CA2553993A1 - Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength - Google Patents

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

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CA2553993A1
CA2553993A1 CA002553993A CA2553993A CA2553993A1 CA 2553993 A1 CA2553993 A1 CA 2553993A1 CA 002553993 A CA002553993 A CA 002553993A CA 2553993 A CA2553993 A CA 2553993A CA 2553993 A1 CA2553993 A1 CA 2553993A1
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substituted
tetrakis
independently
carbon atoms
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CA2553993C (en
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Michael D. Jensen
Joel L. Martin
Max P. Mcdaniel
Qing Yang
Matthew G. Thorn
Elizabeth A. Benham
Ted H. Cymbaluk
Ashish M. Sukhadia
Rajendra K. Krishnaswamy
Mark E. Kertok
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Chevron Phillips Chemical Co LP
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Chevron Phillips Chemical Company Lp
Michael D. Jensen
Joel L. Martin
Max P. Mcdaniel
Qing Yang
Matthew G. Thorn
Elizabeth A. Benham
Ted H. Cymbaluk
Ashish M. Sukhadia
Rajendra K. Krishnaswamy
Mark E. Kertok
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Priority to CA2736014A priority Critical patent/CA2736014C/en
Publication of CA2553993A1 publication Critical patent/CA2553993A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/07—Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/941—Synthetic resins or natural rubbers -- part of the class 520 series having the transition metal bonded directly to carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

This invention relates to catalyst compositions comprising a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound. This invention also relates to methods to prepare and use the catalyst compositions and new polyolefins.
The compositions and methods disclosed herein provide ethylene polymers and copolymers with lower MI, increased melt strength, and good MD tear properties.

Claims (41)

1. A catalyst composition comprising a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:
a) the first metallocene compound has the following formula:

(X1)(X2)(X3)(X4)Zr;

wherein (X1) and (X2) axe independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, ally one of which having from 1 to 20 carbon atoms;
wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
b) wherein the second metallocene compound has the following formula:

(X5)(X6)(X7)(X8)M; wherein 1) M is Zr;
(X5) and (X6) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
2) M is Zr;
(X5) and (X6) are independently a cyclopentadienyl, an indenyl, a fluoroenyl, 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 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 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 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, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
c) the chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion; and d) the organoaluminum compound has the following formula:
Al(X9)n(X10)3-n;
wherein (X9) is a hydrocarbyl having from 1 to 20 carbon atoms; (X10) is an alkoxide or aryloxide having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.
2. The catalyst composition of Claim 1, wherein the second metallocene compound has the following formula:
(X5)(X6)(X7)(X8)Zr;
wherein (X5) and (X6) are independently 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;

wherein each substituent on (X5) and (X6) is independently a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
wherein (X7), (X8), and any substituent on the substituted aliphatic group on (X5) and (X6) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen.
3. The catalyst composition of Claim 2, wherein both (X5) and (X6) are at least disubstituted.
4. The catalyst composition of Claim 2, wherein:
a) the first metallocene compound has the formula (.eta.5-C5H4R1)2ZrX11 2, wherein R1 in each instance is independently a linear or branched aliphatic group having from 1 to 20 carbon atoms, and wherein X11 in each instance is independently F, Cl, Br, I, OMe, OEt, O-n-Pr, O-i-Pr, O-n-Bu, O-t-Bu, NMe2, or NEt2;
b) the second metallocene compound has the formula (.eta.5-C5H3R1 2)2ZrX11 2, wherein R1 in each instance is independently a linear or branched aliphatic group having from 1 to 20 carbon atoms, and X11 in each instance is independently F, Cl, Br, I, OMe, OEt, O-n-Pr, O-i-Pr, O-n-Bu, O-t-Bu, NMe2, or NEt2;
c) the chemically-treated solid oxide is fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, or any combination thereof; and d) the organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, disobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.
5. The catalyst composition of Claim 2, wherein:
a) the first metallocene compound has the formula (.eta.5-C5H4 11Bu)2ZrCl2;
b) the second metallocene compound has the formula (.eta.5-C5H3 11BuR2)2ZrCl2, wherein R2 is Me, Et, n-Pr, I-Pr, n-Bu, s-Bu, i-Bu, or t-Bu;

c) the chemically treated solid oxide is fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, or any combination thereof; and d) the organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, disobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.
6. The catalyst composition of Claim 2, wherein:
a) the first metallocene compound has the formula (.eta.5-C5H4n Bu)2ZrCl2;
b) the second metallocene compound has the formula (.eta.5-C5H3n BuMe)2ZrCl2;
c) the chemically-treated solid oxide is fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, or any combination thereof; and d) the organoaluminum compound is triethylaluminum or triisobutylaluminum.
7. The catalyst composition of Claim 1, wherein the second metallocene compound is an ansa-metallocene having the following formula:
(X5)(X6)(X7)(X8)Zr;
wherein (X5) and (X6) are independently a cyclopentadienyl, an indenyl, a fluorenyl, a partially saturated analog thereof, or a substituted analog thereof; wherein (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);
wherein (X7), (X8), any substituent on the substituted bridging group connecting (X5) and (X6), any substituent on (X5), and any substituent on (X6) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen.
8. The catalyst composition of Claim 7, wherein a) the first metallocene compound has the formula (.eta.5-C5H4R1)2ZrCl2, wherein R1 in each instance is independently a linear or branched aliphatic group having from 1 to 20 carbon atoms;

b) the second metallocene compound is [µ-CH2(CH2)n CH2](.eta.5-9-C13H8)2ZrX12 2, [µ-CH2(CH2)n CH2](.eta.5-9-C13H16)2ZrX12, [µ-CH2(CH2)n CH2](.eta.5-1-C9H6)2ZrX12 2, [µ-CH2(CH2)n CH2](.eta.5-1-C9H10)2ZrX12 2, or any combination thereof, wherein n is from 1 to 3, and wherein X12, in each occurrence, is independently an aliphatic group, an aromatic group, an alkoxide group, an aryloxide group, an alkylamide group, an arylamide group, a dialkylamide group, a diarylamide group, an alkyl arylamide group, an alkylthiolate group, an arylthiolate group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
c) the chemically-treated solid oxide is fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, or any combination thereof; and d) the organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, disobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.
9. The catalyst composition of Claim 8, wherein X12 is independently F, Cl, Br, I, OMe, OEt, O-n-Pr, O-i-Pr, O-n-Bu, O-t-Bu, NMe2, or NEt2.
10. The catalyst composition of Claim 7, wherein:
a) the first metallocene compound has the following formula (.eta.5-C5H4R1)2ZrCl2, wherein R1 in each instance is independently a linear or branched aliphatic having from 1 to 20 carbon atoms; and b) the second metallocene compound is:
1,3-propanediylbis(.eta.5-9-fluorenyl)zirconium dichloride;
1,4-butanediylbis(.eta.5-9-fluorenyl)zirconium dichloride;
1,5-pentanediylbis(.eta.5-9-fluorenyl)zirconium dichloride;
1,3-propanediylbis(.eta.5-1-indenyl)zirconium dichloride;
1,4-butanediylbis(.eta.5-1-indenyl)zirconium dichloride;
1,5-pentanediylbis(.eta.5-1-indenyl)zirconium dichloride;
1,3-propanediylbis(.eta.5-9-fluorenyl)di-n-butoxyzirconium;
1,4-butanediylbis(.eta.5-9-fluorenyl)di-n-butoxyzirconium;
1,5-pentanediylbis(.eta.5-9-fluorenyl)di-n-butoxyzirconium;

1,3-propanediylbis(.eta.-1-indenyl)di-n-butoxyzirconium;
1,4-butanediylbis(.eta.5-1-indenyl)di-n-butoxyzirconium;
1,5-pentanediylbis(.eta.5-1-indenyl)di-n-butoxyzirconium;
1,3-propanediylbis(.eta.5-9-fluorenyl)zirconium dimethyl;
1,4-butanediylbis(.eta.5-9-fluorenyl)zirconium dimethyl;
1,5-pentanediylbis(.eta.5-9-fluorenyl)zirconium dimethyl;
1,3-propanediylbis(.eta.5-1-indenyl)zirconium dimethyl;
1,4-butanediylbis(.eta.5-1-indenyl)zirconium dimethyl;
1,5-pentanediylbis(.eta.5-1-indenyl)zirconium dimethyl;
or any combination thereof;
c) the chemically-treated solid oxide is fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, or any combination thereof; and d) the organoaluminum compound is triethylaluminum or triisobutylaluminum.
11. The catalyst composition of Claim 1, wherein the second metallocene compound has the following formula:
(X5)(X6)(X7)(X8)Hf;
wherein (X5) and (X6) are independently a monosubstituted cyclopentadienyl, a monosubstituted indenyl, a monosubstituted fluorenyl, or a monosubstituted, partially saturated analog thereof;
wherein each substituent on (X5) and (X6) is independently a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
wherein (X7), (X8), and any substituent on the substituted aliphatic group on (X5) and (X6) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen.
12. The catalyst composition of Claim 11, wherein:
a) the first metallocene compound has the following formula (.eta.5-C5H4R1)2ZrX11 2, wherein R1 in each instance is independently a linear or branched aliphatic group having from 1 to 20 carbon atoms, and X is independently F, Cl, Br, I, OMe, OEt, O-n-Pr, O-i-Pr, O-n-Bu, O-t-Bu, NMe2, or NEt2;
b) the second metallocene compound has the following formula (.eta.5-C5H4R1)2HfX11 2, wherein R1 in each instance is independently a linear or branched aliphatic group having from 1 to 20 carbon atoms, and X11 is independently F, Cl, Br, I, OMe, OEt, O-n-Pr, O-i-Pr, O-n-Bu, O-t-Bu, NMe2, or NEt2;
c) the chemically-treated solid oxide is fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, sulfated silica-alumina, or any combination thereof; and d) the organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, disobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.
13. The catalyst composition of Claim 11, wherein:
a) the first metallocene compound has the formula (.eta.5-C5H4n Bu)2ZrCl2;
b) the second metallocene compound has the formula (.eta.5-C5H4n Bu)2HfCl2;
c) the chemically-treated solid oxide is fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, or any combination thereof; and d) the organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, disobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.
14. The catalyst composition of Claim 1, wherein the chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.
15. The catalyst composition of Claim 1, wherein the chemically-treated solid oxide is fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, or any combination thereof.
16. The catalyst composition of Claim 1, wherein the chemically-treated solid oxide further comprises a metal or metal ion comprising zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof.
17. The catalyst composition of Claim 1, wherein the chemically-treated solid oxide further comprises a metal or metal ion and is zinc-impregnated chlorided alumina, zinc-impregnated fluorided alumina, zinc-impregnated chlorided silica-alumina, zinc-impregnated fluorided silica-alumina, zinc-impregnated sulfated alumina, or any combination thereof.
18. The catalyst composition of Claim 1, wherein the weight ratio of the organoalumium compound to the chemically-treated solid oxide is from 10:1 to 1:1,000.
19. The catalyst composition of Claim 1, wherein the organoaluminum compound is trimethylaluminum, triethylaluminum, tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, disobutylaluminum hydride, triisobutylaluminum, or diethylaluminum chloride.
20. The catalyst composition of Claim 1, further comprising an optional cocatalyst comprising at least one aluminoxane, at least one organozinc compound, at least one organoboron compound, at least one ionizing ionic compound, or any combination thereof.
21. The catalyst composition of Claim 1, further comprising an optional cocatalyst comprising at least one aluminoxane compound, wherein the aluminoxane comprises 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 10;
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 50;
a cage aluminoxane having the formula R t5m+.alpha. R b m-.alpha. Al4m O3m, wherein m is 3 or 4 and .alpha.
is = .eta. Al(3)- .eta. O(2)+ .eta. O(4); wherein .eta. Al(3) is the number of three coordinate aluminum atoms, .eta.O(2) is the number of two coordinate oxygen atoms, .eta.O(4) is the number of 4 coordinate oxygen atoms, R t represents a terminal alkyl group, and R b represents a bridging alkyl group; wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms; or any combination thereof.
22. The catalyst composition of Claim 21, wherein the molar ratio of the aluminum in the aluminoxane to the combined first metallocene compound and second metallocene compound in the catalyst composition is from 1:10 to 100,000:1.
23. The catalyst composition of Claim 21, wherein the aluminoxane compound is methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentyl-aluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or a combination thereof.
24. The catalyst composition of Claim 1, further comprising an optional cocatalyst comprising at least one organozinc compound, wherein the organozinc compound has the following formula:
Zn(X13)(X14);
wherein (X13) is a hydrocarbyl having from 1 to 20 carbon atoms; (X14) is a hydrocarbyl, an alkoxide or an aryloxide having from 1 to 20 carbon atoms, halide, or hydride;
25. The catalyst composition of Claim 1, further comprising an optional cocatalyst comprising at least one organozinc compound, wherein the organozinc compound is dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilymethyl)zinc, or any combination thereof.
26. The catalyst composition of Claim 1, further comprising an optional cocatalyst comprising at least one organoboron compound, wherein the organoboron compound is 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 a combination thereof.
27. The catalyst composition of Claim 26, wherein the molar ratio of the organoboron compound to the combined first metallocene compound and second metallocene compound in the catalyst composition is from 0.1:1 to 10:1.
28. The catalyst composition of Claim 1, further comprising an optional cocatalyst comprising at least one ionizing ionic compound, wherein the ionizing ionic compound is tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethyl)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, tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammonium tetrakis(m-tolyl)aluminate, tri(n-butyl)ammonium tetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)aluminate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(p-tolyl)aluminate, N,N-dimethylanilinium tetrakis(m-tolyl)aluminate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis (pentafluorophenyl)aluminate, 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(pentafluoro-phenyl)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, or any combination thereof.
29. A catalyst composition consisting essentially of a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:
a) the first metallocene compound has the following formula:
(X1)(X2)(X3)(X4)Zr;
wherein (X1) and (X2) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X') and (X2) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
b) wherein the second metallocene compound has the following formula:
(X5)(X6)(X7)(X8)M; wherein 1) M is Zr;
(X5) and (X6) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
2) M is Zr;
(X5) and (X6) are independently 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 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 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 (X~) and (X~) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
c) the chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion; and d) the organoaluminum compound has the following formula:

Al(X9)n(X10)3-n;

wherein (X9) is a hydrocarbyl having from 1 to 20 carbon atoms; (X10) is alkoxide or aryloxide having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.
30. A catalyst composition comprising the contact product of a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:
a) the first metallocene compound has the following formula:

(X1)(X2)(X3)(X4)Zr;

wherein (X1) and (X2) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
b) wherein the second metallocene compound has the following formula:

(X5)(X6)(X7)(X8)M; wherein 1) M is Zr;

(X~) and (X~) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
2) M is Zr;
(X5) and (X6) are independently 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 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 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 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, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
c) the chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion; and d) the organoaluminum compound has the following formula:

Al(X9)n(X10)3-n;

wherein (X9) is a hydrocarbyl having from 1 to 20 carbon atoms; (X10) is alkoxide or aryloxide having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.
31. A process to produce a catalyst composition comprising contacting a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:
a) the first metallocene compound has the following formula:

(X1)(X2)(X3)(X4)Zr;

wherein (X1) and (X2) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
b) wherein the second metallocene compound has the following formula:

(X5)(X6)(X7)(X8)M; wherein 1) M is Zr;
(X5) and (X6) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
2) M is Zr;
(X5) and (X6) are independently 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 t0 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;

(X) and (X') are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 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 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, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
c) the chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion; and d) the organoaluminum compound has the following formula:

Al(X9)n(X10)3-n;

wherein (X9) is a hydrocarbyl having from 1 to 20 carbon atoms; (X10) is alkoxide or aryloxide having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.
32. 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 a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:
a) the first metallocene compound has the following formula:

(X1)(X2)(X3)(X4)Zr;

wherein (X1) and (X2) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;

wherein (X3), (X4), and any substituent on the substituted aliphatic group on (X1) and (X2) 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, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
b) wherein the second metallocene compound has the following formula:

(X5)(X6)(X7)(X8)M; wherein 1) M is Zr;
(X5) and (X6) are independently 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 20 carbon atoms;
2) M is Zr;
(X5) and (X6) are independently 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 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 a linear or branched aliphatic group, wherein the aliphatic group is unsubstituted or substituted, any one of which having from 1 to 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 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, an inorganic group, an organometallic group, or a substituted derivative thereof, any one of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
c) the chemically-treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion; and d) the organoaluminum compound has the following formula:

Al(X9)n(X10)3-n;

wherein (X9) is a hydrocarbyl having from 1 to 20 carbon atoms; (X10) is alkoxide or aryloxide having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.
33. The process of Claim 32, wherein the catalyst composition is contacted with ethylene and at least one other olefin comprising 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, or 3-heptene.
34. The process of Claim 32, wherein the catalyst composition is contacted with ethylene and 1-hexene.
35. The process of Claim 32, wherein the catalyst composition is contacted with ethylene.
36. A polymer or copolymer of ethylene, wherein the melt index is from 0.3 to 2.0 dg/min;
the density from 0.94 to 0.91 g/cm3; the CY-a parameter is from 0.45 to 0.70;
the polydispersity index (M w/M n) is from 2 to 6; the HLMI/MI ratio is from 16.5 to 25; the Elmendorf MD tear resistance is greater than 150 g for 1 mil blown film; the Elmendorf TD tear resistance is greater than 350 g for a 1 mil blown film; the film haze is less than 25% for a 1 mil blown film; the Dart impact strength is greater than 600 g for a 1 mil blown film; and the Spencer impact strength is greater than 0.7 J for a 1 mil blown film.
37. A polymer or copolymer of ethylene, wherein the melt index is from 0.5 to 1.5 dg/min;
the density is from 0.935 to 0.915 g/cm3; the CY-a parameter is from 0.50 to 0.65; the polydispersity index (M w/M n) is from 2.2 to 5.0; the HLMI/MI ratio is from 17 to 24; the Elmendorf MD tear resistance is greater than 200 g for a 1 mil blown film; the Elmendorf TD
tear resistance is greater than 380 g for a 1 mil blown film; the film haze is less than 15% for a 1 mil blown film; the Dart impact strength is greater than 800 g for a 1 mil blown film; and the Spencer impact strength is greater than 0.9 J for a 1 mil blown film.
38. A polymer or copolymer of ethylene, wherein the melt index is from 0.8 to 1.3 dg/min;
the density is from 0.925 to 0.915 g/cm3; the CY-a parameter is from 0.55 to 0.62; the polydispersity index (M w/M n) is from 2.6 to 4.0; the HLMI/MI ratio is from 17.5 to 23; the Elmendorf MD tear resistance is greater than 250 g for a 1 mil blown film; the Elmendorf TD
tear resistance is greater than 450 g for a 1 mil blown film; the film haze is less than 10% for a 1 mil blown film; the Dart impact strength is greater than 1200 g for a 1 mil blown film; and the Spencer impact strength is greater than 1.00 J for a 1 mil blown film.
39. A polymer produced by a process as defined in any of Claims 32 to 35.
40. A catalyst composition produced by a process as defined in Claim 31 or 32.
41. Use of a catalyst composition as defined in any of Claims 1 to 30 or 40, or as produced by a process as defined in Claim 31 or 32, in an olefin polymerization reaction.
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