Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins
View Patent ↗Compositions useful for activating catalysts for olefin polymerization are provided. The compositions are derived from at least carrier having at least two hydrogen bonded hydroxyl groups, organoaluminum compound, Lewis base, and Bronsted acid, wherein the Lewis base and the Bronsted acid form at least one ionic Bronsted acid.
1. A composition comprising:
a) a Bronsted acidic cation [Q m H] + , wherein H is a proton, m is 1 or 2, each Q is Lewis base, and each Lewis base Q can be the same as, or different from, any other Lewis base Q; and
b) aluminate anion chemically bonded to at least one type of carrier, wherein each of a majority of aluminum atoms in the aluminate anion is chemically bonded to at least two oxygen atoms on the surface of the carrier forming chelating aluminum centers.
2. The composition of claim 1 wherein the carrier contains at least two hydroxyl groups.
3. The composition of claim 2 wherein a majority of the hydroxyl groups are in hydrogen bonded form.
4. The composition of claim 1 derived from at least:
a) the carrier, said carrier having at least two hydroxyl groups;
b) organoaluminum compound;
c) the Q m , and
d) Bronsted acid.
5. The composition of claim 4 wherein a majority of the hydroxyl groups are in hydrogen bonded form.
6. The composition of claim 4 further comprising an alkylated transition metal component.
7. The composition of claim 6 wherein a majority of the hydroxyl groups are in hydrogen bonded form.
8. The composition of claim 6 , wherein the carrier comprises an inorganic oxide.
9. The composition of claim 8 , wherein the inorganic oxide has a micro pore volume of not less than about 0.3 ml/g and an average particle diameter of about 10 micrometers to about 500 micrometers.
10. The composition of claim 8 wherein the inorganic oxide comprises silica, alumina, silica-alumina, magnesia, titania, zirconia, or clays.
11. The composition of claim 8 wherein the inorganic oxide comprises silica.
12. The composition of claim 11 wherein the silica is non-calcined.
13. The composition of claim 6 wherein the carrier was calcined at a temperature up to 400° C., or at a temperature of about 100° C. to about 400° C.
14. The composition of claim 6 wherein the organoaluminum compound comprises AlR n (XR 1 ) (3-n) wherein
Al is aluminum;
each R is hydrogen or a hydrocarbyl group having up to about 20 carbon atoms, and each R may be the same as, or different from, any other R;
for each XR 1 , X is a hetero atom and R 1 is an organic group bonded to the Al through the hetero atom and having up to about 20 carbon atoms;
each XR 1 may be the same as, or different from, any other XR 1 ; and
n is 1, 2, or 3.
15. The composition of claim 6 wherein the organoaluminum compound comprises triethylaluminum, triisobutylaluminum, trimethylaluminum, trioctylaluminum, diisobutylaluminum hydride, diethylaluminum hydride, dimethylaluminum hydride, (2,6-di-tert-butyl-4-methylphenoxy)diisobutylaluminum, bis(2,6-di-tert-butyl-4-methylphenoxy) isobutylaluminum, (2,6-di-tert-butyl-4-methylphenoxy)diethylaluminum, bis(2,6-di-tert-butyl-4-methylphenoxy)ethylaluminum, (2,6-di-tert-butyl-4-methylphenoxy) dimethylaluminum, or bis(2,6-di-tert-butyl-4-methylphenoxy) methylaluminum.
16. The composition of claim 6 wherein the ratio of (mmol OH on the carrier)/(g carrier) to (mmol organoaluminum compound)/(g carrier) is from about 1.80:1 to about 2.20:1.
17. The composition of claim 6 wherein the Lewis base comprises a tertiary amine NR 2 3 , wherein each R 2 is hydrogen or hydrocarbyl group having up to about 20 carbon atoms, and each R 2 may be the same as, or different from, any other R 2 .
18. The composition of claim 6 wherein i) the Lewis base comprises N,N-dimethylaniline, N,N-dimethylbenzylamine, triethylamine, or trimethylamine, or ii) wherein the Bronsted acid comprises pentafluorophenol, 2,6-difluorophenol, or 4-fluorophenol; or iii) combinations of i) and ii).
19. The composition of claim 6 , wherein the composition is suitable for activating an alkylated transition metal component by protonation.
20. A method of polymerizing monomer comprising combining a composition according to claim 6 , and a monomer.
21. A composition comprising:
a) carrier having at least two hydroxyl groups;
b) an organoaluminum compound comprising AlR n (XR 1 ) (3-n) wherein
Al is aluminum;
each R is hydrogen or a hydrocarbyl group having up to about 20 carbon atoms, and each R may be the same as, or different from, any other R;
for each XR 1 , X is a hetero atom and R 1 is an organic group bonded to the Al through the hetero atom and having up to about 20 carbon atoms;
each XR 1 may be the same as, or different from, any other XR 1 , and
n is 1, 2, or 3;
c) Lewis base; and
d) a Bronsted acid,
wherein the ratio of (mmol OH on the carrier)/(g carrier) to (mmol organoaluminum compound)/(g carrier) is from about 1.80:1 to about 2.20.