# Patent

## Title
Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers

## Abstract

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 α-branched substituent in either of the two available 2-positions of the indenyl ligands. The substituent in the 2-position of one indenyl ligand can be any radical comprising hydrogen, methyl, or any other C2-C40 hydrocarbon which is not branched in the α-position, and substituent in the 2-position of the other indenyl ligand can be any C5-C40 hydrocarbon radical with the proviso that this hydrocarbon radical is branched in the β-position and that the β-carbon atom is a quarternary carbon atom and part of a non-cyclic hydrocarbon system. This metallocene topology affords high melting point, very high molar mass homo polypropylene and very high molar mass propylene-based copolymers. Furthermore, the activity/productivity levels of catalysts comprising the metallocenes of the present invention are exceptionally high.

## Background
BACKGROUND
1. Field of the Invention
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.
2. Background of the Art
One of the most important factors determining the success of a catalyst is its versatility, that is the possibility to use it for the broadest possible range of products. For a long time, the limitations for the development of metallocene catalysts for polypropylene has been their inability to produce propylene-ethylene copolymers of high molar mass, due to the fact that ethylene behaves as a chain transfer agent with most metallocenes. This effect has been observed for all basic metallocene structures, such as the syndiospecific Cs symmetric Me2C(Cp)(Flu)ZrCl2, the aspecific C2v symmetric Me2Si(Flu)2ZrCl2, and both the C2 symmetric rac-Me2C(3-iPr—Ind)2ZrCl2 and the fluxional (2-Ph-Ind)2ZrCl2 catalysts for elastomeric polypropylene. This effect has also been found for the isospecific C2 symmetric rac-Me2Si(2-Me-4,5-Benz-Ind)2ZrCl2 and rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 [L. Resconi, C. Fritze, “Metallocene Catalysts for Propylene Polymerization” In Polypropylene Handbook (N. Pasquini, Ed.), ch. 2.2, Hanser Publishers, Munic 2005]. While the 2-Me substitution of this catalyst family suppresses the β-hydrogen transfer to the propylene monomer and thus prevents the formation of low molar mass polymer, it fails to prevent the β-hydrogen transfer to the ethylene comonomer in case of the latter's presence. This β-hydrogen transfer to the ethylene comonomer becomes the favored chain termination mechanism and leads to the formation of low molar mass propylene-ethylene copolymers [A. Tynys et al., Macromol. Chem. Phys. 2005, vol. 206, pp. 1043-1056: “Ethylene-Propylene Copolymerizations: Effect of Metallocene Structure on Termination Reactions and Polymer Microstructure”]. Exceptions have been found in some zirconocenes with highly bulky ligands, such as rac-Me2C(3-tBu-Ind)2ZrCl2, which show a marked increase in molar masses by ethylene incorporation. This catalyst, however, has shortcomings in terms of homopolymer molar mass and activity.
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. Within the rao-Alk2Si(2-Alk-Ind)2ZrCl2 catalyst family, the stereospecificity and regioselectivity has continuously been improved during the last 15 years. EP-A1 834 519 relates to metallocenes of the rac-Me2Si(2-Me-4-Ar—Ind)2ZrCl2 for the production of high rigid, high Tm polypropylenes with very high stereoregularity and very low amounts of regio errors. 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 rao-Me2Si(2-Alk-4-Ar—Ind)2ZrCl2 family. High molar masses in the propylene/ethylene rubber were achieved when both Alk substituents were i-propyl groups. WO 02/002576 discloses bridged metallocenes of the (2-R-4-Ph-Ind)2ZrCl2 family having particular combinations of substituents in the 2-positions of the indenyl ligands and substituents in the benzene ring. A high polypropylene (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—Ind)2ZrCl2 catalysts if both ligands R are branched in the α-position. WO 03/002583 discloses bridged metallocenes of the (2-R-4-Ph-Ind)2ZrCl2 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. One major shortcoming is the very low activity/productivity of the rac-Me2Si(2-R-4-Ar—Ind)2ZrCl2 catalysts if both ligands R are branched in the α-position. Moreover, the highest possible molar masses of the homopolymers produced by using such catalysts are relatively low which corresponds to relatively high melt flow rates. This, in turn excludes such metallocenes from catering applications such as pipe, blown film, cast film and injection stretch blow molding.
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 α-position. WO 04/106351 relates to metallocenes having substituents in the 2-positions of the indenyl ligands with the proviso that one ligand is unbranched or bound via an sp2-hybridized carbon atom and the other ligand is branched in the α-position. Such catalysts afford high Tm homopolymers and high molar mass propylene/ethylene copolymers. However, there still are limitations with regard to catalyst activity/productivity and lowest achievable homopolymer melt flow rate.
PCT/US2007/022614, a co-pending applications by the present inventors, demonstrated that metallocenes having ligands being β-branched in the 2-position created surprising increases in activity of the metallocene catalyst and also created products with unexpectedly superior properties than previously known metallocenes. The inventors now have discovered a species of the previously revealed genus that unexpectedly produces even significantly higher increases in catalyst activity and improvements in product properties.
In summary, 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. As a consequence, when compared to Ziegler/Natta catalysts, the industrial usefulness of these catalysts is limited because certain applications that require a combination of a high melting point, a very low melt flow rate, and/or a high molar mass copolymer or copolymer component, such as in impact copolymers, are not available at cost competitive productivities.
An object of the present invention is to address this shortcoming of the state of the art metallocene compounds and to provide metallocenes that increase desirable characteristics such as high melting point, high molar mass homopolymers and high molar mass copolymers, and do so at higher productivities when used as components of supported catalysts under industrially relevant polymerization conditions at temperatures of from 50° C. to 100° C. In addition, the inventions of the current example provide these advantages by using a metallocene with symmetrically substituted 2 positions on the indenyl group. This is significantly more cost effective, and therefore far more desirable, than the comparative examples that have asymmetric substitution.
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.
Furthermore, it is an objective of the present invention to provide 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.
SUMMARY
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 α-branched substituent in either of the two available 2-positions of the indenyl ligands. The substituent in the 2-position of one indenyl ligand can be any radical comprising hydrogen, methyl, or any other C2-C40 hydrocarbon which is not branched in the α-position, and the substituent in the 2-position of the other indenyl ligand can be any C5-C40 hydrocarbon radical with the proviso that this hydrocarbon radical is branched in the β-position and that the β-carbon atom is a quarternary carbon atom and part of a mono-cyclic hydrocarbon system. It is even more preferred, that the substituents in the 2-position of both indenyl ligands are identical and are any C5-C40 hydrocarbon radical with the proviso that this hydrocarbon radical is branched in the β-position and that the β-carbon atom is a quarternary carbon atom and part of a mono-cyclic hydrocarbon system. This metallocene topology affords high melting point, very high molar mass homo polypropylene and very high molar mass propylene-based copolymers. Furthermore, the activity/productivity levels of catalysts comprising the metallocenes of the present invention are exceptionally high.
While various metallocenes are described, for example, in U.S. Publication No. 2006/0116490, the improvement in olefin polymerization achieved by the metallocene topology of the present invention is new and unexpected.
One embodiment described herein is a bridged metallocene having the general Formula 1 shown below:




where M1 is a metal of Group IVb of the Periodic Table of the Elements,

R1 and R2 are identical or different and are selected from the group consisting of 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 NR232 group, where R32 is an alkyl group of from 1 to about 10 carbon atoms and an aryl group of from 6 to about 14 carbon atoms, and wherein R1 and R2 may form one or more ring system(s),
R4 and R4′ are identical or different and are selected from the group consisting of a hydrogen atom and a linear, cyclic or branched hydrocarbon group optionally containing one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br,
R10 is a bridging group wherein R10 is selected from:




where
R40 and R41, even when bearing the same index, can be identical or different and can optionally contain heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, Cl and Br, and are 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, an alkyl(aryl)silyl group, an arylsilyl group, and an arylalkenyl group of from 8 to about 40 carbon atoms, and wherein R40 and R41 together with the atoms connecting them can form one or more cyclic systems,
x is an integer from 1 to 18,
M12 is silicon, germanium or tin, and
R10 can optionally link two units of the formula 1 to one another,
R11 and R11′ are identical or different and are each a divalent C2-C40 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 R11 and R11′ optionally contain the heteroatoms Si, Ge, N, P, O or S within the ring system fused onto the cyclopentadienyl ring, and

    
    
        R300 has the structure
    
    






    
    
        where R301 is a linear, cyclic or branched hydrocarbon group selected from the group consisting of 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, wherein each of 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 where R302 is a hydrocarbon group selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, and an substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, and wherein those 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 further wherein R302 forms a monocyclic ring with the β carbon atom.
    
    


R3 has the meaning of R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group which optionally can contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl or Br, or R3 is selected from the group consisting of an alkyl group of from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, and an alkylarylalkenyl group of from 9 to about 40 carbon atoms, with the proviso that, in any case, R3 is not branched in the α-position.
Another embodiment described herein is a process for olefin polymerisation comprising contacting one or more olefins each having from 2 to about 20 carbon atoms under olefin polymerisation reaction conditions with a catalyst system including a bridged metallocene component having Formula 1 shown above.
Yet another embodiment described herein is a bridged metallocene having the general Formula 1a shown below:




where M1 is a metal of Group IVb of the Periodic Table of the Elements,

R1 and R2 are identical or different and are selected from the group consisting of 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 NR232 group, where R32 is an alkyl group of from 1 to about 10 carbon atoms and an aryl group of from 6 to about 14 carbon atoms and R1 and R2 may form one or more ring system(s),
R4 and R4′ are identical or different and are selected from the group consisting of a hydrogen atom and a linear, cyclic or branched hydrocarbon group optionally containing one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br,
R10 is a bridging group wherein R10 is selected from:




where
R40 and R41, even when bearing the same index, can be identical or different and can optionally contain heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, Cl and Br, 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, an alkyl(aryl)silyl group, an arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms and wherein R40 and R41 together with the atoms connecting them may form one or more cyclic systems,
x is an integer from 1 to 18,
M12 is silicon, germanium or tin, and
R10 can optionally link two units of the formula 1 to one another, and

    
    
        R300 has the structure:
    
    






    
    
        where R301 is a linear, cyclic or branched hydrocarbon group selected from the group consisting of 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, wherein 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 where R302 is a hydrocarbon group selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, and an substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, and 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, wherein R302 forms a monocyclic ring with the β carbon atom.
    
    


R3 has the meaning of R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group which optionally can contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl or Br or R3 is selected from the group consisting of an alkyl group of from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, and an alkylarylalkenyl group of from 9 to about 40 carbon atoms, with the proviso that R3, in any case, is not branched in the α-position,
and where R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ are identical or different and are each selected from the group consisting of a hydrogen atom, a linear, cyclic or branched hydrocarbon group or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group and wherein each of 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 further wherein adjacent radicals R5, R6 or R6, R7 or R7, R8 and also R5′, R6′ or R6′, R7′ or R7′, R8′ in each case may form a hydrocarbon ring system.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates individual steps of the process for producing transition metal compounds of the bridged metallocene compound of the invention.
FIG. 2 is a photograph of the copolymer obtained in Comparative Example 20.
FIG. 3 is a photograph of the copolymer obtained in Example 19.



DETAILED DESCRIPTION
We have found that this object is achieved by 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 a further additive component. According to the present invention, 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 a further additive component.
The first embodiment of the invention relates to a substituted, bridged metallocene component of the general Formula 1 below,




where M1 is a metal of Group IVb of the Periodic Table of the Elements, preferably zirconium or hafnium, and particularly preferably zirconium.

R1 and R2 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 NR232 group, where R32 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 R1 and R2 may form one or more ring system(s). Preferably, R1 and R2 are identical or different and are an alkyl 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 or a halogen atom, or R1 and R2 together may form one or more ring system(s). Particularly preferably, R1 and R2 are identical or different and are methyl, chlorine or phenolate.
R4 and R4′ 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 20 carbon atoms, an alkenyl group of from 2 to 20 carbon atoms, an aryl group of from 6 to 20 carbon atoms, an arylalkyl group of from 7 to 40 carbon atoms, an alkylaryl group of from 8 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. The group 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. Preferably, R4 and R4′ 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 10 carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms, an alkylaryl group of from 8 to about 20 carbon atoms, or an arylalkenyl group of from 8 to about 20 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or an arylsilyl group. The groups may be halogenated. Particularly preferably, R4 and R4′ are both hydrogen.
R10 is a bridging group wherein R10 is selected from:




where
R40 and R41, even when bearing the same index, can be identical or different and are each a hydrogen atom, a C1-C40 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. R40 and R41 together with the atoms connecting them can form one or more cyclic systems or R40 and/or R41 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,
M12 is silicon, germanium or tin, and
R10 may also link two units of the formula 1 to one another.
Preferably, R10 is R40R41Si═, R40R41Ge═, R40R41C═ or —(R40R41C—CR40R41) where R40 and R41 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 atoms, an arylalkyl group of from 7 to about 14 carbon atoms, an alkylaryl group of from 7 to about 14 carbon atoms or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl or an arylsilyl group.
Particularly preferably, the bridging unit R10 is R40R41Si═ or R40R41Ge═, where R40 and R41 are identical or different and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl, naphthyl, benzyl, trimethylsilyl or 3,3,3-trifluoropropyl.
R11 and R11′ are identical or different and are each a divalent C2-C40 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 R11 and R11′ may contain the heteroatoms Si, Ge, N, P, O or S within the ring system fused onto the cyclopentadienyl ring. Preferably, the groups R11 and R11′ are identical or different and are each a divalent group selected from those given in Formulae 1 , γ, δ, φ, and ν and Formulae 1 ′, γ′, δ′, Φ′, and ν′, respectively. The asterisks “*” and “**” in Formula 1 and Formulae 1α-ν and 1α′-ν′, respectively, denote the chemical bonds joining R11 and R11′ to the cyclopentadienyl rings. For illustration, if R11 is represented by Formula 1γ and R11′ is represented by Formula 1γ′, then the structure given in Formula 1a (see below) is obtained. Particularly preferably, R11 and R11′ are identical or different and R11 is a divalent group according to Formula 1γ and R11′ is selected from the divalent groups in Formulae 1α′, β′, and γ′ or R11 and R11′ are identical or different and are divalent groups according to Formula 1α and 1α′ or Formula 1β and 1β′ or Formula 1γ and 1γ′ or Formula 1δ and 1δ′ or Formula 1φ and 1φ′ or Formula 1ν and 1ν′, respectively,







R5, R6, R7, R8, and R9 and also R5′, R6′, R7′, R8′ and R9′ as well as R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ 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(aryl)silyl group or an arylsilyl group. Two adjacent radicals R5, R6 or R5′, R6′ or R6, R7 or R6′, R7′ or R7, R8 or R7′, R8′ or R8, R9 or R8′, R9′ as well as R55, R66 or R55′, R66′ or R66, R77 or R66′, R77′ or R77, R88 or R77′, R88′ or R88, R99 or R88′, R99′ in each case may form a saturated or unsaturated 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.
Preferably, R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ are each a hydrogen atom and R5, R6, R7, R8 and R9 and also R5′, R6′, R7′, R8′ and R9′ 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 and 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. The two adjacent radicals R5/R6 and also R5′/R6′ may form a hydrocarbon ring system or R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.
Particularly preferably, R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ are each a hydrogen atom and R5, R6, R7, R8 and R9 and also R5′, R6′, R7′, R8′ and R9′ 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. The two adjacent radicals R5, R6 and also R5′, R6′ together may form a ring system or R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.
R300 is a




group, where R301 is 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or an arylsilyl group, and 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.

Preferably R301 is a is 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 10 carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, or an arylalkenyl group of from 8 to about 20 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 substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or an arylsilyl group, and 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.
Particular preferably R301 is a is a linear, cyclic or branched hydrocarbon group, for example an alkyl group of from 1 to about 4 carbon atoms, an aryl group of from 6 to about 10 carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, and 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.
Most particular preferably R301 is a linear or branched hydrocarbon group, for example an alkyl group of from 1 to about 4 carbon atoms,
R302 is a hydrocarbon group which is building a mono-cyclic ring with the β-carbon atom, for example a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, an substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, and 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.
Preferably R302 is a hydrocarbon group which is building a mono-cyclic ring with the β-carbon atom, for example a substituted or unsubstituted alkyl group of from 2 to about 10 carbon atoms, and 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.
Particularly preferably R302 is a hydrocarbon group which is building a mono-cyclic ring with the β-carbon atom, for example a substituted or unsubstituted alkyl group of from 3 to about 7 carbon atoms, and 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, with the proviso that R300 contain more than 6 carbon atoms.
R3 may be chosen from the same set that described R300 (but R3 need not be identical to R300) or R3 is a hydrogen atom, a linear, cyclic or branched hydrocarbon group which may be halogenated and/or may contain one or more hetero atoms like Si, B, Al, O, S, N or P, for example an alkyl group of from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an alkylarylalkenyl group of from 9 to about 40 carbon atoms, with the proviso that R3 is not cyclic or branched in α-position.
Preferably, R3 is chosen from the same set that described R300 (but R3 need not be identical to R300) or R3 is a linear, cyclic or branched hydrocarbon group of from 1 to about 20 carbon atoms, for example an alkyl group of from 1 to 20 carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms or an alkylarylalkenyl group of from 9 to about 20 carbon atoms with the proviso that R3 is not cyclic or branched in α-position.
More preferably, R3 and R300 are identical or R3 is a methyl group or a linear, cyclic or branched hydrocarbon group of from 7 to about 10 carbon atoms which may be halogenated, an alkylaryl group of from 7 to about 10 carbon atoms or an alkylalkenyl group of from 7 to about 10 carbon atoms with the proviso that R3 is not cyclic or branched in α-position.
Particularly preferably, R3 and R300 are identical with the proviso that R3 and R300 contain more than 6 carbon atoms.
Preferable, either of R3 and R300, or both are not cyclic or, in the alternative, are not branched in the α-carbon position.
Preferably, the specifically substituted, bridged metallocene component of the first embodiment of the invention is as given in Formula 1a below.




M1, R1, R2, R3, R4, R4′, R10 and R300 have the meaning set forth above with respect to Formula 1.

For the substituents R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ of Formula 1a, there are two equitable substitution patterns.
In the first substitution pattern, R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ 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. 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 R5, R6 or R6, R7 or R7, R8 and also R5′, R6′ or R6′, R7′ or R7′, R8′ in each case may form a hydrocarbon ring system.
Preferably, R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ 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, and/or the two adjacent radicals R5, R6 and also R5′, R6′ may form a saturated or unsaturated hydrocarbon ring system.
Particularly preferably, R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ 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 R5, R6 and also R5′, R6′ together may form a saturated or unsaturated ring system.
In the second substitution pattern, R6, R7, R8 and also R6′, R7′ and R8′ 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. Two adjacent radicals R6, R7 or R7, R8 as well as R6′, R7′ or R7′, R8′ 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. R5 and R5′ 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, Al, O, S, N or P, and/or may contain halogen atoms like F, Cl or Br.
Preferably, R6, R7 and R8 and also R6′, R7′ and R8′ are identical or different and ate 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. R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.
Particularly preferably, R6, R7 and R8 and also R6′, R7′ and R8′ 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. R5 and R5′ are identical or different and are each naphthyl, 4-(C1-C10-alkyl)phenyl or 4-(C6-C20-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-(C1-C10-fluoroalkyl)-phenyl, 3-(C1-C10-alkyl)-phenyl, 3-(C1-C10-fluoroalkyl)-phenyl, 3-(C6-C20-aryl)phenyl like 3-biphenyl, 3,5-di-(C1-C10-alkyl)-phenyl such as 3,5-dimethyl-phenyl, 3,5-di-(C1-C10-fluoroalkyl)-phenyl, such as 3,5-di(trifluoromethyl)-phenyl or 3,5-(C6-C20-aryl)phenyl like 3,5-terphenyl.
Non-limiting examples for the particularly preferred metallocene compounds according to Formula 1 and 1a are given below:

    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(tert-butyl phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(tert-butyl phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[1-methylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl)-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propyl-cyclooctyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[1-propylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(5-methyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(5-ethyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(2,2,5-trimethyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(2,2-dimethyl-5-ethyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(3-methyl-oxetan-3-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(3-ethyl-oxetan-3-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-methylcyclohex-3-en-1-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
    Dimethylsilandiylbis[2-[(1-ethylcyclohex-3-en-1-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride

as well as the analogous zirconiumdimethyl-compounds and zirconium-biphenolates and zirconium-bisphenolates.



Instead of the preferred pure chiral bridged racemic or pseudoracemic metallocene compounds of formulas 1 and 1a, mixtures of the metallocenes of formulas 1 and 1a and the corresponding meso or pseudomeso metallocenes may be used in the catalyst preparation. However, 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.
As used herein the term “racemic” (or “rac”) 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,




in which the variables R and M1 have the meaning specified above, including the preferred embodiments, comprising the steps of:

    
    
        a) Deprotonation of the compound of formula 2:
    
    






    
    
        with a base, in which R300, R4′, R5′, R6′, R7′, and R8′ have the meaning specified above.
        b) If R10 has the meaning M12R40R41, where M12, R40, and R41 have the meanings specified above, then the further production proceeds by the reaction of the deprotonated compounds from step (a) with R40R41M12X2 to form the compound of formula 3 or formula 4, depending on the quantitative proportions used, where R40, R41, and M12 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.
    
    






    
    
        c) After the production of chlorosilane indenes or chlorogermane indenes of formula 3, these are reacted with a metal-indene compound of formula 5
    
    






    
    
         in which M stands for Li, Na, or K, and R3, R4, R5, R6, R7, and R8 have the meanings specified above, to obtain the compound of formula 6.
    
    






    
    
        d) Reaction of the compound of formula 4 or 6 with a base and addition of M1Cl4, in which M1 stands for zirconium, titanium, or hafnium, to form the compound of formula 1a.
    
    


In step (a), the compound of formula 2, for example, 2-(1-methyl-cyclohexylmethyl)-7-(4-tert-Butyl-phenyl)-1H-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, n-butyllithium. The deprotonation is carried out at temperatures of −70° C. to 80° C., and preferably 0° C. to 80° 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. Preferential production of the compound of formula 3 or the compound of formula 4 can be achieved by adjustment of the quantitative proportions. Compounds of formula 3 are reacted in step (c) with a metal-indenyl compound of formula 5. In the following step (d), the bis(indenyl)silanes of formula 4 or 6 are doubly deprotonated with a strong base, such as n-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. The deprotonation is carried out at temperatures of −70° C. to 80° C., and preferably 0° C. to 80° C. Depending on the nature of the ligand system of formula 4 or 6, the metallocenes can be isolated either 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.
In FIG. 1, the individual steps of the process of the invention for producing transition-metal compounds of formulas 1a are shown once again for the example of a preferred embodiment.
In addition, 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 7.

(R—Al—O)p  (Formula 7).

Examples for cyclic, linear or cage structures of aluminoxanes are depicted in the formulas 8, 9 and 10:




The radicals R in the formulas (7), (8), (9) and (10) can be identical or different and are each a C1-C20 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.

Preferably, the radicals R are identical and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
If the 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. To prepare an aluminoxane having different alkyl groups R, two different trialkylaluminums (AlR3+AlR′3) corresponding to the desired composition and reactivity are reacted with water, cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0 302 424.
Regardless of the method of preparation, all aluminoxane solutions have in common a variable content of unreacted aluminum starting compound which is present in free form or as an adduct.
Furthermore, instead of the aluminoxane compounds of the formulas 7, 8, 9 or 10, 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. However, 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. In the case of methylaluminoxane, preference is given to using ≧30% strength toluene solutions, but the use of 10% strength solutions is also possible.
As Lewis acid, preference is given to using compounds of the formula 11

M2X1X2X3  (Formula 11)

where M2 is an element of Group 13 of the Periodic Table of Elements, in particular B, Al or Ga, preferably B or Al, X1, X2 and X3 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 X1, X2 and X3 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.
Particular preference is given to tris(pentafluorophenyl)borane.
As ionic cocatalysts, preference is given to using compounds which contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate, tetraphenylborate, SbF6−, CF3SO3− or ClO4−. Suitable counterions are either Lewis acid or Broenstedt acid cation.
As Broensted acids, particular preference is given to 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, N,N-dimethylbenzylammonium, N,N-dimethylcyclohexylammonium,
Suitable Lewis-acid cations are cations of the formula 12

[(Ya+)Q1Q2 . . . Qz]d+  (Formula 12)

where Y is an element of Groups 1 to 16 of the Periodic Table of the Elements, Q1 to Qz are singly negatively charged groups such as C1-C28-alkyl, C6-C15-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,

a is an integer from 1-6,
z is an integer from 0 to 5 and
d corresponds to the difference a-z, but d is larger than or equal to 1.
Particularly 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,
    N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,
    N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate
    N,N-dimethylaniliniumtetra(phenyl)borate,
    N,N-diethylaniliniumtetra(phenyl)borate,
    N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,
    N,N-dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,
    di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,
    di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate,
    triphenylphosphoniumtetrakis(phenyl)borate,
    triethylphosphoniumtetrakis(phenyl)borate,
    diphenylphosphoniumtetrakis(phenyl)borate,
    tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,
    tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,
    triphenylcarbeniumtetrakis(pentafluorophenyl)borate,
    triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,
    triphenylcarbeniumtetrakis(phenyl)aluminate,
    ferroceniumtetrakis(pentafluorophenyl)borate and/or
    ferroceniumtetrakis(pentafluorophenyl)aluminate.


Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
It is also possible to use mixtures of all of the above and below mentioned cation-forming compounds. Preferred mixtures comprise aluminoxanes and an ionic compound, and/or a Lewis acid.
Other useful cocatalyst components are likewise borane or carborane compounds such as

    7,8-dicarbaundecaborane(13),
    undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,
    dodecahydrido-1-phenyl-1,3-dicarbanonaborane,
    tri(butyl)ammoniumun decahydrido-8-ethyl-7,9-dicarbaundecaborate,
    4-carbanonaborane(14),
    bis(tri(butyl)ammonium)nonaborate,
    bis(tri(butyl)ammonium)undecaborate,
    bis(tri(butyl)ammonium)dodecaborate,
    bis(tri(butyl)ammonium)decachlorodecaborate,
    tri(butyl)ammonium-1-carbadecaborate,
    tri(butyl)ammonium-1-carbadodecaborate,
    tri(butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,
    tri(buyl)ammoniumbis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III), tri(butyl)ammonium bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III).


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 Ri17M3(—O-M3Rj18)v or Ri18M3(—O-M3Rj17)v (formula 13), as described in Patent Application WO 99/40129, are likewise important as cocatalyst systems.
In this regard, R17 and R18 are the same or different and represent a hydrogen atom, a halogen atom, a C1-C40 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. R17 may also be an —OSiR513 group, in which the R51 groups are the same or different and have the same meaning as R17, M3 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.
Suitable cocatalyst systems according to formula 13 are compounds of formulas (A) and (B)




where R17 and R18 have the same meaning as specified above.

Furthermore, 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).




in which

    R27 may be a hydrogen atom or a boron-free C1-C40 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 R17, R18 have the same meaning as specified above,
    D is an element of main Group VI of the periodic table of elements or an NR61 group, where R61 is a hydrogen atom or a C1-C20 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.


The bimetallic compounds of formula 13 are possibly combined with an organometallic compound of formula 14, i.e., [M4R19q]k, in which M4 is an element of main Group I, II, or III of the periodic table of the elements, R19 is the same or different and represents a hydrogen atom, a halogen atom, a C1-C40 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.
The organometallic compounds of formula 14 are preferably neutral Lewis acids, in which M4 stands for lithium, magnesium, and/or aluminum, especially aluminum. Examples of preferred organometallic compounds of formula 14 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-tolylalan.
The catalyst system of the invention contains an organoboroaluminum compound, which contains units of formula 13, as the cocatalytically active chemical compound. Compounds of formula 13 in which M3 stands for boron or aluminum are preferred. The compounds that contain units of formula 13 may be present as monomers or as linear, cyclic, or cage-like oligomers. Two or more chemical compounds that contain units of formula 13 may also form dimers, trimers, or higher combinations among themselves by Lewis acid-base interactions.
Preferred cocatalytically active bimetallic compounds correspond to formulas 15 and 16,




in which R100 and R200 have the same meaning as the substituents R17 and R18 in formula 13.

Examples of the cocatalytically active compounds of formulas 15 and 16 are







The compounds named in 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 be used as additional cocatalysts, which may be present in unsupported or supported form.

The amount of cocatalysts of formula 13 and/or 15 and/or 16 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 17,

M5(R22)r(R23)s(R24)t  (Formula 17)

wherein

    
    
    M5 is an alkali, an alkali earth metal or a metal of Group 13 of the Periodic Table of the Elements,
    R22 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,
    R23 and R24 are each a hydrogen atom, a halogen atom, alkyl of from 1 to about 10 carbon atoms, C6-C15-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 M5,

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 17.



Among the metal compounds of the formula 17 preference is given to those in which M5 is lithium, magnesium or aluminum and R23 and R24 are each alkyl of from 1 to about 10 carbon atoms. Particularly preferred metal compounds of the formula 17 are n-butyllithium, n-butyl-n-octyl-magnesium, n-butyl-n-heptylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, triethylaluminum, trimethylaluminum or mixtures thereof.
If a metal compound of the formula 17 is used, it is preferably present in the catalyst system in such an amount that the molar ratio of M5 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, ZrO2, TiO2 or B2O3, CaO, ZnO, ThO2, Na2O, K2O, LiO2 or mixed oxides like Al/Si oxides, Mg/Al oxides or Al/Mg/Si oxides. Other suitable inorganic support materials are Na2CO3, K2CO3, CaCO3, MgCl2, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2 and Al(NO3)3.
Suitable polymer powders are homopolymers, copolymers, crosslinked polymers or polymer blends. Examples of such 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 m2/g, a pore volume in the range from 0.1 to 5 cm3/g and a mean particle size of from 1 to 500 μm. Preference is given to supports having a specific surface area in the range from 50 to 500 m2/g, a pore volume in the range from 0.5 to 3.5 cm3/g and a mean particle size in the range from 5 to 250 μm. Particular preference is given to supports having a specific surface area in the range from 200 to 400 m2/g, a pore volume in the range from 0.8 to 3.0 cm3/g and a mean particle size of from 10 to 100 μm.
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.
If 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° C. to 1000° C., preferably from 150° C. to 800° C. and most preferred from 150° C. to 400° C. The duration of the drying process can be from 1 to 24 hours. But shorter or longer drying periods are also possible.
In a preferred embodiment of the present invention, 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 %.
In addition or alternatively, 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.
As outlined above, 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.
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.
In one embodiment of the present invention, 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.
As an example, 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.
In another embodiment of this invention 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.
In a further embodiment of this invention the catalyst is prepared according to the procedure disclosed in WO 06/60544 (an application by the present inventors), WO 00/05277, WO 98/01481, U.S. Pat. No. 7,355,058, U.S. Pat. No. 7,193,100, U.S. Pat. No. 6,492,292, U.S. Pat. No. 6,107,230 or U.S. Pat. No. 6,355,594 using at least one compound of formulas 1 or 1a as the metallocene component.
As an example, in WO 06/60544, a free flowing and, if desired, prepolymerized supported catalyst system is prepared 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.
Thus, as an example, 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 30° C. followed by keeping the mixture at about 20° C. for 0 to 12 hours, subsequently heating the resulting mixture to a temperature of 30 to 200° 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 a temperature of 0 to 100° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 10 to 100° C.,
c) Applying the mixture prepared in b) to the aluminoxane loaded support material produced in a), at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,
d) Removing the major part of the solvent from the resulting mixture and optionally washing the resulting supported catalyst with a suitable solvent,
e) Isolating the supported catalyst system and
f) Optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
More specifically, as an example, the process according to WO 06/60544 for preparing a free-flowing and, if desired, prepolymerized supported catalyst system comprises the following steps:
the process for preparing a free-flowing supported catalyst system according to the present invention 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 20° C. followed by keeping the mixture at about 20° C. for 0.15 to 2 hours, subsequently heating the resulting mixture to a temperature of 50 to 160° C. and keeping the mixture at 50 to 160° 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 at least 0.1 mol % of the employed second portion of an aluminoxane or of a mixture of aluminoxanes per g support material of at least one metallocene of formula 1 and/or 1a in a second solvent or suspension medium at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° C.,
c) Applying the mixture prepared in b) to the aluminoxane loaded support material produced in a), at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,
d) Removing the major part of the solvent from the resulting mixture and
e) Optionally washing the resulting supported catalyst with a suitable solvent, and/or drying the resulting supported catalyst at temperatures of 30 to 60° C.,
and
f) Optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
In a preferred embodiment, as an example, 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 20° C. followed by subsequently heating the resulting mixture to a temperature of 50 to 110° C. and keeping the mixture at 50 to 110° 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 aluminoxanes per g support material of at least one metallocene of formula 1 and/or 1a in toluene at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° C.,
c) Applying the mixture prepared, in b) to the aluminoxane loaded support material produced in a), at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,
d) Removing the major part of the toluene from the resulting mixture and
e) Optionally washing the resulting supported catalyst with a suitable solvent, and/or drying the resulting supported catalyst at temperatures of 30 to 60° C.,
and
f) Optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
In a more preferred embodiment, as an example, 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° C. followed by subsequently heating the resulting mixture to a temperature of 110° C. and keeping the mixture at 110° 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 per g support material and at least 0.1 mol % of the employed second portion of methylaluminoxane per g support material of at least one metallocene of formula 1 and/or 1a in toluene at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° C.,
c) Applying the mixture prepared in b) to the methylaluminoxane loaded support material produced in a), by passing the impregnation suspension or solution b) through the methylaluminoxane loaded support material in a direct flow or by using an incipient wetness impregnation technique, where the volume of the impregnation suspension or solution or the total liquid volume used in the impregnation step, respectively, does not exceed 250% of the total pore volume of the support material, at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,
d) Removing the major part of the toluene from the resulting mixture and
e) Optionally washing the resulting supported catalyst with a suitable solvent, and/or drying the resulting supported catalyst at temperatures of 30 to 60° C.,
and
f) Optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
In a particular preferred embodiment, as an example, 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° C. followed by subsequently heating the resulting mixture to a temperature of 110° C. and keeping the mixture at 110° 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 per g support material and at least 0.1 mol % of the employed second portion of methylaluminoxane per g support material of at least one metallocene of formula 1a in toluene at a temperature of 20 to 50° C., optionally followed by a preactivation time of 1 minute to 200 hours at a temperature of 20 to 30° C.,
c) Applying the mixture prepared in b) to the methylaluminoxane loaded support material produced in a), by passing the impregnation suspension or solution b) through the aluminoxane loaded support material a) in a direct flow or by using an incipient wetness impregnation technique, where the volume of the impregnation suspension or solution or the total liquid volume used in the impregnation step, respectively, does not exceed 250% of the total pore volume of the support material, at a temperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,
d) Removing the major part of the toluene from the resulting mixture and
e) Optionally washing the resulting supported catalyst with a suitable solvent, and/or drying the resulting supported catalyst at temperatures of 30 to 60° C.,
and
f) Optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer(s), to obtain a prepolymerized supported catalyst system.
According to the present invention, for preparing a free-flowing and, if desired, prepolymerized supported catalyst system, in step b) of the catalyst preparations as mentioned above, 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, diisopropyl aluminum hydride, dimethyl aluminum(trimethylsiloxide), dimethyl aluminum(triethylsiloxide), phenylalan, pentafluorophenylalan, and o-tolylalan, can be used. Preferred aluminum alkyls are trimethylaluminum, triethylaluminum, tri isobutylaluminum.
In an even further embodiment of the present invention a free flowing and, if desired, prepolymerized supported catalyst system is prepared 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 like 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-dimethylbenzylamine, N,N-diethylbenzylamine, N-methyl-N-ethylbenzylamine, N-methyldibenzylamine and N-ethyldi(benzyl)amine,
c) removing the major part of solvent from the resulting mixture to obtain a supported cocatalyst,
d) preparing a metallocene/supported cocatalyst mixture in a suitable solvent or suspension medium, where the metallocene component has one of the above-described structures,
e) 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.
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 ethyl benzene.
For a preactivation, 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° 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° C. to 100° 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° C. to 100° C. However, lower or higher temperatures are also possible.
While the solvent is completely or mostly removed from the supported catalyst system, the mixture can be stirred and, if desired, also heated. Preferably, 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. During the drying process, 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° C. to 60° C. The free solvent is the visible portion of the solvent in the mixture. For the purposes of the present invention, residual solvent is the portion present in the pores.
As an alternative to the complete removal of the solvent, 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.
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.
As additive, it is possible to add, during or after the preparation of the supported catalyst system, a small amount of an olefin, preferably an alpha-olefin such as styrene or phenyldimethylvinylsilane as activity-increasing component or an antistatic, as described in U.S. 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. For the purposes of the present invention, the term polymerization refers to both homopolymerization and copolymerization and the term copolymerization includes terpolymerisation or copolymerisation of more than three different monomers.
Preference is given to polymerizing olefins of the formula Rm—CH═CH—Rn, where Rm and Rn are identical or different and are each a hydrogen atom or a radical having from 1 to 20 carbon atoms, in particular from 1 to 10 carbon atoms, and Rm and Rn together with the atoms connecting them can form one or more rings.
Suitable olefins are 1-olefins, eg. 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, norbornadiene, ethylnorbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methylnorbornene. In the process of the present invention, preference is given to homopolymerizing propene or ethene or copolymerizing propene with ethene and/or one or more 1-olefins having from 4 to 20 carbon atoms, eg. 1-butene or hexene, and/or one or more dienes having from 4 to 20 carbon atoms, eg. 1,4-butadiene, norbornadiene, ethylidenenorbornene or ethylnorbornadiene. 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° C. to 300° C., preferably from 50° C. to 200° C., very particularly preferably from 50° C. to 95° 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. As an example, 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.
To prepare olefin polymers having a broad or bimodal molecular weight distribution or a broad or bimodal melting range, it is recommended to use a catalyst system comprising two or more different metallocenes and/or two or more different cocatalysts. Alternatively two or more different catalyst systems of the present invention can be used as a mixture.
As molar mass regulator and/or to increase the activity, 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.
Furthermore, 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. In general it is possible to use all antistatics which are suitable in olefin polymerization processes. It is preferred to dose the antistatic directly into the polymerization system, either together with or separately from the catalyst system used.
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.
The 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.
EXAMPLES
General Procedures
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 1H-NMR spectroscopy using a Bruker DMX 500 spectrometer, operating at 500 MHz using CDCl3 as the solvent.
The polymers produced were characterized by 1H-NMR, 13C-NMR, DSC, GPC, TREF/ATREF, Melt Flow Rate and IR spectroscopy.
1. Gel Permeation Chromatography (GPC), Determination of Mw and Mw/Mn
A Waters Alliance/GPCV2000 equipped with a refractometer, a triple capillary online viscometer (Waters Corporation, 34 Maple Street, Milford, Mass., 01757 USA) and a light scattering detector PD 2040 (Precision Detectors Inc., 34 Williams Way, Bellingham, Mass., USA) was used for the determination of the molar mass data of the samples. 0.05 wt % solutions of the samples in 1,2,4-trichlorobenzene were analyzed at a temperature of 145° 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.
2. NMR Spectroscopy of Polymers
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° C. and mixed until a homogeneous solution was formed (typically 1-4 hours). Spectra were obtained at 120° C. on a Varian Inova 500 instrument (Varian Inc., 3120 Hansen Way, Palo Alto, Calif., 94304, USA) operating at a 13C-spectrometer frequency of 125.7 MHz and using a 10 mm probe. Spectra were obtained using 5000 scans employing a π/2 pulse of 10.0 μs, 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 nOe (Nuclear Overhauser enhancement). 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.
3. Differential Scanning Calorimetry (DSC), Determination of the Polymer Melting Point Tm
DSC measurements were carried out using a Mettler Toledo DSC 822e (Mettler-Toledo Inc., 1900 Polaris Parkway, Columbus, Ohio, 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° C. at a heating rate of 20° C./min, maintained at this temperature for 5 min, then cooled down to −55° C. at a cooling rate of 20° C./min, maintained at the same temperature for 5 min, then heated to 220° 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.
4. Melt Flow Rate (MFR)
The MFR of the samples were determined according to ISO 1133 at 230° C. Two different loads were used: 2.16 kg and 5 kg. Values are reported as MFR(230/2.16) and MFR(230/5), respectively.
5. Productivity
The productivity of a catalyst is determined by dividing the produced mass of polypropylene by the mass of catalyst used and the reaction time.
6. Yield
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.
The following abbreviations are employed:


    PP=polypropylene
    MC=metallocene
    Cat=supported catalyst system
    h=hour
    Tg=glass transition temperature in ° C., determined by differential scanning calorimetry (DSC, conditions see above)

7. Loss on Dryness (LOD)/Loss on Ignition CLOÏ\



The Loss on Dryness and the Loss on Ignition are determined by thermogravimetric measurement. The Loss on Dryness is the weight loss that the support material experiences by heating it from room temperature to 300° C. and keeping this temperature until a constant weight is obtained. Loss on Dryness is that weight loss as expressed as percentage of the weight of the original support material. Subsequently the support material is heated from 300° C. to 1000° C. and is kept at this temperature until a constant weight is obtained. The Loss of Ignition is defined as the weight loss between the weight of the sample at 1000° C. and at room temperature expressed as a percentage of the weight of the original support material.
As an example to illustrate the above, a 10 gram sample (at room temperature) is heated to 300 C where it maintains a constant weight at that temperature of 9 grams. The Loss on Dryness is 10.0%, which is:




  100
  ×
  
    (
    
      
        (
        
          10
          -
          9
        
        )
      
      10
    
    )
  




The sample is then further healed to 1000 C where it maintains a constant weight of 8.37 grams. The Loss on Ignition is 16.3%, which is:





  100
  ×
  
    (
    
      
        (
        
          10
          -
          8.37
        
        )
      
      10
    
    )
  




Synthesis of Metallocenes
Comparative Example 1
Dimethylsilandiylbis[2-(cyclohexylmethyl)-4-(4-tert-butylphenyl)-1-indenyl]-zirconium dichloride
(2-Bromo-ethyl)-cyclohexane




In a 1 l-roundbottom flask equipped with a reflux condenser 164 g concentrated sulphuric acid and 200 g hydrobromic acid (48% in water) were added subsequently under cooling with an ice bath to 88.7 g (0.693 mole) 2-cyclohexyl-ethanol. The mixture was refluxed for 6 h and after cooling to room temperature it was poured onto 400 g of ice. The aqueous phase was extracted with 400 ml pentane. The organic layer was washed with a 2 M NaOH-solution and with water, dried over magnesium sulphate, and the solvent was removed in vacuo. The product was distilled in vacuo to yield 1112.7 g (85%) of (2-bromo-ethyl)-cyclohexane as a colourless oil 1H-NMR (4-MHz, CDCl3): δ=3.40 (2H, t, CH2Br), 1.73-1.61 (m, 7H), 1.44 (m, 1H), 1.26-1.11 (m, 3H), 0.92-0.84 (m, 2H) ppm.
1-(2-Chloro-phenyl)-3-cyclohexyl-propan-1-one




15.57 g (640 mmole) Magnesium turnings were placed in a 1 l-roundbottom flask equipped with a dropping funnel and a reflux condenser, and 50 ml of tetrahydrofuran (THF) were added. The magnesium was etched slightly with a few crystals of iodine and then 2 g of (2-bromo-ethyl)-cyclohexane were added and the mixture was heated locally. After the start of the Grignard-formation the rest of the (2-bromo-ethyl)-cyclohexane in 350 ml of THF (112.65 g in total, 589 mmole) were added within a period of 20 min. The mixture was refluxed for 1.5 h and then cooled to room temperature. In a separate 2 l-roundbottom flask 70.5 g (5.13 mmole) of 2-chloro-benzonitrile and 156 mg (0.16 mole %) copper(I)iodide were dissolved in 130 ml of THF. The Grignard-solution was added dropwise over a period of 30 min and the reaction mixture was refluxed for 3 h. After standing overnight at room temperature, a mixture of 190 ml water and 127 ml concentrated hydrochloric acid were added very carefully, causing a strongly exothermic reaction. The mixture was stirred at 50° C. for 1 h and the layers were separated. The aqueous layer was extracted twice with 150 ml of toluene each. The combined organic layers were washed twice with 2 M sulphuric acid, once with a saturated sodium bicarbonate solution and once with a saturated sodium chloride solution. After drying over magnesium sulphate the solvent was evaporated in vacuo to yield 133.5 g (quant.) of the desired phenone as slightly brown oil. 1H-NMR (400 MHz, CDCl3): δ=7.41-7.14 (m, 4H, aromatic), 2.91 (t, 2H, COCH2), 1.71-1.55, 1.28-1.10, 0.93-0.85 (3×m, 13H) ppm.
7-Chloro-2-cyclohexylmethyl-indan-1-one




66 g (263 mmole) 1-(2-Chloro-phenyl)-3-cyclohexyl-propan-1-one, 77.5 g (2.1 eq.) urotropine and 72.6 g (2.7 eq.) of acetic anhydride were placed in a 500 ml roundbottom flask and the mixture was stirred at 80° C. for 4 h. Then 100 ml water and 100 ml 2M NaOH were added and the mixture was extracted two times with 200 ml dichloromethane each. The organic layer was washed two times with 100 ml saturated aqueous ammonium chloride and dried over magnesium sulphate. The solvent amount was reduced in vacuo to a total of 150 ml volume and the solution was added dropwise over a period of 2.5 h to 660 g of hot (70-75° C.) concentrated sulphuric acid. After stirring for an additional 30 min at 75° C. the mixture was allowed to stand overnight at room temperature. The mixture was poured onto approx. 500 g of ice and extracted three times with 150 ml dichloromethane each. The organic layer was washed twice with 150 ml of a saturated sodium bicarbonate solution and once with 100 ml of a saturated sodium chloride solution. After drying over magnesium sulphate the solvent was removed in vacuo. The product was purified by column chromatography on silica (heptane/dichloromethane 5:1) to yield 40.0 g (61%) of the desired product as a slightly off-white oil, which slowly crystallized. 1H-NMR (400 MHz, CDCl3): δ=7.42 (t, 1H, aromatic), 7.29 (d, 1H, aromatic), 7.24 (d, 1H, aromatic), 3.25 (dd, 1H, COCH), 2.71 (m, 2H, benzylic), 1.78-0.87 (m, 13H, aliphatic) ppm.
7-(4-tert-Butyl-phenyl)-2-cyclohexylmethyl-indan-1-one




60 g (228 mmole) 7-Chloro-2-cyclohexylmethyl-indan-1-one, 49 g (1.2 eq.) 4-tert-butyl-benzene boronic acid, 53 g sodium carbonate, 750 ml ethylene glycol and 150 ml water were placed in a 2 l-roundbottom flask equipped with a mechanical stirrer and a reflux condenser. The mixture was degassed three times by slight evacuation and recharging with argon. A premixed catalyst solution consisting of 103 mg (0.2 mole %) palladium acetate, 3 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of water was added and the mixture was refluxed at 125° C. until complete conversion (approx. 4 h). 300 ml of water were added and the mixture was extracted three times with 150 ml of toluene each. The combined organic layers were washed twice with 100 ml water and once with 100 ml of a saturated sodium chloride solution. Drying over magnesium sulphate and evaporation of the solvent in vacuo yielded 87.2 g (quant.) of the desired product as a yellow sticky oil. 1H-NMR (400 MHz, CDCl3): δ=7.54 (t, 1H, aromatic), 7.43, 7.38 (2×d, 4H, aromatic), 7.24 (m, 2H, aromatic), 3.30 (m, 1H, COCH), 2.80-2.67 (3×m, 2H, benzylic), 1.85-1.47 (m, 7H, aliphatic), 1.35 (s, 9H, C(CH3)3), 1.27-0.87 (m, 6H, aliphatic) ppm.
4-(4-tert-Butyl-phenyl)-2-cyclohexylmethyl-1H-indene




82.3 g (229 mmole) 7-(4′-tert-Butyl-phenyl)-2-cyclohexylmethyl-indan-1-one were dissolved in 292 ml toluene in a 1 l-roundbottom flask equipped with a reflux condenser. 9.5 g (1.1 eq.) sodium borohydride were added. Then 40 ml (4.3 eq.) methanol were added at 50° C. and the mixture was stirred for 3 h at 50° C. An additional 1 g of sodium borohydride and 5 ml methanol were added and the mixture was stirred another 2 h at 50° C. 2M sulphuric acid was added until the gas evolution ceased. After addition of 100 ml water the layers were separated and the organic layer was washed two times with 2M sulphuric acid and once with a saturated sodium chloride solution. The solvent was evaporated and the crude indanol was dissolved in approx. 350 ml of toluene. After addition of 0.7 g p-toluene sulfonic acid the mixture was heated to reflux using a Dean-Stark-trap until TLC showed complete conversion (90 min). The solution was washed twice with a saturated NaHCO3-solution, once with water and once with a saturated sodium chloride solution. Drying over magnesium sulphate, evaporation of the solvent and crystallization from 800 ml ethanol afforded 67.3 g (86%) of the desired indene as white crystals. 1H-NMR (400 MHz, CDCl3): δ=7.45, 7.33, 7.25, 7.14 (4×m, 7H, aromatic), 6.69 (s, 1H, ═CH), 3.35 (s, 2H, benzylic), 2.34 (d, 2H, aliphatic), 1.71-1.50 (m, 6H, aliphatic), 1.39 (s, 9H, C(CH3)3), 1.24-0.87 (m, 5H, aliphatic) ppm.
Dimethylsilandiylbis[2-(cyclohexylmethyl)-4-(4-tert-butylphenyl)-1-indenyl]-zirconium dichloride




20 g (58 mmole) 7-(4-tert-Butyl-phenyl)-2-cyclohexyl-methyl-1H-indene were dissolved in 340 ml toluene and 20 ml of THF in a 1000 ml-roundbottom flask. 24.4 ml of n-butyl lithium (2.6 M in toluene, 63.4 mmole, 1.1 eq.) were added at room temperature and the solution was stirred for 1 h at 80° C. After cooling to 40° C. 3.5 ml (3.74 g, 29 mmole, 0.5 eq.) dimethyldichlorosilane were added in one portion and the mixture was stirred at 60° C. for 8.5 h. The solvent mixture was removed in vacuo (purity of the ligand >99% according to GC-analysis) and the ligand was dissolved in 200 ml of diethyl ether (yellowish suspension due to LiCl). 23.8 ml of n-butyl lithium (61.9 mmole, 1.07 eq. regarding to “indene”, 2.6 M in toluene) were added at room temperature and the mixture was stirred overnight at room temperature. Then 7.1 g (30.5 mmole, 0.525 eq. regarding to “indene”) zirconium tetrachloride were added in portions. The orange-yellow suspension was stirred for 5 h at room temperature and the solid was isolated by filtration. Washing with 2 portions of 30 ml diethyl ether each and drying in vacuo yielded 22.7 g of the crude complex (rac/meso=1.5:1, containing lithium chloride). The racemic complex was isolated by fractional crystallization from toluene. Yield: 8.1 g (9 mmol, 31%) as a bright yellow powder. 1H-NMR (400 MHz, CDCl3): δ=7.61 (d, 2H, aromatic), 7.57, 7.44 (2×d, 8H, aromatic), 7.36 (d, 2H, aromatic), 7.22, 7.15, 7.07 (3×m, 10H, aromatic+toluene), 6.94 (s, 2H, indenyl-H), 2.64 (“dd”, 2H, indenyl-CH2), 2.34 (s, toluene) 2.13 (“dd”, 2H, indenyl-CH2), 1.75-1.45 (m, 10H, aliphatic), 1.33 (s, 18H, C(CH3)3), 1.31 (s, 6H, Si(CH3)2), 1.12-0.76 (m, 12H, aliphatic) ppm.
Comparative Example 2
Dimethylsilandiylbis[(2-(2,2-dimethylpropyl)-4-(4′-tert-butylphenyl)-1-indenyl]-zirconium dichloride
1-Bromo-3,3-dimethyl-butane




In a 1 l-roundbottom flask equipped with a reflux condenser 232 g concentrated sulphuric acid and 283 g hydrobromic acid (48% in water) were added successively under cooling with an ice bath to 100 g (0.98 mole) 3,3-dimethyl-1-butanol. The mixture was refluxed for 6 h and after cooling to room temperature, it was poured onto 400 g of ice. The aqueous phase was extracted with 400 ml pentane. The organic layer was washed with a 2 M NaOH-solution and with water, dried over magnesium sulphate, and the solvent was removed in vacuo. The product was distilled in vacuo to yield 88.1 g (55%) of 1-bromo-3,3-dimethyl-butane as a colourless oil. 1H-NMR (400 MHz, CDCl3): δ=3.35 (m, 2H, CH2Br), 1.80 (m, 2H, CH2), 0.90 (s, 9H, t-Bu) ppm.
1-(2-Chloro-phenyl)-4,4-dimethyl-pentan-1-one




14.1 g (580 mmole) Magnesium turnings were placed in a 1 l-roundbottom flask equipped with a dropping funnel and a reflux condenser, and 60 ml of THF were added. The magnesium was etched slightly with a few crystals of iodine and then 2 g of 1-bromo-3,3-dimethyl-butane were added and the mixture was heated locally. After the start of the Grignard-formation the rest of the 1-bromo-3,3-dimethyl-butane in 350 ml of THF (88.1 g in total, 533 mmole) were added within a period of 20 min. The mixture was refluxed for 1.5 h and then cooled to room temperature. In a separate 2 l-roundbottom flask 63.9 g (464 mmole) of 2-chloro-benzonitrile and 141 mg (0.16 mole %) copper(I)iodide were dissolved in 265 ml of THF. The Grignard-solution was added dropwise over a period of 30 min and the reaction mixture was refluxed for 3 h. After standing overnight at room temperature, a mixture of 190 ml water and 127 ml concentrated hydrochloric acid were added very carefully, causing a strongly exothermic reaction. The mixture was stirred at 50° C. for 1 h and the layers were separated. The aqueous layer was extracted twice with 150 ml of toluene each. The combined organic layers were washed twice with 2 M sulphuric acid, once with a saturated sodium bicarbonate solution and once with a saturated sodium chloride solution. After drying over magnesium sulphate the solvent was evaporated in vacuo to yield 103.8 g (quant.) of the desired phenone as slightly brown oil. 1H-NMR (400 MHz, CDCl3): δ=7.41-7.26 (m, 4H, aromatic), 2.87 (m, 2H, COCH2), 1.59 (m, 2H, CH2-t-Bu), 0.90 (s, 9H, t-Bu) ppm.
7-Chloro-2-(2,2-dimethylpropyl)-indan-1-one




101.8 g (453 mmole) 1-(2-Chloro-phenyl)-4,4-dimethyl-pentan-1-one, 133.4 g (2.1 eq.) urotropine and 124.7 g (2.7 eq.) of acetic anhydride were placed in a 1000 ml roundbottom flask and the mixture was stirred at 80° C. for 4 h. Then 200 ml water and 200 ml 2M NaOH were added and the mixture was extracted two times with 250 ml dichloromethane each. The organic layer was washed two times with 150 ml saturated aqueous ammonium chloride and dried over magnesium sulphate. The solvent amount was reduced in vacuo to a total of 250 ml volume and the solution was added dropwise over a period of 2.5 h to 1000 g of hot (70-75° C.) concentrated sulphuric acid. After stirring for an additional 30 min at 75° C. the mixture was allowed to stand overnight at room temperature. The mixture was poured onto approx. 800 g of ice and extracted three times with 250 ml dichloromethane each. The organic layer was washed twice with 250 ml of a saturated sodium bicarbonate solution and once with 200 ml of a saturated sodium chloride solution. After drying over magnesium sulphate the solvent was removed in vacuo. The product was purified by column chromatography on silica (heptane/dichloromethane 1:1) to yield 79.4 g (74%) of the desired product as a slightly off-white oil, which slowly crystallized. 1H-NMR (400 MHz, CDCl3): δ=7.44 (t, 1H, aromatic), 7.30 (d, 1H, aromatic), 7.27 (d, 1H, aromatic), 3.38 (dd, 1H, COCH), 2.79, 2.60 (2×m, 2H, benzylic), 2.10, 1.21 (2×m, 1H, CH2-t-Bu), 0.90 (s, 9H, t-Bu) ppm.
7-(4-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-indan-1-one




35 g (148 mmole) 7-Chloro-2-(2,2-dimethyl-propyl)-indan-1-one, 31.6 g (1.2 eq.) tert-butylphenyl boronic acid, 34.5 g sodium carbonate, 438 ml ethylene glycol and 88 ml water were placed in a 1 l-roundbottom flask equipped with a mechanical stirrer and a reflux condenser. The mixture was degassed three times by slight evacuation and recharging with argon. A premixed catalyst solution consisting of 67 mg (0.2 mole %) palladium acetate, 1.94 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of water was added and the mixture was refluxed at 125° C. until complete conversion (approx. 4 h). 100 ml of water were added and the mixture was extracted three times with 100 ml of toluene each. The combined organic layers were washed twice with 100 ml water and once with 100 ml of a saturated sodium chloride solution. Drying over magnesium sulphate and evaporation of the solvent in vacuo yielded 58.82 g (quant.) of the desired product as a yellow sticky oil. 1H-NMR (400 MHz, CDCl3): δ=7.58 (t, 1H, aromatic), 7.48-7.17 (m, 6H, aromatic), 3.48 (m, 1H, (C═O)CH), 2.88, 2.63 (2×m, 2H, benzylic), 2.38 (s, 1H), 2.13 (m, 1H, CH2-t-Bu), 1.40 (s, 9H, Ph-t-Bu), 1.03 (s, 9H, CH2-t-Bu) ppm.
4-(4-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-1H-indene




50 g (150 mmole) 7-(4′-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-indan-1-one were dissolved in 180 ml toluene in a 500 ml-roundbottom flask equipped with a reflux condenser. 6.22 g (1.1 eq.) sodium borohydride were added. Then 26.1 ml (4.3 eq.) methanol were added at 50° C. and the mixture was stirred for 4 h at 50° C. Another 3.11 g sodium borohydride and 10.3 g methanol were added and the mixture was stirred at 50° C. overnight. 2M sulphuric acid was added until the gas evolution ceased. After addition of 100 ml water the layers were separated and the organic layer was washed two times with 2M sulphuric acid and once with a saturated sodium chloride solution. The solvent was evaporated and the crude indanol was dissolved in approx. 300 ml of toluene. After addition of 1 g p-toluene sulfonic acid the mixture was heated to reflux using a Dean-Stark-trap until TLC showed complete conversion (90 min). The solution was washed twice with a saturated NaHCO3-solution, once with water and once with a saturated sodium chloride solution. Drying over magnesium sulphate, evaporation of the solvent and recrystallization from 500 ml ethanol afforded 35.3 g (74%) of the desired indene as white crystals. 1H-NMR (400 MHz, CDCl3): δ=7.47 (s, 4H, aromatic), 7.34 (d, 1H, aromatic), 7.25 (d, 1H, aromatic), 7.16 (t, 1H, aromatic), 6.72 (s, 1H, C═CH), 3.44 (s, 2H, benzylic), 2.36 (s, 2H, CH2-t-Bu), 1.37 (s, 9H, Ph-t-Bu), 0.96 (s, 9H, CH2-t-Bu) ppm.
Dimethylsilandiylbis[2-(2,2-dimethylpropyl)-4-(4-tert-butylphenyl)-1-indenyl]zirconium dichloride




2 g (6.28 mmole) 4-(4-tert-Butyl-phenyl)-2-(2,2-dimethylpropyl)-1H-indene were dissolved in 34 ml toluene and 2 ml of THF in a 100 ml-roundbottom flask. 2.64 ml of n-butyl lithium (2.5 M in toluene, 6.6 mmole, 1.05 eq.) were added at room temperature and the solution was stirred for 1 h at 80° C. After cooling to 40° C. 405 mg (3.2 mmole, 0.5 eq.) dimethyldichlorosilane were added in one portion and the mixture was stirred at 60° C. for 17 h. The solvent was removed in vacuo and 20 ml diethyl ether were added. 2.64 ml of n-butyl lithium (2.5 M in toluene, 6.6 mmole, 1.05 eq.) were added at room temperature and the mixture was stirred overnight at room temperature. After cooling to room temperature 776 mg (3.3 mmole, 0.53 eq. regarding to “indene”) zirconium tetrachloride were added in portions. The orange-yellow suspension was stirred for 5 h at room temperature and the complex was isolated by filtration and washing with diethyl ether to yield 1.59 g crude complex. The racemic form was isolated by fractional recrystallization from toluene. Yield: 0.65 g (24%) as a bright yellow powder. 1H-NMR (400 MHz, CDCl3): δ=7.62 (d, 2H, aromatic), 7.58, 7.45 (2×d, 8H, aromatic), 7.37 (d, 2H, aromatic), 7.23, 7.16, 7.08 (3×m, 10H, aromatic+toluene), 6.93 (s, 2H, indenyl-H), 2.64 (d, 2H, indenyl-CH2), 2.34 (s, toluene), 2.15 (d, 2H, indenyl-CH2), 1.35 (s, 6H, Si(CH3)2), 1.32 (s, 18H, Ph-t-Bu), 0.83 (s, 18H, CH2-t-Bu) ppm.
Comparative Example 3
Dimethylsilandiylbis[2-(1-adamantylmethyl)-4-(4-tert-butylphenyl)-1-indenyl]-zirconium dichloride
1-(2-Bromo-ethyl)-adamantane




In a 1 l-roundbottom flask equipped with a reflux condenser 164 g concentrated sulphuric acid and 200 g hydrobromic acid (48% in water) were added subsequently under cooling with an ice bath to 126.20 g (0.70 mole) 2-(1-adamantyl)ethanol. The mixture was refluxed for 6 h and after cooling to room temperature, it was poured onto 400 g of ice. The aqueous phase was extracted with 400 ml pentane. The organic layer was washed with a 2 M NaOH-solution and with water, dried over magnesium sulphate, and the solvent was removed in vacuo. The product was distilled in vacuo to yield 153.2 g (90%) of (1-(2-Bromo-ethyl)-adamantane as a colourless oil. 1H-NMR (400 MHz, CDCl3): δ=3.29 (t, 2H, CH2Br), 1.71 (t, 2H, CCH2CH2Br), 1.56-1.17 (m, 15H, aliphatic) ppm.
1-(2-Chloro-phenyl)-3-(1-adamantyl)-propan-1-one




15.57 g (640 mmole) Magnesium turnings were placed in a 1 l-roundbottom flask equipped with a dropping funnel and a reflux condenser, and 50 ml of THF were added. The magnesium was etched slightly with a few crystals of iodine and then 2 g of (1-(2-bromo-ethyl)-adamantane were added and the mixture was heated locally. After the start of the Grignard-formation the rest of the (1-(2-bromo-ethyl)-adamantane in 350 ml of THF (143.5 g in total, 590 mmole) were added within a period of 20 min. The mixture was refluxed for 1.5 h and then cooled to room temperature. In a separate 2 l-roundbottom flask 70.5 g (513 mmole) of 2-chloro-benzonitrile and 156 mg (0.16 mole %) copper(I)iodide were dissolved in 130 ml of THF. The Grignard-solution was added dropwise over a period of 30 min and the reaction mixture was refluxed for 3 h. After standing overnight at room temperature, a mixture of 190 ml water and 127 ml concentrated hydrochloric acid were added very carefully, causing a strongly exothermic reaction. The mixture was stirred at 50° C. for 1 h and the layers were separated. The aqueous layer was extracted twice with 150 ml of toluene each. The combined organic layers were washed twice with 2 M sulphuric acid, once with a saturated sodium bicarbonate solution and once with a saturated sodium chloride solution. After drying over magnesium sulphate the solvent was evaporated in vacuo to yield 178.7 g (quant.) of the desired phenone as slightly brown oil. 1H-NMR (400 MHz, CDCl3): δ=7.39-7.12 (m; 4H, aromatic), 2.55 (t, 2H, COCH2), 1.40-1.13 (m, 17H, aliphatic) ppm.
7-Chloro-2-(1-adamantylmethyl)-indan-1-one




78.7 g (260 mmole) 1-(2-Chloro-phenyl)-3-(1-adamantyl)-propan-1-one, 77.5 g (2.1 eq.) urotropine and 72.6 g (2.7 eq.) of acetic anhydride were placed in a 500 ml roundbottom flask and the mixture was stirred at 80° C. for 4 h. Then 100 ml water and 100 ml 2M NaOH were added and the mixture was extracted two times with 200 ml dichloromethane each. The organic layer was washed two times with 100 ml saturated aqueous ammonium chloride and dried over magnesium sulphate. The solvent amount was reduced in vacuo to a total of 150 ml volume and the solution was added dropwise over a period of 2.5 h to 660 g of hot (70-75° C.) concentrated sulphuric acid. After stirring for an additional 30 min at 75° C. the mixture was allowed to stand overnight at room temperature. The mixture was poured onto approx. 500 g of ice and extracted three times with 150 ml dichloromethane each. The organic layer was washed twice with 150 ml of a saturated sodium bicarbonate solution and once with 100 ml of a saturated sodium chloride solution. After drying over magnesium sulphate the solvent was removed in vacuo. The product was purified by column chromatography on silica (heptane/dichloromethane 5:1) to yield 58 g (71%) of the desired product as a slightly off-white glassy solid. 1H-NMR (400 MHz, CDCl3): δ=7.39 (t, 1H, aromatic), 7.27 (d, 1H, aromatic), 7.21 (d, 1H, aromatic), 3.37 (dd, 1H, COCH), 2.70 (m, 2H, benzylic), 1.36-1.18 (m, 17H, aliphatic) ppm.
7-(4-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-indan-1-one




71.8 g (228 mmole) 7-Chloro-2-(1-adamantylmethyl)-indan-1-one, 49 g (1.2 eq.) 4-tert-butyl-benzene boronic acid, 53 g sodium carbonate, 750 ml ethylene glycol and 150 ml water were placed in a 2 l-roundbottom flask equipped with a mechanical stirrer and a reflux condenser. The mixture was degassed three times by slight evacuation and recharging with argon. A premixed catalyst solution consisting of 103 mg (0.2 mole %) palladium acetate, 3 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of water was added and the mixture was refluxed at 125° C. until complete conversion (approx. 6 h). 300 ml of water were added and the mixture was extracted three times with 150 ml of toluene each. The combined organic layers were washed twice with 100 ml water and once with 100 ml of a saturated sodium chloride solution. Drying over magnesium sulphate and evaporation of the solvent in vacuo yielded 94.1 g (quant.) of the desired product as a yellow sticky oil. 1H-NMR (400 MHz, CDCl3): δ=7.52 (t, 1H, aromatic), 7.41, 7.36 (2×d, 4H, aromatic), 7.21 (m, 2H, aromatic), 3.37 (m, 1H, COCH), 2.77-2.68 (m, 2H, benzylic), 1.42-1.18 (m, 26H, aliphatic & C(CH3)3) ppm.
4-(4-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-1H-indene




94.0 g (228 mmole) 7-(4′-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-indan-1-one were dissolved in 291 ml toluene in a 1 l-roundbottom flask equipped with a reflux condenser. 9.5 g (1:1 eq.) sodium borohydride were added. Then 40 ml (4.3 eq.) methanol were added at 50° C. and the mixture was stirred for 6 h at 50° C. 2M sulphuric acid was added until the gas evolution ceased. After addition of 100 ml water the layers were separated and the organic layer was washed two times with 2M sulphuric acid and once with a saturated sodium chloride solution. The solvent was evaporated and the crude indanol was dissolved in approx. 350 ml of toluene. After addition of 0.7 g p-toluene sulfonic acid the mixture was heated to reflux using a Dean-Stark-trap until TLC showed complete conversion (90 min). The solution was washed twice with a saturated NaHCO3-solution, once with water and once with a saturated sodium chloride solution. Drying over magnesium sulphate, evaporation of the solvent and crystallization from 900 ml ethanol afforded 76.9 g (85%) of the desired indene as white crystals. 1H-NMR (400 MHz, CDCl3): δ=7.44, 7.32, 7.23, 7.12 (4×m, 7H, aromatic), 6.63 (s, 1H, ═CH), 3.32 (s, 2H, benzylic), 2.29 (d, 2H, aliphatic), 1.69-1.15 (m, 15H, aliphatic), 1.38 (s, 9H, C(CH3)3) ppm.
Dimethylsilandiylbis[2-(1-adamantylmethyl)-4-(4-tert-butylphenyl)-1-indenyl]-zirconium dichloride




23 g (58 mmole) 7-(4-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-1H-indene were dissolved in 340 ml toluene and 20 ml of THF in a 1000 ml-roundbottom flask. 24.4 ml of n-butyl lithium (2.6 M in toluene, 63.4 mmole, 1.1 eq.) were added at room temperature and the solution was stirred for 1 h at 80° C. After cooling to 40° C. 3.5 ml (3.74 g, 29 mmole, 0.5 eq.) dimethyldichlorosilane were added in one portion and the mixture was stirred at 60° C. for 8.5 h. The solvent mixture was removed in vacuo (purity of the ligand >94% according to GC-analysis) and the ligand was dissolved in 200 ml of diethyl ether (yellowish suspension due to LiCl). 23.8 ml of n-butyl lithium (61.9 mmole, 1.07 eq. regarding to “indene”, 2.6 M in toluene) were added at room temperature and the mixture was stirred overnight at room temperature. Then 7.1 g (30.5 mmole, 0.525 eq. regarding to “indene”) zirconium tetrachloride were added in portions. The orange-yellow suspension was stirred overnight at room temperature and the solid was isolated by filtration. Washing with 2 portions of 35 ml diethyl ether each and drying in vacuo yielded 25.1 g of the crude complex (rac/meso=1.6:1, containing lithium chloride). The racemic complex was isolated by fractional crystallization from toluene. Yield: 9.8 g (9.7 mmol, 33%) as a bright yellow powder. 1H-NMR (400 MHz, CDCl3): δ=7.62 (d, 2H, aromatic), 7.55, 7.42 (2×d, 8H, aromatic), 7.32 (d, 2H, aromatic), 7.21, 7.15, 7.08 (3×m, 10H, aromatic+toluene), 6.83 (s, 2H, indenyl-H), 2.53 (“dd”, 2H, indenyl-CH2), 2.34 (s, toluene) 2.09 (“dd”, 2H, indenyl-CH2), 1.75-1.15 (m, 30H, aliphatic), 1.34 (s, 18H, C(CH3)3), 1.32 (s, 6H, Si(CH3)2) ppm.
Comparative Example 4
Dimethylsilanediylbis[2-methyl-4-(4-tert-butylphenyl)-1-indenyl]zirconium dichloride




143 g (0.54 moles) of 2-methyl-4-(4-tert-butylphenyl)-1-indene were introduced into 2.4 L of toluene and 143 mL of tetrahydrofuran, and 234 mL of an n-butyllithium solution (2.5 M in toluene) were added without interruption at room temperature. After this addition was complete, the mixture was heated to 80° C. and stirred for one hour at this temperature. It was allowed to cool to 40° C., then 33.6 g (0.26 moles) of dimethyldichlorosilane were added dropwise to this reaction solution. The reaction solution was stirred for three hours at 60° C. It was cooled to room temperature, and then 218 mL of an n-butyllithium solution (2.5 M in toluene) were added dropwise. After this addition was complete, the solution was heated to 80° C. and stirred for one hour at this temperature. It was allowed to cool to room temperature, then 71.1 g (0.305 moles) of zirconium tetrachloride were added in portions. The solution was stirred for two hours at 45° C. and the precipitate that forms was separated by filtration through a G3 fitted glass filter and then carefully washed with 700 mL portions of tetrahydrofuran. 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.
1H-NMR (400 MHz, CDCl3):
7.63-6.85 (m, 16H, arom-H), 2.44 (s, 3H, meso-CH3), 2.24 (s, 3H, rac-CH3), 1.46 (s, 1.5H, meso-SiMe2), 1.33-1.29 (m, 21H, tert-butyl, rac-SiMe2), 1.23 (s, 1.5H, meso-CH3).
Comparative Example 5
Dimethylsilanediyl(2-methyl-4-(4-tert-butylphenyl)indenyl)(2-isopropyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride
Dimethylsilanediyl(2-methyl-4-(4-tert-butylphenyl)-1-indene)(2-isopropyl-4-(4-tert-butylphenyl)-1-indene)




16.8 g (57.7 mmoles) of 2-isopropyl-4-(4-tert-butylphenyl)-1-indene were introduced into 131 mL of toluene and 5.0 mL of THF, and 21.5 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 heated to 80° C. and stirred for one hour at this temperature. It was then allowed to cool to room temperature. The resulting reaction solution was added dropwise to a solution of 20.5 g (57.7 mmoles) of (2-methyl-4-(4-tert-butylphenyl)-1-indenyl)dimethylchlorosilane in 246 mL of toluene over a period of one hour. The mixture was stirred overnight at room temperature. Then 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%).
1H-NMR (400 MHz, CDCl3):
7.51-7.1 (m, 14H, arom-H), 6.71, 6.62 (each s, each 1H, olefin-H-indene), 3.35, 3.31 (each s, each 2H, CH2—H), 2.65 (m, 1H, CH-isopropyl), 2.41 (s, 3H CH3—H), 1.35, 1.33 (each s, each 9H, tert-butyl), 1.15 (d, 6H, isopropyl-CH3), 0.2, 0.0 (each d, each 3H, SiCH3).
Dimethylsilanediyl(2-methyl-4-(4-tert-butylphenyl)-1-indenyl)(2-isopropyl-4-(4-tert-butylphenyl)-1-indenyl)zirconium dichloride




36.6 g (60 mmoles) of dimethylsilanediyl(2-methyl-4-(4-tert-butylphenyl)-1-indene)(2-isopropyl-4-(4-tert-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 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.
1H-NMR (400 MHz, CDCl3):
7.7-6.9 (m, 14H, arom-H), 3.26 (m, 1H, CH-isopropyl), 2.23 (s, 3H, CH3), 1.31 (s, 18H, tert-butyl), 1.33, 1.32 (each s, each 3H, Si—CH3), 1.08, 1.03 (each d, each 3H, isopropyl-CH3).
Example 6
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-tert-butyl phenyl)-1-indenyl]-zirconium dichloride
2-(2-Bromo-benzyl)-malonic acid diethyl ester




In a 4-neck 4 l round bottom flask equipped with a reflux condenser, gas outlet, thermometer and stirrer are placed 2 l of ethanol. A solution of sodium ethoxide in ethanol is prepared by gradually adding 25.5 g (1.11 mol) of sodium cut in small pieces to the reaction mixture. At a reaction temperature of 40-45° C. the sodium addition and reaction is finished after  ̃1.5 h. The solution is cooled to room temperature and 192.5 g (1.20 mol) of malonic acid diethyl ester are added. The mixture is stirred at this temperature for 15 minutes. Then 250 g (1.00 mol) 2-bromobenzyl bromide are added via a dropping funnel in a way that the reaction temperature raises to 40-45° C. After the addition is completed the reaction mixture is heated to reflux for 3 h.
For workup, most of the ethanol is distilled off, and 300 ml of water are added to the residue. The water phase is extracted with 300 and 2 times 150 ml of diethyl ether. The combined organic phases are washed with 200 ml of water. The ether is removed under reduced pressure and the crude product is distilled in a vacuum at a pressure of 1 mbar. To obtain pure 2-(2-Bromo-benzyl)-malonic acid diethyl ester (Yield: 230 g, 70%). 1H-NMR (500 MHz, CDCl3, ppm): δ=7.50 (m, 1H, aromatic), 7.22 (m, 1H, aromatic), 7.17 (m, 1H, aromatic), 7.06 (m, 1H, aromatic), 4.13 (m, 4H, —O—CH2CH3), 3.82 (t, 1H, —CH2—CH(CO2Et)2), 3.31 (d, 2H, Ar—CH2—CH(CO2Et)2, 1.18 (t, 6H, —O—CH2CH3).
3-(2-Bromo-phenyl)-propionic acid




A 4-neck 2 litre round bottom flask with equipped with a reflux condenser, thermometer and stirrer, is charged with 230 g (0.70 mol) of 2-(2-Bromo-benzyl)-malonic acid diethyl ester and placed in an oil bath. A solution of 225.8 g (4.02 mol) potassium hydroxide in 225 ml water is slowly added with stirring. The reaction temperature is carefully monitored and the addition of the potassium hydroxide solution is interrupted as soon as a significantly exothermic reaction starts. The temperature may rise up to 80° C. The remaining potassium hydroxide solution is added as soon as the initial reaction starts to subside. It may happen that no change in temperature is observed while adding the potassium hydroxide solution. If this happens, the reaction mixture is carefully and slowly heated to 80° C. The exothermic reaction may suddenly start. As soon as the initial reaction starts to subside, the reaction mixture is heated to 100° C. and stirred for 6 h at this temperature.
To separate most of the ethanol, 225 ml of water are added and about half of the total volume is removed on a rotary evaporator in a vacuum. Thereafter 200 ml of water are again added and concentrated hydrochloric acid is carefully added (neutralisation is exothermic) until the solution is strongly acidic. 2-(2-Bromo-benzyl)-malonic acid precipitates. The acid is filtered off on a frit and washed with water until the washing water has a pH of approximately 3-4.
The dicarboxylic acid is dried under reduced pressure, transferred into a round bottom flask with a suitable gas outlet and a bouble counter. The flask is immersed into an oil bath at 165° C. and left there until the gas evolution stops. After approx. 20 minutes a yellow oil forms which may solidify at lower temperatures. The crude product is dissolved in 400 ml of Ethanol and placed in a −30° C. fridge. Pure 3-(2-Bromo-phenyl)-propionic acid precipitates over night and is filtered off. A further crop of pure product can be recovered from the filtrate by removing about 3⁄4 of the ethanol and again cooling the remaining solution to −30° C. over night (Combined yield: 128.2 g, 80%).
1H-NMR (500 MHz, CDCl3, ppm): δ=7.53 (m, 1H, aromatic), 7.28-7.20 (m, 2H, aromatic), 7.07 (m, 1H, aromatic), 3.06 (t, 2H, Ar—CH2—CH2—CO2H), 2.70 (t, 2H, Ar—CH2—CH2—CO2H).
4-Bromo-indan-1-one




128.2 g (0.559 mol) of 3-(2-Bromo-phenyl)-propionic acid are placed in a 2-neck round bottom flask with gas outlet and stirrer. 133.2 g (1.12 mol) of thionyl chloride are added and the mixture is heated under reflux for 2 h with stirring in an argon atmosphere and excess thionyl chloride is removed in a vacuum. The resulting yellow oil is dissolved in 700 ml of methylene chloride, cooled to 0° C. and 82.0 g (0.615 mol) anhydrous aluminium chloride are added in small portions. The reaction mixture is stirred at 0° C. for 2 h and then hydrolyzed by carefully pouring it on crushed ice. The organic layer is separated. The aqueous layer is acidified with concentrated hydrochloric acid and extracted twice with methylene chloride. The combined organic layers are washed once with 2 M HCl, once with water, dried over anhydrous magnesium sulphate and the solvent is removed under reduced pressure (110.0 g, 87%).
1H-NMR (500 MHz, CDCl3, ppm): δ=7.75 (m, 1H, aromatic), 7.70 (m, 1H, aromatic), 7.27 (m, 1H, aromatic), 3.08 (m, 2H, —CH2—), 2.72 (m, 2H, —CH2—).
4-(4-tert-Butyl-phenyl)-indan-1-one




22.9 g (0.109 mol) of 4-Bromo-indan-1-one, 23.18 g (0.130 mol) of 4-tert-butylphenylboronic acid, 23.0 g (0.217 mol) sodium carbonate, 67 ml water and 357 ml of ethylene glycol are placed into a round bottom flask with reflux condenser and stirrer. The flask is evacuated and refilled with argon three times to remove any oxygen. 49 mg (0.22 mmol) of Palladium(II) acetate and 1.4 ml (0.87 mmol) of a 0.6 M solution of NaTPPTS (tris-sodiumtriphenylphosphine-3,3′,3′′-trisulfonate) are premixed in 2 ml of water and added to the reaction mixture which is subsequently heated to reflux. The progress of the reaction is monitored via TLC. Complete conversion should be achieved within 3.5 to 5 hours. The mixture is cooled to room temperature and water and toluene are added until two clearly discernible phases form. The layers are separated and the water phase is extracted three times with toluene. The combined organic layers are washed twice with a saturated sodium chloride solution, dried over anhydrous magnesium sulphate and the solvent is removed in a vacuum to yield an oily product. The GC-determined purity of the crude product is 92%. Pure product can be obtained by treating the oily residue with 35 ml of ethanol at room temperature. Solid 4-(4-tert-Butyl-phenyl)-indan-1-one precipitates and is filtered of. The filtrate still contains significant amounts of product which can be isolated by evaporating the filtrate to dryness mixing it with 50 ml of heptane and storing the mixture at −30° C. over night. The filtrate is filtered off, washed with two portions of cold (30° C.) heptane and dried in a vacuum (Combined yield: 23.71 g, 82%).
1H-NMR (500 MHz, CDCl3, ppm): δ=7.75 (m, 1H, aromatic), 7.59 (m, 1H, aromatic), 7.48 (m, 2H, aromatic), 7.44 (m, 1H, aromatic), 7.39 (m, 2H, aromatic), 3.16 (m, 2H, —CH2—), 2.68 (m, 2H, —CH2—), 1.37 (s, 9H, —C(CH3)3).
Aldol condensation between 4-(4-tert-butyl-phenyl)-indan-1-one and 1-methyl-cyclohexanecarbaldehyde




18.35 g (69.4 mmol) of 4-(4-tert-butyl-phenyl)-indan-1-one, 9.20 g (72.9 mmol) of 1-methyl-cyclohexyl-carbaldehyde, 12.85 g (93.0 mmol) of potassium carbonate and 184 ml of ethanol are placed into a round bottom flask. The mixture is heated to a temperature of 76-78° C. with stirring for 54 h. 10% hydrochloric acid is added until no gas evolution is observed anymore and the precipitating salts are dissolved by adding enough water to dissolve them. The aqueous phase is extracted twice with 175 ml of methylene chloride. The combined organic phases are dried over MgSO4 and the solvent is removed in a vacuum to yield 26.03 g of crude product The crude product was used as-is for the subsequent steps.
Hydrogenation of 4-(4-tert-butyl-phenyl)-2-[(1-methylcyclohexyl)methylene]-indan-1-one




28.62 g of crude 4-(4-tert-butyl-phenyl)-2-(1-methylcyclo-hexylmethylene)-indan-1-one (GC:  ̃83% purity) are dissolved in 286 ml of ethyl acetate in a flask with gas inlet and stirrer. 2 g of palladium on activated carbon (10 wt-% palladium) are added. The system is evacuated and refilled with argon three times to remove oxygen and then evacuated and refilled with hydrogen three times. The stirrer is started and the reaction mixture is vigorously stirred to help the diffusion of hydrogen gas into the liquid reaction mixture. The hydrogen uptake is monitored and stirring is continued until the hydrogen uptake ceases. Filtering the crude reaction mixture over a paper filter and removing the solvent in a vacuum leaves crude 4-(4-tert-butyl-phenyl)-2-(1-methyl-cyclohexylmethyl)-indan-1-one (yield 27.99 g, GC:  ̃84% purity). The obtained crude product was used without further purification for the subsequent reduction/elimination-sequence.
7-(4-tert-Butyl-phenyl)-2-[(1-methylcyclohexyl)methyl]-1H-indene




27.9 g of crude 4-(4-tert-butyl-phenyl)-2-[(1-methylcyclohexyl)methyl]-indan-1-one ( ̃83% purity), 2.82 g (74.5 mmol) of NaBH4 and 70.5 ml of toluene are charged in a flask equipped with reflux condenser, dropping funnel and magnetic stirring bar. The mixture is warmed to 50° C. and 14 ml of methanol are slowly added with stirring and stirring is continued for 2.5 h to ensure a complete reaction. Excess NaBH4 is carefully hydrolyzed with approx. 40 ml of 2n H2SO4. The organic phase is separated and the water phase is washed with another 35 ml of toluene. The combined organic phases are twice extracted with 2n H2SO4 and dried over anhydrous MgSO4. Most of the solvent is removed in a vacuum and replaced by fresh toluene up to a total volume of 100 ml and 0.3 g of p-toluenesulfonic acid are added. The reaction flask is fitted with a water separator and the reaction mixture is heated to reflux for 1.5 h. The conversion can be monitored by TLC. Once the dehydration is complete, the solution is washed with a saturated NaHCO3 solution and dried over anhydrous MgSO4. The solvent is thoroughly removed in a vacuum and 25.85 g of a brown oil is obtained. Purification of the indene is carried out via a column chromatography. Yield: 18.85 g ( ̃85%) of 7-(4-tert-Butyl-phenyl)-2-[(1-methylcyclohexyl)methyl]-1H-indene.
1H-NMR (500 MHz, CDCl3, ppm): δ=7.48-7.44 (m, 4H, aromatic), 7.29 (m, 1H, aromatic), 7.25 (m, 1H, aromatic), 7.13 (m, 1H, aromatic), 6.56 (s, 1H, ═CH), 3.47 (s, 2H, benzylic), 2.38 (s, 2H, aliphatic), 1.55-1.2 (br m, 10H, aliphatic), 1.37 (s, 9H, —C(CH3)3), 0.91 (s, 3H, CH3).
Bis[4-(4-tert-butyl-phenyl)-2-[(1-methylcyclohexyl)methyl]-1H-inden-1-yl]-dimethyl-silane




24.4 g (68.0 mmol) 7-(4-tert-Butyl-phenyl)-2-((1-methyl cyclohexyl)methyl)-1H-indene were dissolved in 414 ml of toluene and 122 ml of THF in a 1000 ml-round bottom flask. 28.6 ml of n-butyl lithium (2.5 M in toluene, 1.05 eq.) were added at room temperature and the solution was stirred 1 h at 80° C. After cooling to 40° C. 4.13 ml (0.5 eq.) of dimethyldichlorosilane were added in one portion and the mixture was stirred at 60° C. for 20 h. After cooling to room temperature 250 ml of water were added and the phases were separated. The aqueous layer was extracted once with 100 ml of toluene and the combined organic layers were washed once with 200 ml of saturated NaCl-solution, dried over magnesium sulphate and the solvent was evaporated in a vacuum. The crude product was purified via a column chromatography to yield 16.8 g (64%) of an isomeric mixture of the desired product. 1H-NMR (500 MHz, CDCl3, ppm): δ=7.51-7.14 (multiple m's, 14H, aromatic), 6.82 and 6.80 (2×s, 2H, ═CH), 3.94 and 3.85 (2×s, 2H, CH—SiMe2), 2.53/2.35 and 2.38/2.21 (2×[2×“d”], 4H, CH2—), 1.51-1.16 (multiple m's, 20H, aliphatic), 1.382 and 1.376 (2×s, 18H, —C(CH3)3), 0.85 and 0.80 (2×s, 6H, CH3), −0.08, −0.28 and −0.52 (3×s, 6H, SiCH3).
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride




To 9.2 g (11.8 mmol) of Bis[4-(4-tert-butyl-phenyl)-2-[(1-methyl-cyclohexyl)methyl]-1H-inden-1-yl]-dimethylsilane were added 92 ml of dry diethyl ether in a 250 ml round bottom flask. Approx. 20 minutes after adding 9.8 ml of n-butyllithium (2.5 M in toluene, 2.05 eq.) at room temperature the initial suspension transformed into a clear orange solution. The mixture was stirred over night at this temperature and then was cooled to 0° C. 2.77 g (1 eq.) of zirconium tetrachloride were added and after warming to room temperature stirring was continued for 5 h. The crude reaction mixture was filtered over a G4 frit and the residue was washed twice with 10 ml of diethyl ether. The filter cake was extracted once with 30 ml, once with 20, once with 15 and once with 10 ml of hot toluene, from the filtrate 2.95 g of the metallocene with a rac/meso-ratio of 5:1 were obtained. For further r/m enrichment the product was crystallized from toluene. 1H-NMR (500 MHz, CDCl3, ppm): δ=7.61 (m, 2H, aromatic), 7.53 (m, 4H, aromatic), 7.40 (m, 2+4H, aromatic), 7.33 (m, 2H, aromatic), 7.05 (m, 2H, aromatic), 6.91 (s, 2H, indenyl-H), 2.65 and 2.23 (2×“d”, 2×2H, indenyl-CH2), 1.48-1.08 (multiple m's, 20H, ring), 1.35 (s, 6H, CH3Si), 1.32 (s, 18H, C(CH3)3), 0.75 (s, 6H, CH3).
Example 7
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-tert-butyl phenyl)-1-indenyl]-zirconium dichloride
Aldol condensation between 4-(4-tert-butyl-phenyl)-indan-1-one and 1-methyl-cyclopentanecarbaldehyde




15.4 g (58.3 mmol) of 4-(4-tert-butyl-phenyl)-indan-1-one, 6.9 g (61.5 mmol) of 1-methyl-cyclopentylcarbaldehyde, 10.8 g (78.1 mmol) of potassium carbonate and 160 ml of ethanol are placed into a round bottom flask. The mixture is heated to a temperature of 76-78° C. with stirring for 50 h. 10% hydrochloric acid is added until no gas evolution is observed anymore and the precipitating salts are dissolved by adding enough water to dissolve them. The aqueous phase is extracted twice with 150 ml of methylene chloride. The combined organic phases are dried over MgSO1 and the solvent is removed in a vacuum to yield 21.1 g of crude product. The crude product was used as-is for the subsequent steps.
Hydrogenation of 4-(4-tert-butyl-phenyl)-2-[(1-methylcyclopentyl)methylene]-indan-1-one




21.0 g of crude 4-(4-tert-butyl-phenyl)-2-(1-methyl-cyclo-hexylmethylene)-indan-1-one (GC:  ̃83% purity) are dissolved in 220 ml of ethyl acetate in a flask with gas inlet and stirrer. 1.5 g of palladium on activated carbon (10 wt-% palladium) are added. The system is evacuated and refilled with argon three times to remove oxygen and then evacuated and refilled with hydrogen three times. The stirrer is started and the reaction mixture is vigorously stirred to help the diffusion of hydrogen gas into the liquid reaction mixture. The hydrogen uptake is monitored and stirring is continued until the hydrogen uptake ceases. Filtering the crude reaction mixture over a paper filter and removing the solvent in a vacuum leaves crude 4-(4-tert-butyl-phenyl)-2-((1-methylcyclohexyl)methyl)-indan-1-one (yield 19.9 g, GC:  ̃86% purity). The obtained crude product was used without further purification for the subsequent reduction/elimination-sequence.
7-(4-tert-Butyl-phenyl)-2-[(1-methylcyclopentyl)methyl]-1H-indene




19.5 g of crude 4-(4-tert-butyl-phenyl)-2-[(1-methylcyclopentyl)methyl]-indan-1-one ( ̃86% purity), 2.06 g (54.5 mmol) of NaBH4 and 52 ml of toluene are charged in a flask equipped with reflux condenser, dropping funnel and magnetic stirring bar. The mixture is warmed to 50° C. and 10 ml of methanol are slowly added with stirring and stirring is continued for 2.5 h to ensure a complete reaction. Excess NaBH4 is carefully hydrolyzed with approx. 30 ml of 2n H2SO4. The organic phase is separated and the water phase is washed with another 26 ml of toluene. The combined organic phases are twice extracted with 2n H2SO4 and dried over anhydrous MgSO4. Most of the solvent is removed in a vacuum and replaced by fresh toluene up to a total volume of 75 ml and 0.22 g of p-toluenesulfonic acid are added. The reaction flask is fitted with a water separator and the reaction mixture is heated to reflux for 1.5 h. The conversion can be monitored by TLC. Once the dehydration is complete, the solution is washed with a saturated NaHCO3 solution and dried over anhydrous MgSO4. The solvent is thoroughly removed in a vacuum and a brown oil is obtained. Purification of the indene is carried out via a column chromatography. Yield: 13.8 g ( ̃86%) of 7-(4-tert-Butyl-phenyl)-2-[(1-methylcyclopentyl)methyl]-1H-indene.
Bis[4-(4-tert-butyl-phenyl)-2-[(1-methylcyclopentyl)methyl]-1H-inden-1-yl]-dimethyl-silane




13 g (37.7 mmol) 7-(4-tert-Butyl-phenyl)-2-((1-methyl-cyclopentyl)methyl)-1H-indene were dissolved in 228 ml of toluene and 67 ml of THF in a 500 ml-round bottom flask. 15.8 ml of n-butyl lithium (2.5 M in toluene, 1.05 eq.) were added at room temperature and the solution was stirred 1 h at 80° C. After cooling to 40° C. 2.27 ml (0.5 eq.) of dimethyldichlorosilane were added in one portion and the mixture was stirred at 60° C. for 20 h. After cooling to room temperature 120 ml of water were added and the phases were separated. The aqueous layer was extracted once with 60 ml of toluene and the combined organic layers were washed once with 100 ml of saturated NaCl-solution, dried over Magnesium sulphate and the solvent was evaporated in a vacuum. The crude product was purified via a column chromatography to yield 9.4 g (67%) of the desired product.
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride




To 9.0 g (12.1 mmol) of Bis[4-(4-tert-butyl-phenyl)-2-[(1-methyl cyclopentyl)-methyl]-1H-inden-1-yl]dimethyl-silane were added 94 ml of dry diethyl ether in a 250 ml round bottom flask. Approx. 20 minutes after adding 9.9 ml of n-butyllithium (2.5 M in toluene, 2.05 eq.) at room temperature the initial suspension transformed into a clear orange solution. The mixture was stirred over night at this temperature and then was cooled to 0° C. 2.82 g (1 eq.) of zirconium tetrachloride were added and after warming to room temperature stirring was continued for 5 h. The crude reaction mixture was filtered over a G4 frit and the residue was washed twice with 10 ml of diethyl ether. The filter cake was extracted once with 30 ml, once with 20, once with 15 and once with 10 ml of hot toluene, from the filtrate 2.95 g of the metallocene with a rac/meso-ratio of 4:1 were obtained. For further r/m enrichment the product was crystallized from toluene.
Example 8
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-tert-butylphenyl)-1-indenyl]-zirconium dichloride
Aldol condensation between 4-(4-tert-butyl-phenyl)-indan-1-one and 1-ethyl-cyclohexanecarbaldehyde




18.6 g (70.4 mmol) of 4-(4-tert-butyl-phenyl)-indan-1-one, 10.3 g (73.5 mmol) of 1-ethyl-cyclohexylcarbaldehyde, 13.0 g (94.1 mmol) of potassium carbonate and 160 ml of ethanol are placed into a round bottom flask. The mixture is heated to a temperature of 76-78° C. with stirring for 50 h. 10% hydrochloric acid is added until no gas evolution is observed anymore and the precipitating salts are dissolved by adding enough water to dissolve them. The aqueous phase is extracted twice with 150 ml of methylene chloride. The combined organic phases are dried over MgSO4 and the solvent is removed in a vacuum to yield 25.9 g of crude product. The crude product was used as-is for the subsequent steps.
Hydrogenation of 4-(4-tert-butyl-phenyl)-2-[(1-ethylcyclohexyl)methylene]-indan-1-one




25.0 g of crude 4-(4-tert-butyl-phenyl)-2-(1-ethylcyclo-hexylmethylene)-indan-1-one (GC:  ̃83% purity) are dissolved in 250 ml of ethyl acetate in a flask with gas inlet and stirrer. 1.75 g of palladium on activated carbon (10 wt-% palladium) are added. The system is evacuated and refilled with argon three times to remove oxygen and then evacuated and refilled with hydrogen three times. The stirrer is started and the reaction mixture is vigorously stirred to help the diffusion of hydrogen gas into the liquid reaction mixture. The hydrogen uptake is monitored and stirring is continued until the hydrogen uptake ceases. Filtering the crude reaction mixture over a paper filter and removing the solvent in a vacuum leaves crude 4-(4-tert-butyl-phenyl)-2-(1-ethyl-cyclohexylmethyl)-indan-1-one (yield 24.4 g, GC:  ̃82% purity). The obtained crude product was used without further purification for the subsequent reduction/elimination-sequence.
7-(4-tert-Butyl-phenyl)-2-[(1-ethylcyclohexyl)methyl]-1H-indene




24.0 g of crude 4-(4-tert-butyl-phenyl)-2-[(1-ethylcyclohexyl)methyl]indan-1-one ( ̃82% purity), 2.4 g (63.4 mmol) of NaBH4 and 60 ml of toluene are charged in a flask equipped with reflux condenser, dropping funnel and magnetic stirring bar. The mixture is warmed to 50° C. and 12 ml of methanol are slowly added with stirring and stirring is continued for 2.5 h to ensure a complete reaction. Excess NaBH4 is carefully hydrolyzed with approx. 35 ml of 2n H2SO4. The organic phase is separated and the water phase is washed with another 30 ml of toluene. The combined organic phases are twice extracted with 2n H2SO4 and dried over anhydrous MgSO4. Most of the solvent is removed in a vacuum and replaced by fresh toluene up to a total volume of 90 ml and 0.26 g of p-toluenesulfonic acid are added. The reaction flask is fitted with a water separator and the reaction mixture is heated to reflux for 1.5 h. The conversion can be monitored by TLC. Once the dehydration is complete, the solution is washed with a saturated NaHCO3 solution and dried over anhydrous MgSO4. The solvent is thoroughly removed in a vacuum and 22.4 g of a brown oil is obtained. Purification of the indene is carried out via a column chromatography. Yield: 15.3 g ( ̃81%) of 7-(4-tert-Butyl-phenyl)-2-[(1-ethylcyclohexyl)methyl]-1H-indene.
Bis[4-(4-tert-butyl-phenyl)-2-[(1-ethylcyclohexyl)methyl]-1H-inden-1-yl]-dimethyl-silane




15 g (40.3 mmol) 7-(4-tert-Butyl-phenyl)-2-((1-ethyl cyclohexyl)methyl)-1H-indene were dissolved in 245 ml of toluene and 72 ml of THF in a 1000 ml-round bottom flask. 16.9 ml of n-butyl lithium (2.5 M in toluene, 1.05 eq.) were added at room temperature and the solution was stirred 1 h at 80° C. After cooling to 40° C. 2.43 ml (0.5 eq.) of dimethyldichlorosilane were added in one portion and the mixture was stirred at 60° C. for 20 h. After cooling to room temperature 150 ml of water were added and the phases were separated. The aqueous layer was extracted once with 60 ml of toluene and the combined organic layers were washed once with 150 ml of saturated NaCl-solution, dried over magnesium sulphate and the solvent was evaporated in a vacuum. The crude product was purified via a column chromatography to yield 10.0 g (62%) of the desired product.
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride




To 9.8 g (12.2 mmol) of Bis[4-(4-tert-butyl-phenyl)-2-[(1-ethyl-cyclohexyl)methyl]-1H-inden-1-yl]-dimethylsilane were added 95 ml of dry diethyl ether in a 250 ml round bottom flask. Approx. 20 minutes after adding 10.0 ml of n-butyllithium (2.5 M in toluene, 2.05 eq.) at room temperature the initial suspension transformed into a clear orange solution. The mixture was stirred over night at this temperature and then was cooled to 0° C. 2.84 g (1 eq.) of zirconium tetrachloride were added and after warming to room temperature stirring was continued for 5 h. The crude reaction mixture was filtered over a G4 frit and the residue was washed twice with 10 ml of diethyl ether. The filter cake was extracted once with 30 ml, once with 20, once with 15 and once with 10 ml of hot toluene, from the filtrate 2.80 g of the metallocene with a rac/meso-ratio of 5:1 were obtained. For further r/m enrichment the product was crystallized from toluene.
Preparation of Methylaluminoxane Treated Silica
Example 9
To a stirred suspension of 293 g of silica (Grace XPO2107, dried at 180° C. and 1 mbar for 16 hours, LOD<0.5 wt % and LOI=2.6 wt %) in 1500 mL of toluene is added slowly 300 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation) at room temperature. During the addition the temperature must not exceed 30° C. After the addition is complete, the mixture is stirred for two hours at room temperature and separated by filtration. 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 10
There is no Example 10 in this application. In order to make it easier for the reader to correlate the metallocenes made in Examples 1 thru 8, to the catalysts made in Examples 11 through 18, example 10 has been omitted. In this manner, the metallocene of Example 1 is used to prepare the catalyst in Example 11, similarly, the metallocene of Comparative Example 4 is now used to produce the catalyst of Comparative Example 14, etc.
Preparation of Supported Metallocene Catalysts
Comparative Example 11
10.0 g of the methylaluminoxane treated silica prepared in Example 9 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. In a separate flask 326 mg of rac-Dimethylsilanediylbis(2-(cyclohexylmethyl)-4-(4-tert-butyl-phenyl)-1-indenyl)-zirconium dichloride (prepared in Comparative Example 1) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 reddish powder in a yield of 12.0 g.
Comparative Example 12
10.0 g of the methylaluminoxane treated silica prepared in Example 9 are placed in a flitted 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. In a separate flask 307 mg of rac-Dimethylsilanediylbis(2-(tert-butylmethyl)-4-(4-tert-butylphenyl)-1-indenyl)-zirconium dichloride (prepared in Comparative Example 2) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 reddish powder in a yield of 11.4 g.
Comparative Example 13
10.0 g of the methylaluminoxane treated silica prepared in Example 9 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. In a separate flask 363 mg of rac-Dimethylsilanediylbis(2-(1-adamantylmethyl)-4-(4-tert-butylphenyl)-1-indenyl)-zirconium dichloride (prepared in Comparative Example 3) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added, on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 reddish powder in a yield of 11.8 g.
Comparative Example 14
10.0 g of the methylaluminoxane treated silica prepared in Example 9 are placed in a fitted 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. In a separate flask 267 mg of rac-Dimethylsilanediylbis(2-methyl-4-(4-tert-butylphenyl)-1-indenyl)-zirconium dichloride (prepared in Comparative Example 4) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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.
Comparative Example 15
10.0 g of the methylaluminoxane treated silica prepared in Example 9 are placed in a fitted 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. In a separate flask 277 mg of rac-Dimethylsilanediyl(2-methyl-4-(4-tert-butylphenyl)indenyl)(2-isopropyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride (prepared in Comparative Example 5) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 16
10.0 g of the methylaluminoxane treated silica prepared in Example 9 are placed in a flitted 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. In a separate flask 336 mg of rac-Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride (prepared in Example 6) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 11.6 g.
Example 17
10.0 g of the methylaluminoxane treated silica prepared in Example 9 are placed in a fitted 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. In a separate flask 326 ng of rac-Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride (prepared in Example 7) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 11.3 g.
Example 18
10.0 g of the methylaluminoxane treated silica prepared in Example 9 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. In a separate flask 346 mg of rac-Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride (prepared in Example 8) are mixed with 27 mL of toluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry is stirred at room temperature for one hour to give an orange solution. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 tour. 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 19
The reader will note that in the tables comparing results, Example 19 and Comparative Example 20 are separated from the comparisons made between all other inventive Examples and Comparative Examples. The reason for this is that the catalysts for both inventive Example 18 and Comparative Example 19 were prepared by a special process previously revealed by the inventors in U.S. Pat. No. 7,169,864 that has been demonstrated to increase the activity of metallocene catalysts over standard preparation methods. It would be inaccurate to compare catalysts made by the '864 method to those made by standard metallocene preparation methods.
To a stirred suspension of 100 g of silica (Grace XPO8001, dried at 180° C. and 1 mbar for 16 hours, LOD<0.5 wt % and LOI=2.5 wt %) in 480 mL of toluene is added slowly 250 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation) at room temperature. For safety reasons not related to the efficacy of the process or the catalyst, during the addition the temperature should not exceed 30° C. After the addition is complete, the mixture is stirred for half an hour at room temperature and then heated and allowed to reflux for four hours. After cooling down to room temperature the solvent is separated by filtration. The residue is washed with two 500 mL portions of toluene and three 500 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 180 g.
10.0 g of the methylaluminoxane treated silica are placed in a fitted 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. In a separate flask 336 mg of rac-Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride (prepared in Example 6) are mixed with 10 mL of toluene and 33.4 mL of a 10 wt-% solution of triisobutylaluminum in heptane (Akzo Nobel). The slurry is stirred at room temperature for one hour. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 powder in a yield of 12 g.
Comparative Example 20
To a stirred suspension of 100 g of silica (Grace XPO8001, dried at 180° C. and 1 mbar for 16 hours, LOD<0.5 wt % and LOI=2.5 wt %) in 480 mL of toluene is added slowly 250 mL of a 30 wt-% solution of methylaluminoxane in toluene (Albemarle Corporation) at room temperature. During the addition the temperature must not exceed 30° C. After the addition is complete, the mixture is stirred for half an hour at room temperature and then heated and allowed to reflux for four hours. After cooling down to room temperature the solvent is separated by filtration. The residue is washed with two 500 mL portions of toluene and three 500 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 180 g.
10.0 g of the methylaluminoxane treated silica 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. In a separate flask 326 mg of rac-Dimethylsilanediylbis(2-(cyclohexylmethyl)-4-(4-tert-butyl-phenyl)-1-indenyl)-zirconium dichloride (prepared in Comparative Example 1) are mixed with 10 mL of toluene and 33.4 mL of a 10 wt-% solution of triisobutylaluminum in heptane (Akzo Nobel). The slurry is stirred at room temperature for one hour. This solution is then carefully added on top of the methylaluminoxane treated silica and slowly filtered off within approximately 30 minutes. When the surface of the colored solution reaches the top of the silica, 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 powder in a yield of 11.8 g.
Polymerizations:
Polymerization Procedure (Batch Propylene Homo- and Co-Polymerization):
A dry and nitrogen purged 5 dm3 autoclave equipped with a stirrer is charged with if desired 100 g of metallocene polymer seed bed. Optionally, a certain amount of hydrogen is metered in. Triisobutylaluminum (1 cm3 of a 10 wt.-% solution in heptane), liquid propylene (one-half of the total amount used for the run), and optionally, a certain amount of ethylene are metered in and the mixture is stirred for at least 5 minutes (stirrer speed 200 rpm) at 20° C. Then supported metallocene catalyst, suspended in 5 cm3 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° C.) within 11 minutes. The polymerization reaction is allowed to proceed at the run temperature for either 15 or 60 minutes. During the 60 min copolymerization runs 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.







TABLE 1







Polymerisations






















Polym.
Polym.

Productivity


Poly.
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Example
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]



















1
Comp 11
—
1838
—
61
65
60
478
7,800


2
Comp 11
50
1837
—
55
65
60
1117
19,900


3
Comp 11
—
1192
 25
30
60
60
183
6,100


4
Comp 11
—
1182
 38
30
60
60
135
4,500


5
Comp 11
—
1836
 60
75
65
15
190
10,100


6
Comp 11

1185
 75
30
60
60
108
3,600


7
Comp 11
—
1115
110
30
60
60
98
3,300


8
Comp 11
—
1767
120
75
65
15
195
10,400


9
Comp 11
—
1700
180
75
65
15
210
11,200


10
Comp 11
—
55
100
50
60
60


11
Comp 11
—
55
125
50
60
60


12
Comp 11
—
55
142
50
60
60


13
Comp 12
—
1837
—
105
65
60
422
4,000


14
Comp 12
50
1836
—
26
65
60
457
17,500


15
Comp 12
—
55
142
50
60
60


16
Comp 13
—
1837
—
97
65
60
410
4,200


17
Comp 13
50
1836
—
30
65
60
490
17,500


18
Comp 13
—
55
142
50
60
60


19
Comp 14
—
1830
—
105
65
60
517
4,920


20
Comp 14
50
1830
—
56
65
60
667
11,910


21
Comp 14
—
55
142
50
60
60


22
Comp 15
—
1836
—
104
65
60
215
2,070


23
Comp 15
50
1834
—
61
65
60
581
9,520


24
Comp 15
—
55
142
50
60
60


25
Ex 16
—
1830
—
100
65
60
820
8,200


26
Ex 16
50
1831
—
41
65
60
1125
27,400


27
Ex 16
—
1189
 25
30
60
60
242
8,050


28
Ex 16
—
1240
 40
30
60
60
238
7,900


29
Ex 16
—
1845
 60
75
65
15
211
11,250


30
Ex 16
—
1264
 80
32
60
60
206
6,400


31
Ex 16
—
1010
100
28
60
60
188
6,700


32
Ex 16
—
1800
120
75
65
15
248
13,200


33
Ex 16
—
1610
170
75
65
15
296
15,800


34
Ex 16
—
55
100
50
60
60


35
Ex 16
—
55
125
50
60
60


36
Ex 16
—
55
142
50
60
60


37
Ex 17
—
1820
—
98
65
60
808
8,100


38
Ex 17
50
1835
—
40
65
60
1013
25,300


39
Ex 17
—
55
142
30
60
60


40
Ex 18
—
1800
—
100
65
60
790
7,900


41
Ex 18
50
1820
—
39
65
60
824
21,100


42
Ex 18
—
55
142
30
60
60


43
Ex 19
—
1835
—
45
65
60
443
9,800


44
Ex 19
50
1835
—
15
65
60
923
61,500


45
Ex 19
—
55
142
30
60
60
260
8,700


46
Ex 19
—
1809
 60
50
65
15
173
13,850


47
Ex 19
—
1752
120
50
65
15
245
19,600


48
Ex 19
—
1696
180
30
65
15
175
23,000


49
Ex 19
—
1628
240
30
65
5
145
58,000


50
Ex 19
14
234
558
30
65
45
320
14,200


51
Ex 19
25
1806
 60
50
65
15
250
20,000


52
Ex 19
25
1749
120
50
65
15
285
22,800


53
Ex 19
25
1697
180
30
65
15
170
36,000


54
Ex 19
25
1630
240
30
65
5
140
56,000


55
Ex 19
25
1224
 5
51
70
15
333
26,300


56
Ex 19
25
1225
 15
51
70
15
314
24,500


57
Ex 19
25
1225
 25
52
70
15
276
21,200


58
Ex 19
25
1223
 35
53
70
15
283
21,200


59
Comp 20
—
1830
—
45
65
60
362
8,000


60
Comp 20
50
1840
—
16
65
60
518
32,400


61
Comp 20
—
55
142
30
60
60
















TABLE 2







Polymer Properties:















Catalyst








Poly.
From
C2
Tm
MFR 2.16
MFR 5
Mw


Example
Example
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn

















1
Comp 11
—
151
0.14
0.4
846
3.4


2
Comp 11
—
151
11
34
235
2.6


3
Comp 11
1.3
140
0.2
0.9
582
2.7


4
Comp 11
1.7
137
0.3
1.2
544
2.5


5
Comp 11
2.1
135
0.5
1.7
523
2.9


6
Comp 11
3.8
123
0.8
3.0
413
2.6


7
Comp 11
5.7
111
0.6
2.5
454
2.9


8
Comp 11
4.3
118
0.8
3.1
422
2.9


9
Comp 11
6.5
103
0.4
1.5
491
2.8


10
Comp 11
39.7
amorphous
6.9
21
280
2.7


11
Comp 11
49.1
amorphous
11.5
35
188
2.8


12
Comp 11
56.0
amorphous
16.7
51.5
166
2.6


13
Comp 12
—
151
<0.1
0.2
763
2.7


14
Comp 12
—
150
18
55
172
2.3


15
Comp 12
57.1
amorphous
0.5
1.7
440
2.7


16
Comp 13
—
152
<0.1
<0.1
920
2.6


17
Comp 13
—
153
11
30
241
2.6


18
Comp 13
56.0
amorphous
<0.1
0.2
760
2.7


19
Comp 14

151
0.35
1.8
730
4.0


20
Comp 14

151
4.3
12
216
3.9


21
Comp 14
49.5
amorphous
25.4
81.0
170
3.3


22
Comp 15
—
153
1.2
4.0
387
2.8


23
Comp 15
—
155
45.3
152
146
2.4


24
Comp 15
53.2
amorphous
0.2
0.7
632
2.9


25
Ex 16
—
152
<0.1
<0.1
910
2.9


26
Ex 16
—
153
11
35
232
2.8


27
Ex 16
1.4
140
0.1
0.3
682
2.8


28
Ex 16
1.5
138
0.1
0.4
678
2.5


29
Ex 16
2.4
133
0.1
0.3
692
3.1


30
Ex 16
4.1
121
0.2
0.4
659
2.7


31
Ex 16
6.0
110
0.1
0.3
684
2.6


32
Ex 16
4.5
118
0.2
0.4
649
2.6


33
Ex 16
7.2
102
0.1
0.3
662
2.6


34
Ex 16
41.3
amorphous
0.1
0.4
659
2.9


35
Ex 16
51.9
amorphous
0.2
0.8
614
2.5


36
Ex 16
56.0
amorphous
0.1
0.6
676
2.7


37
Ex 17
—
153
0.1
0.2
683
2.8


38
Ex 17
—
153
16
61
202
2.9


39
Ex 17
54.0
amorphous
0.2
0.7
646
2.9


40
Ex 18
—
151
0.2
0.8
629
2.6


41
Ex 18
—
152
21
76
189
3.3


42
Ex 18
52.1
amorphous
0.2
0.7
648
3.1


43
Ex 19
—
153
<0.1
0.3
726
3.2


44
Ex 19
—
153
15
—
215
2.9


45
Ex 19
55.3
amorphous
0.1
0.4
682
2.8


46
Ex 19
2.1
133
0.12
0.6
581
2.7


47
Ex 19
6.8
118
0.1
0.5
568
2.5


48
Ex 19
10.1
102
0.1
0.3
606
3.2


49
Ex 19
12.4
 92
0.1
0.4
641
2.7


50
Ex 19
57.4
—
0.1
0.4
709
2.9


51
Ex 19
2.3
134
8.8
31
267
2.7


52
Ex 19
4.3
119
2.5
9.4
306
3.3


53
Ex 19
7.1
103
1.6
7.4
355
3.3


54
Ex 19
9.3
 91
1.4
4.7
382
3.2


55
Ex 19
0.4
153
15
—
209
2.7


56
Ex 19
1.2
147
12
—
210
2.8


57
Ex 19
2.0
142
10
—
227
2.8


58
Ex 19
2.8
139
9
—
232
2.9


59
Comp 20
—
151
0.1
0.4
729
3.5


60
Comp 20
—
151
12
37
225
2.8


61
Comp 20
56.0
amorphous
18
55
149
2.9
















TABLE 3





Propylene, NO Hydrogen, NO Ethylene






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
Example
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





1
Comp 11
—
1838
—
61
65
60
478
7,800


13
Comp 12
—
1837
—
105
65
60
422
4,000


16
Comp 13
—
1837
—
97
65
60
410
4,200


19
Comp 14
—
1830
—
105
65
60
517
4,920


22
Comp 15
—
1836
—
104
65
60
215
2,070


25
Ex 16
—
1830
—
100
65
60
820
8,200


37
Ex 17
—
1820
—
98
65
60
808
8,100


40
Ex 18
—
1800
—
100
65
60
790
7,900


43
Ex 19
—
1835
—
45
65
60
443
9,800


59
Comp 20
—
1830
—
45
65
60
362
8,000


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







1
—
151
0.14
0.4
846
3.4



13
—
151
<0.1
0.2
763
2.7



16
—
152
<0.1
<0.1
920
2.6



19
—
151
0.35
1.8
730
4.0



22
—
153
1.2
4.0
387
2.8



25
—
152
<0.1
<0.1
910
2.9



37
—
153
0.1
0.2
683
2.8



40
—
151
0.2
0.8
629
2.6



43
—
153
<0.1
0.3
726
3.2



59
—
151
0.1
0.4
729
3.5

















TABLE 4





Propylene, Hydrogen, NO Ethylene






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





2
Comp 11
50
1837
—
55
65
60
1117
19,900


14
Comp 12
50
1836
—
26
65
60
457
17,500


17
Comp 13
50
1836
—
30
65
60
490
17,500


20
Comp 14
50
1830
—
56
65
60
667
11,910


23
Comp 15
50
1834
—
61
65
60
581
9,520


26
Ex 16
50
1831
—
41
65
60
1125
27,400


38
Ex 17
50
1835
—
40
65
60
1013
25,300


41
Ex 18
50
1820
—
39
65
60
824
21,100


44
Ex 19
50
1835
—
15
65
60
923
61,500


60
Comp 20
50
1840
—
16
65
60
518
32,400


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







2
—
151
11
34
235
2.6



14
—
150
18
55
172
2.3



17
—
153
11
30
241
2.6



20
—
151
4.3
12
216
3.9



23
—
155
45.3
152 
146
2.4



26
—
153
11
35
232
2.8



38
—
153
16
61
202
2.9



41
—
152
21
76
189
3.3



44
—
153
15
—
215
2.9



60
—
151
12
37
225
2.8

















TABLE 5





Propylene/Ethylene ratio ~48, No Hydrogen






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





3
Comp 11
—
1192
25
30
60
60
183
6,100


27
Ex 16
—
1189
25
30
60
60
242
8,050


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







3
1.3
140
0.2
0.9
582
2.7



27
1.4
140
0.1
0.3
682
2.8

















TABLE 6





Propylene/Ethylene ratio ~31, No Hydrogen






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





4
Comp 11
—
1182
38
30
60
60
135
4,500


28
Ex 16
—
1240
40
30
60
60
238
7,900


5
Comp 11
—
1836
60
75
65
15
190
10,100


29
Ex 16
—
1845
60
75
65
15
211
11,250


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







4
1.7
137
0.3
1.2
544
2.5



28
1.5
138
0.1
0.4
678
2.5



5
2.1
135
0.5
1.7
523
2.9



29
2.4
133
0.1
0.3
692
3.1

















TABLE 7





Propylene/Ethylene ratio ~16, No Hydrogen






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





6
Comp 11

1185
75
30
60
60
108
3,600


30
Ex 16
—
1264
80
32
60
60
206
6,400


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







6
3.8
123
0.8
3.0
413
2.6



30
4.1
121
0.2
0.4
659
2.7

















TABLE 8





Propylene/Ethylene ratio ~15, No Hydrogen






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





8
Comp 11
—
1767
120
75
65
15
195
10,400


32
Ex 16
—
1800
120
75
65
15
248
13,200


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







8
4.3
118
0.8
3.1
422
2.9



32
4.5
118
0.2
0.4
649
2.6

















TABLE 9





Propylene/Ethylene ratio ~10, No Hydrogen






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





7
Comp 11
—
1115
110
30
60
60
98
3,300


31
Ex 16
—
1010
100
28
60
60
188
6,700


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







7
5.7
111
0.6
2.5
454
2.9



31
6.0
110
0.1
0.3
684
2.6

















TABLE 10





Propylene/Ethylene ratio ~9.4, No Hydrogen






























Polym.
Polym.

Productivity


Test
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Run
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





9
Comp 11
—
1700
180
75
65
15
210
11,200


33
Ex 16
—
1610
170
75
65
15
296
15,800


















Test
C2
Tm
MFR 2.16
MFR 5
Mw




Run
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn







9
6.5
103
0.4
1.5
491
2.8



33
7.2
102
0.1
0.3
662
2.6

















TABLE 11





Propylene/Ethylene ratio ~0.55, No Hydrogen






























Polym.
Polym.

Productivity


Poly.
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Example
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





10
Comp 11
—
55
100
50
60
60


34
Ex 16
—
55
100
50
60
60
















Poly.
C2
Tm
MFR 2.16
MFR 5
Mw



Example
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn





10
39.7
amorphous
6.9
21
280
2.7


34
41.3
amorphous
0.1
0.4
659
2.9
















TABLE 12





Propylene/Ethylene ratio ~0.44, No Hydrogen






























Polym.
Polym.

Productivity


Poly.
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Example
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





11
Comp 11
—
55
125
50
60
60


35
Ex 16
—
55
125
50
60
60
















Poly.
C2
Tm
MFR 2.16
MFR 5
Mw



Example
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn





11
49.1
amorphous
11.5
35
188
2.8


35
51.9
amorphous
0.2
0.8
614
2.5
















TABLE 13





Propylene/Ethylene ratio ~.38, No Hydrogen






























Polym.
Polym.

Productivity


Poly.
Catalyst
H2
C3
C2
Catalyst
Temp.
Time
Yield
[g polymer/g


Example
from
[mg]
[g]
[g]
[mg]
[° C.]
[min]
[g]
catalyst*hour]





12
Comp 11
—
55
142
50
60
60


15
Comp 12
—
55
142
50
60
60


18
Comp 13
—
55
142
50
60
60


21
Comp 14
—
55
142
50
60
60


24
Comp 15
—
55
142
50
60
60


36
Ex 16
—
55
142
50
60
60


39
Ex 17
—
55
142
30
60
60


42
Ex 18
—
55
142
30
60
60


45
Ex 19
—
55
142
30
60
60
260
8,700


61
Comp 20
—
55
142
30
60
60
















Poly.
C2
Tm
MFR 2.16
MFR 5
Mw



Example
[wt %]
[deg C.]
[g/10′]
[g/10′]
[kg/mol]
Mw/Mn





12
56.0
amorphous
16.7
51.5
166
2.6


15
57.1
amorphous
0.5
1.7
440
2.7


18
56.0
amorphous
<0.1
0.2
760
2.7


21
49.5
amorphous
25.4
81.0
170
3.3


24
53.2
amorphous
0.2
0.7
632
2.9


36
56.0
amorphous
0.1
0.6
676
2.7


39
54.0
amorphous
0.2
0.7
646
2.9


42
52.1
amorphous
0.2
0.7
648
3.1


45
55.3
amorphous
0.1
0.4
682
2.8


61
56.0
amorphous
18
55
149
2.9









Table 1 and Table 2 represent the raw data presented by sixty-one polymerization test runs. The remaining tables 3-13 break that data out by the ratio of propylene to ethylene (or if it is a propylene homopolymer) and whether hydrogen was used in the polymerization process. Only those results can be directly compared, where essentially the same polymerisation conditions, like temperature, polymerisation time etc. were applied. Further more many of the tables contain two sets of data that are not comparable with each other. The difference between those data sets is the way the catalyst preparation was performed. As explained above, the catalysts of Comparative Examples 11-15 and Examples 16-18 were prepared by a different catalyst preparation procedure than Comparative Example 20 and Example 19 and hence different polymerisation conditions are reflected by these sets of data. These data sets can only be compared among themselves.
Propylene Homopolymers
Analysis 1: Production of Propylene Polymers without the Ethylene Comonomer and without Hydrogen.
Table 3 shows the results of four experimental Metallocene catalysts conforming to the requirements of the invention compared to six comparative examples.
The individual catalyst comparisons of the first set of comparable results between inventive samples 16, 17 and 18 and comparative examples 11 to 15 show in general a higher activity of all the inventive catalysts over the comparative catalysts. Even the inventive catalyst with the lowest productivity (Ex. 18) shows a 13% increase in activity compared to the highest activity comparative catalyst (Comp. 11). When the melting points are compared it is obvious that similar melting points are obtained, and the highest melting point of 153° C. is obtained by one inventive example (Ex. 17) as well as by one comparative example (Comp. 15). The direct comparison of these two examples shows that the activity of the inventive example 17 is almost fourfold higher than the activity of comparative example 15. Since the molecular weight of the inventive example 17 is almost twice as high as the comparative example 15, this is a dramatic improvement.
A general comparison of the molecular weight shows that the highest molecular weights of 920 kg/mol and 910 kg/mol are reached by the comparative example 13 and the inventive example 16, respectively. These molecular weights can be considered equal within the experimental error. At the same time the activity of the inventive example 16 is almost twice as high as the activity of the comparative example 13, while the melting points of these two examples both are 152° C.
It is also most important to note that the metallocenes of Comparative Examples 1 through 3, and the corresponding catalysts of Comparative Examples 11 through 13, would fall under the claims of the inventor's co-pending patent application PCT/US2007/022614 (the “genus application”), which the inventors have, inter alia, directed to the genus of β-branched hydrocarbons in the 2-position, but these Comparative Example do not fall under the claims of the instant species application. Table 3 shows that, in the case of propylene without a hydrogen moderator, the species catalysts of the current invention, on average, are an astonishing 51.2% more active than the comparative catalysts claimed under the genus application. Further, the species catalysts of the present invention also demonstrate the more desirable properties of a higher Tm and MFR 2.16 and MFR 5 values over the tested catalysts that would fall under the claims of the co-pending genus application.
The superiority of the catalysts of the current species invention over the catalysts of the genus application is again demonstrated when hydrogen is introduced as a moderator. In this case, Table 4 shows that the activity of the species catalyst of the present invention increases, on average, a remarkable 34.4% over those of the catalyst of the genus application. Once again, the products of the species catalysts of the current invention show improvements in the desirable properties of a Tm and MFR 2.16 and MFR 5 values over those products made from the catalyst of the genus application (see also Analysis 2).
The second set of comparable results consists of the catalyst derived from example 19 and comparative example 20. The catalyst preparation of these two catalysts differs from the one of the already discussed results and hence they need to be compared separately. Clearly it can be seen that the inventive example shows a superior performance compared to the comparative example 20. The productivity of the inventive example 19 is around 22% increased compared to the comparison example 20, while the molecular weights and the MFR values are comparable. The melting point of the inventive example of 153° C. is two degrees higher than the one of the comparative example 20.
Hence, independent of the catalyst preparation procedure it can be seen that the inventive examples show dramatic improvements over the comparative examples.
Analysis 2: Production of Propylene Polymers without the Ethylene Comonomer and with the Presence of Hydrogen.
Table 4 shows the results of four experimental Metallocene catalysts conforming to the requirements of the invention compared to six comparative examples. However, in this case, hydrogen was added during the polymerization process to enhance catalyst productivity and to regulate the Molecular Weight.
The individual catalyst comparisons of the first set of comparable results between inventive samples 16, 17 and 18 and comparative examples 11 to 15 show in general a higher activity of all the inventive catalysts over the comparative catalysts. Even the inventive catalyst with the lowest productivity (Ex. 18) shows a 6% increase in activity compared to the highest activity comparative catalyst (Comp. 11), while the inventive example 16 even exhibits a 37% increase in productivity over comparative example 11. This is a dramatic improvement. When comparing the molecular weights, the highest molecular weight of the comparative examples is given with 241 kg/mol for comparative example 13, while the highest molecular weight of the inventive examples is 232 kg/mole of example 16. These values can be considered equal within the experimental error, hence the inventive example 16 is reaching a similar molecular weight, but at a much higher productivity level (56% increase compared to Comp. 13). The melting point for this set of comparable results is ranging between 150 and 155° C. The inventive catalyst not only show a higher activity than all the comparative catalyst, they also provide with 152° C.-153° C. melting points of in the upper region of this range. The only catalyst that is able to achieve a higher melting point is comparative catalyst 15 with 155° C., but this is achieved at the lowest activity (9,520 g/g h, 36% lower than inventive example 16) and the lowest molecular weight (146 kg/g, 37% lower than inventive example 16) of all the catalyst in this set of results.
The second set of comparable results consists of the catalyst derived from example 19 and comparative example 20. The catalyst preparation of these two catalysts differs from the one of the already discussed results and hence they need to be compared separately. The inventive catalyst 19 clearly shows a dramatically improved performance over the comparative catalyst 20. The productivity of the inventive catalyst 19 is almost doubled compared to the one of the comparative catalyst 20, while obtaining almost identical molecular weights and MFR values. The melting point obtained with the inventive catalyst 19 with 153° C. by 2° C. higher than the melting point of the comparative catalyst 20.
Propylene/Ethylene Copolymers
The properties of products made from the inventive catalysts were tested at various levels of an ethylene/propylene mix to form copolymers. With the introduction of a new variable, the propylene to ethylene ration, far fewer datapoints were taken for the copolymers at each ratio because resources became limited. In each case the inventive catalyst from example 16 was tested, usually against the comparative catalyst from example 11.
Analysis 3: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 48 and without the Presence of Hydrogen.
In this case, only one inventive catalyst (example 16) was tested against one comparative catalyst, (comparative example 11), the results being presented in Table 5. The inventive catalyst showed significant improvements over the comparative catalyst. The inventive catalyst 16 showed a 31% increase in productivity over the comparative example 11. Comparing the MFR 2.16 values shows that the MFR of the inventive example is with 0.1 g/10′ only half of the MFR of the comparative example, which is also reflected in the 17% increase in molecular weight compared to the comparative example 11. The melting points and the incorporated C2 level are identical for these two catalysts within experimental error and hence the inventive catalysts show a significant improvement in performance compared to the inventive example.
Analysis 4: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 31 and without the Presence of Hydrogen.
In this case, the inventive catalyst 16 and the comparative catalyst 11 were tested under two different polymerisation conditions. The first set of conditions is defined by a polymerization temperature of 60° C. and a polymerization time of 60 minutes, while the second set of conditions is determined by a polymerization temperature of 65° C. and a polymerization time of only 15 minutes. The results are summarized in table 6.
Under the first set of conditions the inventive catalyst shows a 76% increase in productivity compared to the comparative example 11. While the C2-incorporation and the melting point of the polymers are similar, the MFR 2.16 value of the inventive example 16 is only one-third of the comparative example 11. This is also reflected in a 25% increase of the molecular weight compared to the comparative example 11.
The second set of conditions again shows the superior performance of the inventive catalyst. The productivity of the inventive example 16 shows an 11% increase compared to the comparative example 11. The slightly lower melting point of 133° C. for the inventive catalyst 16 is a result of the higher C2-incorporation of the inventive catalyst under this set of conditions (2.4 compared to 2.1% for the comparative example 11). The MFR 2.16 value of the inventive example 16 is only one-fifth of the comparative example 11. This is also reflected in a 32% increase of the molecular weight compared to the comparative example 11.
Analysis 5: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 16 and without the Presence of Hydrogen.
In this case, one inventive catalyst (examples 16) and one comparative catalyst (comparative example 11) were tested, the results being presented in Table 7. The productivity of the inventive example 16 shows a 78% increase compared to comparative example 11. Also the molecular weight of the inventive example 16 shows an increase for the inventive catalyst, namely 59% compared to the comparative example 11. This is also reflected in the values for the MFR 2.16, which is for the inventive example only one-fourth of the comparative example 11. Since the C2-incorporation of the inventive catalyst 16 is slightly higher than for the comparative catalyst 11, it is not surprising, that the melting point for the inventive example is slightly lower. Under these conditions the superiority of the inventive catalyst is clearly visible.
Analysis 6: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 15 and without the Presence of Hydrogen.
In this case, the inventive catalyst 16 and the comparative catalyst 11 were tested, the results being presented in Table 8. As with all the analyses before, the inventive catalyst 16 in this example achieves better productivity (27%). This is achieved at a similar C2-incorporation and the same melting point of 118° C. as the comparative example 11.
The molecular weight of the inventive example is significantly enhanced by 54% compared to the comparative example 11. This fact can also be seen in the value of the MFR 2.16 for the inventive example 16, that is only one-fourth of the value of the comparative catalyst.

Analysis 7: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 10 and without the Presence of Hydrogen.

In this case, one inventive catalyst (examples 16) and one comparative catalyst (comparative example 11), were tested, the results being presented in Table 9. The inventive catalyst shows a large enhancement of the productivity and the molecular weight compared to the comparative catalyst 11, while showing a similar C2-incorporation and a similar melting point. The productivity is doubled compared to the comparative catalyst 11 and the molecular weight is increased by a factor of 1.5. This is also reflected by the MFR 2.16 value, which is for the inventive example 16 only one-sixth of the value obtained for the comparative catalyst 11.
Analysis 8: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 9 and without the Presence of Hydrogen.
The inventive catalyst 16 and the comparative catalyst 11 were tested, and the results are presented in Table 10. As with all the analysis before, the inventive catalyst 16 in this example achieves a better productivity by 41%. This is achieved at a similar C2-incorporation and the slightly lower melting point (1° C.) of inventive example 11 can be rationalised by the higher C2-incorporation of 7.2% compared to 6.5% of the comparative example 11. The molecular weight of the inventive catalyst 16 is increased by 35% compared to the comparative catalyst 11. The higher molecular weight is also reflected in the MFR 2.16 value, which is only one-fourth of the value of the comparative catalyst 11.
Analysis 9: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 0.55 and without the Presence of Hydrogen.
Table 11 shows the results of the inventive catalyst 16 and the comparative example 11 at a propylene/ethylene ratio of approximately 0.55. The productivity of these samples could not be determined because in all of these examples and comparative examples amorphous propylene/ethylene rubbers have been produced. Such polymers generally stick to the autoclace walls and to the stirrer and a quantitative discharge of the autoclave was not possible which makes the determination of the productivities unreliable. Commercially, polymers containing such rubber components are produced in a two step polymerisation where in a first step a homo polymer is produced and in a second step the rubber is produced. This measure reduces the stickiness of the material and allows the commercial production and use of such important materials for applications where low temperature toughness is required (applications like bumpers for cars, frigerator and deep freezer food packaging, crates and pails).
Under the specified conditions the C2-incorporation of the catalysts is quite similar, although the inventive catalyst 16 shows a slightly higher value of 41.3% compared to 39.7% for the comparative catalyst 11. The example of the inventive catalyst shows a dramatic improvement over the comparative examples in gains of molecular weight, and reductions in the MFR values. The molecular weight of the comparative example 11 is more than two times lower than the one obtained with the inventive catalyst 11 (280 kg/mol vs. 659 kg/mol). This result is also reflected in the MFR 2.16 values, which is 0.1 g/10′ for the inventive catalyst and 6.9 g/10′ for the comparative example 11. Hence the inventive catalyst shows a much superior performance under these conditions, since it delivers a polymer with a much higher molecular weight at a similar C2 incorporation.
Analysis 10: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 0.44 and without the Presence of Hydrogen.
In this case, one inventive catalyst (examples 16) and one comparative catalyst (comparative example 11), were tested, the results being presented in Table 12. The productivity of these samples could not be determined because in all of these examples and comparative examples amorphous propylene/ethylene rubbers have been produced. Such polymers generally stick to the autoclace walls and to the stirrer and a quantitative discharge of the autoclave was not possible which makes the determination of the productivities unreliable. Commercially, polymers containing such rubber components are produced in a two step polymerisation where in a first step a homo polymer is produced and in a second step the rubber is produced. This measure reduces the stickiness of the material and allows the commercial production and use of such important materials for applications where low temperature toughness is required (applications like bumpers for cars, frigerator and deep freezer food packaging, crates and pails).
As with Analysis 9, the inventive catalyst in this example achieves a much higher molecular weight, while still creating a product with comparable C2-incorporation. The molecular weight of the inventive catalyst 11 is by a factor 2.3 higher than the molecular weight of the comparative catalyst. This result is also reflected in the MFR 2.16 values, which is 0.2 g/10′ for the inventive catalyst and 11.5 g/10′ for the comparative example 11. Hence the inventive catalyst shows a much superior performance under these conditions, since it delivers a polymer with a much higher molecular weight at a similar C2 incorporation.
Analysis 11: Production of Propylene/Ethylene Copolymers with a Propylene/Ethylene Ratio of Approximately 0.38 and without the Presence of Hydrogen.
In this case, four inventive catalysts and six comparative catalysts, were tested, the results being presented in Table 13. The productivity of many of these samples could not be determined because in all of these examples and comparative examples amorphous propylene/ethylene rubbers have been produced. Such polymers generally stick to the autoclace walls and to the stirrer and a quantitative discharge of the autoclave was not possible which makes the determination of the productivities unreliable. Commercially, polymers containing such rubber components are produced in a two step polymerisation where in a first step a homo polymer is produced and in a second step the rubber is produced. This measure reduces the stickiness of the material and allows the commercial production and use of such important materials for applications where low temperature toughness is required (applications like bumpers for cars, frigerator and deep freezer food packaging, crates and pails). A generally applicable commercial catalyst has to show a high versatility, meaning a high performance under all the conditions relevant for producing commercially available materials. Under the conditions applied here this means that copolymers with very low MFR 2.16 values below 0.5 g/10′ have to be obtained in order to obtain materials where toughness at very low temperatures is required. All the inventive catalysts fulfill this requirement, even more, they are able in all cases to obtain an MFR 2.16 value of 0.2 g/10′ or lower (example 16, 17, 18 and also 19). The only comparative catalyst that obtains a lower MFR 2.16 (<0.1 g/10′) is the one from comparative example 13. Since a MFR 2.16 value of <0.1 g/10′ does not mean a commercial advantage compared to values of up to 0.5 g/10′ and this catalyst has been shown to have a much lower productivity under all other conditions tested, it can be rationalized, that it has not such a high versatility as the inventive catalysts.
The molecular weights of the inventive catalysts 16, 17, 18 are all in the range of 600 and 700 kg/mol, and only the comparative examples 13 and 15 can reach such high molecular weights. But as explained before at much lower productivities for all other conditions tested.
The second set of comparable results consists of the catalyst derived from example 19 and comparative example 20. The catalyst preparation of these two catalysts differs from the one of the already discussed results and hence they need to be compared separately. This second set of conditions showed an unexpected result. As explained earlier under the conditions applied here sticky materials are obtained and hence the reproducible determination of the yield is not possible. In the case of inventive example 19 the copolymer obtained was not sticky and it showed a nice morphology, as shown in the photograph of FIG. 3. This photo shows the copolymer rubber obtained in polymerisation example 45 using the catalyst from Example 19. The yield could be determined to be 8,700 g/g h. The comparative example 20 produced a sticky polymer, shown in FIG. 2. This photo shows the copolymer rubber obtained in polymerisation Example 61 using catalyst from Comparative Example 20. As with many analyses before, the inventive example 19 was producing a much higher molecular weight and a much lower MFR value than the comparative example 20 at comparable C2-introduction. The molecular weight obtained for the inventive example 19 is by a factor 4.6 higher than that of the comparative example 20. This is also reflected by a much lower MFR value of 0.1 g/10′ compared to 18 g/10′ for the comparative example 20.
Conclusion of the Analysis:
The different polymerization conditions tested represent the most applied conditions to obtain commercially relevant polypropylene-based materials. The inventive catalysts have shown under all conditions higher productivities than the corresponding comparative catalysts and most of the time better or at least similar properties of the resulting materials. Hence the inventive catalysts show a much higher versatility than the state-of-the-art catalysts and a better performance under all commercially relevant polymerization conditions.
While the above description contains many specifics, these specifics should not be construed as limitations of the invention, but merely as exemplifications of embodiments thereof. Those skilled in the art will envision many other embodiments within the scope and spirit of the invention as defined by the claims appended hereto.

## Claims

1. A bridged metallocene having the general Formula 1 below,




where M1 is a metal of Group IVb of the Periodic Table of the Elements,
R1 and R2 are identical or different and are selected from the group consisting of 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 NR232 group, where R32 is an alkyl group of from 1 to about 10 carbon atoms and an aryl group of from 6 to about 14 carbon atoms, and wherein R1 and R2 optionally form one or more ring system(s),
R4 and R4′ are identical or different and are selected from the group consisting of a hydrogen atom and a linear, cyclic or branched hydrocarbon group optionally containing one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br,
R10 is a bridging group wherein R10 is selected from:





where
R40 and R41, even when bearing the same index, are identical or different and optionally contain heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, Cl and Br, and are 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, an alkyl(aryl)silyl group, an arylsilyl group, and an arylalkenyl group of from 8 to about 40 carbon atoms, and wherein R40 and R41 together with the atoms connecting them optionally form one or more cyclic systems,
x is an integer from 1 to 18,
M12 is silicon, germanium or tin, and
R10 optionally links two units of the formula 1 to one another,
R11 and R11′ are identical or different and are each a divalent C2-C40 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 R11 and R11′ optionally contain the heteroatoms Si, Ge, N, P, O or S within the ring system fused onto the cyclopentadienyl ring, and
R300 has the structure





where R301 is a linear, cyclic or branched hydrocarbon group selected from the group consisting of 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, wherein each of the groups optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contain halogen atoms selected from the group consisting of F, Cl and Br,
and where R302 is a hydrocarbon group selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, and an substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, and wherein those groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and/or halogen atoms selected from the group consisting of F, Cl and Br, and further wherein R302 forms a monocyclic ring with the β carbon atom, and
R3 has the meaning of R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group which optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, or R3 is selected from the group consisting of an alkyl group of from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, and an alkylarylalkenyl group of from 9 to about 40 carbon atoms, with the proviso that, in any case, R3 is not branched in the α-position.

2. The metallocene of claim 1 wherein R1 and R2 are identical or different and are selected from the group consisting of an alkyl 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, and a halogen atom, and wherein R1 and R2 together optionally form one or more ring system(s), and wherein M1 is zirconium or hafnium.

3. The metallocene of claim 1 wherein R1 and R2 are identical or different and are methyl, chlorine or phenolate.

4. The metallocene of claim 1 wherein R4 and/or R4′ are selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 20 carbon atoms, an alkenyl group of from 2 to 20 carbon atoms, an aryl group of from 6 to 20 carbon atoms, an arylalkyl group of from 7 to 40 carbon atoms, an alkylaryl group of from 8 to about 40 carbon atoms, an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group.

5. The metallocene of claim 1 wherein R4 and/or R4′ are selected from the group consisting of a hydrogen atom, 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 10 carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms, an alkylaryl group of from 8 to about 20 carbon atoms, an arylalkenyl group of from 8 to about 20 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group.

6. The metallocene of claim 1 wherein R4 and R4′ are both hydrogen.

7. The metallocene of claim 1 wherein R10 is R40R41Si═, R40R41Ge═, R40R41C═ or —(R40R41C—CR40R41)—, where R40 and R41 are identical or different and each is selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms, an alkylaryl group of from 7 to about 14 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group.

8. The metallocene of claim 1 wherein the bridging unit R10 is R40R41Si═ or R40R41Ge═, where R40 and R41 are identical or different and each is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl, naphthyl, benzyl, trimethylsilyl and 3,3,3-trifluoropropyl.

9. The metallocene of claim 1 wherein the groups R11 and R11′ identical or different and each is selected from the group consisting of a divalent group selected from those given in Formulae 1 (α, β, γ, δ, φ, and v and Formulae 1 α′, β′, γ′, δ′, φ′, and v′, respectively, wherein the asterisks “*” and “*” in Formula 1 and Formulae 1α-v and 1α′-v′, respectively, denote the chemical bonds joining R11 and R11′ to the cyclopentadienyl rings






wherein R5, R6, R7, R8, and R9 and also R5′, R6′, R7′, R8′ and R9′ as well as R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ are identical or different and are each selected from the group consisting of a hydrogen atom, and a linear, cyclic or branched hydrocarbon group with or without heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and wherein said R5, R6, R7, R8, R9, R5′, R6′, R7′, R8′, R9′, R55, R66, R77, R88, R99, R55′, R66′, R77′, R88′ and R99′ are individually selected from the group consisting of 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 aryl alkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group, and wherein two adjacent radicals R5, R6 or R5′, R6′ or R6, R7 or R6′, R7′ or R7, R8 or R7′, R8′ or R8, R9 or R8′, R9′ as well as R55, R66 or R55′, R66′ or R66, R77 or R66′, R77′ or R77, R88 or R77′, R88′ or R88, R99 or R88′, R99′ in each case optionally forms a saturated or unsaturated hydrocarbon ring system.

10. The metallocene of claim 9 wherein R11 and R11′ identical or different and R11 is a divalent group according to Formula 1γ and R11′ is selected from the divalent groups in Formulae 1α′, β′, and γ′, or R11 and R11′ identical or different and are selected from the group consisting of divalent groups according to Formula 1α and 1α′, Formula 1β and 1β′ Formula 1γ and 1γ′, Formula 1δ and 1δ′, Formula 1φ and 1φ′, and Formula 1v and 1v′, respectively.

11. The metallocene of claim 9 wherein R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ are each a hydrogen atom and R5, R6, R7, R8 and R9 and also R5′, R6′, R7′, R8′ and R9 are identical or different and each is selected from the group consisting of 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, and an aryl group of from 6 to about 40 carbon atoms wherein each of the groups optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, or wherein the two adjacent radicals R5/R6 and R5′/R6′ form a hydrocarbon ring system, or R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.

12. The metallocene of claim 9 wherein R55, R66, R77, R88 and R99 and R55′, R66′, R77′, R88′ and R99′ are each a hydrogen atom and R5, R6, R7, R8 and R9 and R5′, R6′, R7′, R8′ and R9′ are identical or different and each is selected from the group consisting of a hydrogen atom, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, and wherein the two adjacent radicals R5, R6 and also R5′, R6′ together form a ring system, or R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.

13. The metallocene of claim 1 wherein R301 is a linear, cyclic or branched hydrocarbon group which is optionally halogenated and wherein R302 is selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, and a substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, wherein any of those groups optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contains halogen atoms selected from the group consisting of F, Cl and Br, with the proviso that R302 is a mono-cyclic ring which includes the β-carbon atom.

14. The metallocene of claim 13 wherein R301 is selected from the group consisting of 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, and an arylalkenyl group of from 8 to about 40 carbon atoms and wherein R302 is a substituted or unsubstituted alkyl group of from 3 to about 7 carbon atoms, and that group optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contains halogen atoms selected from the group consisting of F, Cl and Br, with the proviso that R302 is a mono-cyclic ring which includes the β-carbon atom.

15. The metallocene of claim 1 wherein R300 contains more than 6 carbon atoms.

16. The metallocene of claim 1 wherein R3 is chosen from the same set that described R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group of from 1 to about 20 carbon atoms, with the proviso that R3 is not branched in the α-position.

17. The metallocene of claim 16 wherein R3 is selected from the group consisting of an alkyl group of from 1 to 20 carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms and an alkylarylalkenyl group of from 9 to about 20 carbon atoms.

18. The metallocene of claim 1 wherein R3 and R300 are identical or R3 is selected from the group consisting of a methyl group, a linear, cyclic or branched hydrocarbon group of from 7 to about 10 carbon atoms which is optionally halogenated, an alkylaryl group of from 7 to about 10 carbon atoms and an alkylalkenyl group of from 3 to about 10 carbon atoms, with the proviso that R3 is not cyclic or branched in α-position.

19. The metallocene of claim 1 wherein R3 is chosen from the same set that described R300, but need not be identical to R300.

20. The metallocene of claim 19 wherein R3 and R300 each contain more than 6 carbon atoms.

21. A process for olefin polymerisation comprising contacting one or more olefins each having from 2 to about 20 carbon atoms under olefin polymerisation reaction conditions with a catalyst system including a bridged metallocene component having formula 1




where M1 is a metal of Group IVb of the Periodic Table of the Elements,
R1 and R2 are identical or different and are selected from the group consisting of 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 NR232 group, where R32 is an alkyl group of from 1 to about 10 carbon atoms and an aryl group of from 6 to about 14 carbon atoms and R1 and R2 optionally form one or more ring system(s),
R4 and R4′ are identical or different and are selected from the group consisting of a hydrogen atom and a linear, cyclic or branched hydrocarbon group optionally containing one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br,
R10 is a bridging group wherein R10 is selected from





where
R40 and R41, even when bearing the same index, are identical or different and optionally contain heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, Cl and Br, and are 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, an alkyl(aryl)silyl group, an arylsilyl group, and an arylalkenyl group of from 8 to about 40 carbon atoms and wherein R40 and R41 together with the atoms connecting them optionally form one or more cyclic systems,
x is an integer from 1 to 18,
M12 is silicon, germanium or tin, and
R10 optionally links two units of the formula 1 to one another,
R11 and R11′ are identical or different and are each a divalent C2-C40 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 R11 and R11′ optionally contain the heteroatoms Si, Ge, N, P, O or S within the ring system fused onto the cyclopentadienyl ring, and
R300 has the structure:





where R301 is a linear, cyclic or branched hydrocarbon group selected from the group consisting of 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, wherein each of the groups optionally contain one or more hetero atoms Si, B, Al, O, S, N or P, and optionally contain halogen atoms selected from the group consisting of F, Cl and Br, and where R302 is a hydrocarbon group which is selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, and an substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, wherein those groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contain halogen atoms selected from the group consisting of F, Cl and Br, and further wherein R302 forms a monocyclic ring with the β carbon atom, and
R3 has the meaning of R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group which optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, or R3 is selected from the group consisting of an alkyl group of from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, and an alkylarylalkenyl group of from 9 to about 40 carbon atoms, with the proviso that R3, in any case, is not branched in the α-position.

22. The process of claim 21 wherein R1 and R2 are identical or different and are selected from the group consisting of an alkyl 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, and a halogen atom, and wherein R1 and R2 together optionally form one or more ring system(s), and wherein M1 is zirconium or hafnium.

23. The process of claim 21 wherein R1 and R2 are identical or different and are methyl, chlorine or phenolate.

24. The process of claim 21 wherein R4 and/or R4′ are selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 20 carbon atoms, an alkenyl group of from 2 to 20 carbon atoms, an aryl group of from 6 to 20 carbon atoms, an arylalkyl group of from 7 to 40 carbon atoms, an alkylaryl group of from 8 to about 40 carbon atoms, an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group.

25. The process of claim 21 wherein R4 and/or R4′ are selected from the group consisting of a hydrogen atom, 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 10 carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms, an alkylaryl group of from 8 to about 20 carbon atoms, an arylalkenyl group of from 8 to about 20 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group.

26. The process of claim 21 wherein R4 and R4′ are both hydrogen.

27. The process of claim 21 wherein R10 is R40R41Si═, R40R41Ge═, R40R41C═, or —(R40R41C—CR40R41)—, where R40 and R41 are identical or different and each is selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms, an alkylaryl group of from 7 to about 14 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, and an arylsilyl group.

28. The process of claim 21 wherein the bridging unit R10 is R40R41Si═ or R40R41Ge═, where R40 and R41 are identical or different and each is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl, naphthyl, benzyl, trimethylsilyland 3,3,3-trifluoropropyl.

29. The process of claim 21 wherein the groups R11 and R11′ are identical or different and each is selected from the group consisting of a divalent group selected from those given in Formulae 1 (α, β, γ, δ, φ, and v and Formulae 1α′, β′, γ′, δ′, φ′, and v′, respectively, wherein the asterisks “*” and “**” in Formula 1 and Formulae 1α-v and 1α′-v′, respectively, denote the chemical bonds joining R11 and R11′ to the cyclopentadienyl rings







wherein R5, R6, R7, R8, and R9 and also R5′, R6′, R7′, R8′ and R9′ as well as R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ are identical or different and each is selected from the group consisting of a hydrogen atom, and a linear, cyclic or branched hydrocarbon group with or without heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and wherein said R5, R6, R7, R8, R9, R5′, R6′, R7′, R8′, R9′, R55, R66, R77, R88, R99, R55′, R66′, R77′, R88′ and R99′ are individually selected from the group consisting of 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, an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, and wherein two adjacent radicals R5, R6 or R5′, R6′ or R6, R7 or R6′, R7′ or R7, R8 or R7′, R8′ or R8, R9 or R8′, R9′ as well as R55, R66 or R55′, R66′ or R66, R77 or R66′, R77′ or R77, R88 or R77′, R88′ or R88, R99 or R88′, R99′ in each case optionally forms a saturated or unsaturated hydrocarbon ring system.

30. The process of claim 29 wherein R11 and R11′ are identical or different and R11 is a divalent group according to Formula 1γ and R11′ is selected from the divalent groups in Formulae 1α′, β′, and γ′, or R11 and R11′ are identical or different and are selected from the group consisting of divalent groups according to Formula 1α, and 1α′, Formula 1β and 1β′, Formula 1γ and 1γ′, Formula 1δ and 1δ′, Formula 1φ and 1φ′, and Formula 1v and 1v′, respectively.

31. The process of claim 29 wherein R55, R66, R77, R88 and R99 and also R55′, R66′, R77′, R88′ and R99′ are each a hydrogen atom and R5, R6, R7, R8 and R9 and also R5′, R6′, R7′, R8′ and R9′ are identical or different and each is selected from the group consisting of 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, and an aryl group of from 6 to about 40 carbon atoms wherein any of the groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and further wherein the two adjacent radicals R5/R6 and R5′/R6′ form a hydrocarbon ring system, or R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.

32. The process of claim 29 wherein R55, R66, R77, R88 and R99 and R55′, R66′, R77′, R88′ and R99′ are each a hydrogen atom and R5, R6, R7, R8 and R9 and R5′, R6′, R7′, R8′ and R9′ are identical or different and are each selected from the group consisting of a hydrogen atom, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, and an aryl group of from 6 to about 40 carbon atoms, and wherein the two adjacent radicals R5, R6 and also R5′, R6′ together form a ring system, or R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.

33. The process of claim 21 wherein R301 is a linear, cyclic or branched hydrocarbon group which is optionally halogenated and wherein R302 is selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms and a substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, wherein any of those groups optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contains halogen atoms selected from the group consisting of F, Cl and Br, with the proviso that R302 is a mono-cyclic ring which includes the β-carbon atom.

34. The process of claim 33 wherein R301 is selected from the group consisting of 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 20 carbon atoms, anarylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, and an arylalkenyl group of from 8 to about 40 carbon atoms and wherein R302 is a substituted or unsubstituted alkyl group of from 3 to about 7 carbon atoms, and that group optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contains halogen atoms selected from the group consisting of F, Cl and Br, with the proviso that R302 is a mono-cyclic ring which includes the β-carbon atom.

35. The process of claim 21 wherein R300 contains more than 6 carbon atoms.

36. The process of claim 21 wherein R3 is chosen from the same set that described R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group of from 1 to about 20 carbon atoms, with the proviso that R3 is not branched in the α-position.

37. The process of claim 36 wherein R3 is selected from the group consisting of an alkyl group of from 1 to 20 carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms and an alkylarylalkenyl group of from 9 to about 20 carbon atoms.

38. The process of claim 21 wherein R3 and R300 are identical or R3 is selected from the group consisting of a methyl group or a linear, cyclic or branched hydrocarbon group of from 7 to about 10 carbon atoms which is optionally halogenated, an alkylaryl group of from 7 to about 10 carbon atoms and an alkylalkenyl group of from 3 to about 10 carbon atoms, with the proviso that R3 is not branched in α-position.

39. The process of claim 21 wherein R3 is chosen from the same set that described R300, but need not be identical to R300.

40. The process of claim 39 wherein R3 and R300 each contain more than 6 carbon atoms.

41. The process of claim 21 wherein the olefins include propylene and/or ethylene.

42. The process of claim 21 wherein the olefins include at least one olefin having the formula Rm—CH═CH—Rn wherein Rm and Rn are identical or different and are each individually a hydrogen atom or a radical having from 1 to about 20 carbon atoms, and Rm and Rn together optionally form one or more rings.

43. The process of claim 21 wherein the olefins include one or more compounds selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene, ethylnorbornadiene, norbornene, tetracyclododecene and methylnorbornene.

44. A bridged metallocene having the general Formula 1a below,




where M1 is a metal of Group IVb of the Periodic Table of the Elements,
R1 and R2 identical or different and are selected from the group consisting of 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 NR232 group, where R32 is an alkyl group of from 1 to about 10 carbon atoms and an aryl group of from 6 to about 14 carbon atoms and R1 and R2 optionally form one or more ring system(s),
R4 and R4′ are identical or different and are selected from the group consisting of a hydrogen atom and a linear, cyclic or branched hydrocarbon group optionally containing one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br,
R10 is a bridging group wherein R10 is selected from:





where
R40 and R41, even when bearing the same index, are identical or different and optionally contain heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, Cl and Br, 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, an alkyl(aryl)silyl group, an arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms and wherein R40 and R41 together with the atoms connecting them optionally form one or more cyclic systems,
x is an integer from 1 to 18,
M12 is silicon, germanium or tin, and
R10 optionally links two units of the formula 1 to one another, and
R300 has the structure:






where R301 is a linear, cyclic or branched hydrocarbon group selected from the group consisting of 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 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, an alkoxy group of from 1 to about 20 carbon atoms, an aryloxy group of from 6 to about 20 carbon atoms, or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, wherein the groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contain halogen atoms selected from the group consisting of F, Cl and Br,
and where R302 is a hydrocarbon group selected from the group consisting of a substituted or unsubstituted alkyl group of from 2 to about 20 carbon atoms, and an substituted or unsubstituted alkenyl group of from 3 to about 20 carbon atoms, and the groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contain halogen atoms selected from the group consisting of F, Cl and Br, wherein R302 forms a monocyclic ring with the β carbon atom,
R3 has the meaning of R300, but R3 need not be identical to R300, or R3 is a linear, cyclic or branched hydrocarbon group which optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br or R3 is selected from the group consisting of an alkyl group of from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, and an alkylarylalkenyl group of from 9 to about 40 carbon atoms, with the proviso that R3, in any case, is not branched in the α-position,

and where R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ are identical or different and are each selected from the group consisting of a hydrogen atom, a linear, cyclic or branched hydrocarbon group or a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group and wherein each of the groups optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contains halogen atoms selected from the group consisting of F, Cl and Br, and further wherein adjacent radicals R5, R6 or R6, R7 or R7, R8 and also R5′, R6′ or R6′, R7′ or R7′, R8′ in each case optionally forms a hydrocarbon ring system.

45. The metallocene of claim 44, wherein R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ are identical or different and are each selected from the group consisting of a hydrogen atom, a linear, cyclic or branched hydrocarbon group selected from 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, an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, and wherein those groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N and P, and optionally contain halogen atoms selected from the group consisting of F, Cl and Br, and further wherein adjacent radicals R5, R6 or R6, R7 or R7, R8 and also R5′, R6′ or R6′, R7′ or R7′, R8′ in each case optionally forms a hydrocarbon ring system.

46. The metallocene of claim 45, wherein the linear, cyclic or branched hydrocarbon groups contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and/or adjacent radicals R5, R6 or R6, R7 or R7, R8 and also R5′, R6′ or R6′, R7′ or R7′, R8′ in each case optionally forms a hydrocarbon ring system.

47. The metallocene of claim 44, wherein R5, R6, R7 and R8 and also R5′, R6′, R7′ and R8′ are identical or different and are each selected from the group consisting of 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, and an aryl group of from 6 to about 40 carbon atoms and wherein the adjacent radicals R5, R6 and also R5′, R6′ optionally form a saturated or unsaturated hydrocarbon ring system.

48. The metallocene of claim 44, wherein R6, R7, R8 and also R6′, R7′ and R8′ are identical or different and are each selected from the group consisting of a hydrogen atom, a linear, cyclic or branched hydrocarbon group selected from 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, an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, and wherein adjacent radicals R6, R7 or R7, R8 as well as R6′, R7′ or R7′, R8′ in each case optionally forms a hydrocarbon ring system and further wherein the groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br,
and where R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms which optionally contains one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br.

49. The metallocene of claim 48, wherein the linear, cyclic or branched hydrocarbon groups contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br.

50. The metallocene of claim 44, wherein R6, R7 and R8 and also R6′, R7′ and R8′ are identical or different and are each are selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkylsilyl, an arylsilyl group, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 10 carbon atoms, wherein any of these groups optionally contain one or more hetero atoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cl and Br, and further wherein R5 and R5′ are identical or different and are each a substituted or unsubstituted aryl group of from 6 to about 40 carbon atoms.

51. The metallocene of claim 44, wherein R6, R7 and R8 and also R6′, R7′ and R8′ are identical or different and are each selected from the group consisting of a hydrogen atom, a linear, cyclic or branched alkyl group of from 1 to about 10 carbon atoms, and an aryl group of from 6 to about 10 carbon atoms, and where R5 and R5′ are identical or different and are each selected from the group consisting of naphthyl, 4-(C1-C10-alkyl)phenyl or 4-(C6-C20-aryl)phenyl, 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-(C1-C10-fluoroalkyl)-phenyl, 3-(C1-C10-alkyl)-phenyl, 3-(C1-C10-fluoroalkyl)-phenyl, 3-(C6-C20-aryl)phenyl, 3-biphenyl, 3,5-di-(C1-C10-alkyl)-phenyl, 3,5-dimethyl-phenyl, 3,5-di-(C1-C10-fluoroalkyl)-phenyl, 3,5-di(trifluoromethyl)-phenyl, 3,5-(C6-C20-aryl)phenyl and 3,5-terphenyl.

52. The metallocene of claim 44 wherein the metallocene is a compound selected from the group consisting of:
Dimethylsilandiylbis[2-[(1-methylcyclohexy)methyl]-4-[tert-butylphenyl)-1-indeny]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohepty)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexy)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-[tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilaηdiylbis[2-[1-ethylcyclononyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(1-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohexy)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloocty)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-phenyl-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[1-methylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(2-naphthyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methyl cyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propyl-cyclooctyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(4-trimethylsilyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclopentyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclononyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclopentyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclononyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-ethylcyclobutyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopentyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclononyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclobutyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-propylcyclopropyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(5-methyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(5-ethyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(2,2,5-trimethyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(2,2,-dimethyl-5-ethyl-1,3-dioxan-5-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(3-methyl-oxetan-3-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(3-ethyl-oxetan-3-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride
Dimethylsilandiylbis[2-[(1-methylcyclohex-3-en-1-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride and
Dimethylsilandiylbis[2-[(1-ethylcyclohex-3-en-1-yl)methyl]-4-(tert-butylphenyl)-1-indenyl]-zirconium dichloride,

as well as the analogous zirconiumdimethyl-compounds and zirconium-biphenolates and zirconium-bisphenolates of each of the above.

53. A process for olefin polymerisation comprising contacting one or more olefins each having from 2 to about 20 carbon atoms under olefin polymerisation reaction conditions with a catalyst system including a bridged metallocene component according to claim 44.

54. The process of claim 53 wherein the olefins include propylene and/or ethylene.

55. The process of claim 53 wherein the olefins include at least one olefin having the formula Rm—CH═CH—Rn wherein Rm and Rn are identical or different and are each individually a hydrogen atom or a radical having from 1 to about 20 carbon atoms, and Rm and Rn together optionally form one or more rings.

56. The process of claim 53 wherein the olefins include one or more compounds selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene, ethylnorbornadiene, norbornene, tetracyclododecene and methylnorbornene.

57. A process for olefin polymerisation comprising contacting one or more olefins each having from 2 to about 20 carbon atoms under olefin polymerisation reaction conditions with a catalyst system including a bridged metallocene component according to claim 52.

58. The process of claim 57 wherein the olefins include propylene and/or ethylene.

59. The process of claim 57 wherein the olefins include at least one olefin having the formula Rm—CH═CH—Rn wherein Rm and Rn are identical or different and are each individually a hydrogen atom or a radical having from 1 to about 20 carbon atoms, or Rm and Rn together optionally form one or more rings.

60. The process of claim 57 wherein the olefins include one or more compounds selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene, ethylnorbornadiene, norbornene, tetracyclododecene and methylnorbornene.