Modifications of sulfated bentonites and uses thereof in metallocene catalyst systems for olefin polymerization
Sulfated bentonite compositions are characterized by a total pore volume from 0.4 to 1 mL/g, a total BET surface area from 200 to 400 m 2 /g, and an average pore diameter from 55 to 100 Angstroms. The sulfated bentonite compositions also can be characterized by a d50 average particle size in a range from 15 to 50 μm and a ratio of d90/d10 from 3 to 15. The sulfated bentonite compositions can contain a sulfated bentonite and from 10 to 90 wt. % of colloidal particles, or the sulfated bentonite compositions can contain a sulfated bentonite and from 0.2 to 10 mmol/g of zinc and/or phosphorus. These compositions can be utilized in metallocene catalyst systems to produce ethylene based polymers.
1 . A sulfated bentonite composition comprising:
a sulfated bentonite; and
from 15 to 80 wt % of colloidal particles, based on a total weight of the sulfated bentonite composition.
2 . The sulfated bentonite composition of claim 1 , wherein the sulfated bentonite composition comprises from 25 to 60 wt % of the colloidal particles.
3 . The sulfated bentonite composition of claim 1 , wherein the colloidal particles comprise a colloidal silica, a colloidal aluminum-zirconium, or a combination thereof.
4 . The sulfated bentonite composition of claim 1 , wherein the sulfated bentonite composition comprises from 30 to 50 wt % of the colloidal particles.
5 . The sulfated bentonite composition of claim 1 , wherein the colloidal particles comprise a colloidal silica.
6 . The sulfated bentonite composition of claim 5 , wherein the sulfated bentonite composition comprises from 20 to 70 wt % of the colloidal particles.
7 . The sulfated bentonite composition of claim 1 , wherein the colloidal particles comprise a colloidal aluminum-zirconium.
8 . The sulfated bentonite composition of claim 7 , wherein the sulfated bentonite composition comprises from 20 to 70 wt % of the colloidal particles.
9 . The sulfated bentonite composition of claim 1 , wherein the sulfated bentonite composition has:
a total pore volume from 0.4 to 1 mL/g;
a total BET surface area from 200 to 400 m 2 /g; and
an average pore diameter from 55 to 100 Angstroms (Ang).
10 . The sulfated bentonite composition of claim 1 , wherein the sulfated bentonite composition has:
a d50 average particle size in a range from 15 to 50 μm; and
a ratio of d90/d10 from 3 to 15.
11 . The sulfated bentonite composition of claim 1 , wherein the sulfated bentonite composition contains from 0.2 to 10 mmol/g of zinc, phosphorus, or both, per g of the sulfated bentonite.
12 . The sulfated bentonite composition of claim 1 , wherein the sulfated bentonite composition contains from 25 to 35 wt % silicon.
13 . A catalyst composition comprising:
a metallocene compound;
a co-catalyst; and
a sulfated bentonite composition comprising:
(i) a sulfated bentonite; and
(ii) from 15 to 80 wt % of colloidal particles, based on a total weight of the sulfated bentonite composition.
14 . The catalyst composition of claim 13 , wherein the co-catalyst comprises an organoaluminum compound, an organozinc compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
15 . The catalyst composition of claim 13 , wherein the colloidal particles comprise a colloidal silica, a colloidal aluminum-zirconium, or a combination thereof.
16 . The catalyst composition of claim 15 , wherein the metallocene compound comprises a bridged metallocene compound.
17 . The catalyst composition of claim 15 , wherein the metallocene compound comprises an unbridged metallocene compound.
18 . The catalyst composition of claim 15 , wherein the catalyst composition comprises two or more metallocene compounds.
19 . The catalyst composition of claim 15 , wherein the co-catalyst comprises an organoaluminum compound and/or an organozinc compound.
20 . The catalyst composition of claim 13 , wherein the sulfated bentonite composition comprises from 25 to 60 wt % of the colloidal particles.
21 . The catalyst composition of claim 13 , wherein the colloidal particles comprise a colloidal silica.
22 . The catalyst composition of claim 13 , wherein the sulfated bentonite composition has:
a d50 average particle size in a range from 15 to 50 μm; and
a ratio of d90/d10 from 3 to 15.
23 . An ethylene polymer having:
a Mw in a range from 350 to 700 kg/mol;
a ratio of Mw/Mn in a range from 2 to 4;
a ratio of Mz/Mw in a range from 1.8 to 4;
a CY-a parameter in a range from 0.4 to 0.65; and
a relaxation time as a function of Mz that is greater than 9.818×10 −7 (Mz) 2 +0.001503(Mz)−0.5, wherein Mz is in kg/mol and the relaxation time is in sec, and/or
a viscosity at 0.1 sec −1 as a function of Mz that is greater than 0.0985(Mz) 2 +890.7(Mz)−300,000, wherein Mz is in kg/mol and the viscosity is in Pa-sec.
24 . The ethylene polymer of claim 23 , wherein:
the Mw is from 400 to 700 kg/mol;
the ratio of Mw/Mn is from 2 to 3.5;
the ratio of Mz/Mw is from 1.8 to 3; and
the CY-a parameter is from 0.45 to 0.6.
25 . The ethylene polymer of claim 23 , wherein the ethylene polymer has a density from 0.90 to 0.96 g/cm 3 .
26 . The ethylene polymer of claim 25 , wherein the ethylene polymer has a HLMI from 0 to 80 g/10 min.
27 . The ethylene polymer of claim 26 , wherein:
the density is from 0.92 to 0.95 g/cm 3 ; and
the HLMI is from 0 to 25 g/10 min.
28 . The ethylene polymer of claim 25 , wherein:
the relaxation time as a function of Mz is greater than 9.818×10 −7 (Mz) 2 +0.001503(Mz)−0.5, wherein Mz is in kg/mol and the relaxation time is in sec, and
the viscosity at 0.1 sec −1 as a function of Mz is greater than 0.0985(Mz) 2 +890.7(Mz)−300,000, wherein Mz is in kg/mol and the viscosity is in Pa-sec.
29 . The ethylene polymer of claim 25 , wherein:
the Mw is from 400 to 700 kg/mol;
the ratio of Mw/Mn is from 2 to 3.5;
the ratio of Mz/Mw is from 1.8 to 3; and
the CY-a parameter is from 0.45 to 0.6.