초록 ▼

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, ty

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.

대표청구항 ▼

1. A method of polymerizing olefins, comprising: contacting an olefin monomer and an optional α-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer;wherein the catalyst composition comprises a contact product of: a) at least one first metalloce

1. A method of polymerizing olefins, comprising: contacting an olefin monomer and an optional α-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer;wherein the catalyst composition comprises a contact product of: a) at least one first metallocene; b) at least one second metallocene; c) optionally, at least one organoaluminum compound; and d) at least one activator, 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) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;at least one substituent on (X2) is 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; or a halide;(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 trialkylaluminum compound, a dialkylaluminum halide compound, a dialkylaluminum alkoxide compound, a dialkylaluminum hydride compound, or any combination thereof; andd) the at least one activator comprises an organoaluminoxane compound, an organoboron or organoborate compound, or any combination thereof;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. 2. The method of claim 1, wherein the at least one first metallocene comprises a compound having the formula: M1A is titanium, zirconium, or hafnium;X3A and X4A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;EA is C or Si;R1A and R2A 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 R1A and R2A is an aryl group;R3A and R4A are independently H or CH3;n is an integer from 0 to 5, inclusive; andR5A and R6A are 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 12 carbon atoms. 3. The method of claim 1, wherein the at least one first metallocene is: or any combination thereof. 4. The method of claim 1, wherein the at least one second metallocene comprises an unbridged metallocene having the formula: i) (X5)(X6)(X7)(X8)M2  (M2-B), whereinM2 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; 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, any of which having 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 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. 5. The method of claim 1, wherein the at least one second metallocene comprises a compound having the formula: i)  or any combination thereof, wherein M2A is, independently, zirconium or hafnium;X7A and X8A, in each occurrence, are independently F, Cl, Br, I, benzyl, phenyl, or methyl; andR7A and R8A, in each occurrence, are independently H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH2CH2CH2Ph, CH2CH═CH2, CH2CH2CH═CH2, or CH2CH2CH2CH═CH2;ii) M3A is zirconium or hafnium;R9A is H or CH3;R10A is H, CH2CH═CH2, CH2CH2CH═CH2, CH2CH2CH2CH═CH2, CH2CH2CH2Ph, or CH2CH2CH2CH3; andX11A and X12A are independently F, Cl, Br, I, benzyl, phenyl, or methyl; or iii) any combination thereof. 6. The method of claim 1, wherein the at least one second metallocene comprises a compound having the formula: or any combination thereof. 7. The method of claim 1, wherein the at least one second metallocene is: or any combination thereof. 8. The method of claim 1, 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. 9. The method of claim 1, wherein the at least one activator comprises an organoaluminoxane compound. 10. The method of claim 1, wherein the at least one activator comprises an organoboron compound, an organoborate compound, or a combination thereof. 11. The method of claim 1, wherein: a) the at least one first metallocene comprises a compound having the formula: M1B is zirconium or hafnium;R2B is methyl or phenyl;R3B and R4B are independently H or CH3; andn is an integer from 0 to 5, inclusive;b) the at least one second metallocene comprises a compound having the formula: i) M2C is zirconium or hafnium; andX7C and X8C are independently benzyl, Cl, or methyl;ii) M3B is zirconium or hafnium;R9B is H or CH3; andR10B is H, CH2CH═CH2, CH2CH2CH═CH2, CH2CH2CH2Ph, or CH2CH2CH2CH3;or iii) any combination thereof. 12. The method of claim 1, wherein: a) the at least one first metallocene comprises a compound having the formula: M1A is zirconium or hafnium;X3A and X4A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;EA is C or Si;R1A and R2A 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 R1A and R2A is an aryl group;R3A and R4A are independently H or CH3;n is an integer from 0 to 5, inclusive; andR5A and R6A are 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 12 carbon atoms;b) the at least one second metallocene comprises a compound having the formula: i)  or any combination thereof, wherein M2A is, independently, zirconium or hafnium;X7A and X8A, in each occurrence, are independently F, Cl, Br, I, benzyl, phenyl, or methyl; andR7A and R8A, in each occurrence, are independently H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH2CH2CH2Ph, CH2CH═CH2, CH2CH2CH═CH2, or CH2CH2CH2CH═CH2;ii) M3A is zirconium or hafnium;R9A is H or CH3;R10A is H, CH2CH═CH2, CH2CH2CH═CH2, CH2CH2CH2CH═CH2, CH2CH2CH2Ph, or CH2CH2CH2CH3; andX11A and X12A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;Or iii) any combination thereof;c) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; andd) the organoaluminoxane compound comprises methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or any combination thereof; andthe organoboron or organoborate compound comprises tris(pentafluorophenyl)boron, tris [3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)-borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis [3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or any combination thereof. 13. The method of claim 1, wherein: a) the at least one first metallocene comprises:  or any combination thereof;b) the at least one second metallocene comprises:  or any combination thereof;c) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; andd) the at least one activator comprises an organoaluminoxane compound. 14. The method of claim 1, wherein: a) the at least one first metallocene is:  or any combination thereof;b) the at least one second metallocene is:  or any combination thereof;c) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; andd) the at least one activator comprises an organoboron compound, an organoborate compound, or a combination thereof. 15. The method of claim 1, wherein: a) the at least one first metallocene comprises a compound having the formula: M1B is zirconium or hafnium;R2B is methyl or phenyl;R3B and R4B are independently H or CH3; andn is an integer from 0 to 5, inclusive;b) the at least one second metallocene comprises a compound having the formula:  or any combination thereof, wherein M2B is zirconium or hafnium;X7B and X8B are independently benzyl, Cl, or methyl; andR7B and R8B are independently H, methyl, ethyl, n-propyl, n-butyl, CH2CH═CH2, CH2CH2CH═CH2, or CH2CH2CH2CH═CH2; andd) the organoaluminoxane compound comprises methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or any combination thereof; andthe organoboron or organoborate compound comprises tris(pentafluorophenyl)boron, tris [3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)-borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis [3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or any combination thereof. 16. The method of claim 1, wherein: a) the at least one first metallocene comprises a compound having the formula: M1B is zirconium or hafnium;R2B is methyl or phenyl;R3B and R4B are independently H or CH3; andn is an integer from 0 to 5, inclusive;b) the at least one second metallocene comprises a compound having the formula: M3B is zirconium or hafnium;R9B is H or CH3; andR10B is H, CH2CH═CH2, CH2CH2CH═CH2, CH2CH2CH2Ph, or CH2CH2CH2CH3; andd) the organoaluminoxane compound comprises methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or any combination thereof; andthe organoboron or organoborate compound comprises tris(pentafluorophenyl)boron, tris [3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)-borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis [3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or any combination thereof. 17. The method of claim 1, wherein the at least one first metallocene comprises a compound having the formula: M1A is titanium, zirconium, or hafnium;X3A and X4A are independently Cl or Ph;EA is C or Si;R1A and R2A are Ph;R3A and R4A are independently H or CH3;n is an integer from 0 to 5, inclusive; andR5A and R6A are t-Bu. 18. The method of claim 1, wherein the olefin monomer is ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, a normal octene, a normal nonene, a normal decene, or a combination thereof. 19. The method of claim 1, wherein the olefin monomer is ethylene and the optional α-olefin comonomer is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or 1-decene. 20. The method of claim 1, wherein the method is conducted in a slurry reactor, a gas phase reactor, a solution reactor, a high pressure tubular reactor, a high pressure autoclave reactor, or a combination thereof. 21. A method of polymerizing olefins, comprising: contacting an olefin monomer and an optional α-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer;wherein the catalyst composition comprises a contact product of: a) at least one first metallocene; b) at least one second metallocene; and c) at least one activator, 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) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;at least one substituent on (X2) is 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; or a halide;(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; andc) the at least one activator comprises an organoaluminoxane compound, an organoboron or organoborate compound, or any combination thereof. 22. The method of claim 21, wherein: the organoaluminoxane compound comprises methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or any combination thereof; andthe organoboron or organoborate compound comprises tris(pentafluorophenyl)boron, tris [3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)-borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis [3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or any combination thereof. 23. The method of claim 21, wherein the olefin monomer is ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, a normal octene, a normal nonene, a normal decene, or a combination thereof. 24. The method of claim 21, wherein the olefin monomer is ethylene and the optional α-olefin comonomer is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or 1-decene. 25. The method of claim 21, wherein the method is conducted in a slurry reactor, a gas phase reactor, a solution reactor, a high pressure tubular reactor, a high pressure autoclave reactor, or a combination thereof. 26. A method of polymerizing olefins, comprising: contacting an olefin monomer and an optional α-olefin comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer;wherein the catalyst composition comprises a contact product of: a) at least one first metallocene; b) at least one second metallocene; c) at least one organoaluminum compound; and d) at least one activator, 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) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;at least one substituent on (X2) is 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; or a halide;(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)m(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 comprises an organoaluminoxane compound, an organoboron compound or organoborate compound, or any combination thereof. 27. The method of claim 26, wherein: a) the at least one first metallocene comprises a compound having the formula: M1A is zirconium or hafnium;X3A and X4A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;EA is C or Si;R1A and R2A 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 R1A and R2A is an aryl group;R3A and R4A are independently H or CH3;n in formula (IA) is an integer from 0 to 5, inclusive; andR5A and R6A are 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 12 carbon atoms;b) the at least one second metallocene comprises a compound having the formula: i)  or any combination thereof, wherein M2A is, independently, zirconium or hafnium;X7A and X8A, in each occurrence, are independently F, Cl, Br, I, benzyl, phenyl, or methyl; andR7A and R8A, in each occurrence, are independently H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, CH2CH2CH2Ph, CH2CH═CH2, CH2CH2CH═CH2, or CH2CH2CH2CH═CH2;ii) M3A is zirconium or hafnium;R9A is H or CH3;R10A is H, CH2CH═CH2, CH2CH2CH═CH2, CH2CH2CH2CH═CH2, CH2CH2CH2Ph, or CH2CH2CH2CH3; andX11A and X12A are independently F, Cl, Br, I, benzyl, phenyl, or methyl;or iii) any combination thereof;c) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; andd) the organoboron or organoborate compound comprises tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis [3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or any combination thereof; and the organoaluminoxane compound comprises: i) a cyclic aluminoxane having the formula: wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 3 to about 10; ii) a linear aluminoxane having the formula: wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 1 to about 50; iii) a cage aluminoxane having the formula Rt5m+αRbm−αAl4mO3m, wherein m is 3 or 4 and α is =nAl(3)−nO(2)+nO(4); wherein nAl(3) is the number of three coordinate aluminum atoms, nO(2) is the number of two coordinate oxygen atoms, nO(4) is the number of 4 coordinate oxygen atoms, Rt represents a terminal alkyl group, and Rb represents a bridging alkyl group; wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms; oriv) any combination thereof. 28. The method of claim 26, wherein the olefin monomer is ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, a normal octene, a normal nonene, a normal decene, or a combination thereof. 29. The method of claim 26, wherein the olefin monomer is ethylene and the optional α-olefin comonomer is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or 1-decene. 30. The method of claim 26, wherein the method is conducted in a slurry reactor, a gas phase reactor, a solution reactor, a high pressure tubular reactor, a high pressure autoclave reactor, or a combination thereof