IP Library Granted Patent US 12,234,348
Granted Patent B2
US 12,234,348 · App. 17/745,962 · Granted Feb 25, 2025

Blow molding polymers with improved cycle time, processability, and surface quality

Inventors: Carlos A. Cruz (Kingwood, TX); Yongwoo Inn (Bartlesville, OK); Justin Lumbley (Bartlesville, OK); Brandy Rutledge-Ryal (Bartlesville, OK); John R. Rathman (Bartlesville, OK); Jennifer L Hicks (Bartlesville, OK); Jay M. Chaffin (Bartlesville, OK)
Assignee: Chevron Phillips Chemical Company LP
C08L23/0815C08F4/6592C08F210/16C08K3/08C08F2500/07C08F2500/17C08K2003/0881C08L2207/062C08L2207/07
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Quick Facts
Patent No.
US 12,234,348
App. No.
17/745,962
Granted
Feb 25, 2025
Kind
B2
Abstract

Ethylene-based polymers having a density of 0.952 to 0.965 g/cm 3 , a high load melt index (HLMI) from 5 to 25 g/10 min, a weight-average molecular weight from 275,000 to 450,000 g/mol, a number-average molecular weight from 15,000 to 40,000 g/mol, a viscosity at HLMI from 1400 to 4000 Pa-sec, and a tangent delta at 0.1 sec −1 from 0.65 to 0.98 degrees. These polymers have the processability of chromium-based resins, but with improved stress crack resistance, and can be used in large-part blow molding applications.

Claims (57)

1. An ethylene polymer having:

a density in a range from about 0.952 to about 0.965 g/cm 3 ;

a high load melt index (HLMI) in a range from about 5 to about 25 g/10 min;

a weight-average molecular weight (Mw) in a range from about 275,000 to about 450,000 g/mol;

a number-average molecular weight (Mn) in a range from about 15,000 to about 40,000 g/mol;

a viscosity at HLMI (η @ HLMI) in a range from about 1400 to about 4000 Pa-sec; and

a tan δ at 0.1 sec −1 in a range from about 0.65 to about 0.98 degrees.

2. The polymer of claim 1 , wherein the ethylene polymer has an environmental stress crack resistance (ESCR) of at least 500 hours.

3. The polymer of claim 1 , wherein the ethylene polymer has a ratio of Mw/Mn in a range from about 8 to about 20.

4. A blow molded article comprising the ethylene polymer of claim 1 .

5. The polymer of claim 1 , wherein the ethylene polymer has:

a CY-a parameter in a range from about 0.18 to about 0.36; and

a viscosity at 100 sec −1 in a range from about 1600 to about 2800 Pa-sec.

6. The polymer of claim 1 , wherein the ethylene polymer has:

less than about 0.008 long chain branches per 1000 total carbon atoms; and

a reverse comonomer distribution.

7. The polymer of claim 1 , wherein the ethylene polymer contains, independently, less than 0.08 ppm by weight of chromium and titanium.

8. The polymer of claim 1 , wherein:

the density is in a range from about 0.952 to about 0.96 g/cm 3 ;

the HLMI is in a range from about 7 to about 15 g/10 min;

the Mw is in a range from about 300,000 to about 400,000 g/mol;

the Mn is in a range from about 17,000 to about 35,000 g/mol;

the η @ HLMI is in a range from about 1600 to about 3900 Pa-sec; and

the tan δ at 0.1 sec −1 is in a range from about 0.7 to about 0.97 degrees.

9. The polymer of claim 8 , wherein the ethylene polymer comprises an ethylene/l-butene copolymer, an ethylene/l-hexene copolymer, and/or an ethylene/l-octene copolymer.

10. An article comprising the ethylene polymer of claim 9 .

11. A polymerization process, the process comprising contacting a catalyst composition with ethylene and an α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the ethylene polymer has:

a density in a range from about 0.952 to about 0.965 g/cm 3 ;

a HLMI in a range from about 5 to about 25 g/10 min;

a Mw in a range from about 275,000 to about 450,000 g/mol;

a Mn in a range from about 15,000 to about 40,000 g/mol;

a viscosity at HLMI (η @ HLMI) in a range from about 1400 to about 4000 Pa-sec; and

a tan δ at 0.1 sec −1 in a range from about 0.65 to about 0.98 degrees; and

the catalyst composition comprises:

an unbridged metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group;

a bridged metallocene compound with a cyclopentadienyl group and fluorenyl group, and an alkenyl substituent on the cyclopentadienyl group and/or on the bridging group;

an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and

an organoaluminum compound.

12. The process of claim 11 , wherein:

the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; and

the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof.

13. An ethylene polymer having:

a density in a range from about 0.952 to about 0.965 g/cm 3 ;

a high load melt index (HLMI) in a range from about 7 to about 15 g/10 min;

a weight-average molecular weight (Mw) in a range from about 275,000 to about 450,000 g/mol;

a number-average molecular weight (Mn) in a range from about 15,000 to about 40,000 g/mol;

a viscosity at HLMI (η @ HLMI) in a range from about 1400 to about 4000 Pa-sec; and

a tan δ at 0.1 sec −1 in a range from about 0.65 to about 0.98 degrees.

14. The polymer of claim 13 , wherein the ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

15. A blow molded article comprising the ethylene polymer of claim 14 .

16. The polymer of claim 14 , wherein the ethylene polymer has an environmental stress crack resistance (ESCR) of at least 500 hours.

17. The polymer of claim 14 , wherein the ethylene polymer has an environmental stress crack resistance (ESCR) of at least 1000 hours.

18. The polymer of claim 14 , wherein the Mn is in a range from about 15,000 to about 28,000 g/mol.

19. The polymer of claim 14 , wherein the ethylene polymer contains, independently, less than 0.08 ppm by weight of chromium and titanium.

20. The polymer of claim 14 , wherein the ethylene polymer has:

a ratio of Mw/Mn in a range from about 8 to about 20; and

a viscosity at 100 sec −1 in a range from about 1600 to about 2800 Pa-sec.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 11, 2022
From: CRUZ, CARLOS A.; INN, YONGWOO; LUMBLEY, JUSTIN; RUTLEDGE-RYAL, BRANDY; RATHMAN, JOHN R.; HICKS, JENNIFER L.; CHAFFIN, JAY M.
To: CHEVRON PHILLIPS CHEMICAL COMPANY LP
Reel/Frame 060777/0281 →
Continuity (2)
Continuation 16522788 · Jul 26, 2019
Related Publication 20220275183A1 · Sep 1, 2022
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