Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength

A catalyst composition consisting essentially of at least one a first metallocene compound, at least one a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:

• a) the at least one first metallocene compound has the following formula:
• (X1)(X2)(X3)(X4)Zr;
• wherein (X1) and (X2) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• wherein each substituent on (X1) and (X2) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• b) wherein the at least one second metallocene compound has the following formula:
• (X5)(X6)(X7)(X8)M;
• wherein
• 1) M is Zr;
• (X5) and (X6) are independently selected from a substituted cyclopentadienyl, a substituted indenyl, a substituted fluorenyl, or a substituted, partially saturated analog thereof, wherein at least one of (X5) and (X6)is at least disubstituted;
• and
• each substituent on (X5) and (X6) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• 2) M is Zr;
• (X5) and (X6) are independently selected from a cyclopentadienyl, an indenyl, a fluorenyl, a partially saturated analog thereof, or a substituted analog thereof;
• and
• (X5) and (X6) are connected by a substituted or unsubstituted bridging group comprising from 3 to 5 contiguous ansa carbon atoms in a chain, one end of which is bonded to (X5) and the other end of which is bonded to (X6);
• or
• 3) M is Hf;
• (X5) and (X6) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• and
• each substituent on (X5) and (X6) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• and
• wherein (X7), (X8), any substituent on (X5), any substituent on (X6), any substituent on the substituted aliphatic group on (X5) and (X6), and any substituent on the substituted bridging group connecting (X5) and (X6) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• c) the at least one chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion;
• and
• d) the at least one organoaluminum compound has the following formula:
• Al(X9)n(X10)3-n;
• wherein (X9) is a hydrocarbyl having from 1 to about 20 carbon atoms;
• (X10) is selected from alkoxide or aryloxide having from 1 to about 20 carbon atoms, halide, or hydride;
• and n is a number from 1 to 3, inclusive.

A catalyst composition comprising the contact product of at least one first metallocene compound, at least one second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:

• a) the at least one first metallocene compound has the following formula:
• (X1)(X2)(X3)(X4)Zr;
• wherein (X1) and (X2) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• wherein each substituent on (X1) and (X2) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —QAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• b) wherein the at least one second metallocene compound is:
• 1,3-propanediylbis(η5-9-fluorenyl)zirconium dichloride;
• 1,4-butanediylbis(η5-9-fluorenyl)zirconium dichioride;
• 1,5-pentanediylbis(η5-9-fluorenyl)zirconium dichloride;
• 1,3-propanediylbis(η5-1-indenyl)zirconium dichioride;
• 1,4-butanediylbis(η5-1-indenyl)zirconium dichioride;
• 1,5-pentanediylbis(η5-1-indenyl)zirconium dichloride;
• 1,3-propanediylbis(η5-9-fluorenyl)di-n-butoxyzirconium;
• 1,4-butanediylbis(η5-9-fluorenyl)di-n-butoxyzirconium;
• 1,5-pentanediylbis(η5-9-fluorenyl)di-n-butoxyzirconium;
• 1,3-propanediylbis(η5-1-indenyl)di-n-butoxyzirconium;
• 1,4-butanediylbis(η5-1-indenyl)di-n-butoxyzirconium;
• 1,5-pentanediylbis(η5-1-indenyl)di-n-butoxyzirconium;
• 1,3-propanediylbis(η5-9-fluorenyl)zirconium dimethyl;
• 1,4-butanediylbis(η5-9-fluorenyl)zirconium dimethyl;
• 1,5-pentanediylbis(η5-9-fluorenyl)zirconium dimethyl;
• 1,3-propanediylbis(η5-1-indenyl)zirconium dimethyl;
• 1,4-butanediylbis(η5-1-indenyl)zirconium dimethyl;
• 1,5-pentanediylbis(η5-1-indenyl)zirconium dimethyl;
• (η5-C5H3nBuMe)2ZrCl2;
• (η5-C5H4nBu)2HfCl2;
• (η5-C5H4Me) HfCl2;
• (η5-C5H4Et)2HfCl2;
• (η5-C5H4nPr)2HfCl2;
• (η5-C5H4iPr)2HfCl2;
• (η5-C5H4iBu)2HfCl2;
• (η5-C5H4sBu)2HfCl2;
• (η5-C5H4tBu)2HfCl2;
• (η5-C5H4nBu)(η5-C5H4Me)HfCl2;
• or any combination thereof;
• c) the at least one chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion;
• and
• d) the at least one organoaluminum compound has the following formula:
• Al(X9)n(X10)3-n;
• wherein (X9) is a hydrocarbyl having from 1 to about 20 carbon atoms;
• (X10) is selected from alkoxide or aryloxide having from 1 to about 20 carbon atoms, halide, or hydride;
• and n is a number from 1 to 3, inclusive.

A process to produce a catalyst composition comprising contacting at least one a first metallocene compound, at least one a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:

• a) the at least one first metallocene compound has the following formula:
• (X1)(X2)(X3)(X4)Zr;
• wherein (X1) and (X2) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• wherein each substituent on (X1) and (X2) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• b) wherein the at least one second metallocene compound has the following formula:
• (X5)(X6)(X7)(X8)M;
• wherein
• 1) M is Zr;
• (X5) and (X6) are independently selected from a substituted cyclopentadienyl, a substituted indenyl, a substituted fluorenyl, or a substituted, partially saturated analog thereof, wherein at least one of (X5) and (X6) is at least disubstituted;
• and
• each substituent on (X5) and (X6) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• 2) M is Zr;
• (X5) and (X6) are independently selected from a cyclopentadienyl, an indenyl, a fluorenyl, a partially saturated analog thereof, or a substituted analog thereof;
• and
• (X5) and (X6) are connected by a substituted or unsubstituted bridging group comprising from 3 to 5 contiguous ansa carbon atoms in a chain, one end of which is bonded to (X5) and the other end of which is bonded to (X6);
• or
• 3) M is Hf;
• (X5) and (X6) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• and
• each substituent on (X5) and (X6) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• and
• wherein (X7), (X8), any substituent on (X5), any substituent on (X6), any substituent on the substituted aliphatic group on (X5) and (X6), and any substituent on the substituted bridging group connecting (X5) and (X6) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• c) the at least one chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion;
• and
• d) the at least one organoaluminum compound has the following formula:
• Al(X9)n(X10)3-n;
• wherein (X9) is a hydrocarbyl having from 1 to about 20 carbon atoms;
• (X10) is selected from alkoxide or aryloxide having from 1 to about 20 carbon atoms, halide, or hydride;
• and n is a number from 1 to 3, inclusive.

A process for polymerizing olefins in the presence of a catalyst composition, comprising contacting the catalyst composition with at least one type of olefin monomer, wherein the catalyst composition comprises the contact product of at least one first metallocene compound, at least one a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:

• a) the at least one first metallocene compound has the following formula:
• (X1)(X2)(X3)(X4)Zr;
• wherein (X1) and (X2) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• wherein each substituent on (X1) and (X2) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OsiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X2, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• b) wherein the at least one second metallocene compound has the following formula:
• (X5)(X6)(X7)(X8)M;
• wherein
• 1) M is Zr;
• (X5) and (X6) are independently selected from a substituted cyclopentadienyl, a substituted indenyl, a substituted fluorenyl, or a substituted, partially saturated analog thereof, wherein at least one of (X5) and (X6) is at least disubstituted;
• and
• each substituent on (X5) and (X6) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• 2) M is Zr;
• (X5) and (X6) are independently selected from a cyclopentadienyl, an indenyl, a fluorenyl, a partially saturated analog thereof, or a substituted analog thereof;
• and
• (X5) and (X6) are connected by a substituted or unsubstituted bridging group comprising from 3 to 5 contiguous ansa carbon atoms in a chain, one end of which is bonded to (X5) and the other end of which is bonded to (X6);
• or
• 3) M is Hf;
• (X5) and (X6) are independently selected from a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
• and
• each substituent on (X5) and (X6) is independently selected from a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to about 20 carbon atoms;
• and
• wherein (X7), (X8), any substituent on (X5), any substituent on (X6), any substituent on the substituted aliphatic group on (X5) and (X6), and any substituent on the substituted bridging group connecting (X5) and (X6) are independently selected from 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, —SO2X, —OAlX2, —OSiX3, —OPX2, —SX, —OSO2X, —AsX2, —As(O)X3, or —PX2, wherein X is selected independently from halide, H, NH2, OR, or SR, wherein R is a hydrocarbyl, or a substituted derivative thereof, any one of which having from 1 to about 20 carbon atoms;
• a halide;
• or hydrogen;
• c) the at least one chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion;
• and
• d) the at least one organoaluminum compound has the following formula:
• Al(X9)n(X10)3-n;
• wherein (X9) is a hydrocarbyl having from 1 to about 20 carbon atoms;
• (X10) is selected from alkoxide or aryloxide having from 1 to about 20 carbon atoms, halide, or hydride;
• and n is a number from 1 to 3, inclusive.