Patent EA-004472-B1 (EA)
Title: Delayed activity supported olefin polymerization catalyst compositions and method for making and using the same
Inventor: CARNAHAN EDMUND M
IPC: C08F4/659
Filed: 2000-03-28
Abstract: 1. A method for preparing an olefin polymerization catalyst comprising: (a) selecting a metal complex, which corresponds to the formula: wherein Cp is an anionic, delocalized, pi-bonded group that is bound to M, containing up to 50 non-hydrogen 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-C30 conjugated diene represented by the formula: wherein R<1>, R<2>, R<3>, and R<4> 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) preparing a cocatalyst from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; non-polymeric, compatible, non-coordinating, 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 the value Kc which is at least 10 percent less than the Kc 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 di-substituted ammonium complex, wherein Kc 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). 2. The method of Claim 1, wherein the metal complex corresponds to the formula: wherein: M is titanium, zirconium or hafnium in the +2 or +4 formal oxidation state; R in each occurrence independently is 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 orgermadiyl group) thereby forming a fused ring system, each X is a C4-C30 conjugated diene represented by the formula: wherein R<1>, R<2>, R<3>, and R<4> are each independently 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*-, -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 fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 30 carbon or silicon atoms. 3. The method of Claim 1, wherein each X is a C6-C30 conjugated diene represented by the formula: wherein R<1>, R<2>, R<3>, and R<4> are each independently aromatic, substituted aromatic, fused aromatic, substituted fused aromatic, aliphatic, substituted aliphatic, heteroatom-containing aromatic, heteroatom-containing fused aromatic, or silyl radical. 4. The method of Claims 1, wherein the cocatalyst is represented by the following general formula: (L*-H)d <+> (A')<D-> wherein: L* is a neutral Lewis base; (L*-H)<+> is a Bronsted acid; A'<D-> is a non-coordinating, compatible anion having a charge of d-, and d is an integer from 1 to 3; more preferably A'<D-> corresponds to the formula: [M*Q4]<->; wherein: M* is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxide, hydrocarbyloxy substituted-hydrocarbyl, organometal substituted-hydrocarbyl, organometalloid substituted hydrocarbyl, halohydrocarbyloxy, halohydrocarbyloxy substituted hydrocarbyl, halocarbylsubstituted hydrocarbyl, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. 5. The method of Claim 1, wherein the cocatalyst is represented by the formula: (L*-H)<+> (BQ4)<->; wherein: L* is a neutral Lewis base; B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of up to 20 non-hydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl. 6. The method of Claim 1, wherein the cocatalyst is represented by the formula: [L*-H]<+>[(C6F5)3BC6H4-O-MR<C>X-1X<A>y]<-> wherein M is a metal or metalloid selected from Groups 1-14 of the Periodic Table of the Elements, R<C> independently each occurrence is hydrogen or a group having from 1 to 80 non-hydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilylhydrocarbyl; X<A> is a noninterfering group having from 1 to 100 nonhydrogen atoms which is halosubstituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is a nonzero integer which may range from 1 to an integer equal to the valence of M; y is zero or a nonzero integer which may range from 1 to an integer, equal to 1 less than the valence of M; and x + y equals the valence of M. 7. The method of Claim 1, wherein R<1> and R<4> are each a benzyl radical or substituted benzyl radical. 8. The method of Claim 1, wherein R<1> and R<4> are each a phenyl radical or substituted phenyl radical. 9. A supported catalyst composition comprising: (a) a metal complex corresponding to the formula: wherein Cp is an anionic, delocalized, pi-bonded group that is bound to M, containing up to 50 non-hydrogen atoms; M is a metal of Group 4 of the Periodic Table of the Elements in the +2 or +4 format oxidation state; X is a C4-C30 conjugated diene represented by the formula: wherein R<1>, R<2>, R<3>, and R<4> are 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-, -PR-; and Z is SiR2, CR2, SiR2SiR2, CR2CR2, CR=CR, CR2SiR2, or GeR2, BR2, B(NR2)2, BR2BR2 or B(NR2)2B(NR2)2; wherein R in each occurrence independently is 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 orgermadiyl group) thereby forming a fused ring system, (b) a cocatalyst selected from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; non-polymeric, compatible, non-coordinating, 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 the value Kc which is at least 10 percent less than the Kc 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 di-substituted ammonium complex, wherein Kc 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). 10. The supported catalyst composition of Claim 9, wherein R<1> and R<4> are each a benzyl radical or substituted benzyl radical. 11. The supported catalyst composition of Claim 9, wherein R<1> and R<4> are each a phenyl radical or substituted phenyl radical.