Dual catalyst system for producing LLDPE copolymers with a narrow molecular weight distribution and improved processability

Patent metadata

Field	Value
Publication number	US-10000594-B2
Application number	US-201615345586-A
Country	US
Kind code	B2
Filing date	Nov 8, 2016
Priority date	Nov 8, 2016
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

Disclosed herein are ethylene-based polymers generally characterized by a Mw ranging from 70,000 to 200,000 g/mol, a ratio of Mz/Mw ranging from 1.8 to 20, an IB parameter ranging from 0.92 to 1.05, and an ATREF profile characterized by one large peak. These polymers have the dart impact, tear strength, and optical properties of a metallocene-catalyzed LLDPE, but with improved processability, melt strength, and bubble stability, and can be used in blown film and other end-use applications.

First claim

We claim:

1. An ethylene polymer having:
a Mw in a range from about 70,000 to about 200,000 g/mol;
a ratio of Mz/Mw in a range from about 1.8 to about 20;
an IB parameter in a range from about 0.92 to about 1.05; and
a peak ATREF temperature in a range from about 68 to about 78° C.

2. An article of manufacture comprising the ethylene polymer of claim 1 .

3. The polymer of claim 1 , wherein:
the Mw is in a range from about 80,000 to about 160,000 g/mol;
the ratio of Mz/Mw is in a range from about 1.9 to about 8; and
the IB parameter is in a range from about 0.94 to about 1.03.

4. The polymer of claim 1 , wherein the ethylene polymer has:
a melt index in a range from about 0.5 to about 5 g/10 min;
a density in a range from about 0.90 to about 0.93 g/cm 3 ; and
a CY-a parameter in a range from about 0.15 to about 0.5.

5. The polymer of claim 4 , wherein:
the ethylene polymer has a unimodal molecular weight distribution; and
the ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

6. An article of manufacture comprising the ethylene polymer of claim 5 .

7. The polymer of claim 1 , wherein the ethylene polymer has:
a melt index in a range from about 0.5 to about 2.5 g/10 min; and
a density in a range from about 0.905 to about 0.925 g/cm 3 .

8. The polymer of claim 7 , wherein the ethylene polymer has:
a ratio of Mw/Mn in a range from about 2 to about 9; and
a CY-a parameter in a range from about 0.15 to about 0.35.

9. The polymer of claim 8 , wherein:
the ratio of Mw/Mn is in a range from about 2.4 to about 4; and
the ratio of Mz/Mw is in a range from about 2.2 to about 7.

10. The polymer of claim 1 , wherein the ethylene polymer has:
a Mp in a range from about 70,000 to about 120,000 g/mol; and
a Mn in a range from about 25,000 to about 60,000 g/mol.

11. The polymer of claim 10 , wherein the ethylene polymer has:
a zero-shear viscosity in a range from about 3000 to about 50,000 Pa-sec; and
a density in a range from about 0.91 to about 0.925 g/cm 3 .

12. An article of manufacture comprising the ethylene polymer of claim 11 .

13. The article of claim 12 , wherein the ethylene polymer has a unimodal molecular weight distribution.

14. The polymer of claim 1 , wherein the ethylene polymer has the following polymer fractions in an ATREF test:
from about 0.5 to about 5 wt. % of the polymer eluted below a temperature of 40° C.;
from about 20 to about 40 wt. % of the polymer eluted between 76 and 86° C.;
from about 7 to about 20 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. An article of manufacture comprising the ethylene polymer of claim 14 .

16. A blown film comprising the polymer of claim 1 , wherein the film has an average thickness in a range from about 0.5 to about 8 mils.

17. The blown film of claim 16 , wherein the film has:
a dart impact strength of greater than or equal to about 300 g/mil;
a MD Elmendorf tear strength in a range from about 40 to about 500 g/mil; and
a TD Elmendorf tear strength in a range from about 350 to about 800 g/mil.

18. An ethylene polymer having:
a Mw in a range from about 70,000 to about 200,000 g/mol;
a ratio of Mz/Mw in a range from about 1.8 to about 20;
an IB parameter in a range from about 0.92 to about 1.05; and
the following polymer fractions in an ATREF test:

from about 0.5 to about 5 wt. % of the polymer eluted below a temperature of 40° C.;
from about 20 to about 40 wt. % of the polymer eluted between 76 and 86° C.;
from about 7 to about 20 wt. % of the polymer eluted above a temperature of 86° C.;
and the remaining percentage of the polymer eluted between 40 and 76° C.

19. An article of manufacture comprising the ethylene polymer of claim 18 .

20. The polymer of claim 18 , wherein the ethylene polymer has:
a melt index in a range from about 0.5 to about 5 g/10 min;
a density in a range from about 0.90 to about 0.93 g/cm 3 ; and
a CY-a parameter in a range from about 0.15 to about 0.5.

21. The polymer of claim 18 , wherein:
the ethylene polymer has a ratio of Mw/Mn in a range from about 2 to about 9, and a CY-a parameter in a range from about 0.15 to about 0.35; and
the ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

22. The polymer of claim 21 , wherein:
the ratio of Mw/Mn is in a range from about 2.4 to about 4; and
the ratio of Mz/Mw is in a range from about 2.2 to about 7.

23. An ethylene polymer having:
a Mw in a range from about 70,000 to about 200,000 g/mol;
a ratio of Mz/Mw in a range from about 1.8 to about 20;
an IB parameter in a range from about 0.92 to about 1.05;
a peak ATREF temperature in a range from about 70 to about 77° C., and no other peaks on the ATREF curve above a dW/dT of 2 in height; and
the following polymer fractions in an ATREF test:

from about 0.1 to about 3 wt. % of the polymer eluted below a temperature of 40° C.;
from about 25 to about 38 wt. % of the polymer eluted between 76 and 86° C.;
from about 9 to about 18 wt. % of the polymer eluted above a temperature of 86° C.;
and the remaining percentage of the polymer eluted between 40 and 76° C.

24. The polymer of claim 23 , wherein the ethylene polymer has a density in a range from about 0.91 to about 0.925 g/cm 3 .

25. An article of manufacture comprising the ethylene polymer of claim 24 .

26. A blown film comprising an ethylene polymer having:
a Mw in a range from about 70,000 to about 200,000 g/mol;
a ratio of Mz/Mw in a range from about 1.8 to about 20; and
an IB parameter in a range from about 0.92 to about 1.05;

wherein the film has:
an average thickness in a range from about 0.5 to about 8 mils;
a haze of less than or equal to about 8%;
a MD shrink in a range from about 65 to about 90%; and
a TD shrink in a range from about 2 to about 30%.

27. The blown film of claim 26 , wherein the ethylene polymer has:
a melt index in a range from about 0.5 to about 5 g/10 min;
a density in a range from about 0.90 to about 0.93 g/cm 3 ;
a CY-a parameter in a range from about 0.15 to about 0.5; and
a ratio of Mw/Mn in a range from about 2.4 to about 4.

28. The blown film of claim 26 , wherein the ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Tso Chung Ching
• Inn Yongwoo
• Gagan Deloris R
• Muninger Randy S

Classifications

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65916

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

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title

• C08J2201/03

  Extrusion of the foamable blend · CPC title

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title