2. The polymer of claim 1 , wherein the olefin polymer has:
a Mn in a range from about 8,000 to about 30,000 g/mol; and
a ratio of Mw/Mn in a range from about 4 to about 10.

3. The polymer of claim 1 , wherein the olefin polymer has:
a density in a range from about 0.91 to about 0.94 g/cm 3 ;
a ratio of HLMI/MI in a range from about 10 to about 100;
a Mw in a range from about 50,000 to about 300,000 g/mol; and
a ratio of Mz/Mw in a range from about 2 to about 5.

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

5. An article comprising the olefin polymer of claim 4 .

6. The polymer of claim 1 , wherein the olefin polymer has:
a melt index in a range from about 0.1 to about 10 g/10 min;
a ratio of Mw/Mn in a range from about 4.1 to about 8;
a density in a range from about 0.915 g/cm 3 to about 0.945 g/cm 3 ; and
a percentage of data points deviating from the average short chain branch content, determined over the range from D15 to D85, by greater than 1 short chain branch per 1000 total carbon atoms of less than or equal to about 5%.

7. The polymer of claim 6 , wherein the olefin polymer is an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

8. The polymer of claim 7 , wherein the olefin polymer has:
less than about 0.008 long chain branches per 1000 total carbon atoms; and
a bimodal molecular weight distribution.

9. The polymer of claim 7 , wherein the olefin polymer has:
a ratio of HLMI/MI in a range from about 10 to about 250; and
a ratio of Mz/Mw in a range from about 2 to about 4.

10. An article comprising the olefin polymer of claim 7 .

11. An ethylene copolymer having a melt index of less than or equal to about 50 g/10 min, a ratio of Mw/Mn in a range from about 4 to about 20, a density in a range from about 0.90 g/cm 3 to about 0.945 g/cm 3 , and a percentage of data points deviating from the average short chain branch content, determined over the range from D15 to D85, by greater than 0.5 short chain branches per 1000 total carbon atoms of less than or equal to about 15%.

12. The copolymer of claim 11 , wherein the ethylene copolymer has:
a Mn in a range from about 8,000 to about 30,000 g/mol; and
a ratio of Mw/Mn in a range from about 4 to about 10.

13. The copolymer of claim 12 , wherein the ethylene copolymer is an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

14. An article comprising the ethylene copolymer of claim 13 .

15. The copolymer of claim 13 , wherein the ethylene copolymer has:
a melt index in a range from about 0.1 to about 10 g/10 min;
a density in a range from about 0.915 g/cm 3 to about 0.945 g/cm 3 ; and
a percentage of data points deviating from the average short chain branch content, determined over the range from D15 to D85, by greater than 0.5 short chain branches per 1000 total carbon atoms of less than or equal to about 10%.

16. The copolymer of claim 15 , wherein the ethylene copolymer has:
a ratio of HLMI/MI in a range from about 10 to about 100; and
less than about 0.008 long chain branches per 1000 total carbon atoms.

17. An article comprising the ethylene copolymer of claim 15 .

18. An ethylene copolymer having a melt index of less than or equal to about 50 g/10 min, a ratio of Mw/Mn in a range from about 4 to about 20, a density in a range from about 0.90 g/cm 3 to about 0.945 g/cm 3 , and a slope of a plot of the number of short chain branches per 1000 total carbon atoms versus the logarithm of molecular weight of the copolymer, determined via linear regression over the range from D15 to D85, in a range from about −0.6 to about 0.6.

19. The copolymer of claim 18 , wherein the ethylene copolymer has:
a Mn in a range from about 8,000 to about 30,000 g/mol; and
a ratio of Mw/Mn in a range from about 4 to about 10.

20. The copolymer of claim 19 , wherein the ethylene copolymer is an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

21. An article comprising the ethylene copolymer of claim 20 .

22. The copolymer of claim 20 , wherein the ethylene copolymer has:
a melt index in a range from about 0.1 to about 10 g/10 min;
a density in a range from about 0.915 g/cm 3 to about 0.945 g/cm 3 ; and
a slope of a plot of the number of short chain branches per 1000 total carbon atoms versus the logarithm of molecular weight of the copolymer, determined via linear regression over the range from D15 to D85, in a range from about −0.4 to about 0.4.

23. The copolymer of claim 22 , wherein the ethylene copolymer has:
a ratio of HLMI/MI in a range from about 10 to about 100; and
less than about 0.008 long chain branches per 1000 total carbon atoms.

24. An article comprising the ethylene copolymer of claim 22 .

Assignees

• Chevron Phillips Chemical Co

Inventors

• Yang Qing
• Greco Jeff F
• Mcdaniel Max P
• Yu Youlu
• Glass Gary L
• Crain Tony R

Classifications

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F210/16 Primary

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

• C08F110/02

  Ethene · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title