Dual metallocene catalysts for polymerization of bimodal polymers
First Claim
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1. A composition comprising a contact product of:
- 1) at least one first metallocene;
2) at least one second metallocene; and
3) at least one activator-support, wherein;
a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-A),
whereinM1 is titanium, zirconium, or hafnium;
(X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;
one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group;
at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;
(X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and
any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-A),
whereinM2 is titanium, zirconium, or hafnium;
(X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;
(X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB, wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and
any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-A),
whereinM3 is titanium, zirconium, or hafnium;
(X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;
(X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;
(X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and
any additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
oriii) any combination thereof;
andc) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.
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Abstract
This invention relates to catalyst compositions, methods, and polymers encompassing at least one first Group 4 metallocene compound comprising bridging η5-cyclopentadienyl-type ligands, in combination with at least one second Group 4 metallocene with non-bridging η5-cyclopentadienyl-type ligands, typically in combination with at least one cocatalyst, and at least one activator. The compositions and methods disclosed herein provide ethylene polymers with a bimodal molecular weight distribution.
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Citations
37 Claims
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1. A composition comprising a contact product of:
- 1) at least one first metallocene;
2) at least one second metallocene; and
3) at least one activator-support, wherein;a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-A),
whereinM1 is titanium, zirconium, or hafnium; (X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group; at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-A),
whereinM2 is titanium, zirconium, or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB, wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-A),
whereinM3 is titanium, zirconium, or hafnium; (X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;or iii) any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 33, 34, 35, 36, 37)
wherein M2 is zirconium or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH4, F, Cl, Br, or I; and any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, any of which having from 1 to 20 carbon atoms.
- 1) at least one first metallocene;
-
3. A composition according to claim 1, wherein the metallocene (X9)(X10)(X11)(X12)M3 (M3-A) has the formula:
-
(X9)(X10)(X11)(X12)M3
(M3-B),wherein M3 is zirconium or hafnium; (X9) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having up to 12 carbon atoms; (X10) is a substituted indenyl group, wherein any substituent is independently an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 20 carbon atoms; and (X11) and (X12) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH4, F, Cl, Br, or I.
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4. A composition according to claim 1, wherein the at least one second metallocene comprises an unbridged metallocene having the formula:
-
i) (X5)(X6)(X7)(X8)M2
(M2-B),wherein M2 is zirconium or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH4, F, Cl, Br, or I; and any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, any of which having up from 1 to 20 carbon atoms;
ii) (X9)(X10)(X11)(X12)M3
(M3-B),
whereinM3 is zirconium or hafnium; (X9) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having up from 1 to 12 carbon atoms; (X10) is a substituted indenyl group, wherein any substituent is independently an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 20 carbon atoms; and (X11) and (X12) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH4, F, Cl, Br, or I; or iii) any combination thereof.
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5. A composition according to claim 1, wherein the at least one first metallocene comprises a compound having the formula:
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6. A composition according to claim 1, wherein the at least one second metallocene comprises a compound having the formula:
i)
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7. A composition according to claim 1, wherein the at least one activator-support is a solid oxide treated with an electron-withdrawing anion, wherein:
-
the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluoro silicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, or any combination thereof.
-
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8. A composition according to claim 1, wherein the solid oxide treated with an electron withdrawing anion further comprises a metal or metal ion selected from zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.
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9. A composition according to claim 1, wherein the at least one first metallocene comprises a compound having the formula:
-
10. A composition according to claim 1, wherein the at least one first metallocene is selected from
-
11. A composition according to claim 1, wherein the at least one second metallocene comprises a compound having the formula:
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12. A composition according to claim 1, wherein the at least one second metallocene comprises a compound having the formula:
-
13. A composition according to claim 1, wherein the at least one second metallocene comprises a compound having the formula:
-
14. A composition according to claim 1, wherein the at least one second metallocene is selected from
-
15. A composition according to claim 1, wherein:
a) the at least one first metallocene comprises a compound having the formula;
-
16. A composition according to claim 1, wherein a molar ratio of the at least one first metallocene to the at least one second metallocene in the composition is from about 1:
- 10 to about 10;
1.
- 10 to about 10;
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17. A composition according to claim 1, wherein the at least one activator-support is selected from chlorided alumina, fluorided alumina, fluorided aluminophosphate, sulfated alumina, fluorided silica-alumina, or any combination thereof.
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18. A composition according to claim 1, wherein the contact product further comprises:
- 4) at least one organoaluminum compound having the formula;
Al(X13)n(X14)3-n,wherein (X13) is a hydrocarbyl having from 1 to 20 carbon atoms;
(X14) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and
n is a number from 1 to 3, inclusive.
- 4) at least one organoaluminum compound having the formula;
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19. A composition according to claim 18, wherein the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.
-
20. A composition according to claim 18, wherein:
a) the at least one first metallocene comprises a compound having the formula;
-
21. A composition according to claim 18, wherein:
a) the at least one first metallocene comprises
-
22. A composition according to claim 18, wherein:
a) the at least one first metallocene is selected from
-
23. A composition according to claim 1, wherein the contact product further comprises:
- 5) an ionizing ionic compound selected from tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)-ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethyl-phenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, triphenylcarbenium tetrakis(p-tolyl)aluminate, triphenylcarbenium tetrakis(m-tolyl)aluminate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, tropylium tetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate, tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropylium tetrakis(3,5-dimethylphenyl)aluminate, tropylium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)-aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis (3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, triphenylcarbenium tris(2,2′
,2″
-nonafluorobiphenyl)fluoroaluminate, silver tetrakis(1,1,1,3,3,3-hexafluoroisopropanolato)-aluminate, or silver tetrakis(perfluoro-t-butoxy)aluminate, or any combination thereof.
- 5) an ionizing ionic compound selected from tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)-ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl) borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethyl-phenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, triphenylcarbenium tetrakis(p-tolyl)aluminate, triphenylcarbenium tetrakis(m-tolyl)aluminate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, tropylium tetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate, tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropylium tetrakis(3,5-dimethylphenyl)aluminate, tropylium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)-aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis (3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, triphenylcarbenium tris(2,2′
-
33. A composition according to claim 18, wherein:
a) the at least one first metallocene comprises a compound having the formula;
-
34. A composition according to claim 18, wherein:
a) the at least one first metallocene comprises a compound having the formula;
-
35. A composition according to claim 18, wherein the contact product further comprises at least one organoaluminoxane compound, at least one organoboron or organoborate compound, or a combination thereof.
-
36. A composition according to claim 18, wherein the at least one first metallocene comprises a compound having the formula:
-
37. A composition according to claim 1, wherein the at least one first metallocene comprises a compound having the formula:
-
24. A catalyst composition comprising a contact product of:
- 1) at least one first metallocene;
2) at least one second metallocene;
3) optionally, at least one organoaluminum compound; and
4) at least one activator-support, wherein;a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-A),
whereinM1 is titanium, zirconium, or hafnium; (X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group; at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-A),
whereinM2 is titanium, zirconium, or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB, wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-A),
whereinM3 is titanium, zirconium, or hafnium; (X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;or iii) any combination thereof; c) the at least one organo aluminum compound comprises a compound having the formula;
Al(X13)n(X14)3-n,wherein (X13) is a hydrocarbyl having from 1 to 20 carbon atoms;
(X14) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and
n is a number from 1 to 3, inclusive; andd) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion; wherein the at least one organoaluminum compound is optional when at least one of the following conditions exist; 1) a) at least one of (X3) and (X4) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
b) at least one of (X7) and (X8) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; and
c) at least one of (X11) and (X12) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;2) the catalyst composition comprises at least one organoaluminoxane compound;
or3) both conditions 1 and 2 exist.
- 1) at least one first metallocene;
-
25. A catalyst composition comprising a contact product of:
- 1) at least one first metallocene;
2) at least one second metallocene; and
3) at least one activator-support, wherein;a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-B),
whereinM1 is titanium, zirconium, or hafnium; (X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group; at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
wherein at least one of (X3) and (X4) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; andany additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-C),
whereinM2 is titanium, zirconium, or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB, wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
wherein at least one of (X7) and (X8) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; andany substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-C),
whereinM3 is titanium, zirconium, or hafnium; (X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
wherein at least one of (X11) and (X12) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; andany additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;or iii) any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion. - View Dependent Claims (26, 27, 28, 29)
- 1) at least one first metallocene;
-
30. A process for producing a composition comprising contacting:
- 1) at least one first metallocene;
2) at least one second metallocene; and
3) at least one activator-support, wherein;a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-A),
whereinM1 is titanium, zirconium, or hafnium; (X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group; at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-A),
whereinM2 is titanium, zirconium, or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-A),
whereinM3 is titanium, zirconium, or hafnium; (X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;or iii) any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.
- 1) at least one first metallocene;
-
31. A process for producing a polymerization catalyst composition comprising contacting:
- 1) at least one first metallocene;
2) at least one second metallocene;
3) optionally, at least one organoaluminum compound; and
4) at least one activator-support, wherein;a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-A),
whereinM1 is titanium, zirconium, or hafnium; (X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group; at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-A),
whereinM2 is titanium, zirconium, or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-A),
whereinM3 is titanium, zirconium, or hafnium; (X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; andany additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;or iii) any combination thereof; c) the at least one organoaluminum compound comprises a compound having the formula;
Al(X13)n(X14)3-n,wherein (X13) is a hydrocarbyl having from 1 to 20 carbon atoms;
(X14) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and
n is a number from 1 to 3, inclusive; andd) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion; wherein the at least one organoaluminum compound is optional when at least one of the following conditions exist; 1) a) at least one of (X3) and (X4) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
b) at least one of (X7) and (X8) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; and
c) at least one of (X11) and (X12) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;2) the catalyst composition comprises at least one organoaluminoxane compound;
or3) both conditions 1 and 2 exist.
- 1) at least one first metallocene;
-
32. A process for producing a polymerization catalyst composition comprising contacting:
- 1) at least one first metallocene;
2) at least one second metallocene; and
3) at least one activator-support, wherein;a) the at least one first metallocene comprises an ansa-metallocene having the formula;
(X1)(X2)(X3)(X4)M1
(M1-B),
whereinM1 is titanium, zirconium, or hafnium; (X1) and (X2) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X1) and (X2) is a bridging group having the formula ER1R2, wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X1) and (X2), and wherein R1 and R2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R1 and R2 is an aryl group; at least one substituent on (X1) or (X2) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X3) and (X4) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRA2 or SO3RA, wherein RA is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
wherein at least one of (X3) and (X4) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; andany additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;b) the at least one second metallocene comprises an unbridged metallocene having the formula;
i) (X5)(X6)(X7)(X8)M2
(M2-C),
whereinM2 is titanium, zirconium, or hafnium; (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl; (X7) and (X8) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRB2 or SO3RB, wherein RB is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
wherein at least one of (X7) and (X8) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; andany substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;
ii) (X9)(X10)(X11)(X12)M3
(M3-C),
whereinM3 is titanium, zirconium, or hafnium; (X9) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X10) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms; (X11) and (X12) are independently;
1) F, Cl, Br, or I;
2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH4;
3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;
or
4) OBRC2 or SO3RC, wherein RC is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
wherein at least one of (X11) and (X12) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH4; andany additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;
a halide;
or hydrogen;or iii) any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion.
- 1) at least one first metallocene;
Specification