Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F17/00—Metallocenes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• the present invention relates to a method for producing alkyl-bonded ligand systems and transition metal compounds.
• metallocenes are known per se (US 4,752,597; ' US 5, 017, 714; EP-A-320762; EP-A-416815; EP-A-537686; EP-A-669340; HH Brintzinger et al .; Angew. Chem., 107 (1995), 1255; HH Brintzinger et al., J. Organo et. Chem. 232 (1982), 233).
• indenyl-metal compounds can be reacted with halides of transition metals such as titanium, zirconium and hafnium.
• Metallocenes can be used as a catalyst component for the polymerization and copolymerization of olefins.
• halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex (EP-A-129368).
• the polymerization properties of a metallocene compound can be controlled by the ligand system.
• Derivatives of zirconocene dichloride in which the two substituted indenyl groups are connected to one another by a bridge can be used as catalysts for the isospecific polymerization of olefins due to their conformative rigidity. By varying this bridge, the properties of the catalyst and the resulting polymer can be specifically controlled (Chemical Reviews 2000, Volume 100, Issue 4).
• dialkylsilanediyl-bridged metallocenes ethylidene-bridged metallocenes are also known (DE 19713549).
• Organo etallics 1992, 11, 1869-1876 describes the synthesis of 2, 3-butylene-l, 1 'bis (indenyl) zirconium dichloride. This metal complex, which is unsubstituted on the indenyl ligand, is obtained in 18% yield.
• the present invention thus relates to a process for the preparation of compounds of the formula I:
• M 1 is Ti, Zr or Hf, particularly preferably zirconium, R 1 are the same or different and are hydrogen, a -C 20
• C 8 -C 8 alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl, C 2 -C ⁇ 0 alkenyl, C 3 -Ci 5 alkylalkenyl, C ⁇ -cis-aryl, C -C 8 heteroaryl, C 7 -C 2 o Arylalkyl, C 7 -C 20 alkylaryl, fluorine-containing C ⁇ -C ⁇ 2 alkyl, fluorine-containing C ⁇ -Cia-aryl, fluorine-containing C 7 -C 0
• R 2 are the same or different and are hydrogen, a C ⁇ -C 2 o
• Ci-Ci ⁇ -alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or Cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl, C 2 -C ⁇ 0 alkenyl, C 3 -Ci 5 alkylalkenyl, C ö -Ci ⁇ aryl, C 4 -Ci 8 heteroaryl, C -C 20 - Arylalkyl, C 7 -C 0 alkylaryl, fluorine-containing C ⁇ -C ⁇ 2 alkyl, fluorine-containing C 6 -C 18 aryl, fluorine-containing C 7 -
• R 3 are the same or different and are a hydrogen atom or a C 6 -C ⁇ 8 aryl group which may optionally be substituted, in particular phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert- butyl phenyl, 4-Methoxypheny1, 1-naphthyl, 9-anthracenyl.
• R 4 are the same or different and either represent a hydrogen atom or form a mono- or polycyclic ring system with R 3 ,
• R 5 , R 6 are in each case identical or different and are a hydrogen atom, a C 1 -C 20 carbon-containing group, preferably C 2 -C 8 alkenyl, C 3 -C 5 alkylalkenyl, C 6 -C 8 aryl, C- Ci 8 heteroaryl, CC 20 arylalkyl, C 7 -C 20 alkylaryl, fluorine-containing C 1 -C 2 alkyl, fluorine-containing C 6 -C aryl, fluorine-containing C 7 -C 20 arylalkyl or fluorine-containing C 7 _C 20 alkylaryl mean.
• R 7 , R 8 , R 9 , R 10 are the same or different and are hydrogen atoms, a C 1 -C 8 carbon-containing group, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl ,.
• a C 1 -C 8 carbon-containing group for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopen
• i is 1 to 10, preferably 1 to 8, very particularly preferably 1 to 3 and
• j is 1 to 10, preferably 1 to 8, very particularly preferably 1 to 3 and
• X 1 , X 2 may be the same or different and are halogen atoms, in particular chlorine, alkyl groups, in particular methyl, or substituted or unsubstituted phenolates.
• X 1 can also form a mono- or polycyclic ring system with one or more X 1 or X 2 radicals.
• Indenyl radical R 3 is phenyl and in the second indenyl radical R 3 is naphthyl.
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meaning as mentioned above and
• R 11 is a hydrogen atom
• R 12 is hydrogen or a group which can be exchanged for a metal, preferably chlorine,
• M 2 is an element of main group I or II of the Periodic Table of the Elements, preferably lithium, sodium, potassium and magnesium, particularly preferably lithium, and
• R 13 is a hydrogen atom, a -C-C 20 - carbon-containing group, preferably Ci-Cis-alkyl, such as methyl, ethyl, n-butyl, n-hexyl, sec-butyl, tert-butyl, cyclohexyl or cyclooctyl, C 2 -C ⁇ 0 -Alkenyl, C 3 -C 5 -alkylalkenyl, Cg-Cia-aryl, C 6 -C 8 -aryl such as phenyl, tolyl xylyl, C 5 -Ci 8 heteroaryl, C 7 -C 2 o-arylalkyl, C 7 -C 20 -alkylaryl, fluorinated C -C ⁇ -alkyl, fluorinated C 6 -C, 8 -aryl fluorinated C 7 -C 20 -arylalkyl or fluorinated C 7
• X 3 is a halogen atom, preferably chlorine, bromine or iodine and
• n 1 or 2
• n 0 or 1
• the compounds of formula III can be used in solution, as a pure substance or as a suspension or can be generated in situ from a metal M 2 such as lithium and an alkyl or aryl halide.
• a metal M 2 such as lithium and an alkyl or aryl halide.
• Non-limiting examples of the preferred compounds of formula III are:
• one or more compounds of formula II can be placed in a reaction vessel.
• the compounds can either be dissolved or suspended in a solvent or else be in substance.
• Both polar aprotic solvents cycloalkyl, dialkyl, alkyl aryl, diaryl ether
• n-pentane such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, -xylene , p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene etc. Mixtures of these.
• the presentation takes place at temperatures between -100 ° C and 300 ° C, preferably between -78 ° C and 100 ° C, particularly preferably at temperatures between -40 ° C and 40 ° C.
• the compound of formula II should advantageously be in dissolved form or as a suspension.
• one or more compounds of the formula III can be added. These can likewise be dissolved or suspended in a solvent or else be present in bulk.
• the solvents already described above or mixtures thereof serve as solvents.
• the addition can take place over a period of 1 minute to 96 hours. An addition within 10 minutes to 8 hours is preferred.
• the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Temperatures between -40 ° C and 40 ° C are particularly preferred.
• the temperature is chosen so that at least one reactant is in the liquid phase.
• the subsequent reaction temperature is in a preferred temperature range between -40 ° C and 100 ° C.
• the reaction can be carried out at normal pressure, but it can also be carried out at elevated pressure, which, however, requires appropriate reactors.
• the stoichiometric ratio in which compounds of the formula II and III are combined is between 1: 1000 and 1: 0.011.
• a stoichiometric ratio between compounds of the formula II and III is preferably between 1: 100 and 1:11.
• a stoichiometric conversion, based on the compounds of the formula II and III, is particularly preferred.
• the reaction can take place both in the order described here and in the inverse order, i.e. by adding compounds of formula II in dissolved form, suspension, or pure substance to compounds of formula III in dissolved form, suspension, or pure substance. The reaction is carried out analogously to the conditions described here.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 11 have the same meaning as mentioned above and
• n 1 or 2
• m 0 or 1.
• R 7 , R 8 , R 9 and R 10 have the same meaning as mentioned above and
• R 14 , R 15 are the same or different and a -C-C 20 - carbon-containing group, for.
• B Ci-Cig-alkyl, such as methyl, ethyl, n-butyl, n-hexyl, sec-butyl, tert-butyl, cyclohexyl or cyclooctyl, C -C ⁇ 0 alkenyl, C 3 -C 5 -Alkylalkenyl,
• C 6 -Ci 8 aryl such as phenyl, tolyl xylyl, C 5 -C 18 heteroaryl, C -C 2 o-arylalkyl, C 7 -C 2 o-alkylaryl, fluorine-containing C ⁇ - C ⁇ 2 -alkyl, fluorinated Cg-cis-aryl, fluorinated C 7 -C 20 -arylalkyl or fluorinated
• Is C 7 _C 2 o-alkylaryl and preferably methyl, ethyl, propyl, i-propyl, n-butyl, s-butyl, t-butyl, pentyl etc., phenyl, tolyl, xylyl, trifluoroethyl, pentafluoroethyl, heptafluoro- propyl, heptafluoroisopropyl etc., particularly preferably methyl, trifluoromethyl, p-tolyl, very particularly preferably trifluoromethyl tet, R 14 and R 15 can also form a non-, partially or perhalogenated cyclic ring system with one another and
• i is 1 to 10, preferably 1 to 8, very particularly preferably 1 to 3 and
• j is 1 to 10, preferably 1 to 8, very particularly preferably 1 to 3.
• one or more compounds of formula IV can be placed in a reaction vessel.
• the compounds can either be dissolved or suspended in a solvent or else be in substance.
• Both polar aprotic solvents cycloalkyl, dialkyl, alkyl aryl, diaryl ether
• non-polar aprotic solvents such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene etc. Mixtures of these.
• the initial charge takes place at temperatures between -100 ° C and 300 ° C, preferably between -78 ° C and 100 ° C, particularly preferably at temperatures between -40 ° C and 40 ° C.
• the compound of formula IV should advantageously be in dissolved form or as a suspension.
• one or more compounds of the formula V can be added. These can also be dissolved or suspended in a solvent but also in
• the addition can take place over a period of 1 minute up to 96 hours. An addition within 10 minutes to 8 hours is preferred.
• the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Temperatures between -40 ° C and 40 ° C are particularly preferred.
• the temperature is chosen so that at least one reactant is in the liquid phase.
• the subsequent reaction temperature is in a preferred temperature range between -40 ° C and 100 ° C.
• the stoichiometric ratio in which compounds of the formula IV and V are combined is between 1:10 and 1: 0.05.
• a stoichiometric ratio between compounds of the formula IV and V of between 1: 2 and 1: 0.25 is preferred.
• a stoichiometric reaction based on the compounds of the formula IV and V is particularly preferred.
• the reaction can also be carried out both in the order described here and in the reverse order, ie by adding compounds of the formula IV in dissolved form, suspension, or pure substance to form compounds of formula V in dissolved form, suspension, or pure substance.
• the reaction is carried out analogously to the conditions described here.
• the reaction mixture is worked up by hydrolysis and removal of water-soluble by-products.
• the product VI can either be purified by chromatography or recrystallization or can be reacted without further purification.
• a ligand system of the formula VI results from the reaction of a compound of the formula IV with a compound of the formula V
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 have the same meaning as mentioned above and
• a compound of the formula VI is reacted with a compound of the formula III.
• the compounds of formula III can in solution as Pure substance or used as a suspension or generated in situ from a metal M 2 such as lithium and an alkyl or aryl halide.
• one or more compounds of the formula VI can be placed in a reaction vessel.
• the compounds can either be dissolved or suspended in a solvent or else be in substance.
• Both polar aprotic solvents cycloalkyl, dialkyl, alkyl aryl, diaryl ether
• polar aprotic solvents such as, for. B.
• n-pentane isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1, 2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene etc. Mixtures of these.
• the presentation takes place at temperatures between -100 ° C and 300 ° C, preferably between -78 ° C and 100 ° C, particularly preferably at temperatures between -40 ° C and 40 ° C.
• the compound of formula VI should advantageously be in dissolved form or as a suspension.
• one or more compounds of the formula III can be added. These can also be dissolved or suspended in a solvent, but can also be in bulk.
• the solvents already described above or mixtures thereof serve as solvents.
• the addition can take place over a period of 1 minute to 96 hours. An addition within 10 minutes to 8 hours is preferred.
• the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Temperatures between -40 ° C and 40 ° C are particularly preferred.
• the temperature is chosen so that at least one reactant is in the liquid phase.
• the subsequent reaction temperature is in a preferred temperature range between -40 ° C and 100 ° C.
• the reaction can be carried out at normal pressure, but it can also be carried out at elevated pressure, which, however, requires appropriate reactors.
• the stoichiometric ratio in which compounds of the formulas VI and III are combined is between 1:10 and 1: 1.
• a stoichiometric ratio between compounds of the formulas VI and III is preferably between 1: 3 and
• reaction can be carried out either in the order described here or in the inverse order, ie by adding compounds of the formula VI in dissolved form, suspension, or pure substance to compounds of the formula III be carried out in dissolved form, suspension, or pure substance.
• the reaction is carried out analogously to the conditions described here.
• a metalated ligand system of the formula VII results from the reaction of a compound of the formula VI with a compound of the formula III
• R 7 , R 8 , R 9 , R 10 , and R 11 have the same meaning as mentioned above and
• n 1 or 2
• the compound of formula VII can be isolated analogously to DE 19739946 or can be prepared and reacted in situ with a compound of formula VIII Ml ( ⁇ l) f (X) g (D) a ( VI H)
• M 1 is titanium, zirconium and hafnium, very particularly preferably zirconium, and
• D is a donor solvent which has at least one oxygen atom or one sulfur atom, preferably 1 to 2
• oxygen atoms or sulfur atoms very particularly preferably 1 to 2 oxygen atoms and
• X 1 and X 2 are the same or different and have the same meaning as mentioned above, preferably halogen atoms or
• Phenolates are, particularly preferably chlorine, bromine or iodine, very particularly preferably chlorine, and
• f is a number between 0 and 4, preferably 1 and 4, and
• g is a number between 0 and 4, preferably 1 and 4, and the sum of f + g corresponds to the oxidation state of the metal ion,
• a is a number between 1 and 100, preferably 1 and 10, particularly preferably 1 and 2.
• the radical D is preferably an ether, cyclic ether, an acetal such as tetrahydrofu, tetrahydropyran, diethyl ether, dimethoxymethane, diethoxymethane, dipropoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1, 3-dimethoxypropane; 1,3-diethoxypropane, 1,3-dipropoxypropane, 1,2-dimethoxybenzene, 1,2-diethoxybenzene and / or 1,2-dipropoxybenzene.
• an ether, cyclic ether, an acetal such as tetrahydrofu, tetrahydropyran, diethyl ether, dimethoxymethane, diethoxymethane, dipropoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,
• R 1 , R 2 are preferably identical and represent a C ⁇ -C 2 o - carbon-containing group, preferably C 1 -C 8 -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl, C 2 -C ⁇ o-alkenyl, C 3 -Ci 5 -alkylalkenyl, C 6 - C ⁇ s-aryl, C -C 18 heteroaryl, C 7 -C 2 o-arylalkyl, C 7 -C 20 alkylaryl, fluorine-containing C 1 -C ⁇ 2 alky
• a compound of the formula VII is reacted with a compound of the formula VIII.
• the compounds of the formula VIII can be used in solution, as pure substance or as a suspension or can be generated in situ from a metal halide of the formula M i -X f X g such as zirconium tetrachloride and a donor solvent D a .
• one or more compounds of formula VII can be placed in a reaction vessel.
• the compounds can either be dissolved or suspended in a solvent or else be in substance.
• Both polar aprotic solvents such as, for. B. dimethyl ether, diethyl ether, - dipropyl ether, diisopropyl ether, di-n-butyl ether, di-s-butyl ether, di-t-butyl ether, t-butyl methyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, tetrahydropyran, anisole, diphenyl ether etc.
• non-polar aprotic solvents such as B. n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, pro pylbenzene etc.
• the presentation takes place at temperatures between -100 ° C and 300 ° C, preferably between -78 ° C and 100 ° C, particularly preferably at temperatures between -40 ° C and 40 ° C.
• the compound of formula VII should advantageously be in dissolved form or as a suspension.
• one or more compounds of the formula VIII can be added. These can also be dissolved or suspended in a solvent, but can also be in bulk.
• the solvents or mixtures thereof already described above serve as solvents.
• the addition can take place over a period of 1 minute to 96 hours. An addition within 10 minutes to 8 hours is preferred.
• the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Particularly preferred are temperatures between -40 ° C C and 40 ° C.
• the temperature is chosen so that at least one reactant is in the liquid phase.
• the subsequent reaction temperature is in a preferred temperature range between -40 ° C and 100 ° C.
• the reaction can be carried out at normal pressure, but it can also be carried out at elevated pressure, which, however, requires appropriate reactors.
• the stoichiometric ratio in which compounds of the formulas VII and VIII are combined is between 1:10 and 1: 0, 1.
• a stoichiometric ratio between compounds of the formulas VII and VIII is preferably between 1: 5 and 1: 0.5.
• a stoichiometric ratio of the compounds of the formulas VII to the compounds of the formula VIII of 1: 1 is particularly preferred.
• the reaction can also be carried out both in the order described here and in the inverse order, ie by adding compounds of the formula VII in dissolved form, suspension, or pure substance to form compounds of formula VIII in dissolved form, suspension, or pure substance. The reaction is carried out analogously to the conditions described here.
• metallocenes which can be prepared via the synthesis sequence described here are: 1, 2-ethanediyl-bis-2-methylindenyl) zirconium dichloride 1, 2-ethanediyl-bis- 2-methyl-4, 5-benzindenyl) -zirconium dichloride 1, 2-ethanediyl-bis- 2-methyl-4-phenylindenyl) zirconium dichloride 1, 2-ethanediyl-bis-2-methyl-4- 4 '-methylpheny1) -indenyl) -zirconium dichloride
• zirconium dichloride 1,2-ethanediyl-bis (2-cyclohexyl-4-14 'tert-butylphenyl) -indenyl) zirconium dichloride
• hafnium dichloride 1,2-ethanediyl-bis- (2-tert-butyl-4- (4'-tert-butylphenyl) -indenyl) hafnium dichloride
• hafnium dichloride 1,2-ethanediyl-bis- (2-cyclopentyl-4- (4'-methoxyphenyl) -indenyl) -ha fnium dichloride
• hafnium dichloride 1,2-cyclohexanediyl-bis-2-ethyl-4- (4'-tert-butylphenyl) -indenyl) hafnium dichloride
• hafnium dichloride 1,2-cyclohexanediyl-bis- (2-tert-butyl-4- ⁇ ⁇ (4'-ethylphenyl) -indenyl) hafnium dichloride
• hafnium dichloride 1,3-propanediylbis (2-isopropyl-4- (4'-tert-butylphenyl) -indenyl) hafnium dichloride
• hafnium dichloride 1,3-propanediylbis (2-tert-butyl-4- (1'-naphthyl) -indenyl) hafnium dichloride
• hafnium dichloride 1,3-propanediylbis (2-cyclohexyl-4- (1'-naphthyl) -indenyl) hafnium dichloride
• the metal ocenes produced by the process according to the invention are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands, the metallocenes can be obtained as a mixture of isomers. The metallocenes are preferably used isomerically pure for the polymerization, but the use of the racemate is sufficient in most cases. The metallocenes produced by the process according to the invention can also be used as catalysts in organic synthesis, the pure enantiomers preferably being used.
• the metal complexes of the formula I prepared by the process according to the invention are particularly suitable as a constituent of catalyst systems for the production of polyolefins by polymerizing at least one olefin in the presence of a catalyst which comprises at least one cocatalyst and at least one metal complex.
• the cocatalyst which, together with a metal complex of the formula I, forms the catalyst system contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with a metal complex, converts the latter into a cationic compound.
• cocatalyst and / or the metal complex can be unsupported or supported. Examples of supported cocatalysts and / or supported metal complexes are described in DE 19962905.
• the carrier component of the catalyst system can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. polyolefins). Examples of suitable carrier materials and carrier methods are described in DE 19962905.
• polymerisation is understood to mean homopolymerization as well as copolymerization.
• the polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C.
• the pressure is 0.5 to 2000 bar, preferably 5 to 64 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. Examples of suitable polymerization processes are described in DE 19962905.
• hydrogen is added as a molecular weight regulator and / or to increase the activity.
• the catalyst system can be fed to the polymerization system neat or inert components such as paraffins, oils or waxes can be added for better metering.
• an antistatic agent can also be metered into the polymerization system together with or separately from the catalyst system used.
• the process according to the invention is characterized in that, using a special bridging reagent of the formula V, multiply substituted ligand systems of the formula VI can be obtained in high yields and purities, which open up efficient access to transition metal complexes of the formula I.
• the solvent was then removed in vacuo and 150 ml of toluene were added to the residue.
• the organic phase was washed successively 1 x with 100 ml of a saturated NaHC0 3 solution, 2 x with 50 ml of a saturated NaHC0 3 solution and 2 x with 100 ml of water.
• the organic phase was dried over magnesium sulfate and the solvent was removed in vacuo.
• the crude product thus obtained was purified by column chromatography on silica gel, the product being obtained in the form of a yellow oil with a yield of 32 g (58 mmol, 77%) and a purity of> 95% (according to GC).
• the mixture was stirred for 1 h at -20 ° C and 13 h at room temperature.
• the solvent was then removed in vacuo and 5 150 ml of toluene were added to the residue.
• the organic phase was washed successively 1 x with 100 ml of a saturated NaHC0 3 solution, 2 x with 50 ml of a saturated NaHC0 3 solution and 2 x with 100 ml of water.
• the organic phase was dried over magnesium sulfate and the solvent was removed in vacuo.
• the crude product thus obtained was purified by column chromatography on silica gel, the product being obtained in the form of a yellow oil with a yield of 7.4 g (13 mmol, 64%) and a purity of> 95% (according to GC).
• the mixture was stirred for 1 h at -20 ° C and 13 h at room temperature.
• the solvent was then removed in vacuo and 150 ml of toluene were added to the residue.
• the organic phase was washed successively 1 x with 100 ml of a saturated NaHC0 3 solution, 2 x with 50 ml of a saturated NaHC0 solution and 2 x with 100 ml of water.
• the organic phase was dried over magnesium sulfate and the solvent was removed in vacuo.
• the crude product thus obtained was purified by column chromatography on silica gel, the product being obtained in the form of a yellow oil with a yield of 37 g (81 mmol, 81%) and a purity of> 95% (according to GC).
• the mixture was stirred for 1 h at -20 ° C and 13 h at room temperature.
• the solvent was then removed in vacuo and 150 ml of toluene were added to the residue.
• the organic phase was washed successively 1 x with 100 ml of a saturated NaHC0 3 solution, 2 x with 50 ml of a saturated NaHC0 3 solution and 2 x with 100 ml of water.
• the organic phase was dried over magnesium sulfate and the solvent was removed in vacuo.
• the crude product thus obtained was purified by column chromatography on silica gel, the product being obtained in the form of a yellow oil with a yield of 43 g (79 mmol, 79%) and a purity of> 95% (according to GC).
• Example 7 1,2-ethanediyl-bis- (2-ethyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride
• Example 8 1,2-ethanediylbis (2-isopropyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride
• Example 10 1, 2-Cyclohexanediyl-bis- (2-propy1-4-phenyl) -indenyl) zirconium dichloride

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