Dual metallocene catalysts for polymerization of bimodal polymers

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, wherein:
• a) the at least one first metallocene comprises an ansa-metallocene having the formula:
• (X1)(X2)(X3)(X4)M1 (M1-B), wherein
• M1 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;
• 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-C), wherein
• M2 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;
• 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-C), wherein
• M3 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;
• 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;
• or
• iii) any combination thereof;
• and
• c) the at least one activator comprises an organoaluminoxane compound, an organoboron or organoborate compound, or any combination thereof.

A catalyst composition comprising a contact product of:

• 1) at least one first metallocene;
• 2) at least one second metallocene;
• 3) at least one organoaluminum compound;
• and 4) 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), wherein
• M1 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;
• 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), wherein
• M2 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), wherein
• M3 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;
• 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;
• and
• d) the at least one activator comprises an organoaluminoxane compound, an organoboron compound or organoborate compound, or any combination thereof.