Supported chemical compound

0001The present invention relates to a covalently supported chemical compound which can have a neutral or ionic structure and, in combination with a transition metal compound such as a metallocene, can form a catalyst system which is suitable for the polymerization of olefins. The use of aluminoxanes such as methylaluminiumoxane as a cocatalyst can be dispensed with, and high catalyst activity can nevertheless be achieved.

0002The role of cationic complexes in Ziegler-Natta polymerization with metallocenes is generally recognized (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41, 1220).

0003MAO as the most effective cocatalyst to date has the disadvantage of being used in large excess. The preparation of cationic alkyl complexes opens the way to MAO-free catalysts with comparable activity. The synthesis of cationic alkyl complexes is successful<ul id="ul0001" list-style="none"><li>a) Protolysis of metallocene compounds with, for example, weakly acidic ammonium salts of the very stable, non-basic tetralpentafluorophenyl) borate, for example [PhMe₂NH]⁺[B (C₆F₅)₄])^-,</li><li>b) by abstraction of an alkyl group from metallocene compounds with the aid of strong Lewis acids, both salts of the form (Ph₃C.⁺BR₄^-) as well as strong, neutral Lewis acids such as B (C₆F₅)₃ can serve or through</li><li>c) Oxidation of metallocene dialkyl complexes with, for example, AgBPh₄ or [Cp₂Fe] [BPh₄].</li></ul>

0004The synthesis of "cation-like" metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991, 113, 3623. In it the alkyl abstraction from a metallocene dialkyl compound is carried out using tris (pentafluorophenyl) borane. EP 427,697 describes this principle of synthesis and a corresponding catalyst system consisting of a neutral metallocene species (for example Cp₂ZrMe₂), a Lewis acid (e.g. B (C₆F₅)₃) and aluminum alkyl claimed. A process for the preparation of salts of the general form LMX⁺ XA^- According to the principle described above, EP 520,732 is claimed.

0005EP 558,158 claims zwitterionic catalyst systems which consist of metallocene dialkyl compounds and salts of the form [R₃NH]⁺[BPh₄]^- being represented. The implementation of such a salt with, for example, Cp *₂ZrMe₂ provides an intermediate zirconocene methyl cation by protolysis with elimination of methane. This reacts via CH activation to the zwitterion Cp *₂Zr⁺- (mC₆H₄) -BPh₃^- from.

0006According to this reaction principle, the protolysis of a metallocene dialkyl species with a perfluorinated [R₃NH]⁺(B (C₆F₅)₄]^--Salt in the first step also a cationic species, whereby the subsequent reaction (CH activation) to zwitterionic complexes is not possible. This gives rise to salts of the form (Cp₂Zr-R-RH]⁺(B (C₆F₅)₄]^-Corresponding systems are claimed in US Pat. No. 5,348,299, dimethylanilinium salts with perfluorinated tetraphenylborate anions being used. The support of such systems serves a better morphology of the polymer and is described in WO 9109882.

0007The disadvantage of previous carrier processes, as described in WO 91/09882, is that the ionic catalyst system is only physically bound to the carrier. It can therefore be easily detached from the carrier surface by solvents. The homogeneous polymerization then carried out leads to a poorer morphology of the polymer.

0008The documents WO 93/11172, WO 96/04319, WO 93/19103, WO 96/23005 and WO 97/19959 each disclose catalyst compositions in which ionic activators which have a metal or metalloid atom such as boron covalently to the surface of a carrier are bound. The ionic groups bonded to the support each have only a single metal or metalloid atom.

0009EP-A 710 663 describes polymers which can be used as cocatalysts for the polymerization of olefins and are obtained by polymerization of boron compound which contain polymerizable vinyl double bonds. In these polymers, too, groups having a boron atom are each fixed to the support.

0010EP-A 560 128 describes neutral metal alkyls bound to a support which can be used in the polymerization of olefins. However, metal alkyls which are substituted with halogenated radicals are not disclosed.

0011The present invention thus relates to a supported chemical compound and a method for producing this supported chemical compound which is covalently bound to a carrier material. Furthermore, it relates to a catalyst system containing at least one transition metal compound and at least one supported chemical compound according to the invention as cocatalyst. A process for the production of polyolefins in the presence of the supported chemical compound is also described.

0012The supported chemical compound consists of a carrier T, y units N of the formula (II) designated below, which are covalently bonded to the carrier, and b units A.

0013The supported chemical compound has the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0824112B1_D0001.tif" /></chemistry>wherein,<dl id="dl0001" compact="compact"><dt>A^c+</dt><dd>is a cation</dd><dt>c</dt><dd>is an integer from 1 to 10,</dd><dt>b</dt><dd>is an integer ≥ 0,</dd><dt>T</dt><dd>is a carrier</dd><dt>y</dt><dd>is an integer ≥ 1,</dd><dt>a</dt><dd>is an integer from 0 to 10, where a · y = c · b, and</dd><dt>N</dt><dd>is a unit of formula (II)</dd></dl><chemistry id="chem0002" num="0002"><img file="EP0824112B1_D0002.tif" /></chemistry>wherein<dl id="dl0002"><dt>R</dt><dd>independently of one another, identical or different, substituents of M are like a halogen atom or a C.₁-C₄₀-Carbon group are like a C₁-C₄₀-Alkyl, C₁-C₄₀-Halogen alkyl, C₆-C₄₀-Aryl, C₆-C₄₀-Halo-aryl-, C₇-C₄₀Arylalkyl or C₇-C₄₀-Halo-arylalkyl group,</dd><dt>X</dt><dd>independently of one another, identical or different, a C₁-C₄₀carbon-containing group are, for example, a double-bonded carbon-containing group such as a C.₁-C₄₀-Alkylene-, C₁-C₄₀-Haloalkylene-, C₆-C₄₀-Arylene-, C₆-C₄₀-Halogen-arylene-, C₇-C_40-Arylalkylene or C₇-C₄₀-Halo-arylalkylene, C₂-C₄₀-Alkynylene-, C₂-C₄₀Haloalkynylene, C₂-C₄₀-Alkenylene or C₂-C_40-Halogen-alkenylene group, or a three-bonded carbon-containing group such as a C₁-C₄₀-Alkanetriyl-, C₁-C₄₀-Halogenalkantriyl-, C₆-C₄₀-Arentriyl-, C₆-C₄₀-Halogenarenetriyl-, C₇-C₄₀-Arenalanetriyl-, C₇-C₄₀-Halogenarenalkantriyl-, C₂-C_40-Alkynetriyl, C₂-C₄₀-Halogenalkintriyl-, C₂-C₄₀-Alkenetriyl- or C₂-C₄₀-Halogenalkentriyl group,</dd><dt>M</dt><dd>are independently the same or different and represent an element from group IIIa of the Periodic Table of the Elements,</dd><dt>d</dt><dd>is 0 or 1, e is 0 or 1, f is 0 or 1,</dd><dt>G</dt><dd>is an integer from 0 to 10, h is an integer from 0 to 10,</dd><dt>k</dt><dd>is an integer from 0 to 10,</dd><dt>i</dt><dd>is an integer from 0 to 1000,</dd><dt>j</dt><dd>is an integer from 1 to 6,</dd><dt>S</dt><dd>are identical or different spacers which connect M covalently to T, S having the formula (III),</dd></dl><chemistry id="chem0003" num="0003"><img file="EP0824112B1_D0003.tif" /></chemistry>wherein<dl id="dl0003"><dt>R '</dt><dd>the same or different a C₁-C₄₀-carbon group is -NR "-, -PR" -, -P (O) R "-, -Si (R")₂-O-Si (R ")₂-, -CO-SiR "₂-, or -CONR "-, where R" is a C₁-C₄₀is a carbon-containing group or R 'is a hetero atom-containing group such as -SO-, -SO₂-, -S-, -CO-, -CO₂-, -O-, -NH- or -PH-,</dd><dt>n</dt><dd>is an integer ≥ 0,</dd><dt>Q</dt><dd>is Si, N, P, S or O,</dd><dt>q</dt><dd>is 0 or 1,</dd><dt>B</dt><dd>Is substituent of Q and NH₂, PH₂ or a C₁-C₄₀-carbon group is, -NR "₂-, COR "-, -CO₂R "-, -PR"₂-, -P (O) R "₂-, -Si (R ")₂-O-Si (R ")₃-, -CO-SiR "₃-, -CONR "₂-, -SOR ", -SO₂R "-, -OR", -SR ", -NHR" or -PHR ", where R" is a C₁-C₄₀-carbon group and</dd><dt>p</dt><dd>is an integer ≥ 0,</dd></dl>B can connect two spacers S and <img file="EP0824112B1_D0004.tif" /> means one or more covalent bonds to the carrier T, in which case B is defined as R 'and w in formula (II) are identical or different 0, 1 or 2 and z in formula (II) is 0, 1 or 2.

0014The supported chemical compound can also be a supported neutral chemical compound of the formula (I)<chemistry id="chem0004" num="0004"><img file="EP0824112B1_D0005.tif" /></chemistry>be what<dl id="dl0004" compact="compact"><dt>A^c+</dt><dd>is a cation</dd><dt>c</dt><dd>is an integer from 1 to 10,</dd><dt>b</dt><dd>is an integer ≥ 0,</dd><dt>T</dt><dd>is a carrier</dd><dt>y</dt><dd>is an integer ≥ 1,</dd><dt>a</dt><dd>0 where a · y = c · b, and</dd><dt>N</dt><dd>is a unit of formula (II)<chemistry id="chem0005" num="0005"><img file="EP0824112B1_D0006.tif" /></chemistry></dd></dl>wherein,<dl id="dl0005"><dt>R</dt><dd>independently of one another, identical or different substituents of M are like a C.₁-C₄₀-Hydrocarbon residue that is halogenated</dd><dt>X</dt><dd>independently of one another, identical or different, a C₁-C₄₀-Carbon group</dd><dt>M</dt><dd>are independently the same or different and represent an element from Group IIa, IIIa, IVa or Va of the Periodic Table of the Elements,</dd><dt>d</dt><dd>is 0 or 1, e is 0 or 1, f is 0 or 1,</dd><dt>G</dt><dd>is an integer from 0 to 10, h is an integer from 0 to 10, k is an integer from 0 to 10, r is an integer from 0 to 10,</dd><dt>i</dt><dd>is an integer from 0 to 1000,</dd><dt>j</dt><dd>is an integer from 1 to 6</dd><dt>S</dt><dd>are identical or different spacers which connect M covalently to T, and where S has the formula (III)<chemistry id="chem0006" num="0006"><img file="EP0824112B1_D0007.tif" /></chemistry></dd></dl>wherein<dl id="dl0006"><dt>R '</dt><dd>the same or different a C₁-C₄₀-carbon group is -NR "-, -PR" -, -P (O) R "-, -Si (R")₂-O-Si (R ")₂-, -CO-SiR "₂- or -CONR "-, where R" is a C₁-C₄₀-carbon group or R 'is a hetero atom group such as -SO-, -SO₂-, -S-, -CO-, -CO₂-, -O-, -NH- or -PH-,</dd><dt>n</dt><dd>is an integer ≥ 0,</dd><dt>Q</dt><dd>is Si, N, P, S or 0,</dd><dt>q</dt><dd>is 0 or 1,</dd><dt>B</dt><dd>Is substituent of Q and NH₂, PH₂ or a C₁-C₄₀-carbon group is, -NR "₂"-COR" -, -CO₂R "-, -PR"₂, p (O) R "₂, -Si (R ")₂-O-Si (R ")₃-, -CO-SiR "₃-, -CONR "₂, -SOR "; -SO₂R "-, -SR", -OR ", -NHR" or -PHR ", where R" is a C₁-C₄₀-carbon group and</dd><dt>p</dt><dd>is an integer ≥ 0,</dd></dl>B can connect two spacers S, and <img file="EP0824112B1_D0008.tif" /> means one or more covalent bonds to the carrier T, in which case B is defined as R ', and w in formula (II) are identical or different 0, 1 or 2 and z in formula (II) is 0, 1 or 2. If a = 0, it is a neutral unit N; if a ≥ 1, it is a negatively charged unit N.

0015Each of the y units N of the formula (II) can be covalently bound to the carrier T from M directly or via one or more spacers S. Each M and each spacer S can have one or more covalent bonds to the carrier T. This is symbolized in formula (I), (II), (III) and (IV) by the sign<img file="EP0824112B1_D0009.tif" />. For the sake of clarity, the bond to the support (ie<img file="EP0824112B1_D0010.tif" />, shown by way of example only for one group MRS, but the other groups MRS can also bind to the carrier. In the MRS groups, in which z = 0 and / or w = 0, M is directly covalently bound to the support.

0016If the supported chemical compound of the formula (I) has several MRS groups, these can be the same or different. The number of substituents R in a group MRS depends on the valency and the binding nature of M. Preferably z = 1 and all w = 0.

0017In the spacer S of the formula (III), R 'is preferably the same or different and a C₁-C₄₀-Alkylene-, C₁-C₄₀-Haloalkylene-, C₆-C₄₀-Arylene-, C₆-C₄₀-Halogen-arylene-, C₇-C₄₀Arylalkylene or C₇-C₄₀-Halo-arylalkylene-, C₂-C₄₀-Alkynylene-, C₂-C₄₀-Halogen-Alkinylen-, C₂-C₄₀Alkenylene, C₂-C₄₀-Halogen-alkenylene-, C₆-C₄₀Aryloxy, C₇-C₄₀-Alkylarylenoxy- or C₇-C₄₀-Arylalkyleneoxy group, -NR "-, -PR" -, -P (O) R "-, -Si (R")₂-O-Si (R ")₂-, -CO-SiR "₂- or -CONR "-, where R" is a C₁-C₄₀-Alkyl-, C₁-C₄₀-Halo-alkyl-, C₆-C₄₀-Aryl-, C₆-C₄₀-Halo-aryl-, C₇-C₄₀Arylalkyl or C₇-C₄₀-Halo-arylalkyl-, C₂-C₄₀-Alkynyl-, C₂-C₄₀-Haloalkynyl, C₂-C₄₀Alkenyl, C₂-C₄₀-Halogen-alkenyl-, C₆-C₄₀Aryloxy, C₇-C_40-Alkylaryloxy or C₇-C₄₀Is arylalkyloxy group, or R 'is a heteroatom-containing group such as -SO-, -SO₂-, -S-, -CO-, -CO₂-, -O-, -NH- or -PH-, n is preferably 0 or 1, B is preferably NH₂, PH₂, a C₁-C₄₀-Alkyl-, C₁-C₄₀-Halo-alkyl-, C₆-C₄₀-Aryl-, C₆-C₄₀-Halo-aryl-, C₇-C₄₀Arylalkyl or C₇-C₄₀-Halo-arylalkyl-, C₂-C₄₀-Alkynyl-, C₂-C₄₀-Haloalkynyl-, C₂-C₄₀Alkenyl, C₂-C₄₀-Halogen-alkenyl-, C₆-C₄₀Aryloxy, C₇-C₄₀-Alkylaryloxy- or a C₇-C₄₀Arylalkyloxy group, NR "₂"-COR" -, -CO₂R "-, -PR"₂, -P (O) R "₂, -Si (R ")₂-O-Si (R ")₃-, -CO-SiR "₃-, -CONR "₂, -SOR "; -SO₂R "-, -SO₂R ", -SR-, -OR", -NHR "or -PHR", where R "is a C₁-C₄₀-Alkyl-, C₁-C₄₀-Halo-alkyl-, C₆-C₄₀-Aryl-, C₆-C₄₀-Halo-aryl-, C₇-C₄₀Arylalkyl or C₇-C₄₀-Halo-arylalkyl-, C₂-C₄₀-Alkynyl-, C₂-C₄₀-Haloalkynyl-, C₂-C₄₀Alkenyl, C₂-C₄₀-Halogen-alkenyl-, C₇-C₄₀Aryloxy, C₇-C₄₀-Alkylaryloxy- or a C₇-C₄₀Arylalkyloxy group, and p is preferably an integer from 0 to 6.

0018If q is 0, R 'binds to the carrier, if q is 1, Q binds to the carrier. B are substituents of Q that do not bind to the support.

0019In formula (III), Q is particularly preferably Si and q = 1.

0020R in formula (II) is preferably a C₁-C₄₀Hydrocarbon residue, which may preferably be halogenated with halogens such as fluorine, chlorine, bromine or iodine, in particular a halogenated, in particular perhalogenated C.₁-C₃₀Alkyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated, in particular perhalogenated C₆-C₃₀Aryl group such as pentafluorophenyl, heptachloronaphthyl, heptafluoronaphthyl, heptafluorotolyl, 3,5-bis (trifluoromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl or 2,2 '(octafluor) biphenyl.

0021X in formula (II) is preferably a C.₆-C₃₀Arylene group, a C₂-C₃₀-Alkenylene group, a C₂-C₃₀-Alkynylene group, a C₆-C_30-Arentriyl group, a C₂-C₃₀-Alkenetriyl group or a C₂-C₃₀-Alkinetriyl group, which can be halogenated, in particular perhalogenated.

0022Preferably j = 1 or 2 when M is a Group IIa element; j = 2 or 3 when M is a Group IIIa element; j = 3 or 4 if M is a Group IVa element and j = 4 or 5 if M is a Group Va element. M is particularly preferably an element from group IIIa, in particular boron. I is preferably an integer from 0 to 6, particularly preferably 0 or 1. a and b are preferably 0, 1 or 2 and c is preferably 1 or 2. g, h, k and r are preferably 0 or 1.

0023As a^{c +} in formula (I) cations of group Ia, IIa, IIIa of the periodic table of the elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound are preferred, in particular carbenium ions (R.₃C.⁺) or quaternary ammonium ions with an acidic H function (R₃NH⁺) prefers. Quaternary ammonium salts with acidic H functions are particularly preferred.

0024In the event that a ≥ 1 and all M are equal to boron, it is preferred that the number of boron atoms is ≥ 4, particularly preferably 2. A particularly preferred embodiment is the supported neutral chemical compound of the formula (IV)<chemistry id="chem0007" num="0007"><img file="EP0824112B1_D0011.tif" /></chemistry>wherein<dl id="dl0007"><dt>M</dt><dd>is an element of group IIIa of the Periodic Table of the Elements,</dd><dt>R</dt><dd>independently of one another, identical or different, a C₁-C₄-Halo-alkyl-, C₆-C₄₀-Halogen aryl, or C₇-C₄₀-Halo-arylalkyl group</dd><dt>j</dt><dd>is an integer from 1 to 4,</dd><dt>e.g.</dt><dd>Is 0, 1 or 2,</dd><dt>T</dt><dd>and</dd><dt>S</dt><dd>have the meaning given above,</dd><dt>a</dt><dd>is 0,</dd><dt>A</dt><dd>can be a cation of group Ia, IIa, IIIa of the Periodic Table of the Elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound,</dd><dt>b</dt><dd>is 0, is and</dd><dt>c</dt><dd>is 1 or 2.</dd></dl>

0025The carrier T is preferably a porous inorganic or organic solid. The y units N are covalently bonded to its surface, optionally via one or more spacers S. The carrier preferably contains at least one inorganic oxide, such as silicon oxide, aluminum oxide, zeolites, MgO, ZrO₂, TiO₂ B₂O₃, CaO, ZnO, ThO₂, N / A₂CO₃, K₂CO₃, CaCO₃, MgCO₃, N / A₂SO₄, As such₄)₃, BaSO₄, KNO₃, Mg (NO₃)₂, Al (NO₃)₃ ,N / A₂OK₂O, or Li₂O, in particular silicon oxide and / or aluminum oxide. The carrier can also contain at least one polymer, for example a homo- or copolymer, a crosslinked polymer or polymer blends. Examples of polymers are polyethylene, polypropylene, polybutene, polystyrene, polystyrene crosslinked with divinylbenzene, polyvinyl chloride, acrylic-butadiene-styrene copolymer, polyamide, polymethacrylate, polycarbonate, polyester, polyacetal or polyvinyl alcohol.

0026The carrier can have a specific surface area in the range of 10 to 1000 m²/ g, preferably from 150 to 500 m²/ g. The average particle size of the carrier can be 1 to 500 μm, preferably 5 to 350 μm, particularly preferably 10 to 200 μm.

0027The carrier is preferably porous with a pore volume of the carrier of 0.5 to 4.0 ml / g, preferably 1.0 to 3.5 ml / g. A porous carrier has a certain proportion of voids (pore volume). The shape of the pores is usually irregular, often spherical. The pores can be connected to one another by small pore openings. The pore diameter is preferably about 2 to 50 nm. The particle shape of the porous support can be irregular or spherical. The carrier can be post-treated thermally, chemically or mechanically. In this way, the particle shape of the carrier can be influenced. The particle size of the carrier can e.g. B. can be set arbitrarily by cryogenic grinding and / or sieving.

0028To produce the supported chemical compound according to the invention, a carrier starting material TH can be reacted with at least one starting compound NG. The surface of the carrier starting material carries functional groups H, which preferably have the following formula (V):         - (D)_s(E)_t     (V), in which<dl id="dl0008" compact="compact"><dt>D</dt><dd>is Al, B, C, Si, N, P, O or S,</dd><dt>s</dt><dd>is 0 or 1,</dd><dt>E</dt><dd>identically or differently, a halogen, a hydroxyl, carboxylic acid chloride, carboxamide, aryl halide, benzyl halide, alkyl halide, alkoxy, aryloxy, alkylamine, arylamine, alkylphosphine, arylphosphine, thioether, thio, cyanate -, Isocyanate, cycloalkadienyl, sulfonic acid, aldehyde, keto, alkenyl or aryllithium group or a carbon-containing group containing cycloalkadienyl or cycloalkadienyllithium groups and</dd><dt>t</dt><dd>is 1, 2, 3, 4 or 5.</dd></dl>

0029The functional groups H of the carrier starting material TH can be inserted by chemical functionalization with reactive compounds or can already be present. The carrier starting material TH can also by heating at temperatures from 50 ° C to 1000 ° C in an inert gas stream or in a vacuum at 0.01 bar to 0.001 bar or by chemical inerting by reaction with aluminum, magnesium, boron or lithium alkylene or by chemical functionalization reactive compounds are treated.

0030For example, carrier starting materials made of SiO₂ be functionalized in the following way. A suspension of the SiO₂ (pretreated: 4h; 200 ° C, 0.01 bar) in a suitable solvent, such as pentane, hexane, heptane, toluene or dichloromethane, is reacted with a silyl chloride compound containing a functional group, heated at boiling temperature for several hours and then washed with a suitable solvent. The reaction temperature is preferably at least 50 ° C, in particular 50 ° C to 150 ° C. The reaction time is 1 to 600 minutes, preferably 1 to 2 hours. The silyl chloride compound is preferably used in an equimolar ratio based on the proportion of hydroxyl groups on the surface of the SiO₂ used. The reaction is carried out under inert conditions. Solvents suitable for the washing process, for example pentane, hexane, heptane, toluene or dichloromethane, are optionally mixed with amines in order to trap the HCl formed. Then solvent residues are removed in vacuo at 20 to 200 ° C and 0.01 to 0.001 bar.

0031In the starting compound NG, N is defined as in formula (II) and G are leaving groups such as -OR² , Hal, -NR²₂, -H, -CO, -SR²₂, -SO₂ or -PR²₃, where R² as R is defined, which are split off when reacting with the carrier starting material TH to form one or more covalent bonds between N and T.

0032Examples of output compounds NG are:<chemistry id="chem0008" num="0008"><img file="EP0824112B1_D0012.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0824112B1_D0013.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP0824112B1_D0014.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP0824112B1_D0015.tif" /></chemistry>

0033The production of starting compounds NG can proceed, for example, according to the following reaction scheme:<chemistry id="chem0012" num="0012"><img file="EP0824112B1_D0016.tif" /></chemistry>

0034Here is<dl id="dl0009"><dt>X</dt><dd>a C₁-C₄₀-Carbon group are like a C₁-C₄₀-Alkylene-, C_1-C.₄₀-Haloalkylene-, C₆-C₄₀-Arylene-, C₆-C₄₀-Halogen-arylene-, C₇-C_40-Arylalkylene or C₇-C₄₀-Halo-arylalkylene-, C₂-C₄₀-Alkynylene-, C₂-C_40-Haloalkynylene, C₂-C₄₀-Alkenylene or C₂-C₄₀-Halogen-alkenylene group,</dd><dt>Y</dt><dd>independently of one another, identical or different, a leaving group, preferably a hydrogen or halogen atom,</dd><dt>R</dt><dd>independently of one another, identically or differently, a halogen atom or a C₁-C₄₀-carbon group like a C₁-C₄₀-Alkyl-, C₁-C_40-Halogen, alkyl, C₆-C₄₀-Aryl-, C₆-C₄₀-Halo-aryl-, C₇-C₄₀Arylalkyl or C₇-C_40-Halogen arylalkyl group,</dd><dt>Bs</dt><dd>a base, preferably an organolithium compound or a Grignard compound,</dd><dt>M</dt><dd>are identical or different and mean an element of groups IIa, IIIa, IVa or Va of the periodic table of the elements and</dd><dt>A</dt><dd>is a cation of group Ia, IIa, IIIa, the periodic table of the elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound,</dd></dl>

0035The reaction of TH with NG can take place in a suitable solvent, such as pentane, heptane, toluene, dichloromethane or dichlorobenzene, in which the carrier starting material TH is suspended and a solution of the starting compound NG is added dropwise. Or the carrier starting material TH is reacted with stirring with a solution of the compound NG in such a way that 50 to 400% of the pore volume of the carrier component is filled. A washing process can then be carried out as described above and solvent residues can be removed in vacuo at 20 to 200 ° C. and 0.01 to 0.001 bar. The preparation of the supported chemical compound according to the invention is carried out at -80 to 200 ° C, preferably at -20 to 100 ° C and a contact time between 15 minutes and 25 hours, preferably between 15 minutes and 5 hours.

0036A cation A^{c +} be introduced. For this purpose, the reaction product of TH and NG can be reacted with a carbon-containing alkali metal or alkaline earth metal compound such as lithium pentafluorobenzene or lithium tris (trifluoromethyl) benzene and then reacted with a compound AV, in which A is as defined in formula (I) and V is a leaving group defined as G.

0037The supported chemical compound according to the invention can be used together with a transition metal compound as a catalyst system for olefin polymerization. When the supported chemical compound of the general formula (I) is reacted with a transition metal compound M stabilized by ligand L.¹L_x (M¹ is a transition metal, L is a ligand and x is an integer from 1 to 6, which depends on the valence of M¹ depends) b neutral compounds AL and b · c catalytically active compounds are formed<chemistry id="chem0013" num="0013"><img file="EP0824112B1_D0017.tif" /></chemistry>as a cocatalyst component.

0038The transition metal compound M¹L_x contains at least one metal central atom M.¹to which at least one π ligand, e.g. B. a cyclopentadienyl ligand is bound. In addition, substituents such as halogen or carbon-containing groups, for example alkyl, alkoxy or aryl groups, can also be attached to the metal central atom M as ligands L.¹ be bound. The metal central atom is preferably an element of III., IV., V. or VI. Subgroup of the Periodic Table of the Elements, in particular from the IV. Subgroup of the Periodic Table of the Elements, such as Ti, Zr or Hf¹L_x a metallocene, especially a chiral metallocene. Cyclopentadienyl ligand is understood to mean unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzoindenyl, fluorenyl, benzofluorenyl, tetrahydrofrofluorenyl, octahydrofluorenyl. The π ligands, e.g. B. Cyclopentadienyl ligands can be bridged or unbridged, whereby single and multiple bridging - also via ring systems - are possible. The term metallocene also includes compounds with more than one metallocene fragment, so-called multinuclear metallocenes. These can have any substitution pattern and bridging variant. The individual metallocene fragments of such multinuclear metallocenes can be either of the same type or different from one another. Examples of such multinuclear metallocenes are e.g. B. described in (EP-A-632063, JP-A-04/80214, JP-A-04/85310, EP-A-654476).

0039Unbridged or bridged metallocenes of the formula VI are particularly preferred<chemistry id="chem0014" num="0014"><img file="EP0824112B1_D0018.tif" /></chemistry>, in which<dl id="dl0010"><dt>M¹</dt><dd>a metal of III., IV., V. or VI. Subgroup of the Periodic Table of the Elements, in particular Zr or Hf,</dd><dt>R¹</dt><dd>are the same or different and represent a hydrogen atom,<maths id="math0001" num=""><img file="EP0824112B1_D0019.tif" /></maths>where R³ the same or different is a hydrogen atom or a C₁-C_40-carbon-containing group such as C₁-C₂₀-Alkyl, C₁-C₁₀-Fluoroalkyl, C₁-C_10-Alkoxy, C₆-C₂₀-Aryl, C₆-C₁₀-Fluoraryl, C₆-C₁₀Aryloxy, C₂-C₁₀Alkenyl, C₇-C₄₀Arylalkyl, C₇-C₄₀-Alkylaryl or C₈-C₄₀Arylalkenyl, or a C₁-C₃₀ - carbon-containing group such as C₁-C₂₅-Alkyl, e.g. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C₂-C₂₅Alkenyl, C₃-C₁₅Alkylalkenyl, C₆-C₂₄-Aryl, C₅-C₂₄Heteroaryl such as pyridyl, furyl or quinolyl, C₇-C_30-Arylalkyl, C₇-C₃₀-Alkylaryl, fluorine-containing C₁-C₂₅-Alkyl, fluorine-containing C_6-C.₂₄-Aryl, fluorine-containing C₇-C₃₀Arylalkyl, fluorine-containing C₇-C₃₀-Alkylaryl or C₁-C₁₂-Alkoxy, or two or more radicals R¹ can be linked together so that the radicals R¹ and the connecting atoms of the cyclopentadienyl ring a C₄-C₂₄Form a ring system, which in turn can be substituted,</dd><dt>R²</dt><dd>are the same or different and represent a hydrogen atom,<maths id="math0002" num=""><img file="EP0824112B1_D0020.tif" /></maths>where R³ the same or different is a hydrogen atom or a C₁-C_40-carbon-containing group such as C₁-C₂₀-Alkyl, C₁-C₁₀-Fluoroalkyl, C₁-C_10-Alkoxy, C₆-C₁₄-Aryl, C₆-C₁₀-Fluoraryl, C₆-C₁₀Aryloxy, C₂-C₁₀Alkenyl, C₇-C₄₀Arylalkyl, C₇-C₄₀-Alkylaryl or C₈-C₄₀Arylalkenyl, or a C₁-C₃₀ - carbon-containing group such as C₁-C₂₅-Alkyl, e.g. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C₂-C₂₅Alkenyl, C₃-C₁₅Alkylalkenyl, C₆-C₂₄-Aryl, C₅-C₂₄Heteroaryl, e.g. B. pyridyl, furyl or quinolyl, C₇-C_30-Arylalkyl, C₇-C₃₀-Alkylaryl, fluorine-containing C₁-C₂₅-Alkyl, fluorine-containing C_6-C.₂₄-Aryl, fluorine-containing C₇-C₃₀Arylalkyl, fluorine-containing C₇-C₃₀-Alkylaryl or C₁-C₁₂-Alkoxy, or two or more radicals R² can be linked together so that the radicals R² and the connecting atoms of the cyclopentadienyl ring a C₄-C₂₄Form a ring system, which in turn can be substituted,</dd><dt>l</dt><dd>is 5 for v = 0 and 1 is 4 for v = 1,</dd><dt>m</dt><dd>is 5 for v = 0, and m is 4 for v = 1,</dd><dt>L</dt><dd>are identical or different and represent a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms, e.g. B. C₁-C₂₀-Alkyl, C₂-C₂₀Alkenyl, C₁-C₂₀-Alkoxy, C₆-C₁₄Aryloxy or C₆-C₄₀-Aryl,</dd><dt>x</dt><dd>is an integer from 1 to 6, where in the case of M¹ = Ti, Zr or Hf x is preferably 4,</dd><dt>Z.</dt><dd>denotes a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1.</dd></dl>

0040Examples of Z are groups M.²R⁴R⁵, where M² Is carbon, silicon, germanium or tin and R⁴ and R⁵ the same or different a C₁-C_20-hydrocarbon-containing group such as C₁-C₁₀-Alkyl, C₆-C₁₄Aryl or trimethylsilyl. Z is preferably CH₂, CH₂CH₂, CH (CH₃) CH₂, CH (C₄H₉) C (CH₃)₂, C (CH₃)₂, (CH₃)₂Themselves₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si, (C₆H₅) (CH₃) Si, (C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Themselves₂Themselves₃)₂, oC₆H₄ or 2,2 '- (C₆H₄)₂. Z can also contain one or more R¹ and / or R² form a mono- or polycyclic ring system.

0041Chiral bridged metallocenes of the formula VI are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted so that they represent an indenyl ring. The indenyl ring is preferably substituted, in particular in the 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2,4,5,6-position, with C.₁-C₂₀carbon-containing groups, such as C₁-C₁₀-Alkyl or C₆-C₂₀Aryl, where two or more substituents of the indenyl ring can together form a ring system.

0042The following examples of metallocenes serve to illustrate the present invention, but have no restrictive character:<ul id="ul0002" list-style="none" compact="compact"><li>Bis (cyclopentadienyl) zirconium dimethyl</li><li>Bis (indenyl) zirconium dimethyl</li><li>Bis (fluorenyl) zirconium dimethyl</li><li>(Indenyl) (fluorenyl) zirconium dimethyl</li><li>(3-methyl-5-naphthylindenyl) (2,7-di-tert-butylfluorenyl) zirconium dimethyl</li><li>(3-methyl-5-naphthylindenyl) (3,4,7-trimethoxyfluorenyl) zirconium dimethyl</li><li>(Pentamethylcyclopentadienyl) (tetrahydroindenyl) zirconium dimethyl</li><li>(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) zirconium dimethyl</li><li>(Indenyl) (1-buten-4-ylcyclopentadienyl) zirconium dimethyl</li><li>[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) zirconium dimethyl</li><li>Bis (cyclopentadienyl) titanium dimethyl</li><li>Dimethylsilanediylbis (indenyl) zirconiumdimethyl</li><li>Dimethylsilanediylbis (tetrahydroindenyl) zirconium dimethyl</li><li>Dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-methylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-ethylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) zirconium dimethyl</li><li>Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (indenyl) zirconiumdimethyl</li><li>Methylphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (tetrahydroindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-methylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-ethylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) zirconium dimethyl</li><li>Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (indenyl) zirconiumdimethyl</li><li>Diphenylsilanediylbis (2-methylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-ethylindenyl) zirconium dimethyl</li><li>Diphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Diphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-methyl-4, 6-diisopropylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (indenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-methylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) zirconium dimethyl</li><li>1 -Silacyclopentane-1, 1-bis (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) zirconium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (indenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (tetrahydroindenyl) zirconium dimethyl</li><li>Ethylene-1-cyclopentadienyl-2- (1-indenyl) zirconium dimethyl</li><li>Ethylene-1-cyclopentadienyl-2- (2-indenyl) zirconium dimethyl</li><li>Ethylene-1-cyclopentadienyl-2- (2-methyl-1-indenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-methylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-ethylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) zirconium dimethyl</li><li>Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) zirconium dimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (indenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (1-indenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (9-fluorenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3, 6-di-tert-butyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] zirconium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (tetrahydroindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-methylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-ethylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) zirconium dimethyl</li><li>Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-methyl-4-phenylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4-phenylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-methyl-4-naphthylindenyl) zirconium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) zirconium dimethyl</li><li>1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl] hexane</li><li>1,6-bis [methylsilyl (2-methyl-4-phenylindenyl) (4,5-benzoindenyl) zirconium dimethyl] hexane</li><li>1- [Methylsilylbis (tetrahydroindenyl) zirconium dimethyl] -6- [ethylstannyl (cyclopentadienyl) - (fluorenyl) zirconium dimethyl] hexane</li><li>1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl] hexane</li><li>1,4-disila-1,4-bis [methylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl] cyclohexane</li><li>[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienyl zirconium dimethyl)</li><li>[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienylzirconium dimethyl)</li><li>[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyl zirconium dimethyl)</li><li>[1- (1-indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadienylzirconium dimethyl)</li><li>[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenylzirconium dimethyl)</li><li>(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) zirconium dimethyl</li><li>(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) zirconium dimethyl</li><li>Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) zirconium dimethyl</li><li>(2,7-dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] zirconium dimethyl</li><li>Dimethylsilylbis (fluorenyl) zirconium dimethyl</li><li>Dibutylstannylbis (2-methylfluorenyl) zirconium dimethyl</li><li>1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) zirconium dimethyl</li><li>Propylene-1- (2-indenyl) -2- (9-fluorenyl) zirconium dimethyl</li><li>1,1-dimethyl-1-silaethylene bis (fluorenyl) zirconium dimethyl</li><li>[4- (Cyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] zirconium dimethyl</li><li>[4- (Cyclopentadienyl) -4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl)] zirconium dimethyl</li><li>[4- (Cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] zirconium dimethyl</li><li>[4- (Cyclopentadienyl) -4, 7-dimethyl-7-butyl (6, 6-diethyltetrahydroindenyl)] zirconium dimethyl</li><li>[4- (3-tert-Butyicyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] zirconium dimethyl</li><li>[4- (1 -indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] zirconium dimethyl</li><li>Bis (cyclopentadienyl) hafnium dimethyl</li><li>Bis (indenyl) vanadium dimethyl</li><li>Bis (fluorenyl) scandium dimethyl</li><li>(Indenyl) (fluorenyl) niobium dimethyl</li><li>(2-methyl-7-naphthylindenyl) (2,6-di-tert-butylfluorenyl) titanium dimethyl</li><li>(Pentamethylcyclopentadienyl) (tetrahydroindenyl) hafnium bromide methyl</li><li>(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) hafniumdimethyl</li><li>(Indenyl) (2-buten-4-ylcyclopentadienyl) titanium dimethyl</li><li>[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) niobium dimethyl</li><li>Dimethylsilanediylbis (indenyl) titanium dimethyl</li><li>Dimethylsilanediylbis (tetrahydroindenyl) hafniumdimethyl</li><li>Dimethylsilanediyl (cyclopentadienyl) (indenyl) titanium dimethyl</li><li>Dimethylsilanediylbis (2-methylindenyl) hafniumdimethyl</li><li>Dimethylsilanediylbis (2-ethylindenyl) scandiummethyl</li><li>Dimethylsilanediylbis (2-butyl-4,5-benzoindenyl) niobium dimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) titanium dimethyl</li><li>Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) titanium dimethyl</li><li>Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) hafnium dimethyl</li><li>Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) scandium methyl</li><li>Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) hafnium dimethyl</li><li>Dimethylsilanediyibis (2-methyl-4-phenylindenyl) niobium dimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) vanadium dimethyl</li><li>Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl</li><li>Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) vanadium dimethyl</li><li>Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) hafnium bromide methyl</li><li>Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>Methylphenylsilanediylbis (indenyl) titanium dimethyl</li><li>Methylphenylsilanediyl (cyclopentadienyl) (indenyl) hafniumdimethyl</li><li>Methylphenylsilanediylbis (tetrahydroindenyl) hafniumdimethyl</li><li>Methylphenylsilanediylbis (2-methylindenyl) titanium dimethyl</li><li>Methylphenylsilanediylbis (2-ethylindenyl) hafniumdimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) hafniumdimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) vanadium dimethyl</li><li>Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) titanium dimethyl</li><li>Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium bromide methyl</li><li>Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) hafniumdimethyl</li><li>Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) hafniumdimethyl</li><li>Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) titanium dimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4-phenylindenyl) hafniumdimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4-phenylindenyl) vanadium dimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) titanium dimethyl</li><li>Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) hafniumdimethyl</li><li>Methylphenylsilanediylbis (2-methyl-4-naphthylindenyl) hafniumdimethyl.</li><li>Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>Diphenylsilanediylbis (indenyl) titanium dimethyl</li><li>Diphenylsilanediylbis (2-methylindenyl) hafniumdimethyl</li><li>Diphenylsilanediylbis (2-ethylindenyl) titanium dimethyl</li><li>Diphenylsilanediyl (cyclopentadienyl) (indenyl) hafniumdimethyl</li><li>Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) titanium dimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) hafniumdimethyl</li><li>Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) hafniumdimethyl</li><li>Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) hafnium dimethyl</li><li>Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>Diphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) titanium dimethyl</li><li>Diphenylsilanediylbis (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4-phenylindenyl) hafniumdimethyl</li><li>Diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) hafniumdimethyl</li><li>Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) hafniumdimethyl</li><li>Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>1-silacyclopentane-1,1-bis (indenyl) hafniumdimethyl</li><li>1-silacyclopentane-1,1-bis (2-methylindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethylindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) titanium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) scandium methyl</li><li>1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) titanium dimethyl</li><li>1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4-phenylindenyl) hafniumdimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) titanium bromide methyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) titanium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) titanium dimethyl</li><li>1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) scandiummethyl</li><li>1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) hafniumdimethyl</li><li>Bis (cyclopentadienyl) titanium dimethyl</li><li>Ethylene-1,2-bis (indenyl) scandium methyl</li><li>Ethylene-1,2-bis (tetrahydroindenyl) titanium dimethyl</li><li>Ethylene-1-cyclopentadienyl-2- (1-indenyl) hafniumdimethyl</li><li>Ethylene-1-cyclopentadienyl-2- (2-indenyl) titanium bromide methyl</li><li>Ethylene-1-cyclopentadienyl-2- (2-methyl-1-indenyl) hafniumdimethyl</li><li>Ethylene-1,2-bis (2-methylindenyl) hafnium dimethyl</li><li>Ethylene-1,2-bis (2-ethylindenyl) hafnium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) hafnium dimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) titanium dimethyl</li><li>Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) titanium dimethyl</li><li>Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) scandium methyl</li><li>Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) hafnium dimethyl</li><li>Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) titanium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4-phenylindenyl) hafniumdimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) hafniumdimethyl</li><li>Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) titanium dimethyl</li><li>Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) titanium dimethyl</li><li>Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) hafniumdimethyl</li><li>Propylene-2,2-bis (indenyl) hafnium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (1-indenyl) titanium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) titanium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (9-fluorenyl) hafniumdimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) hafnium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) hafnium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) titanium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) hafnium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) titanium dimethyl</li><li>Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) hafnium dimethyl</li><li>Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) titanium dimethyl</li><li>Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3,6-di-tert-butyl-9-fluorenyl) titanium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] hafnium dimethyl</li><li>Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) titanium dimethyl</li><li>Propylene-2,2-bis (tetrahydroindenyl) hafnium dimethyl</li><li>Propylene-2,2-bis (2-methylindenyl) hafnium dimethyl</li><li>Propylene-2,2-bis (2-ethylindenyl) titanium dimethyl</li><li>Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) titanium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) hafniumdimethyl</li><li>Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) hafniumdimethyl</li><li>Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) hafnium dimethyl</li><li>Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) hafnium dimethyl</li><li>Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) hafnium dimethyl</li><li>Propylene-2,2-bis (2-methyl-4-phenylindenyl) titanium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4-phenylindenyl) hafniumdimethyl</li><li>Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) titanium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) hafniumdimethyl</li><li>Propylene-2,2-bis (2-methyl-4-naphthylindenyl) titanium dimethyl</li><li>Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) titanium dimethyl</li><li>1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) hafniumdimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) titanium dimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) hafniumdimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) titanium dimethyl] hexane</li><li>1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl] hexane</li><li>1,6-bis [methylsilyl (2-methyl-4-phenylindenyl) (4,5-benzoindenyl) titanium dimethyl] hexane</li><li>1- [Methylsilylbis (tetrahydroindenyl) hafniumdimethyl] -6- [ethylstannyl (cyclopentadienyl) - (fluorenyl) titanium dimethyl] hexane</li><li>1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) hafnium dimethyl] hexane</li><li>1,4-disila-1,4-bis [methylsilylbis (2-methyl-4-phenylindenyl) hafniumdimethyl] cyclohexane</li><li>[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienylhafniumdimethyl)</li><li>[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienylhafniumdimethyl)</li><li>[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyltitanium dimethyl)</li><li>[1- (1-indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadienyltitanium dimethyl)</li><li>[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenylhafniumdimethyl)</li><li>(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) titanium dimethyl</li><li>(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) titanium dimethyl</li><li>Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) hafniumdimethyl</li><li>(2,7-dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] hafniumdimethyl</li><li>Dimethylsilylbis (fluorenyl) titanium dimethyl</li><li>Dibutylstannylbis (2-methylfluorenyl) hafniumdimethyl</li><li>1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) titanium dimethyl</li><li>Propylene-1- (2-indenyl) -2- (9-fluorenyl) hafniumdimethyl</li><li>1,1-dimethyl-1-silaethylenebis (fluorenyl) titanium dimethyl</li><li>[4- (Cyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] titanium dimethyl</li><li>[4- (Cyclopentadienyl) -4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl)] hafniumdimethyl</li><li>[4- (Cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] titanium dimethyl</li><li>[4- (Cyclopentadienyl) -4,7-dimethyl-7-butyl (6,6-diethyltetrahydroindenyl)] hafniumdimethyl</li><li>[4- (3-tert-Butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] hafniumdimethyl</li><li>[4- (1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] titanium dimethyl</li><li>Bis (cyclopentadienyl) zirconium dichloride</li><li>Bis (indenyl) zirconium dichloride</li><li>Bis (fluorenyl) zirconium dichloride</li><li>(Indenyl) (fluorenyl) zirconium dichloride</li><li>Bis (cyclopentadienyl) titanium dichloride</li><li>Dimethylsilanediylbis (indenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (cyclopentadienyl) (indenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2- methylindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-ethylindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dichloride</li><li>Dimethylsilanediylbis (2-methyl-4,6-düsopropyhndenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (indenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (tetrahydroindenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (2-methylindenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (2-ethylindenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (2-methyl-4-phenylindenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) zirconium dichloride</li><li>Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride</li><li>Propylene-2,2-bis (indenyl) zirconium dichloride</li><li>Propylene-2,2- (cyclopentadienyl) (indenyl) zirconium dichloride</li><li>Propylene-2,2- (cyclopentadoenyl) (fluorenyl) zirconium dichloride</li><li>Bis (cyclopentadienyl) (η⁴-butadiene) zirconium</li><li>Bis (methylcyclopentadienyl) (η⁴-butadiene) zirconium</li><li>Bis (n-butyl-cyclopentadienyl) (η⁴-butadiene) zirconium</li><li>Bisindenyl (η⁴-butadiene) zirconium</li><li>(tert.butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane (η^4-butadiene) zirconium</li><li>Bis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methylbenzoinderiyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (n⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium</li><li>Isopropylidene (cyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium</li><li>Isopropylidene (cyclopentadienyl) (indenyl) (η⁴-butadiene) zirconium</li><li>[4-η5-cyclopentadienyl) -4,7,7-trimethyl- (η5-4,5,6,7-tetrahydroindenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilandlylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η^4-butadiene) zirconium</li><li>Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium</li><li>Methylphenylmethylene- (fluorenyl) (cyclopentadienyl) (η⁴-butadiene) zirconium</li><li>Diphenylmethylene- (fluorenyl) (cyclopentadienyl) (η⁴-butadiene) zirconium</li><li>Isopropylidene- (3-methylcyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediyl- (3-tert-butylcyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium</li><li>Diphenylsilanediyl- (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) (η^4-butadiene) zirconium</li><li>Phenylmethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediylbisindenyl (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediylbis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium</li><li>Phenylmethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) (η^4-butadiene) zirconium</li><li>Phenylmethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediylbis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Phenylmethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylene bisindenyl (η⁴-butadiene) zirconium</li><li>Ethylienbis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium</li><li>Ethylene (2-methyl-4,5-benzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylene (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) (η^4-butadiene) zirconium</li><li>Ethylene (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-ethyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium</li><li>Ethylenebis (2-ethyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium</li><li>Dimethylsilanediylbis (2,3,5-trimethylcyclopentadienyl) (η⁴-butadiene) zirconium</li><li>1,6- {bis [methylsilyl-bis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} hexane</li><li>1,6- {bis [methylsilyl-bis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} hexane</li><li>1,6- {bis [methylsilyl-bis (2-methyl-4-naphthyl-indenyl) (η^4-butadiene) zirconium]} hexane</li><li>1,, 6- {bis [methylsilyl-bis (2-methyl-4,5-benzoindenyl) (n⁴-butadiene) -zirconium]} hexane</li><li>1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium]} hexane</li><li>1,2- {bis [methylsilyl-bis (2-methyl-4-phenyl-indenyl) (η4-butadiene) zirconium]} ethane</li><li>1,2- {bis [methylsilyl-bis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} ethane</li><li>1,2- {bis [methylsilyl-bis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) -zirconium]} ethane</li><li>1, 2- {bis [methylsilyl-bis (2-methyl-4,5-benzoindenyl) (η^4-butadiene) zirconium]} ethane</li><li>1, 2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) (η^4-butadiene) zirconium]} ethane.</li></ul>

0043The present invention further relates to a catalyst containing at least one supported chemical compound according to the invention as a cocatalyst and at least one transition metal compound M.¹L_x, for example a metallocene. In addition, a method for producing an olefin polymer by polymerizing at least one olefin in the presence of the catalyst according to the invention is described. The polymerization can be a homo- or a copolymerization.

0044Olefins of the formula R are preferred^α-CH = CH-R^β polymerized, wherein R^α and R^β are identical or different and represent a hydrogen atom, a halogen atom, an alkoxy, hydroxyl, alkylhydroxy, aldehyde, carboxylic acid or carboxylic ester group or a saturated or unsaturated hydrocarbon radical having 1 to 20 C atoms, in particular 1 to 10 C atoms, which can be substituted with an alkoxy, hydroxy, alkylhydroxy, aldehyde, carboxylic acid or carboxylic acid ester group, or R^α and R^β form one or more rings with the atoms connecting them. Examples of such olefins are 1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, cyclic olefins such as norbornene, vinylnorbornene, tetracyclododecene, ethylidene norbornene, dienes such as 1, 3-butadiene or 1,4-hexadiene, biscyclopentadiene or methyl methacrylate.

0045In particular, propylene or ethylene are homopolymerized, ethylene with one or more C.₃-C₂₀-α-olefins, especially propylene, and / or one or more C₄-C₂₀-Dienes, in particular 1,3-butadiene, copolymerized or propylene copolymerized with norbornene and ethylene. The polymerization is preferably carried out at a temperature of -60 to 300 ° C, particularly preferably 30 to 250 ° C. The pressure is 0.5 to 2500 bar, preferably 2 to 1500 bar. The polymerization can be carried out continuously or batchwise, in one or more stages, in solution, in suspension, in the gas phase or in a supercritical medium.

0046The supported system can be resuspended as a powder or still with solvent and metered into the polymerization system as a suspension in an inert suspension medium.

0047A prepolymerization can be carried out with the aid of the catalyst according to the invention. The prepolymerization preferably uses the (or one of the) olefin (s) used in the polymerization.

0048For the production of olefin polymers with a broad molecular weight distribution, catalyst systems are preferably used which contain two or more different transition metal compounds, for example metallocenes.

0049To remove catalyst poisons present in the olefin, cleaning with an aluminum alkyl, for example trimethyl aluminum, triethyl aluminum or triisobutyl aluminum, is advantageous. This cleaning can take place both in the polymerization system itself or the olefin is brought into contact with the Al compound before being added to the polymerization system and then separated again.

0050If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity. The total pressure in the polymerization system is 0.5 to 2500 bar, preferably 2 to 1500 bar. The compound according to the invention is preferably at a concentration, based on the transition metal, of 10^-3 until 10^-8, preferably 10th^-4 until 10^-7 mol of transition metal per dm³ Solvent or per dm³ Reactor volume applied.

0051Suitable solvents for the preparation of both the supported chemical compound according to the invention and the catalyst system according to the invention are aliphatic or aromatic solvents such as hexane or toluene, ethereal solvents such as terahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o- Dichlorobenzene.

0052Before addition of the catalyst system containing at least one supported chemical compound according to the invention and at least one transition metal compound (such as a metallocene), another alkyl aluminum compound such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or isoprenyl aluminum can be used to inert the polymerization system (for example to separate off existing catalyst). be placed in the reactor. This is added to the polymerization system in a concentration of 100 to 0.01 mmol Al per kg reactor content. Triisobutylaluminum and triethylaluminum are preferably used in a concentration of 10 to 0.1 mmol Al per kg reactor content, so that the molar Al / M ratio can be chosen to be small in the synthesis of a supported catalyst system.

0053The following examples serve to explain the invention in more detail.

0054General information: The manufacture and handling of organometallic compounds was carried out with the exclusion of air and moisture under argon protection (Schlenk technique). Before use, all the required solvents were boiled by boiling for several hours using suitable desiccants and then distilling under argon. The compounds are characterized via¹⁹F-NMR spectroscopy.

Reference Example 1: Chlorobis (pentafluorophenyl) borane

00554.69 g (40 mmol) of trichloroborane are condensed in a two-necked flask with a dry ice cooler at -78 ° C. 19.31 g (40 mmol) of dimethylbis (pentafluorophenyl) stannane are added rapidly. The mixture is stirred at room temperature for 30 minutes and stirred at 100 ° C. for a further 2 hours. A very violent reaction occurs, with dichlorodimethylstannane being deposited on the cooler with increasing reaction time. The remaining dichlorodimethylstannane is sublimed out of the resulting light brown suspension and the remaining bottoms are fractionally distilled over a short column.¹⁹F-NMR (C₆D₆): δ = - 129.5 ppm, - 145.4 ppm, - 161.3 ppm

Reference example 2: bis (pentafluorophenyl) borane

00566.9 g (20 mmol) of chlorobis (pentafluorophenyl) borane are cooled to -78 ° C. and 8.9 g (100 mmol) of chlorodimethylsilane are slowly added dropwise. When warmed to room temperature, the borane dissolves and a white precipitate forms. The mixture is stirred for 1 hour, the precipitate is filtered off and washed with 20 ml of pentane.¹⁹F-NMR (C₆D₆): δ = - 134.8 ppm, -148.4 ppm, 160.7 ppm

Reference Example 3: (2,3,5,6-tetrafluorophenyloxymethyl) triethoxysilane

00573.32 g (20 mmol) 2,3,5,6-tetrafluorophenol are dissolved in 50 ml toluene and 8 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. After warming to room temperature, the solution is stirred for a further 2 hours. Then 4.3 g (chloromethyl) triethoxysilane (20 mmol) are added dropwise and the reaction mixture is boiled under reflux for 6 hours. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining light yellow liquid is fractionally distilled.¹⁹F-NMR (C₆D₆): δ = - 141.04 ppm, -163.34 ppm

Reference Example 4: [bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxymethyl) triethoxysilane] borane

00585.6 g (20 mmol) 2,3,5,6- (tetrafluorophenyloxymethyl) triethoxysilane are dissolved in 50 ml diethyl ether and 8 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. The solution is stirred for one hour after warming to room temperature. The light yellow solution is then added dropwise to 7.6 g of chlorobis (pentafluorophenyl) borane (20 mmol) in 50 ml of diethyl ether. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining white solid is recrystallized from diethyl ether / pentane.¹⁹F-NMR (C₆D₆): δ = - 135.8 ppm, - 142.04 ppm, -149.9 ppm, - 165.34 ppm, 161.8 ppm

Reference Example 5: 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane

00593.32 g (20 mmol) 2,3,5,6-tetrafluorophenol are dissolved in 50 ml toluene and 8 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. After warming to room temperature, the solution is stirred for 2 hours. 2.6 g of dichlorodimethylsilane (20 mmol) are then added dropwise. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining colorless liquid is fractionally distilled.¹⁹F-NMR (C₆D₆): δ = - 143.01 ppm, -164.52 ppm

Reference Example 6: [bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane] borane

00602.6 g (10 mmol) of 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane are dissolved in 50 ml of diethyl ether and 4 ml of n-butyllithium (2.5 M in hexane) are added at 0 ° C. The solution is stirred for one hour after warming to room temperature. The light yellow solution is then added dropwise to 3.8 g of chlorobis (pentafluorophenyl) borane (10 mmol) in 50 ml of diethyl ether. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining white solid is recrystallized from diethyl ether / pentane.¹⁹F-NMR (C₆D₆): δ = - 136.3 ppm, - 142.76 ppm, -150.12 ppm, - 165.78 ppm, 162.98 ppm

Reference Example 7: 1,4-bis (dibromoboryl) -2,3,5,6-tetrafluorobenzene

0061To 10 g (40 mmol) BBr₃ 4.44 g (20 mmol) of solid 1,4-bis (trimethylsilyl) -2,3,5,6-tetrafluorobenzene are added in portions. The mixture is heated to 80 ° C for 5 hours. Then volatile me₃SiBr on the oil pump removed. The resulting product is of sufficient purity to be directly implemented further. The yield is 76%.

Reference Example 8: bis (triphenylcarbenium) 1,4-bis {(tri- [pentafluorophenyl]) - boryl} 2,3, 5, 6-tetrafluorobenzene

006219 ml of n-BuLi (30 mmol) are added to 3.8 ml of bromopentafluorobenzene (30 mmol) in 50 ml of diethyl ether at -78 ° C. The mixture is stirred at this temperature for 1 hour. Then 2.5 g of 1,4-bis (dibromoboryl) -2,3,5,6-tetrafluorobenzene (5 mmol) are added in portions. The suspension obtained is slowly warmed to room temperature, a precipitate separating out. This is separated off by filtration and the filtrate obtained is evaporated to dryness in vacuo. The tilithium salt thus obtained is taken up in 100 ml of pentane and 2.8 g (10 mmol) of triphenylmethyl chloride are added at room temperature. After stirring for 8 hours, the orange / red solid is filtered. The filtrate is extracted into methylene chloride to separate the LiCl formed. Precipitation with n-pentane gives an orange / red solid (yield 64%).

Reference Example 9: bis (N, N-dimethylanilinium) 1,4-bis {(tri- [pentafluorophenyl]) - boryl} 2,3,5,6-tetrafluorobenzene

00631.22 g of bromopentafluorobenzene (5 mmol) are dissolved in 40 ml of n-hexane, and 3.2 ml (5 mmol) of n-BuLi are added at -78 ° C. The suspension is stirred at - 78 ° C for 1 hour. Then 2.1 g of 1,4-bis (dipentafluorophenylboryl) -2,3,5,6-tetrafluorobenzene (2.5 mmol) in 40 ml of hexane are added dropwise to the above solution. The suspension obtained is slowly warmed to room temperature, a precipitate separating out. This is separated off by filtration and the filtrate obtained is evaporated to dryness in vacuo. The dilithium salt thus obtained is taken up in 40 ml of pentane, and 1.6 g of dimethylanilinium chloride are added at room temperature. After stirring for 8 hours, the white solid is filtered. The filtrate is extracted into methylene chloride to separate the LiCl formed. Precipitation with pentane gives a white solid (yield 67%).

Example 10: Supporting chlorobis (pentafluorophenyl) borane on silica (cocatalyst A)

00645g SiO₂ (MS 3030, PQ, dried at 200 ° C. in a stream of argon) are stirred in 50 ml of pentane and 3.8 g (10 mmol) of chlorobis (pentafluorophenyl) borane are added at room temperature. The solvent is decanted off and the support material is washed again with pentane. The remaining solvent is then stripped off in vacuo and the support is dried in vacuo.

Example 11: Support of [bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxymethyl) triethoxysilane] borane on silica (cocatalyst B)

00655g SiO₂ (MS 3030, PQ, dried at 200 ° C. in a stream of argon) are stirred in 50 ml of pentane and at room temperature with 6.9 g (10 mmol) of [bis (pentafluorophenyl) -2, 3, 5, 6- (tetrafluorophenyloxymethyl) - triethoxy-silane] -borane added. The suspension is stirred for 1 hour at room temperature, the solvent is decanted off and the support material is washed again with pentane. The remaining solvent is then stripped off in vacuo and the support is dried in vacuo.

Example 12: Supporting 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane on silica (cocatalyst C)

00665g SiO₂ (MS 3030, PQ, dried at 200 ° C. in a stream of argon) are stirred in 50 ml of pentane and 6.0 g (10 mmol) of 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane are added at room temperature. The suspension is stirred for 1 hour at room temperature, the solvent is decanted off and the support material is washed again with pentane. The remaining solvent is then stripped off in vacuo and the support is dried in vacuo

Example 13: Supporting bis (pentafluorophenyl) borane on silica (cocatalyst D)

006710th g SiO₂ (MS 3030, PQ, dried at 200 ° C. in a stream of argon) were suspended in 40 ml of toluene, and 4.76 g of vinyltriethoxysilane were added at room temperature. This mixture was allowed to reflux for 18 hours, then filtered and washed three times with 40 ml of methanol. Residual solvent was removed in an oil pump vacuum. 6.0 g of bis (pentafluorophenyl) borane were dissolved in 40 ml of toluene and added in portions with the modified SiO₂ transferred. The suspension obtained was stirred for 3 hours at room temperature, then filtered off and washed three times with a little toluene. A free-flowing solid was obtained.

Example 14: Representation of catalyst system A and polymerization

0068A solution of 10 mg (0.023 mmol) of dimethylsilanediylbis (2-methylindenyl) zirconium dimethyl in 40 ml of toluene was added in portions with 10 g of cocatalyst A from Example 10. The mixture was stirred at room temperature for 1 h and then the solvent was removed in an oil pump vacuum to constant weight. 10 g of catalyst system A were resuspended in 50 ml of Exxsol in order to be introduced into the polymerization system. Polymerization:<ul id="ul0003" list-style="none" compact="compact"><li>At the same time, a dry 16-dm³Reactor flushed first with nitrogen and then with propylene and with 10 dm³ filled with liquid propylene. Then became 0.5 cm³ a 20% triisobutyl aluminum solution in Varsol with 30 cm³ Diluted Exxsol was added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes.</li><li>The catalyst suspension was then added to the reactor. The reaction mixture was heated to the polymerization temperature of 60 ° C. (4 ° C./min) and the polymerization system was kept at 60 ° C. for 1 hour by cooling. The polymerization was stopped by venting the remaining propylene. The polymer was dried in a vacuum drying cabinet.</li><li>The result is 1.4 kg of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 140 kg PP / g metallocene x h.</li></ul>

Example 15: Representation of the catalyst system B and polymerization

0069A solution of 10 mg (0.023 mmol) of dimethylsilanediylbis (2-methylindenyl) zirconiumdimethyl in 40 ml of toluene was added in portions with 10 g of the cocatalyst B from Example 11. The mixture was stirred at room temperature for 1 h and then the solvent was removed in an oil pump vacuum to constant weight. 10 g of the catalyst system B were resuspended in 50 ml of Exxsol to be introduced into the polymerization system. Polymerization:<ul id="ul0004" list-style="none" compact="compact"><li>At the same time, a dry 16-dm³Reactor flushed first with nitrogen and then with propylene and with 10 dm³ filled with liquid propylene. Then became 0.5 cm³ a 20% triisobutyl aluminum solution in Varsol with 30 cm³ Diluted Exxsol was added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes.</li><li>The catalyst suspension was then added to the reactor. The reaction mixture was heated to the polymerization temperature of 60 ° C. (4 ° C./min) and the polymerization system was kept at 60 ° C. for 1 hour by cooling.</li><li>The polymerization was stopped by venting the remaining propylene. The polymer was dried in a vacuum drying cabinet.</li><li>The result is 1.1 kg of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 110 kg PP / g metallocene x h.</li></ul>