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 - 22 . (canceled)
23 . A fluorided silica-coated alumina having:
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; and
an average pore diameter from 10 to 25 nm and/or from 80 to 99% of pore volume in pores with diameters of greater than 6 nm;
wherein the fluorided silica-coated alumina contains from 20 to 60 wt. % silica, based on a weight of silica-coated alumina.
24 . The fluorided silica-coated alumina of claim 23 , wherein the fluorided silica-coated alumina contains from 0.5 to 18 wt. % F, based on a weight of the fluorided silica-coated alumina.
25 . The fluorided silica-coated alumina of claim 24 , wherein:
from 9.5 to 30% of the pore volume is in pores with diameters of greater than 20 nm;
from 3.5 to 15% of the pore volume is in pores with diameters of greater than 40 nm;
the fluorided silica-coated alumina has a pore volume of from 0.7 to 1.6 mL/g in pores with diameters of greater than 6 nm; and
the fluorided silica-coated alumina has a pore volume of from 0.09 to 0.4 mL/g in pores with diameters of greater than 20 nm.
26 . The fluorided silica-coated alumina of claim 24 , wherein:
from 65 to 98% of surface area is in pores with diameters of greater than 6 nm;
from 19.5 to 55% of surface area is in pores with diameters of greater than 10 nm;
the fluorided silica-coated alumina has a surface area of from 250 to 475 m 2 /g in pores with diameters of greater than 6 nm; and
the fluorided silica-coated alumina has a surface area of from 78 to 200 m 2 /g in pores with diameters of greater than 10 nm.
27 . A catalyst composition comprising:
a metallocene compound;
the fluorided silica-coated alumina of claim 23 ; and
optionally, a co-catalyst.
28 . The catalyst composition of claim 27 , wherein the metallocene compound comprises:
an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group;
a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; or
both.
29 . The catalyst composition of claim 27 , wherein the catalyst composition comprises the co-catalyst, and the co-catalyst comprises an organoaluminum compound.
30 . The catalyst composition of claim 29 , wherein the catalyst composition comprises one metallocene compound.
31 . The catalyst composition of claim 29 , wherein the catalyst composition comprises two or more metallocene compounds.
32 . The fluorided silica-coated alumina of claim 23 , wherein the fluorided silica-coated alumina contains from 25 to 55 wt. % silica, based on the weight of the silica-coated alumina.
33 . The fluorided silica-coated alumina of claim 32 , wherein:
the bulk density is from 0.17 to 0.3 g/mL;
the total pore volume is from 0.9 to 1.5 mL/g;
the BET surface area is from 250 to 450 m 2 /g;
the average pore diameter is from 10 to 25 nm; and
from 80 to 99% of the pore volume is in pores with diameters of greater than 6 nm.
34 . A catalyst composition comprising:
a metallocene compound;
the fluorided silica-coated alumina of claim 33 ; and
optionally, a co-catalyst.
35 . The catalyst composition of claim 34 , wherein the metallocene compound comprises:
an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group;
a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; or
both.
36 . The catalyst composition of claim 34 , wherein the catalyst composition comprises the co-catalyst, and the co-catalyst comprises an organoaluminum compound.
37 . The catalyst composition of claim 36 , wherein the catalyst composition comprises one metallocene compound.
38 . The catalyst composition of claim 36 , wherein the catalyst composition comprises two or more metallocene compounds.
39 . The fluorided silica-coated alumina of claim 33 , wherein:
the fluorided silica-coated alumina contains from 0.5 to 18 wt. % F, based on a weight of the fluorided silica-coated alumina;
the average pore diameter is from 10 to 20 nm; and
from 83 to 98% of the pore volume is in pores with diameters of greater than 6 nm.
40 . A catalyst composition comprising:
a metallocene compound;
the fluorided silica-coated alumina of claim 39 ; and
an organoaluminum co-catalyst.
41 . The catalyst composition of claim 40 , wherein the catalyst composition comprises one metallocene compound.
42 . The catalyst composition of claim 40 , wherein the catalyst composition comprises two or more metallocene compounds.