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US 8,329,834 B2Granted
Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates
AssigneeChevron Phillips Chemical Company LP
InventorsAlbert P. Masino, Rex E. Murray, Qing Yang, Steve J. Secora, Kumudini C. Jayaratne, William B. Beaulieu, Errun Ding, Gary L. Glass, Alan L. Solenberger, Ted H. Cymbaluk
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Abstract
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.
Claims23
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);
- or
- any 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, or
- a 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;
- and
- Cp1 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, or
- a 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;
- and
- R14,R15,R16, and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms;
- and
- wherein 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;
- and
- E5 is a bridging group having the formula —(CH2)n—, wherein n is an integer from 2 to 8, inclusive.
69 more elements
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;
- and
- R5 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;
- and
- 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.
14 more elements
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);
- or
- any 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, or
- a 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;
- and
- Cp1 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, or
- a 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;
- and
- R14, R15, R16, and R17 are independently H or a hydrocarbyl group having up to 18 carbon atoms;
- and
- wherein 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;
- and
- E5 is a bridging group having the formula —(CH2)n—, wherein n is an integer from 2 to 8, inclusive.
69 more elements
Dependencies are inferred from the claim text.