Aluminoxane catalyst activators containing carbocation agents, and use thereof in polyolefin catalysts
View Patent ↗This invention relates to an activator composition comprising (i) an organoaluminum compounds; (ii) a carbocation compound of the formula R 1 (X) n ; wherein R 1 is a hydrocarbyl; n is from 1 to the number of possible substitutions of the hydrocarbyl group and each X is a labile leaving group; and (iii) an aluminoxane. The activator composition may also contain a carrier support. This invention also provides a catalyst composition comprising the activator composition described above and a transition metal component. This invention also provides methods of polymerizing monomer comprising carrying out such polymerization in the presence of one or more catalyst composition according to this invention.
1. A composition comprising:
(i) a supported aluminoxane intermediate composition prepared by:
a) a support; b) an organoaluminum compound; and c) an oxygen source
(ii) a compound having the formula R 1 (X) n ; wherein R 1 is a hydrocarbyl group having from about 1 to about 20 carbon atoms; n is from 1 to the number of possible substitutions of the hydrocarbyl group and each X are optionally substituted on R 1 and is independently halogen, —OSi(R 2 ) 3 , —N(Si(R 2 ) 3 ) 2 , —N(R 2 ) 2 ; —SR 2 ; —P(R 2 ) 2 ; —CN, or —OR 3 ; wherein each R 2 is independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; each R 3 is independently a hydrocarbyl having from 1 to 20 carbon atoms, wherein when at least one R 2 is a hydrocarbyl group; R 1 and R 2 or R 1 and R 3 are optionally linked together to form a cyclic group; provided that at least one X is not directly bonded to an aryl group, and provided that when X is not halogen, X is bonded to a secondary or tertiary carbon, or a —CH 2 -aryl group; and
(iii) a trihydrocarbylaluminum compound having the formula AlR 3 , wherein each R is independently a C 1 -C 20 hydrocarbyl group.
2. The composition of claim 1 , wherein R is C 1 -C 8 alkyl, R 1 is a C 3 -C 8 alkyl or C 7 -C 15 aralkyl, n is 1 to 3, X is halogen or —OR 2 , and R 2 is a C 1 -C 4 alkyl or C 6 -C 15 aralkyl.
3. The composition of claim 1 , wherein R 1 (X) n is (R 4 ) 3 C—OR 5 or (R 4 ) 3 C—N(R 5 ) 2 ; wherein each R 4 is independently a hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms and at least one R 4 is a hydrocarbyl group; R 5 is a hydrocarbyl group having from about 1 to about 20 carbon atoms; or R 4 and R 5 are optionally linked together to form a cyclic group.
4. The composition of claim 1 , wherein R 1 (X) n is: Me 3 CF, Me 3 SiF, C 6 H 5 CH 2 F, C 6 H 5 CF 3 1,3-C 6 H 4 (CF 3 ) 2 , t Bu-OMe, 1,2-( t BuO) 2 C 6 H 4 ; 1,3-( t BuO) 2 C 6 H 4; 1,4-( t BuO) 2 C 6 H 4 ; t BuO—CH 2 —CH 2 —O t Bu; 1-methyl-tetrahydrofuran, 1,2-dimethyl-tetrahydrofuran or mixtures thereof, wherein C 6 H 4 is a phenylene group and t Bu is a tertiary-butyl group.
5. The composition of claim 1 , wherein R 1 (X) n is, tertiary-butyl methyl ether, tertiary-butyl ethyl ether, tertiary-butyl propyl ether, tertiary-butyl butyl ether, 1-tert-butoxy-2,6-di-tert-butylbenzene, 1-trimethylsiloxy-2,6-di-tert-butylbenzene, trimethylsiloxybenzene, trimethylmethoxysilane, benzylmethyl ether, benzyl ethyl ether, benzylpropyl ether, benzyl butyl ether or mixtures thereof.
6. The composition of claim 1 , wherein R 1 (X) n is ethylene oxide, propylene oxide, isobutene oxide, 1-butene oxide, styrene oxide, 4-methyl-styrene oxide, 2,2-dimethyl-trimethylene oxide, 2,2-diphenyl-trimethylene oxide, 1-methyl-ethyleneimine, 1,1,2-trimethylethylenimine, 1,1-diphenyl-2-methyl-ethylenimine, 1-methyl-tetrahydro-pyrrole, 1,1,2-trimethyl-tetrahydro-pyrrole, 1,1-diphenyl-2-methyl-tetrahydro-pyrrole, 1-methyl-piperidine, 1,1,2-trimethyl-piperidine, 1,1-diphenyl-2-methyl-piperidine, or mixtures thereof.
7. The composition of claim 1 , wherein the aluminoxane on a support comprises methylaluminoxane, neopentylaluminoxane, benzylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane.
8. The composition of claim 1 , wherein the trihydrocarbylaluminum compound is trimethylaluminum, trineopentylaluminum, tribenzylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, tri-n-octylaluminum or mixtures thereof.
9. The composition of claim 1 , wherein the support is silica, alumina, silica-alumina, clay, a modified clay composition, or any combination thereof.
10. The composition of claim 1 , wherein the mole ratio of the compound of formula R 1 (X) n to the trihydrocarbylaluminum compound is about 0.01:1 to 2:1 and the mole ratio of X in the compound of formula R 1 (X) n to Al in the supported aluminoxane is about 0.01:1 to 0.8:1.
11. The composition of claim 1 , further comprising a transition metal component.
12. A composition comprising:
(i) a trihydrocarbylaluminum compound having the formula AlR 3 , wherein each R is independently a C 1 -C 20 alkyl;
(ii) a compound having the formula R 1 (X) n ; wherein R 1 is a hydrocarbyl group having from about 3 to about 20 carbon atoms; n is from 1 to the number of possible substitutions of the hydrocarbyl group and each X are optionally substituted on R 1 and is independently, —OSi(R 2 ) 3 , —N(Si(R 2 ) 3 ) 2 , —N(R 2 ) 2 ; —SR 2 ; —P(R 2 ) 2 ; —CN, or —OR 3 ; wherein each R 2 is independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms;
each R 3 is independently a hydrocarbyl having from 1 to 20 carbon atoms, wherein when at least one R 2 is a hydrocarbyl group; R 1 and R 2 or R 1 and R 3 are optionally linked together to form a cyclic group; provided that at least one X is not directly bonded to an aryl group, and provided that X is bonded to a secondary or tertiary carbon, or a —CH 2 -aryl group; and
(iii) an aluminoxane.
13. The composition of claim 12 , wherein R is C 1 -C 8 alkyl, R 1 is a C 3 -C 8 alkyl or C 7 -C 15 aralkyl, n is 1 to 3, X is —OR 2 , and R 2 is a C 1 -C 4 alkyl or C 6 -C 15 aralkyl.
14. The composition of claim 12 , wherein R 1 (X) n is (R 4 ) 3 C—OR 5 or (R 4 ) 3 C—N(R 5 ) 2 ; wherein each R 4 is independently a hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms and at least one R 4 is a hydrocarbyl group; R 5 is a hydrocarbyl group having from about 1 to about 20 carbon atoms; or R 4 and R 5 may be linked together to form a cyclic group.
15. The composition of claim 12 , wherein R 1 (X) n is t Bu-OMe, 1,2-( t BuO) 2 C 6 H 4 ; 1,3-( t BuO) 2 C 6 H 4; 1,4-( t BuO) 2 C 6 H 4 ; t BuO—CH 2 —CH 2 —O t Bu; 1-methyl-tetrahydrofuran, 1,2-dimethyl-tetrahydrofuran or mixtures thereof, wherein C 6 H 4 is a phenylene group and t Bu is a tertiary-butyl group.
16. The composition of claim 12 , wherein the mole ratio of the compound of formula R 1 (X) n to the trihydrocarbylaluminum compound is about 0.01:1 to 0.1:1 and the mole ratio of X in the compound of formula R 1 (X) n to Al in the non-supported solution aluminoxane is about 0.01:1 to 0.8:1.
17. The composition of claim 12 , further comprising a carrier.
18. The composition of claim 12 , further comprising a transition metal component.