High porosity fluorided silica-coated alumina activator-supports and uses thereof in metallocene-based catalyst systems for olefin polymerization
Fluorided silica-coated alumina activator-supports have a bulk density from 0.15 to 0.37 g/mL, a total pore volume from 0.85 to 2 mL/g, a BET surface area from 200 to 500 m 2 /g, an average pore diameter from 10 to 25 nm, and from 80 to 99% of pore volume in pores with diameters of greater than 6 nm. Methods of making the fluorided silica-coated alumina activator-supports and using the fluorided silica-coated aluminas in catalyst compositions and olefin polymerization processes also are described. Representative ethylene-based polymers produced using the compositions and processes have a melt index of 0.1 to 10 g/10 min and a density of 0.91 to 0.96 g/cm 3 , and contain from 70 to 270 ppm solid oxide and from 2 to 18 ppm fluorine.
1. An ethylene polymer having:
a melt index (MI) in a range from 0.1 to 10 g/10 min; and
a density in a range from 0.91 to 0.96 g/cm 3 ;
wherein the ethylene polymer contains:
from 70 to 270 ppm solid oxide; and
from 2 to 18 ppm fluorine.
2. The ethylene polymer of claim 1 , wherein the ethylene polymer contains:
from 100 to 200 ppm solid oxide; and
from 4 to 12 ppm fluorine.
3. The ethylene polymer of claim 1 , wherein the ethylene polymer further contains from 0.5 to 5 ppm of zirconium and/or hafnium.
4. The ethylene polymer of claim 1 , wherein the ethylene polymer contains, independently, less than 0.1 ppm of Mg, V, Ti, and Cr.
5. The ethylene polymer of claim 1 , wherein the solid oxide contains silica and alumina at a weight ratio of silica:alumina from 20:80 to 60:40.
6. The ethylene polymer of claim 1 , wherein the ethylene polymer comprises an ethylene homopolymer and/or an ethylene/α-olefin copolymer.
7. An article of manufacture comprising the ethylene polymer of claim 1 .
8. The ethylene polymer of claim 1 , wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.
9. The ethylene polymer of claim 8 , wherein:
the MI is in a range from 0.3 to 8 g/10 min; and
the density is in a range from 0.915 to 0.956 g/cm 3 ;
wherein the ethylene polymer contains:
from 100 to 250 ppm solid oxide; and
from 3 to 16 ppm fluorine.
10. An article of manufacture comprising the ethylene polymer of claim 9 .
11. The ethylene polymer of claim 9 , wherein the solid oxide contains silica and alumina at a weight ratio of silica:alumina from 25:75 to 55:45.
12. The ethylene polymer of claim 9 , wherein the ethylene polymer further contains from 0.6 to 4 ppm of zirconium and/or hafnium.
13. The ethylene polymer of claim 9 , wherein the ethylene polymer contains, independently, less than 0.08 ppm of Mg, V, Ti, and Cr.
14. The ethylene polymer of claim 1 , wherein the ethylene polymer is further characterized by:
a Mw in a range from 25 to 400 kg/mol; and
a ratio of Mw/Mn in a range from 2 to 25.
15. The ethylene polymer of claim 14 , wherein the ethylene polymer comprises an ethylene homopolymer and/or an ethylene/α-olefin copolymer.
16. The ethylene polymer of claim 1 , wherein the ethylene polymer is further characterized by:
a Mw in a range from 80 to 200 kg/mol; and
a ratio of Mw/Mn in a range from 2 to 5.
17. The ethylene polymer of claim 16 , wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.
18. An article of manufacture comprising the ethylene polymer of claim 17 .