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: a) compound derived from at least (i) carrier having at least one pair of hydrogen bonded hydroxyl groups, (ii) organoaluminum compound, and (iii) Lewis base, such that each of a majority of aluminum atoms in the organoaluminum compound forms chemical bonds with at least two oxygen atoms from the at least one pair of hydrogen bonded hydroxyl groups; and b) Bronsted acid, wherein the molar ratio of the Bronsted acid to the organoaluminum compound is less than or equal to about 2:1.
1. A composition derived from at least:
a) a compound derived from at least (i) a carrier having at least one pair of hydrogen bonded hydroxyl groups, (ii) an organoaluminum compound, and (iii) a Lewis base, such that each of a majority of aluminum atoms in the organoaluminum compound forms chemical bonds with at least two oxygen atoms from the at least one pair of hydrogen bonded hydroxyl groups; and
b) a Bronsted acid, wherein the molar ratio of the Bronsted acid to the organoaluminum compound is less than or equal to about 2:1.
2. The composition of claim 1 wherein the carrier comprises a plurality of hydroxyl groups and a majority of the hydroxyl groups are in hydrogen bonded form.
3. The composition of claim 1 , wherein the carrier comprises an inorganic oxide.
4. The composition of claim 3 , 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.
5. The composition of claim 3 wherein the inorganic oxide comprises silica, alumina, silica-alumina, magnesia, titania, zirconia, or clays.
6. The composition of claim 3 wherein the inorganic oxide comprises silica.
7. The composition of claim 6 wherein the silica is non-calcined.
8. The composition of claim 1 wherein the carrier was calcined at a temperature up to 400° C.
9. The composition of claim 1 wherein the carrier was calcined at a temperature of about 100° C. to about 400° C.
10. The composition of claim 1 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.
11. The composition of claim 1 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.
12. The composition of claim 1 wherein the Lewis base comprises a tertiary amine NR 4 3 , wherein each R 4 is hydrogen or hydrocarbyl group having up to about 20 carbon atoms, and each R 4 may be the same as, or different from, any other R 4 .
13. The composition of claim 1 wherein the Lewis base comprises N,N-dimethylaniline, N,N-dimethylbenzylamine, triethylamine, or trimethylamine.
14. The composition of claim 1 wherein the Bronsted acid comprises pentafluorophenol, 2,6-difluorophenol, or 4-fluorophenol.
15. The composition of claim 1 , wherein the composition is suitable for activating an alkylated transition metal component by protonation.
16. A catalyst composition for olefin polymerization, wherein the catalyst composition is prepared by combining at least a composition according to claim 1 and an alkylated transition metal component.
17. A method of preparing a composition comprising combining at least:
a) a compound derived from at least (i) a carrier having at least one pair of hydrogen bonded hydroxyl groups, (ii) an organoaluminum compound, and (iii) a Lewis base, such that each of a majority of aluminum atoms in the organoaluminum compound forms chemical bonds with at least two oxygen atoms from the at least one pair of hydrogen bonded hydroxyl groups; and
b) a Bronsted acid, wherein the molar ratio of the Bronsted acid to the organoaluminum compound is less than or equal to about 2:1.
18. The method of claim 17 wherein the carrier comprises a plurality of hydroxyl groups and a majority of the hydroxyl groups are in hydrogen bonded form.
19. The method of claim 17 wherein the compound and the Bronsted acid are combined in amounts sufficient and under conditions sufficient such that the composition is suitable for activating alkylated transition metal component by protonation.
20. A method of preparing a catalyst for olefin polymerization, comprising combining an alkylated transition metal component with composition derived from at least a) a compound derived from at least (i) a carrier having at least one pair of hydrogen bonded hydroxyl groups, (ii) an organoaluminum compound, and (iii) a Lewis base, such that each of a majority of aluminum atoms in the organoaluminum compound forms chemical bonds with at least two oxygen atoms from the at least one pair of hydrogen bonded hydroxyl groups; and b) a Bronsted acid, wherein the molar ratio of the Bronsted acid to the omanoaluminum compound is less than or equal to about 2:1.
21. A method of polymerizing monomer comprising carrying out such polymerization in the presence of the catalyst composition according to claim 16 .
22. A method of polymerizing monomer comprising combining a composition according to claim 1 , an alkylated transition metal component, and a monomer.