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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, and an activator,wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof;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 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 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 —CR7BR8BCR7CR8C—, 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 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. 3. The process of claim 1, wherein: the melt index of the olefin polymer produced by the process is in a range from about 0.1 to about 5 g/10 min; anda density of the olefin polymer produced by the process is in a range from about 0.89 to about 0.94 g/cm3. 4. 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. 5. 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, or benzyl, 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. 6. The process of claim 1, wherein catalyst component II comprises:  or a combination thereof. 7. The process of claim 1, wherein the catalyst composition comprises an activator; only one compound having formula (C) or formula (D); and only one compound selected from:  or a compound having the formula 8. The process of claim 1, wherein the catalyst composition further comprises an organoaluminum compound. 9. The process of claim 1, wherein the activator comprises an aluminoxane compound. 10. The process of claim 1, wherein: the molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 6:1 to about 18:1;the amount of the olefin polymer produced per hour by the process is from 10% to about 50% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II; andthe melt index (MI) of the olefin polymer produced by the process is from about 15% to about 80% less than a MI of an olefin polymer obtained under the same polymerization conditions without catalyst component II. 11. The process of claim 1, wherein: catalyst component I comprises:  or a combination thereof and catalyst component II comprises: or a combination thereof. 12. An olefin polymerization process, the process comprising: contacting a catalyst composition with ethylene and an olefin comonomer under polymerization conditions to produce an ethylene polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, and an activator,wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof;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 an amount of the ethylene polymer produced per hour by the process is at least 10% greater than an amount of an ethylene polymer obtained per hour under the same polymerization conditions without catalyst component II;wherein a melt index (MI) of the ethylene polymer produced by the process is at least 10% less than a MI of an ethylene polymer obtained under the same polymerization conditions without catalyst component II;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; 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 group, 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. 13. The process of claim 12, wherein the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof. 14. The process of claim 13, wherein: the molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 7:1 to about 50:1;the amount of the ethylene polymer produced per hour by the process is from 10% to about 50% greater than an amount of an ethylene polymer obtained per hour under the same polymerization conditions without catalyst component II; andthe melt index (MI) of the ethylene polymer produced by the process is from about 15% to about 70% less than a MI of an ethylene polymer obtained under the same polymerization conditions without catalyst component II. 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;R5 is H, methyl, ethyl, propyl, butyl, ethenyl, propenyl, butenyl, pentenyl, or hexenyl; andcatalyst component II comprises:  or a combination thereof. 16. The process of claim 15, wherein catalyst component I comprises:  or a combination thereof. 17. The process of claim 14, wherein: the catalyst composition further comprises an organoaluminum compound;the activator comprises an aluminoxane compound;the melt index of the ethylene polymer produced by the process is in a range from about 0.1 to about 5 g/10 min; anda density of the ethylene polymer produced by the process is in a range from about 0.89 to about 0.94 g/cm3. 18. An olefin polymerization process, the process comprising: contacting a catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, and an activator,wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof;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 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 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. 19. The process of claim 18, wherein: a melt index (MI) of the olefin polymer produced by the process is from about 15% to about 80% less than a MI of an olefin polymer obtained under the same polymerization conditions without catalyst component II;the molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 6:1 to about 18:1; andthe amount of the olefin polymer produced per hour by the process is from 10% to about 50% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II. 20. The process of claim 18, wherein: the olefin monomer comprises ethylene;the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof;the catalyst composition further comprises an organoaluminum compound; andthe activator comprises an aluminoxane compound. 21. The process of claim 18, wherein: catalyst component I comprises:  or a combination thereof; andcatalyst component II comprises: