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The present invention provides dual catalyst systems and polymerization processes employing these dual catalyst systems. The disclosed polymerization processes can produce olefin polymers at higher production rates, and these olefin polymers may have a higher molecular weight and/or a lower melt ind

The present invention provides dual catalyst systems and polymerization processes employing these dual catalyst systems. The disclosed polymerization processes can produce olefin polymers at higher production rates, and these olefin polymers may have a higher molecular weight and/or a lower melt index.

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1. An olefin polymerization process, the process comprising: contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component I

1. An olefin polymerization process, the process comprising: contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound,wherein an amount of the olefin polymer produced per hour by the process is at least 10% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II;wherein a molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 6:1 to about 75:1;wherein a melt index (MI) of the olefin polymer produced by the process is at least 10% less than a MI of an olefin polymer obtained under the same polymerization conditions without catalyst component II;wherein catalyst component I comprises: a compound having formula (C);a compound having formula (D); orany combination thereof, wherein: formula (C) is wherein: M3 is Zr or Hf;X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;E3 is a bridging group selected from: a cyclic or heterocyclic bridging group having up to 18 carbon atoms,a bridging group having the formula >E3AR7AR8A, wherein E3A is C or Si, and R7A and R8A are independently H or a hydrocarbyl group having up to 18 carbon atoms,a bridging group having the formula —CR7BR8B—CR7CR8C—, wherein R7B, R8B, R7C, and R8C are independently H or a hydrocarbyl group having up to 10 carbon atoms, ora bridging group having the formula —SiR7DR8D—SiR7ER8E—, wherein R7D, R8D, R7E, and R8E are independently H or a hydrocarbyl group having up to 10 carbon atoms;R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; andCp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; and formula (D) is wherein: M4 is Zr or Hf;X6 and X7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;E4 is a bridging group selected from: a cyclic or heterocyclic bridging group having up to 18 carbon atoms,a bridging group having the formula >E4AR12AR13A, wherein E4A is C or Si, and R12A and R13A are independently H or a hydrocarbyl group having up to 18 carbon atoms,a bridging group having the formula —CR12BR13B—CR12CR13C—, wherein R12B, R13B, R12C, and R13C are independently H or a hydrocarbyl group having up to 10 carbon atoms, ora bridging group having the formula —SiR12DR13D—SiR12ER13E—, wherein R12D, R13D, R12E, and R13E are independently H or a hydrocarbyl group having up to 10 carbon atoms; andR14,R15,R16, and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms; andwherein catalyst component II comprises: a compound having the formula or any combination thereof, wherein: M5 is Zr or Hf;X8 and X9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;Cp2 and Cp3 are independently a cyclopentadienyl or indenyl, any substituent on Cp2 and Cp3 is independently H or a hydrocarbyl group having up to 18 carbon atoms; andE5 is a bridging group having the formula —(CH2)n—, wherein n is an integer from 2 to 8, inclusive. 2. The process of claim 1, wherein the amount of the olefin polymer produced per hour by the process is from about 10% to about 40% greater than the amount of the olefin polymer obtained per hour under the same polymerization conditions without catalyst component II. 3. The process of claim 1, wherein: a melt index of the olefin polymer produced by the process is in a range from about 0.1 to about 5 g/10 min; ora density of the olefin polymer produced by the process is in a range from about 0.89 to about 0.94 g/cm3; orboth. 4. The process of claim 1, wherein the polymerization process is conducted in the presence of hydrogen at a weight ratio of hydrogen to the olefin monomer in a range from about 10 ppm to about 200 ppm. 5. The process of claim 1, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein: the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof. 6. The process of claim 1, wherein the activator-support comprises 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, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof. 7. The process of claim 1, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof. 8. The process of claim 1, wherein the catalyst composition further comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 9. The process of claim 1, wherein catalyst component I comprises a compound having formula (C), and wherein: X4 and X5 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;E3 is a bridging group selected from: a cyclopentyl or cyclohexyl group,a bridging group having the formula >E3AR7AR8A, wherein E3A is C or Si, and R7A and R8A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,a bridging group having the formula —CR7BR8B—CR7CR8C—, wherein R7B, R8B, R7C, and R8C are independently H or methyl, ora bridging group having the formula —SiR7DR8D—SiR7ER8E—, wherein R7D, R8D, R7E, and R8E are independently H or methyl; andR9 and R10 are independently H or t-butyl. 10. The process of claim 1, wherein catalyst component I comprises a compound having formula (D), and wherein: X6 and X7 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;E4 is a bridging group selected from: a cyclopentyl or cyclohexyl group,a bridging group having the formula >E4AR12AR13A, wherein E4A is C or Si, and R12A and R13A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl,a bridging group having the formula —CR12BR13B—CR12CR13C—, wherein R12B, R13B, R12C, and R13C are independently H or methyl, ora bridging group having the formula —SiR12DR13D—SiR12ER13E—, wherein R12D, R13D, R12E, and R13E are independently H or methyl; andR14, R15, R16, and R17 are independently H or t-butyl. 11. The process of claim 1, wherein the catalyst composition comprises an activator-support; an organoaluminum compound; only one compound having formula (C) or formula (D); and only one compound selected from or a compound having the formula 12. The process of claim 1, wherein the process is conducted in a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination thereof. 13. The process of claim 1, wherein the olefin monomer is ethylene, and the olefin comonomer comprises 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-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof. 14. An olefin polymerization process, the process comprising: contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound,wherein an amount of the olefin polymer produced per hour by the process is at least 10% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II;wherein a melt index (MI) of the olefin polymer produced by the process is at least 10% less than a MI of an olefin polymer obtained under the same polymerization conditions without catalyst component II;wherein a molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 8:1 to about 15:1;wherein catalyst component I comprises a metallocene compound having the formula:  wherein: M is Zr or Hf;X1 and X2 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;R1 and R2 are independently H or an alkyl, alkenyl, or aryl group having up to 12 carbon atoms;R3 and R4 are independently H or an alkyl group having up to 12 carbon atoms; andR5 is H or an alkyl or alkenyl group having up to 12 carbon atoms;wherein catalyst component II comprises:  or a combination thereof;wherein the activator-support comprises 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, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof; andwherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof. 15. The process of claim 14, wherein: X1 and X2 are independently Cl, benzyl, phenyl, or methyl;R1 and R2 are independently methyl, ethyl, propyl, butyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, benzyl, or phenyl;R3 and R4 are independently H or t-butyl; andR5 is H, methyl, ethyl, propyl, butyl, ethenyl, propenyl, butenyl, pentenyl, or hexenyl. 16. The process of claim 14, wherein the catalyst composition is contacted with ethylene and a comonomer comprising 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or a combination thereof. 17. The process of claim 16, wherein: catalyst component I is:  or a combination thereof; andcatalyst component II is: 18. An olefin polymerization process, the process comprising: contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound,wherein an amount of the olefin polymer produced per hour by the process is at least 10% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II;wherein a molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 6:1 to about 75:1;wherein a weight-average molecular weight (Mw) of the olefin polymer produced by the process is at least 10% greater than a weight-average molecular weight (Mw) of an olefin polymer obtained under the same polymerization conditions without catalyst component II;wherein catalyst component I comprises: a compound having formula (C);a compound having formula (D); orany combination thereof, wherein: formula (C)is wherein: M3 is Zr or Hf;X4 and X5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;E3 is a bridging group selected from: a cyclic or heterocyclic bridging group having up to 18 carbon atoms,a bridging group having the formula >E3AR7AR8A, wherein E3A is C or Si, and R7A and R8A are independently H or a hydrocarbyl group having up to 18 carbon atoms,a bridging group having the formula —CR7BR8B—CR7CR8C—, wherein R7B, R8B, R7C, and R8C are independently H or a hydrocarbyl group having up to 10 carbon atoms, ora bridging group having the formula —SiR7DR8D—SiR7ER8E—, wherein R7D, R8D, R7E, and R8E are independently H or a hydrocarbyl group having up to 10 carbon atoms;R9 and R10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; andCp1 is a cyclopentadienyl or indenyl group, any substituent on Cp1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; and formula (D) is wherein: M4 is Zr or Hf;X6 and X7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;E4 is a bridging group selected from: a cyclic or heterocyclic bridging group having up to 18 carbon atoms,a bridging group having the formula >E4AR12AR13A, wherein E4A is C or Si, and R12A and R13A are independently H or a hydrocarbyl group having up to 18 carbon atoms,a bridging group having the formula —CR12BR13B—CR12CR13C—, wherein R12B, R13B, R12C, and R13C are independently H or a hydrocarbyl group having up to 10 carbon atoms, ora bridging group having the formula —SiR12DR13D—SiR12ER13E—, wherein R12D, R13D, R12E, and R17 are independently H or a hydrocarbyl group having up to 10 carbon atoms; andR14, R15, R16, and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms; andwherein catalyst component II comprises:  a compound having the formula  or any combination thereof, wherein:M5 is Zr or Hf;X8 and X9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH4; OBR2 or SO3R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;Cp2 and Cp3 are independently a cyclopentadienyl or indenyl, any substituent on Cp2 and Cp3 is independently H or a hydrocarbyl group having up to 18 carbon atoms; andE5 is a bridging group having the formula —(CH2)n—, wherein n is an integer from 2 to 8, inclusive. 19. The process of claim 18, wherein: the catalyst composition is contacted with ethylene and a comonomer comprising 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or a combination thereof;the activator-support comprises a solid oxide treated with an electron-withdrawing anion; andthe molar ratio of catalyst component I to catalyst component II is in a range from about 8:1 to about 25:1. 20. The process of claim 19, wherein: a melt index of the olefin polymer produced by the process is in a range from about 0.1 to about 5 g/10 min; ora density of the olefin polymer produced by the process is in a range from about 0.89 to about 0.94 g/cm3; orboth. 21. The process of claim 20, wherein: catalyst component I comprises a metallocene compound having the formula:  wherein: M is Zr or Hf;X1 and X2 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;R1 and R2 are independently H or an alkyl, alkenyl, or aryl group having up to 12 carbon atoms;R3 and R4 are independently H or an alkyl group having up to 12 carbon atoms; andR5 is H or an alkyl or alkenyl group having up to 12 carbon atoms;the activator-support comprises 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, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof; andthe organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof. 22. The process of claim 21, wherein the catalyst composition comprises the activator-support, the organoaluminum compound, only one compound having formula (A), and only one compound selected from: or a compound having the formula 23. The process of claim 22, wherein: catalyst component I is:  andcatalyst component II is: