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US 2002/0160907 A1Published application
Delayed activity supported olefin polymerization catalyst compositions and method for making and using the same
OwnerEdmund M. Carnahan, David R. Neithamer +1inventors
InventorsEdmund M. Carnahan, David R. Neithamer, Ravi B. Shankar
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Abstract
A supported catalyst and methods for making and using the same, by employing organometallic Group 4-10 catalysts with specially selected dienes, which, when combined with a cocatalyst, result in a supported catalyst which has improved kinetic profiles in the gas polymerization process.
Claims16
A method for preparing an olefin polymerization catalyst comprising:
- (a) selecting a metal complex which corresponds to the formula:
- 9
- wherein Cp is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;
- M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;
- X is a C4-30 conjugated diene represented by the formula:
- 10
- wherein R1, R2, R3, and R4 were each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical;;
- Y is —O—, —S—, —NR—, or —PR—;
- and
- Z is SiR2, CR2, SiR2SiR2.CR2CR2, CR═CR, CR2SiR2, or GeR2, BR2, B(NR2)2, BR2BR2, B(NR2)2B(NR2)2,
- wherein R is in each occurrence independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R having up to 20 non-hydrogen atoms, or adjacent R groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system.
- (b) selecting a cocatalyst from the group consisting of polymeric or oligomeric alumoxanes;
- neutral Lewis acids;
- nonpolymeric, compatible, noncoordinating, ion forming compounds;
- and combinations thereof;
- (c) supporting the metal complex and the cocatalyst upon a support, wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a kinetic profile which obeys the following inequality:
- Kr=A30/A90≦1.6
- where Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A30) divided by the net activity in grams polymer/gram catalyst hr bar at 90 minutes after the onset of polymerization (A9O).
15 more elements
A method for preparing an olefin polymerization catalyst comprising:
- (a) selecting a metal complex which corresponds to the formula:
- 11
- wherein D is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;
- M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;
- X is a C4-30 conjugated diene represented by the formula:
- 12
- wherein R1, R2, R3 and R4 were each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical;;
- Y is —O—, —S—, —NR—, or —PR—;
- and
- Z is SiR2, CR2, SiR2SiR2, CR2CR2, CR═CR, CR2SiR2, or GeR2, BR2, B(NR2)2, BR2BR2, B(NR2)2B(NR2)2,
- wherein R is in each occurrence independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R having up to 20 non-hydrogen atoms, or adjacent R groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system.
- (b) selecting a cocatalyst from the group consisting of polymeric or oligomeric alumoxanes;
- neutral Lewis acids;
- nonpolymeric, compatible, noncoordinating, ion forming compounds;
- and combinations thereof;
- (c) supporting the metal complex and the cocatalyst upon a support,
- wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a demonstrates a K, which is at least 10 percent less than the Kr for a comparative supported catalyst composition prepared using [tetramethylcyclopentadienyl(dimethylsilyl)(n-t-butylamido)]titanium(II)piperylene and a tetrakis(pentafluorophenyl)borate salt of a long chain alkyl mono- and disubstituted ammonium complex, wherein
- Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A30) divided by the net activity in grams polymer/gram catalyst hr bar at 90 minutes after the onset of polymerization (A90).
15 more elements
A supported catalyst composition comprising:
- (a) a metal complex corresponding to the formula:
- 16
- wherein D is an anionic. delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;
- M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;
- X is a C4-30 conjugated diene represented by the formula:
- 17
- wherein R1 and R2 are each independently aromatic, substituted aromatic, C1-C20 aliphatic, substituted aliphatic, heteroatom-containing aromatic, or silyl radical;
- Y is —O—, —S—, —NR*—, —PR*—;
- and
- Z is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, or GeR*2, wherein R* independently at each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 30 carbon or silicon atoms;
- (b) a cocatalyst selected from the group consisting of polymeric or oligomeric alumoxanes;
- neutral Lewis acids;
- nonpolymeric, compatible, noncoordinating, ion forming compounds;
- and combinations thereof;
- (c) a support,
- wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a kinetic profile which obeys the following inequality:
- Kr=A30/A90≦1.6
- where Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A30) divided by the net activity in grams polymer/gram catalyst hr− bar at 90 minutes after the onset of polymerization (A90).
15 more elements
A supported catalyst composition comprising:
- (a) a metal complex corresponding to the formula:
- 18
- wherein D is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms;
- M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 formal oxidation state;
- X is a C4-30 conjugated diene represented by the formula:
- 19
- wherein R1 and R2 are each independently aromatic, substituted aromatic, C1-C20 aliphatic, substituted aliphatic, heteroatom-containing aromatic, or silyl radical;
- Y is —O—, —S—, —NR*—, —PR*—;
- and
- Z is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, or GeR*2, wherein R* independently at each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 30 carbon or silicon atoms;
- (b) a cocatalyst selected from the group consisting of polymeric or oligomeric alumoxanes;
- neutral Lewis acids;
- nonpolymeric, compatible, noncoordinating, ion forming compounds;
- and combinations thereof;
- (c) a support,
- wherein the catalyst composition, when injected into gas phase polymerization batch reactor, and contacted with ethylene, demonstrates a demonstrates a K, which is at least 10 percent less than the Kr for a comparative supported catalyst composition prepared using [tetramethylcyclopentadienyl(dimethylsilyl)(n-t-butylamido)]titanium(II)piperylene and a tetrakis(pentafluorophenyl)borate salt of a long chain alkyl mono- and disubstituted ammonium complex, wherein
- Kr refers to the cumulative net activity in grams polymer/gram catalyst hr bar ethylene at 30 minutes after the onset of polymerization (A30) divided by the net activity in grams polymer/gram catalyst hr bar at 90 minutes after the onset of polymerization (A90).
14 more elements
A catalyst composition comprising:
- A) an inert support,
- B) a Group 4-10 metal complex corresponding to the formula:
- 20
- where M is a metal from one of Groups 4 to 10 of the Periodic Table of the Elements, which is in the +2 or +4 formal oxidation state,
- Cp is a π-bonded anionic ligand group
- Z is a divalent moiety bound to Cp and bound to M by either covalent or coordinate/covalent bonds, comprising boron or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen;
- X is a neutral conjugated diene ligand group having up to 60 atoms, or a dianionic derivative thereof;
- and
- C) an ionic cocatalyst capable of converting the metal complex into an active polymerization catalyst,
- wherein said catalyst composition is characterized as having an improved kinetic profile in a gas phase polymerization process.
7 more elements
Dependencies are inferred from the claim text.