WO2009054833A2 - Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines - Google Patents

Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines Download PDF

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WO2009054833A2
WO2009054833A2 PCT/US2007/022623 US2007022623W WO2009054833A2 WO 2009054833 A2 WO2009054833 A2 WO 2009054833A2 US 2007022623 W US2007022623 W US 2007022623W WO 2009054833 A2 WO2009054833 A2 WO 2009054833A2
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indenyl
phenyl
methyl
ethyl
zirconiumdichloride
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PCT/US2007/022623
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English (en)
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WO2009054833A3 (fr
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Anita Dimeska
Ralph-Dieter Maier
Nicola Stephanie Paczkowski
Andreas Winter
Matthew Grant Thorn
Joerg Schulte
Thorsten Sell
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Novolen Technology Holdings, C.V.
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Priority to PCT/US2007/022623 priority Critical patent/WO2009054833A2/fr
Priority to EP07852954A priority patent/EP2235071A2/fr
Publication of WO2009054833A2 publication Critical patent/WO2009054833A2/fr
Publication of WO2009054833A3 publication Critical patent/WO2009054833A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to novel metallocene compounds useful as components in polymerization catalysts, to catalysts comprising such metallocene compounds, to a process for the polymerization of olefins and to particularly propylene, and olefin homopolymers, random, and impact copolymers prepared by using the metallocene catalysts.
  • Another key requirement of a metallocene catalyst is its capability to produce polypropylene with a high melting point. This is equivalent with a catalyst that has a very high stereospecificity and regioselectivity.
  • a catalyst that has a very high stereospecificity and regioselectivity.
  • the stereospecificity and regioselectivity has continuously been improved during the last 15 years.
  • EP-A1 834 519 relates to metallocenes of the rac-Me 2 Si(2-Me-4-Ar-lnd) 2 ZrCl 2 for the production of high rigid, high Tm polypropylenes with very high stereoregularity and very low amounts of regio errors.
  • EP-A1 834 519 Although not tested for their copolymerization performance, the metallocenes disclosed in EP-A1 834 519 anticipated substitution patterns in 2-position that would later be identified as particularly suitable for the production of propylene/ethylene random copolymers when combined with additional substituents in certain positions. However, the highly stereo- and regio regular polypropylenes were not obtained under commercially relevant process conditions and suffered from too low activity/productivity levels.
  • US-A1 2001/0053833 discloses metallocenes having substituents in 2- position consisting of an unsubstituted heteroaromatic ring or a heteroaromatic ring having at least one substituent bonded to the ring.
  • Such catalysts afford C3/C2 copolymers with reasonably high molar mass, but fail to produce high Tm homopolymers under conditions typical for commercial scale production, i. e. on a support and at temperatures from 60 deg C and higher. Also, the productivities of this catalyst family are unsatisfactory.
  • WO 01/058970 relates to impact copolymers having a high melting point and a high rubber molar mass, produced by catalysts comprising metallocenes of the rac-Me 2 Si(2-Alk-4-Ar-lnd)2ZrCl2 family. High molar masses in the propylene/ethylene rubber were achieved when both AIk substituents were i-propyl groups.
  • WO 02/002576 discloses bridged metallocenes of the (2-R-4-Ph- lnd) 2 ZrCl 2 family having particular combinations of substituents in the 2-positions of the indenyl ligands and the Ph substituents.
  • a high PP melting point is favored if the Ph group exhibits a substitution pattern in the 3 and 5 positions, particularly in case of butyl substituents.
  • a combination of high homopolymer melting point and high copolymer molar mass is achieved if both substituents R in 2-position are isopropyl groups.
  • the major shortcoming is the very low activity/productivity of the rac-Me2Si(2-R-4-Ar-lnd) 2 ZrCl 2 catalysts if both ligands R are branched in the ⁇ - position.
  • WO 03/002583 discloses bridged metallocenes of the (2-R-4-Ph- lnd) 2 ZrCl 2 family having particular combinations of substituents in the 2-positions of the indenyl ligands and the 4-Ph substituents.
  • a high PP melting point is favored if the Ph group exhibits a substitution pattern in the 2-position, particularly in case of biphenyl substituents.
  • a combination of high homopolymer melting point and high copolymer molar mass is achieved if both substituents R in 2-position of the indenyl ligand are isopropyl groups.
  • EP-A2 1 250 365, WO 97/40075 and WO 03/045551 relate to metallocenes having substituents in the 2-positions of either of the indenyl ligands with the imperative that at least one of the ligands in 2-position is branched or cyclicized in the ⁇ -position.
  • WO 04/106351 relates to metallocenes having subsitutents in the 2-positions of the indenyl ligands with the proviso that one ligand is unbranched or bound via an sp 2 -hybridized carbon atom and the other ligand is branched in the ⁇ -position.
  • Such catalysts afford high Tm homopolymers and high molar mass propylene/ethylene copolymers.
  • catalyst activity/productivity and lowest achievable homopolymer melt flow rate there still are limitations with regard to catalyst activity/productivity and lowest achievable homopolymer melt flow rate.
  • the main deficiency of supported catalyst systems comprising metallocenes of the above mentioned prior art, is that so far no catalyst has been found that, when used for the homopolymerization of propylene, affords isotactic polypropylene with a high melting point and very high molar mass (or very low melt flow rate) and that, when used for the copolymerization of propylene with ethylene, affords high molar mass propylene/ethylene copolymers, all at very high catalyst productivity.
  • the object of the present invention is to address this shortcoming of the state of the art metallocene compounds and to provide metallocenes that afford high melting point, high molar mass homopolymers and high molar mass copolymers at high productivities when used as components of supported catalysts under industrially relevant polymerization conditions at temperatures of from 50 0 C to 100 0 C.
  • Another objective of the present invention is to provide a process for the polymerization of olefins, particularly propylene, ethylene, and optionally one or more higher 1 -olefins.
  • olefin polymers particularly propylene homopolymers, random copolymers of propylene with ethylene and/or higher 1 -olefins, impact copolymers comprised of propylene, ethylene and/or optionally higher 1 -olefins, and random impact copolymers comprised of propylene, ethylene and/or optionally higher 1 -olefins.
  • Certain metallocene compounds are provided that, when used as a component in a supported polymerization catalyst under industrially relevant polymerization conditions, afford high molar mass homo polymers or copolymers like polypropylene or propylene/ethylene copolymers without the need for any ⁇ - branched substituent in either of the two available 2-positions of the indenyl ligands.
  • the substituent in the 2-position of one indenyl ligand is a methyl group and the substituent in the 2-position of the other indenyl ligand is an ethyl group.
  • This metallocene topology affords high melting point, very high molar mass homo polypropylene and very high molar mass propylene-based copolymers.
  • the activity/productivity levels of catalysts comprising the metallocenes of the present invention are exceptionally high. While various metallocenes are disclosed, for example, in U.S. Publication No. 2006/0116490, the improvement in olefin polymerization achieved by the metallocene topology of the present invention is both new and unexpected.
  • a process for olefin polymerization comprising: contacting one or more olefin with a catalyst system under polymerization reaction conditions, wherein said catalyst system includes at least one metallocene component of the general Formula 1 below,
  • M 1 is a metal of Group IVb of the Periodic Table of the Elements
  • R 1 and R 2 are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR 2 32 group, where R 32 is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms and R 1 and R 2 may form one or more ring system(s),
  • R 4 and R 4 are each a hydrogen atom
  • R 10 is a bridging group wherein R 10 is selected from:
  • R 40 and R 41 can be identical or different and are each selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to about 30 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group and an arylalkenyl group of from 8 to about 40 carbon atoms or wherein R 40 and R 41 together with the atoms connecting them form one or more cyclic systems or wherein R 40 and R 41 together with
  • M 12 is silicon, germanium or tin
  • R 10 may also link two units of the formula 1 to one another, and
  • R 11 and R 11 are identical or different and are each a divalent C 2 -C 40 group which together with the cyclopentadienyl ring forms a further saturated or unsaturated ring system having a ring size of from 5 to 7 atoms, with or without heteroatoms selected from the group consisting of Si, Ge, N 1 P, O and S within the ring system fused onto the cyclopentadienyl ring, and wherein the symbols * and ** denote chemical bonds joining R 11 and R 11' to the cyclopentadienyl ring.
  • a supported catalyst system comprising at least one specifically substituted and bridged metallocene, at least one cocatalyst, at least one support and, if desired, at least one metal compound and further one additive component.
  • the catalyst system is prepared by mixing at least one specifically substituted and bridged metallocene, at least one cocatalyst, at least one support and if desired at least one metal compound and one further additive component.
  • the first embodyment of the invention relates to a specifically substituted, bridged metallocene component of the general Formula 1 below,
  • M 1 is a metal of Group IVb of the Periodic Table of the Elements, preferably Zirconium or Hafnium, and particularly preferably Zirconium.
  • R 1 and R 2 are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR 2 32 group, where R 32 is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms and R 1 and R 2 may form one or more ring system(s).
  • R 1 and R 2 are identical or different and are an alkyl group of fromi to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms or a halogen atom, or R 1 and R 2 together may form one or more ring system(s).
  • R 1 and R 2 are identical or different and are methyl, chlorine or phenolate.
  • R 4 and R 4 are each a hydrogen atom
  • R 10 is a bridging group wherein R 10 is selected from:
  • R 40 and R 41 can be identical or different and are each a hydrogen atom, a C 1 -C 40 group such as an alkyl group having from 1 to about 30 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilyl group.or an arylalkenyl group of from 8 to about 40 carbon atoms.
  • a C 1 -C 40 group such as an alkyl group having from 1 to about 30 carbon atoms
  • R 40 and R 41 together with the atoms connecting them can form one or more cyclic systems or R 40 and/or R 41 can contain additional hetero atoms (i.e., non-carbon atoms) like Si, B, Al, O, S, N or P or halogen atoms like Cl or Br, x is an integer from 1 to 18,
  • M 12 is silicon, germanium or tin
  • R 10 may also link two units of the formula 1 to one another,
  • R 40 and R 41 are identical or different and are each a hydrogen atom, a hydrocarbon group of from 1 to about 30 carbon atoms, in particular an alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atom
  • R 11 and R 11 are identical or different and are each a divalent C 2 -C 40 group which together with the cyclopentadienyl ring forms a further saturated or unsaturated ring system having a ring size of from 5 to 7 atoms, where R 11 and R 11 may contain the heteroatoms Si, Ge, N, P, O or S within the ring system fused onto the cyclopentadienyl ring.
  • the groups R 11 and R 11 are identical or different and are each a divalent group selected from those given in Formulae 1 ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , and v and Formulae 1 ⁇ ', ⁇ ', ⁇ ', ⁇ ', and v', respectively.
  • R 11 and R 11 are identical or different and R 11 is a divalent group according to Formula 1 ⁇ and R 11 is selected from the divalent groups in Formulae 1 ⁇ ', ⁇ ', and ⁇ ' or R 11 and R 11 are identical or different and are divalent groups according to Formula 1 ⁇ and 1 ⁇ ' or Formula 1 ⁇ and 1 ⁇ ' or Formula 1 ⁇ and 1 ⁇ ' or Formula 1 ⁇ and 1 ⁇ ' or Formula 1 ⁇ and 1 ⁇ ' or Formula 1v and 1v ⁇ respectively.
  • R 5 , R 6 , R 7 , R 8 , and R 9 and also R 5' , R 6' , R 7' , R 8' and R 9' as well as R 55 , R 66 , R 77 , R 88 and R 99 and also R 55' , R 66' , R 77' , R 88' and R 99' are identical or different and are each a hydrogen atom, a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 2 to about 20 carbon atoms, an alkenyl group of from 2 to about 20 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(ary
  • the groups may contain one or more hetero atoms like Si, B, Al, O, S, N or P, and / or may contain halogen atoms like F, Cl or Br.
  • R 55 , R 66 , R 77 , R 88 and R 99 and also R 55' , R 66' , R 77' , R 88' and R 99' are each a hydrogen atom and R 5 , R 6 , R 7 , R 8 and R 9 and also R 5' , R 6' , R 7' , R 8' and R 9 are identical or different and are each a hydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilyl group, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 40 carbon atoms, which may contain one or more hetero atoms like Si, B, Al, O, S, N or P, and / or may contain halogen atoms like F, Cl or Br.
  • R 5 /R 6 and also R 5' /R 6 may form a hydrocarbon ring system or R 5 and R 5 are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.
  • R 55 , R 66 , R 77 , R 88 and R 99 and also R 55' , R 66' , R 77' , R 88' and R 99' are each a hydrogen atom and R 5 , R 6 , R 7 , R 8 and R 9 and also R 5' , R 6> , R 7 , R 8 and R 9 are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 40 carbon atoms.
  • R 5 , R 6 and also R 5' , R 6 together may form a ring system or R 5 and R 5 are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.
  • the specifically substituted, bridged metallocene component of the first embodyment of the invention is as given in Formula 1a below.
  • M 1 , R 1 , R 2 , R 4 , R 4 and R 10 have the meaning set forth above with respect to Formula 1.
  • R 5 , R 6 , R 7 and R 8 and also R 5' , R 6' , R 7> and R 8 are identical or different and are each a hydrogen atom, a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 1 to about 20 carbon atoms, an alkenyl group of from 2 to about 20 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or an arylsilyl group.
  • a linear, cyclic or branched hydrocarbon group for example an alkyl group of from 1 to about 20 carbon atoms, an alkenyl group of from 2 to about 20
  • the groups may contain one or more hetero atoms like Si, B, Al, O, S, N or P, and / or may contain halogen atoms like F, Cl or Br, and / or two adjacent radicals R 5 , R 6 or R 6 , R 7 or R 7 , R 8 and also R 5' , R 6' or R 6' , R 7' or R 7' , R 8' in each case may form a hydrocarbon ring system.
  • R 5 , R 6 , R 7 and R 8 and also R 5' , R 6' , R 7' and R 8' are identical or different and are each a hydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilyl group, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 40 carbon atoms, which may contain one or more hetero atoms like Si, B, Al, O, S 1 N or P, and / or may contain halogen atoms like F, Cl or Br, and / or the two adjacent radicals R 5 , R 6 and also R 5 , R 6 may form a saturated or unsaturated hydrocarbon ring system.
  • R 5 , R 6 , R 7 and R 8 and also R 5' , R 6' , R 7' and R 8' are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 40 carbon atoms and / or the two adjacent radicals R 5 , R 6 and also R 5 , R 6 together may form a saturated or unsaturated ring system.
  • R 6 , R 7 , R 8 and also R 6' , R 7' and R 8' are identical or different and are each a hydrogen atom, a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or an arylsilyl group.
  • a linear, cyclic or branched hydrocarbon group for example an alkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an
  • R 6 , R 7 or R 7 , R 8 as well as R 6 , R 7 or R 7 , R 8 in each case may form a hydrocarbon ring system.
  • the groups may contain one or more hetero atoms like Si, B, Al, O, S, N or P, and / or may contain halogen atoms like F, Cl or Br.
  • R 5 and R 5 are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms. They may contain one or more hetero atoms like Si, B 1 Al, O, S 1 N or P, and / or may contain halogen atoms like F, Cl or Br.
  • R 6 , R 7 and R 8 and also R 6' , R 7' and R 8' are identical or different and are each a hydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilyl group, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 10 carbon atoms, which may contain one or more hetero atoms like Si, B, Al, O, S, N or P, and / or may contain halogen atoms like F, Cl or Br.
  • R 5 and R 5 are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.
  • R 6 , R 7 and R 8 and also R 6' , R 7' and R 8' are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 10 carbon atoms.
  • R 5 and R 5 are identical or different and are each naphthyl, 4-(C r Cio-alkyl)phenyl or 4-(C 6 -C 2 o-aryl)phenyl such as 4-methyl-phenyl, 4-biphenyl, 4- ethyl-phenyl, 4-n-propyl-phenyl, 4-isopropyl-phenyl, 4-tert-butyl-phenyl, 4-sec- butyl-phenyl, 4-cyclohexyl-phenyl, 4-trimethylsilyl-phenyl, 4-adamantyl-phenyl, 4- (C- ⁇ -Cio-fluoroalkyl)-phenyl, 3-(Ci-C- ⁇ o-alkyl)-phenyl, 3-(Ci-Cio-fluoroalkyl)-phenyl, 3-(C 6 -C 2 o-aryl)phenyl like 3-biphenyl, 3,5-di-(Ci-C
  • Very particularly preferred metallocenes of formula 1a are compounds, where:
  • M1 is Zirconium
  • R 1 and R 2 are identical and are methyl, chlorine or phenolate
  • R 4 and R 4 are hydrogen
  • R 6 , R 7 and R 8 and also R 6' , R 7' and R 8' are identical or different and are each a hydrogen atom or a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, or an aryl group of from 6 to about 10 carbon atoms.
  • R 5 and R 5 are identical and are naphthyl, 4-(Ci-Ci O -alkyl)phenyl or 4-(C 6 - C 2 o-aryl)phenyl such as 4-methyl-phenyl, 4-biphenyl, 4-ethyl-phenyl, 4-n-propyl- phenyl, 4-isopropyl-phenyl, 4-tert-butyl-phenyl, 4-sec-butyl-phenyl, 4-cyclohexyl- phenyl, 4-trimethylsilyl-phenyl, 4-adamantyl-phenyl, 4-(CrCi 0 -fluoroalkyl)-phenyl, 3-(C r Cio-alkyl)-phenyl, 3-(CrCi 0 -fluoroalkyl)-phenyl, 3-(C 6 -C 2 o-aryl)phenyl like 3- biphenyl, 3,5-di-(CrC 10 -
  • mixtures of the metallocenes of formulas 1 and 1a and the corresponding meso or pseudomeso metallocenes may be used in the catalyst preparation.
  • the preparation of the isomerically pure racemic form is especially preferred for the use of metallocenes in the polymerization of olefins to isotactic polyolefins, since the corresponding meso form may produce undesired atactic polypropylene ("PP").
  • the "isomerically pure” racemic form is understood to mean a rac:meso ratio of greater than 5:1 preferably of at least 10:1 , more preferred of at least 15:1 and most preferred of at least 20:1.
  • racemic includes “pseudoracemic” (or “pseudorac”), and the term “meso” includes “pseudomeso.”
  • the present invention also includes a process for producing the transition- metal compounds of formulas 1 and 1a of the invention.
  • An object of the invention is thus a process for producing compounds of formula 1a,
  • R 10 has the meaning M 12 R 40 R 41
  • R 40 R 41 M 12 X 2 to form the compound of formula 3, where R 40 , R 41 , and M 12 have the meanings specified above, and X may be the same or different and means a halogen atom, preferably chlorine, bromine, or iodine, or another leaving group, preferably triflate, tosylate, or mesylate.
  • step (a) the compound of formula 2, for example, 2-(ethyl)-7-(4'-te/f- butylphenyl)indene in an inert solvent, which consists of one or more aromatic or aliphatic hydrocarbons and/or one or more polar, aprotic solvents, is deprotonated with a strong base, for example, /7-butyllithium.
  • the deprotonation is carried out at temperatures of -7O 0 C to 80 0 C, and preferably O 0 C to 8O 0 C.
  • the resulting metal salt is then reacted directly, without further isolation, in step (b) with a silicon compound or germanium compound that contains two leaving groups.
  • step (c) Compounds of formula 3 are reacted in step (c) with a metal-indenyl compound of formula 4 and compounds of formula 5 are formed.
  • step (d) the bis(indenyl)silanes of formula 5 are doubly deprotonated with a strong base, such as /7-butyllithium, in an inert solvent, which consists of one or more aromatic or aliphatic hydrocarbons and/or one or more polar, aprotic solvents, and the bislithium salt formed in this way is reacted, without isolation, directly with a source of Ti, Zr, or Hf to obtain the compound of formula 1a.
  • a strong base such as /7-butyllithium
  • the deprotonation is carried out at temperatures of -70 0 C to 80 0 C, and preferably 0 0 C to 80 0 C.
  • the metallocenes are isolated directly from the reaction mixture with rac:meso ratios or pseudo-rac:meso ratios of greater than 5:1 preferably of at least 10:1 , more preferred of at least 15:1 and most preferred of at least 20:1 or further rac:meso separation steps have to be applied to reach rac:meso ratios or pseudo-rac:meso ratios of at least 5:1 preferably of at least 10:1 , more preferred of at least 15:1 and most preferred of at least 20:1 to obtain a suitable catalyst.
  • the present invention relates to a catalyst system comprising at least one compound of formulas 1 or 1a and at least one cocatalyst.
  • a suitable cocatalyst component which may be present according to the present invention in the catalyst system comprises at least one compound of the type of an aluminoxane, a Lewis acid or an ionic compound which reacts with a metallocene to convert the latter into a cationic compound.
  • Aluminoxanes are oligomeric or polymeric aluminum oxy compounds, which may exist in the form of linear, cyclic, caged or polymeric structures. Although the exact structure(s) of aluminoxanes is still unknown, it is well accepted that alkylaluminoxanes have the general formula 6.
  • the radicals R in the formulas (6), (7), (8) and (9) can be identical or different and are each a Ci -C 2 o group such as an alkyl group of from 1 to about 6 carbon atoms, an aryl group of from 6 to about 18 carbon atoms, benzyl or hydrogen and p is an integer from 2 to 50, preferably from 10 to 35.
  • the radicals R are identical and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen, isobutyl or n-butyl preferably being present in a proportion of from 0.01 to 40% (number of radicals R).
  • the aluminoxane can be prepared in various ways by known methods.
  • One of the methods comprises the reaction of an aluminum-hydrocarbon compound and/or a hydridoaluminum-hydrocarbon compound with water, which may be gaseous, solid, liquid or bound as water of crystallization, in an inert solvent such as toluene.
  • water which may be gaseous, solid, liquid or bound as water of crystallization
  • an inert solvent such as toluene.
  • To prepare an aluminoxane having different alkyl groups R two different trialkylaluminums (AIR 3 MIR' 3 ) corresponding to the desired composition and reactivity are reacted with water, cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-O 302 424.
  • all aluminoxane solutions have in common a variable content of unreacted aluminum starting compound which is present in free form or as an adduct.
  • aluminoxane compounds of the formulas 6, 7, 8 or 9 it is also possible to use modified aluminoxanes in which the hydrocarbon radicals or hydrogen atoms have been partly replaced by alkoxy, aryloxy, siloxy or amide radicals.
  • the amounts of aluminoxane and metallocene used in the preparation of the supported catalyst system can be varied within a wide range.
  • it has been found to be advantageous to use the metallocene compound of formulas 1 or 1a and the aluminoxane compounds in such amounts that the atomic ratio of aluminum from the aluminoxane compounds to the transition metal from the metallocene compound is in the range from 10:1 to 1000:1 , preferably from 20:1 to 500:1 and in particular in the range from 30:1 to 400:1.
  • M 2 is an element of Group 13 of the Periodic Table of Elements, in particular B, Al or Ga, preferably B or Al,
  • X 1 , X 2 and X 3 are the same or different and each are a hydrogen atom, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine.
  • Preferred examples for X 1 , X 2 and X 3 are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl like phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5- di(trifluoromethyl)phenyl.
  • Preferred Lewis acids are trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane, tris(4- fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4- fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta- fluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethyl-phenyl)borane, tris(3,5- difluorophenyl)borane and/or tris (3,4,5-trifluorophenyl)borane.
  • ionic cocatalysts preference is given to using compounds which contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate, tetraphenylborate, SbF ⁇ " , CF 3 SO 3 ' or CIO 4 " .
  • Suitable counterions are either Lewis acid or Broenstedt acid cation.
  • protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N.N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N.N-dimethylanilinium or p-nitro- N.N-dimethylanilinium,
  • Suitable Lewis-acid cations are cations of the formula 11
  • Y is an element of Groups 1 to 16 of the Periodic Table of the Elements
  • Qi to Q z are singly negatively charged groups such as CrC 28 -alkyl, CQ- C-1 5 -aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, cycloalkyl groups of from 3 to about 10 carbon atoms, which may in turn bear alkyl groups of from 1 to about 10 carbon atoms as substitutents, halogen, alkoxy groups of from 1 to 28 carbon atoms, aryloxy groups of from 6 to 15 carbon atoms, silyl or mercaptyl groups.
  • groups such as CrC 28 -alkyl, CQ- C-1 5 -aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl radical and from 1 to 28 carbon atoms in the
  • a is an integer from 1-6
  • z is an integer from 0 to 5
  • d corresponds to the difference a-z, but d is larger than or equal to 1
  • Particulary suitable cations are carbonium cations such as triphenylcarbenium, oxonium cations, sulfonium cations such as tetrahydrothiophenium, phosphonium cations such as triethylphosphonium, triphenylphosphonium and diphenylphosphonium, and also cationic transition metal complexes such as the silver cation and the 1 ,1 '-dimethylferrocenium cation.
  • Preferred ionic compounds which can be used according to the present invention include: triethylammoniumtetra(phenyl)borate, tributylammoniumtetra(phenyl)borate, trimethylammoniumtetra(tolyl)borate, tributylammoniumtetra(tolyl)borate, tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(pentaffluorophenyl) aluminate, tripropylammoniumtetra(dimethylphenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate,
  • triphenylcarbeniumtetrakis ⁇ entafluorophenyl) borate N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • mixtures of all of the above and below mentioned cation-forming compounds comprise aluminoxanes and an ionic compound, and/or a Lewis acid.
  • the amount of Lewis acids or ionic compounds having Lewis-acid or Broensted-acid cations is preferably from 0.1 to 20 equivalents, preferably from 1 to 10 equivalents, based on the metallocene compound of the formulas 1 or 1a.
  • Combinations of at least one Lewis base with bimetallic compounds of the type Rj 17 M 3 (-O-M 3 Rj 18 ) v or Ri 18 M 3 (-O-M 3 R j 17 ) v (formula 12), as described in Patent Application WO 99/40,129, are likewise important as cocatalyst systems.
  • R 17 and R 18 are the same or different and represent a hydrogen atom, a halogen atom, a C 1 -C 40 carbon-containing group, especially an alkyl group of from 1 to about 20 carbon atoms, haloalkyl of from 1 to about 20 carbon atoms, alkoxy of from 1 to about 10 carbon atoms, aryl of from 6 to about 20 carbon atoms, haloaryl of from 6 to about 20 carbon atoms, aryloxy of from 6 to about 20 carbon atoms, arylalkyl of from 7 to about 40 carbon atoms, haloarylalkyl of from 7 to about 40 carbon atoms, alkylaryl of from 7 to about 40 carbon atoms, or haloalkylaryl of from 7 to about 40 carbon atoms.
  • R 17 may also be an -OSiR 51 3 group, in which the R 51 groups are the same or different and have the same meaning as R 17 , M 3 is the same or different and represents an element of main group III of the periodic table of elements, i, j, and v each stands for a whole number 0, 1 , or 2, and i + j + v is not equal to 0.
  • Preferred cocatalyst systems are the compounds of formulas (A) and (B)
  • R 17 and R 18 have the same meaning as specified above.
  • compounds that are generally to be regarded as preferred are those formed by the reaction of at least one compound of formulas (C) and/or (D) and/or (E) with at least one compound of formula (F).
  • R 27 may be a hydrogen atom or a boron-free CrC 40 carbon-containing group, such as an alkyl of from 1 to about 20 carbon atoms, aryl of from 6 to about 20 carbon atoms, arylalkyl of from 7 to about 40 carbon atoms, and alkylaryl of from 7 to about 40 carbon atoms, and in which R 17 , R 18 have the same meaning as specified above, D is an element of main Group Vl of the periodic table of elements or an NR 61 group, where R 61 is a hydrogen atom or a C 1 -C 20 hydrocarbon group, such as alkyl of from 1 to about 20 carbon atoms or aryl of from 6 to about 20 carbon atoms, f is a whole number from 0 to 3, g is a whole number from 0 to 3 where f + g corresponds to the valency of Boron, and h is a whole number from 1 to 10.
  • R 61 is a hydrogen atom or a boron-free
  • the bimetallic compounds of formula 12 are possibly combined with an organometallic compound of formula 13, i.e., [M 4 R 19 q ] k , in which M 4 is an element of main Group I, II, or III of the periodic table of the elements, R 19 is the same or different and represents a hydrogen atom, a halogen atom, a C 1 -C 40 carbon- containing group, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from about 6 to about 40 carbon atoms, arylalkyl of from 7 to about 40 carbon atoms, and alkylaryl of from 7 to about 40 carbon atoms, q is a whole number from 1 to 3, and k is a whole number from 1 to 4.
  • M 4 is an element of main Group I, II, or III of the periodic table of the elements
  • R 19 is the same or different and represents a hydrogen atom, a halogen atom, a C 1 -C 40 carbon- containing group, an al
  • the organometallic compounds of formula 13 are preferably neutral Lewis acids, in which M 4 stands for lithium, magnesium, and/or aluminum, especially aluminum.
  • M 4 stands for lithium, magnesium, and/or aluminum, especially aluminum.
  • preferred organometallic compounds of formula 13 are trimethylaluminum, triethylaluminum, triisopropylaluminum, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisoprene aluminum, dimethyl aluminum monochloride, aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, dimethyl aluminum hydride, aluminum hydride, diisopropyl aluminum hydride, dimethyl aluminum(trimethylsiloxide), dimethyl aluminum(triethylsiloxide), phenylalan, pentafluorophenylalan, and o-
  • the catalyst system of the invention contains an organoboroaluminum compound, which contains units of formula 12, as the cocatalytically active chemical compound.
  • Compounds of formula 12 in which M 3 stands for boron or aluminum are preferred.
  • the compounds that contain units of formula 12 may be present as monomers or as linear, cyclic, or cage-like oligomers. Two or more chemical compounds that contain units of formula 12 may also form dimers, trimers, or higher combinations among themselves by Lewis acid-base interactions.
  • Preferred cocatalytically active bimetallic compounds correspond to formulas 14 and 15,
  • EP-A-924,223, DE 196 22 207.9, EP-A-601 ,830, EP-A-824,112, EP-A-824,113, WO 99/06,414, EP-A-811 ,627, WO 97/11 ,775, DE 196 06 167.9 and DE 198 04 970 can preferably be used as additional cocatalysts, which may be present in unsupported or supported form.
  • the amount of cocatalysts of formula 12 and/or 14 and/or 15 used in the catalyst of the present invention can vary from 0.1 to 500 equivalents, preferably from 1 to 300 equivalents, most preferably from 5 to 150 equivalents, based on the used amount of metallocene compound of the formulas 1 or 1a.
  • the catalyst system of the present invention can further comprise, as additional component, a metal compound of the formula 16,
  • M 5 is an alkali, an alkali earth metal or a metal of Group 13 of the Periodic Table of the Elements
  • R 22 is a hydrogen atom, alkyl of from 1 to about 10 carbon atoms, aryl of from 6 to about 15 carbon atoms, or alkylaryl or arylalkyl each having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part,
  • R 23 and R 24 are each a hydrogen atom, a halogen atom, alkyl of from 1 to about 10 carbon atoms, C 6 -Cis-aryl of from about 6 to about 15 carbon atoms, or alkylaryl, arylalkyl or alkoxy each having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl radical, r is an integer from 1 to 3 and s and t are integers from 0 to 2, where the sum r+s+t corresponds to the valency of M 5 , where this component is not identical with the above mentioned cocatalyst compounds. It is also possible to use mixtures of various metal compounds of the formula 16.
  • metal compounds of the formula 16 preference is given to those in which M 5 is lithium, magnesium or aluminum and R 23 and R 24 are each alkyl of from 1 to about 10 carbon atoms.
  • Particularly preferred metal compounds of the formula 16 are n-butyllithium, n-butyl-n-octyl-magnesium, n-butyl-n- heptylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, triethylaluminum, trimethylaluminum or mixtures thereof.
  • a metal compound of the formula 16 is used, it is preferably present in the catalyst system in such an amount that the molar ratio of M 5 to the transition metal from the metallocene compound of formulas 1 or 1a is from 800:1 to 1 :1 , in particular from 200:1 to 2:1.
  • the support component of the catalyst system of the present invention can be any organic or inorganic inert solid or a mixture of such solids, in particulate porous solids such as hydrotalcites, talc, inorganic oxides and finely divided polymer powders.
  • Suitable inorganic oxides which are preferably employed include from the Periodic Table of Elements Groups 1 , 2, 3, 4, 5, 12, 13 and 14 metal oxides such as silicon dioxide, aluminum oxide, aluminosilicates, zeolites, MgO, ZrO 2 , TiO 2 or B 2 O 3 , CaO, ZnO, ThO 2 , Na 2 O, K 2 O, LiO 2 or mixed oxides like Al/Si oxides, Mg/AI oxides or Al/Mg/Si oxides.
  • metal oxides such as silicon dioxide, aluminum oxide, aluminosilicates, zeolites, MgO, ZrO 2 , TiO 2 or B 2 O 3 , CaO, ZnO, ThO 2 , Na 2 O, K 2 O, LiO 2 or mixed oxides like Al/Si oxides, Mg/AI oxides or Al/Mg/Si oxides.
  • Suitable inorganic support materials are Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCI 2 , Na 2 SO 4 , AI 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 and AI(NO 3 ) 3 .
  • Suitable polymer powders are homopolymers, copolymers, crosslinked polymers or polymer blends.
  • polymers are polyethylene, polypropylene, polybutene, polystyrene, divinylbenzene-crosslinked polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polyamide, polymethacrylate, polycarbonate, polyester, polyacetal or polyvinyl alcohol.
  • the preferred support materials have a specific surface area in the range from 10 to 1000 m 2 /g, a pore volume in the range from 0.1 to 5 cm 3 /g and a mean particle size of from 1 to 500 ⁇ m. Preference is given to supports having a specific surface area in the range from 50 to 500 m 2 /g, a pore volume in the range from 0.5 to 3.5 cm 3 /g and a mean particle size in the range from 5 to 250 ⁇ m. Particular preference is given to supports having a specific surface area in the range from 200 to 400 m 2 /g, a pore volume in the range from 0.8 to 3.0 cm 3 /g and a mean particle size of from 10 to 100 ⁇ m.
  • the support materials can be thermally and/or chemically be pretreated in order to adjust certain properties of the carrier such as the water and/or the hydroxyl group content.
  • the support material has a low moisture content or residual solvent content, dehydration or drying before use can be omitted. If this is not the case, as when using silica gel as support material, dehydration or drying is advisable.
  • Thermal dehydration or drying of the support material can be carried out under reduced pressure with or without simultaneous inert gas blanketing (nitrogen).
  • the drying temperature is in the range from 80 0 C to 1000 0 C, preferably from 150 0 C to 800 0 C and most preferred from 150 0 C to 400 0 C.
  • the duration of the drying process can be from 1 to 24 hours. But shorter or longer drying periods are also possible.
  • support materials with a weight loss on dryness (LOD) of 0.5 wt.% or less, and even more preferred with a LOD of 0.3 wt% or less are used. Higher amounts of physically adsorbed water up to 1 wt% are possible, but result in reduced catalyst activities.
  • the loss on ignition (LOI) of the support material is preferably 1 wt% or greater or even more preferred between 1.5 and 3.5 wt%.
  • the weight loss on dryness (LOD) is thereby defined as the weight loss between room temperature and 300 0 C and the weight loss on ignition (LOI) as the weight loss between 300 0 C and 1000°C.
  • dehydration or drying of the support material can also be carried out by chemical means, by reacting the adsorbed water and/or the surface hydroxyl groups with suitable passivating agents. Reaction with the passivating reagent can convert the hydroxyl groups completely or partially into a form, which does not show any adverse interaction with the catalytically active centers.
  • suitable passivating agents are silicon halides, silanes or amines, eg.
  • silicon tetrachloride chlorotrimethylsilane, dichlorodialkylsilanes, dimethylaminotrichlorosilane, N.N-dimethylanilin or N,N-dimethylbenzylamine or organometallic compounds of aluminum, boron and magnesium, eg. aluminoxanes, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, triethylborane or dibutylmagnesium.
  • aluminoxanes trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, triethylborane or dibutylmagnesium.
  • organic support materials such as finely divided polymer powders, can also be used and should, before use, likewise be freed from any adhering moisture, solvent residues or other impurities by means of appropriate purification and drying operations.
  • silica gels having the defined parameters as support materials Preference is given to using silica gels having the defined parameters as support materials.
  • Spray dried silica grades, which inherently exhibit meso and macro pores, cavities and channels are preferred over granular silica grades.
  • the supported catalyst system according to this invention can be made in various ways.
  • At least one of the above- described metallocene components of formulas 1 or 1a is brought into contact in a suitable solvent with at least one cocatalyst component, preferably giving a soluble reaction product, an adduct or a mixture.
  • the obtained composition is mixed with the dehydrated or passivated support material, the solvent is removed and the resulting supported metallocene catalyst system is dried to ensure that the solvent is completely or mostly removed from the pores of the support material.
  • the supported catalyst is obtained as a free-flowing powder.
  • the process for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps: a) preparing a metallocene/cocatalyst mixture in a suitable solvent or suspension medium, where the metallocene component has one of the above- described structures, b) applying the metallocene/cocatalyst mixture to a porous, preferably inorganic, if necessary thermally or chemically pretreated support, c) removing the major part of solvent from the resulting mixture, d) isolating the supported catalyst system and e) if desired, prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
  • the metallocene / cocatalyst composition is mixed with the dehydrated or passivated support material, the supported catalyst is recovered and optionally washed with an aromatic hydrocarbon and/or paraffinic hydrocarbon solvent.
  • the isolated catalyst is then dispersed in a non-reactive suspension media such as a paraffinic hydrocarbon solvent, a mineral oil or a wax or mixtures thereof.
  • the catalyst is prepared according to the procedure disclosed in WO 06/60544 (U.S. Patent No. 7,169,864), WO 00/05277 (U.S. Patent No. 6,812,185) and WO 98/01481 (U.S. Patent No. 6,265,339).
  • a free flowing and, if desired, prepolymerized supported catalyst system comprising the following steps: a) contacting at least one support material with a first portion of at least one co-catalyst in a suitable solvent b) impregnating the co-catalyst loaded support with a suspension or solution, which comprises at least one metallocene and a second portion of at least one co-catalyst in a suitable solvent c) isolating the supported catalyst system and f) if desired, prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
  • the process according to WO 06/60544 for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps: a) Contacting a support material with a first composition which includes at least one aluminoxane in a first solvent at a temperature of about 10 to 3O 0 C followed by keeping the mixture at about 20 0 C for 0 to 12 hours, subsequently heating the resulting mixture to a temperature of 30 to 200 0 C and keeping the mixture at 30 to 200°C for 30 minutes to 20 hours, optionally followed by removing all or part of the first solvent and/or optionally followed by one or more washing step(s) using a suitable solvent, b) Suspending and/or dissolving, respectively, at least one metallocene of formula 1 and/or 1a and a second portion of an aluminoxane or of a mixture of aluminoxanes or of an ionic compound and/or a Lewis acid in a second solvent or suspension medium at
  • the process according to WO 06/60544 for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps: a) Contacting a support material with a first composition which includes at least 5 mmol of an aluminoxane or of a mixture of aluminoxanes per g support material in a first solvent at a temperature of about 2O 0 C followed by keeping the mixture at about 20 0 C for 0.15 to 2 hours, subsequently heating the resulting mixture to a temperature of 50 to 16O 0 C and keeping the mixture at 50 to 16O 0 C for 1 to 6 hours, optionally followed by removing all or part of the first solvent and/or optionally followed by one or more washing step(s) using a suitable solvent, b) Suspending and/or dissolving, respectively, at least 0.5 mmole of a second portion of an aluminoxane or of a mixture of aluminoxanes per g support material and
  • the process according to WO 06/60544 for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps: a) Contacting an optionally thermally pretreated silica support material with at least 10 mmol of an aluminoxane per g support material in toluene at a temperature of about 2O 0 C followed by subsequently heating the resulting mixture to a temperature of 50 to 11O 0 C and keeping the mixture at 50 to 11O 0 C for 1 to 6 hours, optionally followed by removing all or part of the toluene, and/or optionally followed by one or more washing step(s) using a suitable solvent, b) Suspending and/or dissolving, respectively, at least 0.5 mmole of a second portion of an aluminoxane per g support material and at least 0.1 mol% of the employed second portion of an aluminoxane or of a mixture of aluminox
  • the process according to WO 06/60544 for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps: a) Contacting an optionally thermally pretreated silica support material with a weight loss on dryness (LOD) of 0.5 wt.% or less and a weight loss on ignition (LOI) of 1.0 wt.% or greater with a first composition which includes at least 10 mmol of methylaluminoxane per g support material in toluene at a temperature of about 20 0 C followed by subsequently heating the resulting mixture to a temperature of 110 0 C and keeping the mixture at 11O 0 C for 1 to 6 hours, optionally followed by removing all or part of the toluene, and/or optionally followed by one or more washing step(s) using a suitable solvent, b) Suspending and/or dissolving, respectively, at least 1 mmole of a second portion of methyla
  • the process according to WO 06/60544 for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps: a) Contacting an optionally thermally pretreated silica support material with a weight loss on dryness (LOD) of 0.3 wt.% or less and a weight loss on ignition (LOI) between 1.5 and 3.5 wt.%, with at least 10 mmol of methylaluminoxane per g support material in toluene at a temperature of about 20 0 C followed by subsequently heating the resulting mixture to a temperature of 11O 0 C and keeping the mixture at 110 0 C for 1 to 6 hours, optionally followed by removing all or part of the toluene, and/or optionally followed by one or more washing step(s) using a suitable solvent, b) Suspending and/or dissolving, respectively, at least 1 mmole of a second portion of methylaluminoxane
  • step b) of the catalyst preparations instead of an aluminoxane or a mixture of aluminoxanes, at least one alkyl compound of elements of main Groups I to III of the Periodic Table, for example a magnesium alkyl, a lithium alkyl or an aluminum alkyl like trimethylaluminum, triethylaluminum, triisobutyllaluminum, triisopropylaluminum, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri- n-propylaluminum, triisoprene aluminum, dimethyl aluminum monochloride, aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, dimethyl aluminum hydride, aluminum hydride
  • a free flowing and, if desired, prepolymerized supported catalyst system comprising the following steps: a) preparing a trialkylaluminium/borinic acid mixture in a suitable solvent or suspension medium b) applying the trialkylaluminium/borinic acid mixture to a porous, preferably inorganic, if necessary thermally or chemically pretreated support, which was prior treated with a base such as N,N-diethylbenzylamine, N,N-dimethylbenzylamine, N- benzyldimethylamine, N-benzyldiethylamine, N-benzylbutylamine, N-benzyl tertbutylamine, N-benzylisopropylamine, N-benzylmethylamine, N- benzylethylamine, N-benzyl-1 -phenylethylamine, N-benzyl-2-phenylethylamine, N.N-dimethylbenzyl
  • Preferred solvents for the preparation of the metallocene/cocatalyst mixture are hydrocarbons and hydrocarbon mixtures, which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
  • the solubility of the individual components is, however, not a prerequisite as long as it is ensured that the reaction product of metallocene and cocatalyst components is soluble in the solvent selected.
  • Suitable solvents are alkanes such as pentane, isopentane, hexane, isohexane, heptane, octane and nonane, cycloalkanes such as cyclopentane and cyclohexane and aromatics such as benzene, toluene, ethylbenzene and diethylbenzene. Very particular preference is given to toluene, heptane and ethylbenzene.
  • the metallocene in the form of a solid is dissolved in a solution of the cocatalyst in a suitable solvent. It is also possible to dissolve the metallocene separately in a suitable solvent and subsequently to combine this solution with the cocatalyst solution. Preference is given to using toluene.
  • the preactivation time is from 1 minute to 200 hours. The preactivation can take place at room temperature of 25 0 C. In individual cases, the use of higher temperatures can reduce the required preactivation time and give an additional increase in activity. Elevated temperatures in this case refer to a range from 25 0 C to 100 0 C.
  • the preactivated solution or the metallocene/cocatalyst mixture is subsequently combined with an inert support material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the above mentioned solvents.
  • the support material is preferably used as powder.
  • the preactivated metallocene/cocatalyst solution or the metallocene/cocatalyst mixture can be either added to the initially charged support material, or else the support material can be introduced into the initially charged solution.
  • the volume of the preactivated solution or the metallocene/cocatalyst mixture can exceed 100% of the total pore volume of the support material used or else be up to 100% of the total pore volume.
  • the temperature at which the preactivated solution or the metallocene/cocatalyst mixture is brought into contact with the support material can vary within the range from 0 0 C to 100 0 C. However, lower or higher temperatures are also possible.
  • the mixture can be stirred and, if desired, also heated.
  • both the visible portion of the solvent and the portion in the pores of the support material are removed.
  • the removal of the solvent can be carried out in a conventional way using reduced pressure and/or purging with inert gas.
  • the mixture can be heated until the free solvent has been removed, which usually takes from 1 to 3 hours at a preferred temperature of from 30 0 C to 60 0 C.
  • the free solvent is the visible portion of the solvent in the mixture.
  • residual solvent is the portion present in the pores.
  • the supported catalyst system can also be dried until only a certain residual solvent content is left, with the free solvent having been completely removed. Subsequently, the supported catalyst system can be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
  • a low-boiling hydrocarbon such as pentane or hexane
  • the supported catalyst system prepared according to the present invention can be used either directly for the polymerization of olefins or be prepolymerized with one or more olefinic monomers, with or without the use of hydrogen as molar mass regulating agent, prior to use in a polymerization process.
  • the procedure for the prepolymerization of supported catalyst systems is described in WO 94/28034.
  • an olefin preferably an alpha-olefin such as styrene or phenyldimethylvinylsilane as activity-increasing component or an antistatic, as described in U.S. Patent Application Ser. No. 08/365,280.
  • the molar ratio of additive to metallocene component of formulas 1 or 1a is preferably from 1 : 1000 to 1000: 1 , very particularly preferably from 1 :20 to 20: 1.
  • the present invention also provides a process for preparing a polyolefin by polymerization of one or more olefins in the presence of the catalyst system of the present invention comprising at least one transition metal component of the formulas 1 or 1a.
  • polymerization refers to both homopolymerization and copolymerization and the term copolymerization includes terpolymerisation or copolymerisation of more than three different monomers.
  • Suitable olefins are 1 -olefins, e.g., ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1 ,3-butadiene, 1 ,4-hexadiene, vinylnorbornene, norbomadiene, ethylnorbomadiene and cyclic olefins such as norbornene, tetracyclododecene or methylnorbornene.
  • 1 -olefins e.g., ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1 ,3-butadiene, 1 ,4-hexadiene, vinylnorbornene, nor
  • Very suitable copolymers are ethene-propene copolymers, propene-1-pentene copolymers and ethene-propene- 1-butene, ethene-propene-1-pentene or ethene-propene-1 ,4-hexadiene terpolymers.
  • the polymerization is carried out at from -60 0 C to 300 0 C, preferably from 50 0 C to 200 0 C, very particularly preferably from 50 0 C to 95 0 C.
  • the pressure is from 0.5 to 2000 bar, preferably from 5 to 100 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • impact copolymers are preferably produced in more than one stage.
  • the homopolymer or random copolymer content of such a polymer can be produced in (a) first stage(s) and the copolymer rubber content can be produced in (a) consecutive stage(s).
  • the supported catalyst system prepared according to the present invention can be used as sole catalyst component for the polymerization of olefins or preferably in combination with at least one alkyl compound of elements of main Groups I to III of the Periodic Table, for example an aluminum alkyl, magnesium alkyl or lithium alkyl or an aluminoxane.
  • the alkyl compound is added to the monomer or suspension medium and serves to free the monomer of substances, which can impair the catalytic activity.
  • the amount of alkyl compound added depends on the quality of the monomers used.
  • a catalyst system comprising two or more different metallocenes and/or two or more different cocatalysts.
  • two or more different catalyst systems of the present invention can be used as a mixture.
  • hydrogen is added if required.
  • the catalyst system may be supplied to the polymerization system as a solid or in the form of a paste or suspension in a hydrocarbon or may be treated with inert components, such as paraffins, oils, or waxes, to achieve better metering. If the catalyst system is to be metered into the reactor together with the monomer to be polymerized or the monomer mixture to be polymerized, the mixing unit and the metering line are preferably cooled.
  • an additive such as an antistatic or an alcohol can be used in the process of the present invention, for example to improve the particle morphology of the olefin polymer.
  • an additive such as an antistatic or an alcohol can be used in the process of the present invention, for example to improve the particle morphology of the olefin polymer.
  • the polymers prepared using the catalyst systems of the present invention display an uniform particle morphology and contain no fines. No agglomerates or deposits are obtained in the polymerization using the catalyst system of the present invention.
  • the catalyst systems of the present invention give polymers such as polypropylene having high molecular weight and cover a broad range of stereospecificity and regiospecificity.
  • copolymers which can be prepared using the catalyst system based on metallocenes of formula 1 or 1a of the present invention have a significantly higher molar mass compared to the prior art. At the same time, such copolymers can be prepared using the catalyst system of the present invention at a high productivity and at industrially relevant process parameters without deposit formation.
  • the polymers prepared by the process of the present invention are suitable, in particular, for producing products such as fibers, filaments, injection-molded parts, films, sheets, caps, closures, bottles or large hollow bodies such as pipes with excellent properties.
  • products such as fibers, filaments, injection-molded parts, films, sheets, caps, closures, bottles or large hollow bodies such as pipes with excellent properties.
  • the preparation and handling of the organometallic compounds were carried out under argon using Schlenk techniques or in a glove box. All solvents were purged with argon and dried over molecular sieves before use.
  • the metallocenes produced were characterized by 1 H-NMR spectroscopy using a Bruker DMX 500 spectrometer, operating at 500 MHz using CDCI 3 as the solvent.
  • the polymers produced were characterized by 1 H-NMR 1 13 C-NMR 1 DSC, GPC, TREF/ATREF, Melt Flow Rate and IR spectroscopy.
  • 0.05 wt% solutions of the samples in 1 ,2,4-trichlorobenzene were analyzed at a temperature of 145 0 C using a Mixed B light scattering quality column (Polymer Labs 1110-6100LS) and a Mixed B guard column (Polymer Labs 1110-1120).
  • Weight average molar mass (Mw) and the ratio of weight average molar mass to number average molar mass (Mw/Mn) were calculated using the Cumulative Matching % Broad Standard procedure that is available in the Waters Millenium 3.2 GPC software module.
  • Samples were prepared by weighing 0.32 g of polymer into 2.5 ml of a 1 ,2,4-trichlorobenzene/deuterobenzene-d6 (4:1 volume) mixture. Samples were heated to 125 0 C and mixed until a homogeneous solution was formed (typically 1- 4 hours). Spectra were obtained at 12O 0 C on a Varian Inova 500 instrument (Varian Inc., 3120 Hansen Way, Palo Alto, CA, 94304, USA) operating at a 13 C- spectrometer frequency of 125.7 MHz and using a 10 mm probe.
  • Varian Inova 500 instrument Varian Inc., 3120 Hansen Way, Palo Alto, CA, 94304, USA
  • Spectra were obtained using 5000 scans employing a ⁇ /2 pulse of 10.0 ⁇ s, a recycle delay of 10.0 s and an acquisition time of 2.5 s. Waltz-16 decoupling remained on throughout the pulse sequence to gain the signal to noise enhancement due to the effects of n ⁇ e. Spectra were processed with 1 Hz of line broadening. The mmmm peak in the methyl region of the spectrum was used as an internal chemical shift reference and was set to 21.85 ppm.
  • DSC measurements were carried out using a Mettler Toledo DSC 822e (Mettler-Toledo Inc., 1900 Polaris Parkway, Columbus, OH, 43240, USA). 4 mg of sample were weighed into a standard aluminum pan and subjected to the following temperature schedule:
  • the samples were heated from room temperature to 220 0 C at a heating rate of 20 °C/min, maintained at this temperature for 5 min, then cooled down to - 55 0 C at a cooling rate of 20 °C/min, maintained at the same temperature for 5 min, then heated to 220 0 C at a heating rate of 20 °C/min.
  • the melting point was determined from the second heating run as the temperature where the main peak was observed in the curve.
  • the TREF experiment is carried out on a TREF system built from a modified Waters 2000CV instrument (Waters Corporation, 34 Maple Street, Milford, MA, 01757 USA).
  • the 2000CV instrument is maintained at 140°C in o- dichlorobenzene (ODCB) solvent at 1 ml/min flowrate.
  • ODCB o- dichlorobenzene
  • the system uses a heated infrared IR4 detector (PolymerChar Company, Valencia Technology Park, P.O. Box 176, Valencia, VA, E-46980, PATERNA, Spain).
  • the system For cooling and heating of the TREF column, the system uses a temperature-programmable HAAKE Phoenix Il oil bath (Thermo Electron Corporation, 401 Millcreek Road, Marietta, OH 45750, USA).
  • the TREF separation column is a stainless steel column of 100 mm long and 0.75 mm diameter packed with 20-micrometer cross-linked polystyrene beads. This TREF column is maintained at the 140 0 C temperature in the oil bath before the sample analyses. Polymer samples are dissolved in ODCB solvent at 14O 0 C at a concentration of 2 mg/ml.
  • One ml of the test sample of the resultant ODCB solution is injected into the TREF column by the auto-injection system of the Waters 2000CV instrument with a flowrate of ODCB set at 1 ml/min. Following the sample injection, the ODCB flow is diverted away from the TREF column. As the sample is kept inside the column, the column is allowed to cool down in the oil bath from 140 0 C down to O 0 C at the cooling rate of 1.5 °C/min. In this cooling step, the polymer molecules in the test sample are precipitated onto the packing beads in the TREF column.
  • the MFR of the samples were determined according to ISO 1133 at 230 deg C. Two diffent loads were used: 2.16 kg and 5 kg. Values are reported as MFR(230/2.16) and MFR(230/5), respectively. 6.
  • the productivity of a catalyst is determined by dividing the produced mass of polypropylene by the mass of catalyst used and the reaction time.
  • the yield of a sample is determined by dividing the isolated amount of the desired product divided by the theoretical achievable amount of the product.
  • rac isomer For further enrichment of the rac isomer 1.2 g of diethylsilandiyl(2-ethyl-4-(4'-tert-butyl- phenyl)-indenyl)(2-methyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride in a rac:meso ratio of 7:1 are added to 36 ml of acetone and stirred for one hour at room temperature.
  • the mixture was stirred for 13 h at 60 0 C and then given to 300 ml water.
  • the phases were separated and the aqueous phase was extracted with 250 ml toluene.
  • the combined organic phases were dried over magnesium sulfate and the solvent was removed in vacuo.
  • the product was isolated by chromatography on silica to give a yield of 24.9 g (49 mmole, 49 %).
  • the organic phase was washed with 100 imL of water, and the aqueous phase was extracted three times with a total of 100 ml_ of toluene.
  • the combined organic phases were dried over magnesium sulfate. After separation of the magnesium sulfate, the solvent was removed and the residue was purified by column chromatography. The desired product was isolated in a yield of 8.16 g (84%) (purity 99%).
  • the residue was then dried in a vacuum, and the desired product was obtained in a yield of 1.89 g (50%) with a rac:meso ratio close to 1 :1.
  • the isomers must be separated in a subsequent step to obtain selective catalysts for propylene polymerization.
  • reaction solution was then cooled to room temperature and poured into ice water.
  • aqueous phase was repeatedly extracted with 60 mL of diethyl ether. After the organic phase has been dried with magnesium sulfate, the solvent was removed and the residue was purified by column chromatography. The desired product was isolated in a yield of 4.85 g (60%).
  • the residue was dried in an oil-pump vacuum, and the product was obtained in a yield of 155 g (80%) and with a rac:meso ratio of 1 :1.
  • the isomers must be separated in an additional step to obtain selective catalysts for propylene polymerization.
  • the resulting reaction solution was added dropwise to a solution of 20.5 g (57.7 mmoles) of (2-methyl-4-(4'-ferf-butylphenyl)-1- indenyl)dimethylchlorosilane in 246 mL of toluene over a period of one hour.
  • the mixture was stirred overnight at room temperature.
  • 60 mL of water were added and the phases which form were separated.
  • the organic phase was washed with 100 ml_ of water and the combined aqueous phases were extracted twice with a total of 100 mL of toluene.
  • the combined organic phases were dried over magnesium sulfate. After filtering off the magnesium sulfate, the solvent was removed and the residue was dried in an oil pump vacuum.
  • the desired product was isolated in a yield of 31.6 g (90%) (purity: 90%).
  • 36.6 G (60 mmoles) of dimethylsilanediyl(2-methyl-4-(4'-terf-butylphenyl)-1- indene)(2-isopropyl-4-(4'-terf-butylphenyl)-1-indene) were introduced into 366 ml of diethyl ether, and 44.9 mL of an n-butyllithium solution (2.68 M in toluene) were added without interruption at room temperature. After this addition was complete, the mixture was stirred over night at this temperature. It was then cooled to O 0 C and 14.0 g (60 mmoles) of zirconium tetrachloride were added in portions.
  • the mixture was allowed to warm to room temperature and was stirred for another two hours at this temperature.
  • the precipitate that forms was separated by filtration through a G3 fritted glass filter and was washed with two 50 mL portions of tetrahydrofuran and with one 70 mL portion of pentane.
  • the residue was dried in an oil-pump vacuum, and the product was obtained in a yield of 23.5 g (50%) and with a rac:meso ratio of about 1 :1.
  • the isomers must be separated in a subsequent step to obtain selective catalysts for propylene polymerization.
  • the residue is washed with two 1500 mL portions of toluene and three 1500 mL portions of isohexane and dried in vacuum to constant weight.
  • the methylaluminoxane treated silica is obtained as a free-flowing powder in a yield of 408 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • the filtration process is stopped and the filter cake is carefully and thoroughly stirred by means of a spatula.
  • the catalyst is then allowed to rest for one hour.
  • the residual solvent is filtered off and the catalyst is washed twice with isohexane (20 mL) and dried in a nitrogen purge to constant weight.
  • the catalyst is obtained as free- flowing orange powder in a yield of 10.2 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • the filtration process is stopped and the filter cake is carefully and thoroughly stirred by means of a spatula.
  • the catalyst is then allowed to rest for one hour.
  • the residual solvent is filtered off and the catalyst is washed twice with isohexane (20 ml_) and dried in a nitrogen purge to constant weight.
  • the catalyst is obtained as free-flowing orange powder in a yield of 10.5 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • the filtration process is stopped and the filter cake is carefully and thoroughly stirred by means of a spatula.
  • the catalyst is then allowed to rest for one hour.
  • the residual solvent is filtered off and the catalyst is washed twice with isohexane (20 ml_) and dried in a nitrogen purge to constant weight.
  • the catalyst is obtained as free-flowing orange powder in a yield of 10.0 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • the filtration process is stopped and the filter cake is carefully and thoroughly stirred by means of a spatula.
  • the catalyst is then allowed to rest for one hour.
  • the residual solvent is filtered off and the catalyst is washed twice with isohexane (20 mL) and dried in a nitrogen purge to constant weight.
  • the catalyst is obtained as free- flowing orange powder in a yield of 10.5 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • the filtration process is stopped and the filter cake is carefully and thoroughly stirred by means of a spatula.
  • the catalyst is then allowed to rest for one hour.
  • the residual solvent is filtered off and the catalyst is washed twice with isohexane (20 mL) and dried in a nitrogen purge to constant weight.
  • the catalyst is obtained as free-flowing orange powder in a yield of 11.5 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • the filtration process is stopped and the filter cake is carefully and thoroughly stirred by means of a spatula.
  • the catalyst is then allowed to rest for one hour.
  • the residual solvent is filtered off and the catalyst is washed twice with isohexane (20 ml_) and dried in a nitrogen purge to constant weight.
  • the catalyst is obtained as free- flowing orange powder in a yield of 11.9 g.
  • Example 12 10.0 G of the methylaluminoxane treated silica prepared in Example 12 are placed in a fritted glass filter as a column with a smooth surface. A minimal amount of toluene is added and the treated silica is carefully stirred with a spatula to remove any air pockets in the column. The excess toluene is removed by filtration leaving a smooth surface.
  • a dry and nitrogen purged 5 dm 3 autoclave equipped with a stirrer is charged with if desired 100 g of metallocene polymer seed bed.
  • a certain amount of hydrogen is metered in.
  • a certain amount of ethylene are metered in and the mixture is stirred for at least 5 minutes (stirrer speed 200 rpm) at 20 0 C.
  • supported metallocene catalyst suspended in 5 cm 3 of white oil, is injected with liquid propylene (one-half of total amount used for the run).
  • the reactor is heated to the internally measured run temperature (65, 60 or 30 0 C) within 11 minutes.
  • the polymerization reaction is allowed to proceed at the run temperature for either 15 or 60 minutes.
  • the reactor pressure was maintained by continuous feeding of ethylene and propylene.
  • the polymerization is stopped by releasing the monomer and cooling down the reactor.
  • the polymer is discharged and dried under reduced pressure.
  • inventive examples 13, 14 and 17 ethyl and methyl substituents in the 2 positions and t-butyl-phenyl substituents in the 4 positions of the indenyl groups
  • comparative examples 22 and 23 methyl or isopropyl substituents in the 2 positions and t-butyl-phenyl substituents in the 4 positions of the indenyl groups.
  • Table 1 and Table 2 represent the raw data presented by test run; the remaining tables 3 - 12 break that data out by the ratio of propylene to ethylene or if the polymer is a propylene homopolymer whether hydrogen was used in the polymerization process.
  • Table 3 shows the results of seven experimental Metallocene catalysts conforming to the requirements of the invention compared to four comparative examples.
  • the catalysts of the present invention showed a 70% increase in productivity while at the same time showing a 89% increase in Molecular Weight and more than a two degree Celcius increase in melting point (significant when the range of melting points for homopolymer polypropylene is 144 to 154 degree Celsius).
  • the catalysts of the current invention produced products with an aggregate MFR 2.16 of just about 13% of that of the comparative products and an aggregate MFR 5 of just about 12% of the comparative examples. This dramatic drop in MFR indicates a dramatic increase of Molecular Weight (89%) and opens full access to application fields like film, pipe or sheets, where a high Molecular Weight is mandatory.
  • inventive samples 13, 14 and 17 and comparative examples 22 and 23 are just as dramatic.
  • examples 13, 14 and 17 are compared to comparative examples 22 and 23
  • all inventive examples exhibit significantly lower xylene solubles, lower MFR 2.16, MFR 5 rates and increases in Molecular Weight.
  • MFR 2.16 the inventive examples 13, 14 and 17 show a reduction of 23%, 20%, and 29% of the original value of example 22.
  • the inventive examples 13, 14 and 17 show a respective reduction of 58%, 53% and 57% of the original value of example 22.
  • the inventive examples 13, 14 and 17 show a respective increase of 11 %, 9% and 9% over the original value.
  • inventive examples 13, 14 and 17 showed these dramatic improvements in product properties at significantly higher productivity levels of 20%, 12% and 18%.
  • all three inventive examples exhibit significantly lower MFR 2.16, MFR 5 rates and increases in Molecular Weight.
  • the inventive examples 13, 14 and 17 show a respective reduction of about 78% of the original value of example 23.
  • inventive examples 13, 14 and 17 show a respective reduction of about 80% of the original value of example 23.
  • the inventive examples 13, 14 and 17 show a respective increase of 109%, 105% and 106% over the original value.
  • Productivity was also massively enhanced, respectively by a 186%, 166% and 180% increase over the original value of example 23.
  • Table 4 shows the results of seven experimental Metallocene catalysts conforming to the requirements of the invention compared to four comparative examples.
  • hydrogen was added during the polymerization process to enhance catalyst productivity and to regulate the Molecular Weight.
  • the catalysts of the present invention showed more than a 133% increase in productivity while at the same time showing more than a 90% increase in Molecular Weight and almost a two degree Celcius increase in melting point (significant when the range of melting points for homopolymer polypropylene is 146 to 155).
  • the catalysts of the current invention produced products with an aggregate MFR 2.16 of only 15% of that of the comparative products and an aggregate MFR 5 of only 14% of the comparative examples.
  • inventive examples 13, 14 and 17 show significantly lower MFR 2.16, MFR 5 rates and increases in Molecular Weight.
  • MFR 2.16 the inventive examples 13, 14 and 17 show a respective reduction of 33%, 30%, and 28% of the original value of example 22.
  • the inventive examples 13, 14 and 17 show a respective reduction of 29%, 27% and 26% of the original value of example 22.
  • the inventive examples 13, 14 and 17 show a respective increase of 56%, 52% and 43% over the comparative value. Even more surprisingly is that the inventive examples showed these dramatic improvements in product properties at increased productivity levels of 88%, 71% and 85% over the comparative value.
  • examples 13, 14 and 17 When examples 13, 14 and 17 are compared to comparative example 23, all three inventive examples exhibit significantly lower MFR 2.16, MFR 5 rates and increases in Molecular Weight. Specifically for MFR 2.16, the inventive examples 13, 14 and 17 show a respective reduction of 93% to 94% of the original value of comparative example 23. For MFR 5, inventive examples 13, 14 and 17 show a respective reduction of about 94% of the original value of example 23. For the molecular weight, the inventive examples 13, 14 and 17 show a respective increase of 130%, 124% and 111% over the original value. Productivity was also significantly enhanced, respectively by a 135%, 114% and 131% increase over the comparative value.
  • the polymers based on the inventive metallocenes show an extremely high productivity, a similar incorporation of the ethylene comonomer (content of 1.8 to 2.5 wt.% ethylene), a low MFR 2,16 level (0.7 to 1.5) resp. MFR 5 level (2.0 to 5.1 ) and a high Molecular Weight (389 to 471 ) and open full access to application fields like film, pipe or sheets, where a high Molecular Weight, low MFR and a low content of catalyst residues (achieved by the high catalyst productivity) are mandatory.
  • the polymers based on the inventive metallocenes show an extremely high productivity, a similar incorporation of the ethylene comonomer (content of 4.0 to 5.2 wt.% ethylene), a low MFR 2,16 level (0.9 to 3.2) resp. MFR 5 level (3.2 to 10.1 ) and a high Molecular Weight (231 to 385) and open full access to application fields like film, pipe or sheets, where a high Molecular Weight, low MFR and a low content of catalyst residues (achieved by the high catalyst productivity) are mandatory.
  • the polymers based on the inventive metallocenes 13 to 17 and 19 show an extremely high productivity, a similar incorporation of the ethylene comonomer (content of 9.2 to 11.2 wt.% ethylene), a low MFR 2,16 level (0.5 to 0.75) resp. MFR 5 level (1.4 to 2.0) and a high Molecular Weight (440 to 581 ) and open full access to application fields like film, pipe or sheets, where a high Molecular Weight, low MFR and a low content of catalyst residues (achieved by the high catalyst productivity) are mandatory.
  • copolymers based on catalyst from example 18 open opportunities in the fields of fibre and injection molding applications where slightly higher MFR ' s and slightly lower Molecular Weights combined with a high catalyst productivity and and an excellent comonomer incorporation is required.
  • inventive catalysts from examples 13 to 15 and two comparative catalysts from comparative examples 20 and 21 were tested, the results being presented in Table 10.
  • individual catalyst comparisons with the comparative examples 20 and 21 are not possible because in these cases the substitutions in all positions of the indenyl groups other than the 2 position are not the same as the catalyst from comparative example 20 has no substitution in the 4 positions of the indenylligands and the catalyst from comparative example 21 carries a cyclic system bridging the positions 4 and 5 of the indenylligands, but are provided for informational purposes only.
  • the polymers based on the inventive metallocenes 13 to 15 clearly show the superior performance of the concept of the invention. While the polymerizations based on state of the art catalysts, based on metallocenes from examples 20 and 21 , result in polymers with waxy consistency and extremely low molecular weight which makes the measurement of MFR values impossible, the propylene/ethylene rubber produced with catalyst from example 14 shows still a reasonable high Molecular Weight and low MFR values. Due to capacity limitations, the originally planned polymerization examples 9 and 30 have not been performed.
  • the polymer based on the inventive metallocene 13 clearly shows the superior performance of the concept of the invention. While the polymerizations based on state of the art catalysts, based on metallocenes from examples 20 and 21 , result in polymers with waxy consistency where the measurement of MFR and Molecular Weight was no longer possible, the propylene/ethylene rubber produced with catalyst from example 13 shows still a reasonable high Molecular Weight and low MFR values.
  • inventive catalysts from examples 13 to 15 and three comparative catalysts from comparative examples 20, 21 and 22 were tested, the results being presented in Table 12.
  • the polymerizations based on the inventive catalysts 13 and 14 can be compared with the results from the polymerizations based on the comparative catalyst 22.
  • individual catalyst comparisons with the comparative examples 20 and 21 are not possible because in these cases the substitutions in all positions of the indenyl groups other than the 2 position are not the same as the catalyst from comparative example 20 has no substitution in the 4 positions of the indenylligands and the catalyst from comparative example 21 carries a cyclic system bridging the positions 4 and 5 of the indenylligands, but are provided for informational purposes only.
  • the polymers based on the inventive metallocenes 13 to 15 clearly show the superior performance of the concept of the invention. While the polymerizations based on state of the art catalysts, based on metallocenes from examples 20 and 21 , result in polymers with waxy consistency and extremely low molecular weight ( ⁇ 20) which makes the measurement of MFR values impossible, the propylene/ethylene rubber produced with catalysts from examples 13, 14 and 15 show still reasonable Molecular Weight and MFR values.
  • examples 13 and 14 When examples 13 and 14 are compared to comparative example 22, all inventive examples exhibit significantly lower MFR 2.16 and MFR 5 rates. Specifically for MFR 2.16, the inventive examples 13 and 14 show a respective reduction of more than 40% and 48% of the original value of the comparative example 22. For MFR 5, inventive examples 13 and 14 show a respective reduction of 40 to 42% of the original value of example 22. For the Molecular Weight, the inventive examples 13 and 14 show similar values from 167.5 to 175.3.

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Abstract

L'invention porte sur un procédé de polymérisation d'oléfines qui comprend la mise en contact d'une ou de plusieurs oléfines avec un système catalyseur dans des conditions de réaction de polymérisation, le système catalyseur comprenant un métallocène et un aluminoxane et/ou un acide de Lewis ou un composé ionique capable de convertir le métallocène en un composé cationique. Le procédé est particulièrement avantageux pour la polymérisation de l'éthylène et/ou du propylène.
PCT/US2007/022623 2007-10-25 2007-10-25 Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines WO2009054833A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2007/022623 WO2009054833A2 (fr) 2007-10-25 2007-10-25 Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines
EP07852954A EP2235071A2 (fr) 2007-10-25 2007-10-25 Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines

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WO2019132421A1 (fr) * 2017-12-26 2019-07-04 주식회사 엘지화학 Homopolypropylène et son procédé de préparation
JP2020502309A (ja) * 2017-11-27 2020-01-23 エルジー・ケム・リミテッド ポリプロピレンおよびその製造方法
CN110914316A (zh) * 2017-11-28 2020-03-24 Lg化学株式会社 聚丙烯及其制备方法

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US9988323B2 (en) 2012-12-21 2018-06-05 Borealis Ag Catalyst
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US9598517B2 (en) 2012-12-21 2017-03-21 Borealis Ag Catalysts
US9644047B2 (en) 2013-07-17 2017-05-09 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
US9834628B2 (en) 2013-07-17 2017-12-05 Exxonmobil Chemical Patents Inc. Cyclopropyl substituted metallocene catalysts
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US10487161B2 (en) 2013-07-17 2019-11-26 Exxonmobil Chemical Patents Inc. Cyclopropyl substituted metallocene catalysts
US10155829B2 (en) 2013-07-22 2018-12-18 Basell Poliolefine Italia S.R.L. Sterilizable article made of propylene copolymer
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JP2020502309A (ja) * 2017-11-27 2020-01-23 エルジー・ケム・リミテッド ポリプロピレンおよびその製造方法
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EP3647331A4 (fr) * 2017-11-28 2020-11-18 LG Chem, Ltd. Polypropylène et son procédé de préparation
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US11117990B2 (en) 2017-12-26 2021-09-14 Lg Chem, Ltd. Homopolypropylene and method for preparing the same
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