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US 8,383,754 B2Granted
Catalyst compositions for producing high Mz/Mw polyolefins
AssigneeChevron Phillips Chemical Company LP
InventorsQing Yang, Max P. McDaniel, William B. Beaulieu, Joel L. Martin, Tony R. Crain
Life of this patent
Estimating the term…
Abstract
The present invention provides a polymerization process utilizing a dual ansa-metallocene catalyst system. Polymers produced from the polymerization process are also provided, and these polymers have a reverse comonomer distribution, a non-bimodal molecular weight distribution, a ratio of Mw/Mn from about 3 to about 8, and a ratio of Mz/Mw from about 3 to about 6.
Claims29
An olefin polymerization process, the process comprising:
- contacting a catalyst composition with an olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, and at least one activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein:
- catalyst component I comprises at least one ansa-metallocene compound having formula (I):
- wherein:
- MA is Ti, Zr, or Hf;
- X1A and X2A 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;
- EA is C or Si;
- R1A and R2A are independently H, a hydrocarbyl group having up to 18 carbon atoms, or R1A and R2A are connected to a form a cyclic or heterocyclic group having up to 18 carbon atoms, wherein R1A and R2A are not aryl groups;
- R6A and R7A are independently H or a hydrocarbyl group having up to 18 carbon atoms;
- and
- CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a heteroatom-substituted derivative thereof, any substituent on CpA is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms;
- and
- catalyst component II comprises at least one ansa-metallocene compound having formula (II):
- wherein:
- MB is Ti, Zr, or Hf;
- X1B and X2B 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;
- EB is C or Si;
- R1B and R2B are independently H or a hydrocarbyl group having up to 18 carbon atoms, wherein at least one of R1B and R2B is an aryl group having up to 18 carbon atoms;
- R6B and R7B are independently H or a hydrocarbyl group having up to 18 carbon atoms;
- and
- CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a heteroatom-substituted derivative thereof, any substituent on CpB is independently H or a hydrocarbyl or hydrocarbylsilyl group having up to 36 carbon atoms.
37 more elements
An ethylene polymer having a non-bimodal molecular weight distribution;
- a ratio of Mw/Mn from about 3 to about 8;
- a ratio of Mz/Mw from about 3 to about 6;
- and a reverse comonomer distribution.
An olefin polymerization process, the process comprising:
- contacting a catalyst composition with an olefin monomer and at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, and at least one activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein:
- catalyst component I comprises at least one ansa-metallocene compound having formula (IA):
- wherein:
- MA is Ti, Zr, or Hf;
- X1A and X2A 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 12 carbon atoms;
- or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 12 carbon atoms;
- EA and YA are independently C or Si;
- R1A and R2A are independently H, a hydrocarbyl group having up to 12 carbon atoms, or R1A and R2A are connected to a form a cyclic or heterocyclic group having up to 12 carbon atoms, wherein R1A and R2A are not aryl groups;
- R3A, R4A, R5A are independently H or a hydrocarbyl group having up to 10 carbon atoms;
- R6A and R7A are independently H or a hydrocarbyl group having up to 12 carbon atoms;
- CpA is a cyclopentadienyl, indenyl, or fluorenyl group, or a heteroatom-substituted derivative thereof, any additional substituent on CpA is independently H or hydrocarbyl group having up to 12 carbon atoms;
- and
- at least one of R1A, R2A, R3A, R4A, and R5A is an alkenyl group;
- catalyst component II comprises at least one ansa-metallocene compound having formula (IIB):
- wherein:
- MB is Ti, Zr, or Hf;
- X1B and X2B 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 12 carbon atoms;
- or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 12 carbon atoms;
- EB and YB are independently C or Si;
- R1B and R2B are independently H or a hydrocarbyl group having up to 12 carbon atoms, wherein at least one of R1B and R2B is an aryl group having up to 12 carbon atoms;
- R3B, R4B, and R5B are independently H or a hydrocarbyl group having up to 10 carbon atoms;
- R6B and R7B are independently H or a hydrocarbyl group having up to 12 carbon atoms;
- CpB is a cyclopentadienyl, indenyl, or fluorenyl group, or a heteroatom-substituted derivative thereof, any additional substituent on CpB is independently H or hydrocarbyl group having up to 12 carbon atoms;
- and
- at least one of R1b, R2B, R3B, R4B, and R5B is an alkenyl group;
- and
- the olefin monomer is ethylene and the at least one olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.
42 more elements
Dependencies are inferred from the claim text.