IP Library Granted Patent US 12,319,774
Granted Patent B1
US 12,319,774 · App. 18/653,014 · Granted Jun 3, 2025

Particle size control of silyl chromate catalysts and uses thereof in fluidized bed reactors

Inventors: Max P. McDaniel (Bartlesville, OK); Eric D. Schwerdtfeger (Bartlesville, OK); Jeffrey S. Lowell (Kingwood, TX); Scott E. Kufeld (The Woodlands, TX)
Assignee: Chevron Phillips Chemical Company LP
C08F4/78C08F4/025C08F10/02
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Quick Facts
Patent No.
US 12,319,774
App. No.
18/653,014
Granted
Jun 3, 2025
Kind
B1
Abstract

Supported chromium (VI) catalysts containing a solid oxide, 0.05 to 5 wt. % chromium, and 0.2 to 20 wt. % carbon, in which the solid oxide or the catalyst has a particle size span from 0.5 to 1.4, less than 3 wt. % has a particle size greater than 100 μm, and less than 10 wt. % has a particle size less than 10 μm, can be contacted with an olefin monomer in a fluidized bed reactor or other suitable polymerization reactor to produce an olefin polymer. Representative ethylene-based polymers produced using the chromium catalysts have a HLMI of 4 to 70 g/10 min, a density from 0.93 to 0.96 g/cm 3 , from 150 to 680 ppm solid oxide (such as silica), from 0.5 to 3 ppm chromium, and a film gel count of less than 15 catalyst particle gels per ft 2 of 25 micron thick film and/or a gel count of less than or equal to 50 catalyst particles of greater than 100 μm (in diameter) per five grams of the ethylene polymer.

Claims (33)

1. An ethylene polymer having:

a high load melt index (HLMI) in a range from 4 to 70 g/10 min;

a density in a range from 0.93 to 0.96 g/cm 3 ; and

a film gel count of less than or equal to 15 catalyst particle gels per ft 2 of 25 micron thick film, wherein film gels encompass a size in diameter of greater than 200 μm caused by the catalyst particles; and/or

a gel count of less than or equal to 50 catalyst particles of greater than 100 μm in diameter per 5 grams of the ethylene polymer;

wherein the ethylene polymer contains from 150 to 680 ppm solid oxide and from 0.5 to 1 ppm chromium.

2. The polymer of claim 1 , wherein the film gel count is less than or equal to 2 catalyst particle gels per ft 2 of 25 micron thick film.

3. The polymer of claim 1 , wherein the gel count is less than or equal to 5 catalyst particles of greater than 100 μm in diameter per 5 grams of the ethylene polymer.

4. The polymer of claim 1 , wherein the solid oxide is silica and/or silica-titania.

5. The polymer of claim 1 , wherein the polymer comprises an ethylene homopolymer and/or an ethylene/α-olefin copolymer.

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

7. The polymer of claim 1 , wherein the polymer contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, or Hf.

8. An article comprising the polymer of claim 1 .

9. The article of claim 8 , wherein the article has a gel count of less than or equal to 40 catalyst particles of greater than 100 μm in diameter per 5 grams of the article.

10. The article of claim 8 , wherein the article has a gel count of less than or equal to 5 catalyst particles of greater than 100 μm in diameter per 5 grams of the article.

11. The polymer of claim 1 , wherein:

the film gel count is less than or equal to 10 catalyst particle gels per ft 2 of 25 micron thick film; and

the gel count is less than or equal to 30 catalyst particles of greater than 100 μm in diameter per 5 grams of the ethylene polymer.

12. The polymer of claim 11 , wherein the polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

13. The polymer of claim 12 , wherein:

the solid oxide is silica; and

the polymer contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, or Hf.

14. The polymer of claim 12 , wherein:

the solid oxide is silica-titania; and

the polymer contains, independently, less than 0.1 ppm of Mg, V, Zr, or Hf.

15. An article comprising the polymer of claim 12 .

16. The polymer of claim 12 , wherein the polymer contains from 150 to 500 ppm of the solid oxide.

17. The polymer of claim 12 , wherein the polymer has:

a Mw in a range from 100,000 to 275,000 g/mol; and

a ratio of Mw/Mn in a range from 3 to 25.

18. The polymer of claim 12 , wherein the polymer has:

a CY-a parameter in a range from 0.10 to 0.23; and

a relaxation time in a range from 0.5 to 50 sec.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 16, 2024
From: MCDANIEL, MAX P.; SCHWERDTFEGER, ERIC D.; LOWELL, JEFFREY S.; KUFELD, SCOTT E.
To: CHEVRON PHILLIPS CHEMICAL COMPANY LP
Reel/Frame 068913/0441 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 31, 2024
From: MCDANIEL, MAX P.; SCHWERDTFEGER, ERIC D.; LOWELL, JEFFREY S.; KUFELD, SCOTT E.
To: CHEVRON PHILLIPS CHEMICAL COMPANY LP
Reel/Frame 067577/0001 →
Continuity (1)
Provisional Application 63623889 · Jan 23, 2024
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