WO2000020466A1 - Catalyst system - Google Patents

Catalyst system Download PDF

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Publication number
WO2000020466A1
WO2000020466A1 PCT/EP1999/007087 EP9907087W WO0020466A1 WO 2000020466 A1 WO2000020466 A1 WO 2000020466A1 EP 9907087 W EP9907087 W EP 9907087W WO 0020466 A1 WO0020466 A1 WO 0020466A1
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WO
WIPO (PCT)
Prior art keywords
methyl
indenyl
zirconium dichloride
phenyl
dimethyl
Prior art date
Application number
PCT/EP1999/007087
Other languages
German (de)
French (fr)
Other versions
WO2000020466A9 (en
Inventor
Jörg SCHOTTEK
Cornelia Fritze
Hans Bohnen
Patricia Becker
Original Assignee
Targor Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE1998145240 external-priority patent/DE19845240A1/en
Priority claimed from DE19903306A external-priority patent/DE19903306A1/en
Application filed by Targor Gmbh filed Critical Targor Gmbh
Publication of WO2000020466A1 publication Critical patent/WO2000020466A1/en
Publication of WO2000020466A9 publication Critical patent/WO2000020466A9/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention describes a catalyst system consisting of a
  • Metallocene a co-catalyst, a support material and optionally another organometallic compound.
  • the catalyst system can advantageously be used for the polymerization of olefins.
  • aluminoxanes such as methylaluminoxane (MAO) as a cocatalyst is dispensed with, and high catalyst activity and good polymer morphology are still achieved.
  • MAO methylaluminoxane
  • Metallocenes are generally recognized (H.H. Brintzinger, D. Fischer, R. Mülhaupt, R.
  • EP-A-0 558 158 describes zwitterionic catalyst systems which consist of
  • Metallocendialkyl compounds and salts of the form [R 3 NH] + [B (C ⁇ H 5 ) 4 ] " are shown.
  • the reaction of such a salt with, for example, Cp 2 ZrMe 2 provides an intermediate zirconocenemethyl cation by protolysis with elimination of methane.
  • the Zr atom is covalently bound to a carbon atom of the phenyl ring and is stabilized via agostic hydrogen bonds.
  • US-A-5, 348, 299 describes zwitterionic catalyst systems consisting of
  • EP-A-0 426 637 uses a method in which the Lewis acidic CPh 3 + cation is used for the abstraction of the methyl group from the metal center.
  • B (C 6 F 5 ) 4 also acts as a weakly coordinating anion.
  • metallocene catalysts require heterogenization of the catalyst system in order to ensure an appropriate morphology of the resulting polymer.
  • the support of cationic metallocene catalysts based on the above borate anions is in
  • the catalyst system is formed by applying a dialkyl metallocene compound and a Bronsted acidic, quaternary ammonium compound with a non-coordinating anion, such as tetrakispentafluorophenyl borate, on an inorganic support.
  • the carrier material is modified beforehand with a triaikylaluminium compound.
  • the present invention relates to a supported catalyst system and a method for producing the same.
  • the present invention furthermore relates to the use of the catalyst system according to the invention in
  • the catalyst system according to the invention contains A) at least one metallocene, B) at least one Lewis base of the formula I.
  • R 3 , R 4 , R 5 are the same or different and are a hydrogen atom, ad-C 2 o alkyl, C- ⁇ -C 20 haloalkyl, C 6 -C 4 o aryl, C 6 -C 4 o haloaryl -, C -C 40 alkylaryl or C 7 -C 40 arylalkyl group and two radicals or all three radicals R 3 , R 4 and R 5 can be connected to one another via C 2 -C 2 o carbon units, M 1 is a Element of the 5th main group of the Periodic Table of the Elements, in particular nitrogen or phosphorus C) at least one carrier
  • Halogen atom a C ⁇ -boron-free C 4 o-kohienstoff restroom group such as CC 20 -alkyl, C 2 o-haloalkyl, C ⁇ -C 10 alkoxy, C 6 -C 2 o-aryl, C 6 -C 2 o Haloaryl, C 6 -C 2 o-aryloxy, C 7 -C 4 o-arylalkyl, C 7 -C 4 o-Halogenarylalkyl, C 7 -C 4 o-alkylaryl, C 7 -C 4 o-haloalkylaryl or R 1 can be an OSiR a 3 group, in which R a are the same or different and a hydrogen atom, a halogen atom, a C 1 -C 4 -carbon-containing group such as C 1 -C 2 o -ikyl, C 1 -C 2 o-haiogenalkyl, CrCio -Alkoxy, C
  • R 1 can be a CH (SiR b 3 ) 2 group, in which R b are identical or different and are a hydrogen atom, a halogen atom, a d- C o -carbon-containing group such as C 1 -C 2 o- Alkyl, CrC 2 o-haloalkyl, d-Cio-alkoxy, C 6 -C 2 o-aryl, C 6 -C 2 o-haiogenaryl, C 6 -C 2 o-aryloxy, C 7 -C 0 - arylalkyl, C 7 -C 40
  • X is an element of the Via group of the Periodic Table of the Elements or an NH group
  • M 2 is a purple element of the Periodic Table of the Elements, and k is a natural number from 1 to 100. is built up and is covalently bound to the carrier.
  • Preferred compounds of the formula (I) are triethylamine, triisopropylamine,
  • Triisobutylamine tri (n-butyl) amine, N, N-dimethyianiiin, N, N-diethylaniline, N, N-2,4,6-pentamethylaniline, dicyclohexylamine, pyridine, pyrazine, triphenylphosphine, tri (methylphenyl) phosphine, tri ( dimethylphenyl) phosphine
  • the compounds of formula (II) can exist as a monomer or as a linear, cyclic or cage-like oligomer.
  • the compounds of the formula (II) according to the invention can form dimers, trimers or higher oligomers by means of Lewis acid-base interaction with one another.
  • R 1 , R 2 is particularly preferably a halogenated, in particular perhalogenated C 3 -C 3 -ikyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated C 6 -C 30 aryl group such as pentaflourphenyl, 2,4,6-triflourylhenyl , Heptachloronaphthyl-, Heptaflournaphthyl, Heptaflourtolyl-, 3,5- bis (triflourmethyl) phenyl-, 2,4,6-tris (triflourmethyl) phenyl, Nonaflourbiphenyl- or 4- (triflourmethyl) phenyl.
  • C 3 -C 3 -ikyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisoprop
  • R 1 Also preferred for R 1 are radicals such as phenyl, naphthyl, anisyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl or 2,3-dimethylphenyl.
  • the radicals pentaflourphenyl, phenyl, biphenyl, 3,5- bis (triflourmethyl) phenyl-, 4-triflourmethyl) phenyl, nonafluorobiphenyl- and 4-methylphenyl are particularly preferred.
  • R 1 represents the radicals specified under formula (II).
  • the carrier component of the catalyst system according to the invention 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).
  • Suitable inorganic oxides can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements.
  • oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, ZO 2 , TiO 2 or B 2 O 3 , to name just a few.
  • the carrier materials used have a specific surface area in the range from 10 to 1000 m 2 / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 ⁇ m. Carriers with a specific surface area in the range from 50 to 500 ⁇ m, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from are preferred.
  • Carriers with a specific surface area in the range from 200 to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 ⁇ m are particularly preferred. If the carrier material used naturally has a low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as with the use of Siiicagel as a carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the carrier material can be carried out under vacuum and at the same time inert gas blanket (e.g. Nitrogen).
  • the drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical.
  • the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
  • Dehydration or drying of the carrier material is also possible chemically by reacting the adsorbed water and the hydroxyl groups on the surface with suitable inerting agents.
  • Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane or organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium.
  • the chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture.
  • suitable solvents are e.g. aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xyiol.
  • the inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible.
  • the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
  • the support material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then in an inert gas stream or on
  • Organic carrier materials such as finely divided polyofin powder (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
  • finely divided polyofin powder e.g. polyethylene, polypropylene or polystyrene
  • the chemical compounds of formula (II) according to the invention can be used together with an organometallic transition compound as a catalyst system.
  • an organometallic transition compound e.g. Metallocene compounds used. This can e.g. bridged or unbridged
  • Biscyciopentadienyikompiexe such as e.g. in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 545 304 and EP-A-0 576 970,
  • Monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes which are described, for example, in EP-A-0 416 815, multinuclear cyclopentadienyl complexes as described in EP-A-0 632 063, ⁇ -ligand-substituted tetrahydropentalenes as described in EP-A-0 659 758 or ⁇ substituted tetrahydroindenes as described in EP-A-0 661 300.
  • Organometallic compounds can also be used in which the complexing ligand does not contain a cyciopentadienyl ligand. Examples of this are diamine complexes of III. and IV.
  • Subgroup of the Periodic Table of the Elements as described, for example, in DH McConville, et al, Macromolecules, 1996, 29, 5241 and DH McConville, et ai, J. Am. Chem. Soo, 1996, 1 18, 10008.
  • diimine complexes of subgroup VIII of the Periodic Table of the Elements eg Ni + or Pd 2+ complexes
  • Brookhart et al J. Am. Chem. Soc. 1995, 117, 6414 and, Brookhart et al, J. Am. Chem. Soo, 1996, 118, 267 are used.
  • M is a metal of III., IV, V. or VI.
  • Subgroup of the periodic table of the elements in particular Ti, Zr or Hf,
  • R 10 are identical or different and are a hydrogen atom or SiR 3 12, where R 12 are identical or different, represent a hydrogen atom or a C1-C 40 - carbon-containing group, preferably C ⁇ -C 2 o-alkyl, C ⁇ -C ⁇ 0 fluoroalkyl, C 1 -C 10 - aikoxy, C 6 -C 2 o-aryl, C 6 -C ⁇ o-fluoroaryl, C ⁇ -C-io-aryloxy, C 2 -C ⁇ o-alkenyl, C7-C40-arylalkyl, C 7 -C 40 - Alkylaryl or C 8 -C 4 o-arylalkenyl, or R 10 is a CC 3 o - carbon-containing group, preferably C t -C 25 alkyl, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 Alken
  • R 12 is the same or different a hydrogen atom or a C1-C 40 - carbon-containing group, preferably C 1 -C 2 -alkyi, CrCio-fluoroalkyl, C-rCio- Alkoxy, C 6 -Ci 4 aryl, C 6 -C ⁇ 0 fluoroaryl, C 6 -C 10 aryloxy, C 2 -C ⁇ 0 alkenyl, C 7 -C 40 arylalkyl, C 7 -C 4 o-alkylaryl or C 8 -C 4 o-arylalkenyl, or R 8 is a C 1 -C 30 carbon-containing group, preferably C 1 -C 25 -alkyl, such as methyl, ethyl, tert-butyl, Cyclohexyl or octyl, C 2 -C 25 alkenyl, C
  • L 1 can be the same or different and a hydrogen atom, a C 1 -C- 10 -
  • Hydrocarbon group such as CrC ⁇ o-Alkyi or C ⁇ -Cio-aryl, a halogen atom, or OR 16 , SR 16 , OSiR 3 16 , SiR 3 16 , PR 2 16 or NR 2 16 , wherein R 16 is a halogen atom, a C 1 -C 10 is an alkyl group, a halogenated C 1 -C 10 alkyl group, a C 6 -C 20 aryl group or a halogenated C 6 -C 2 o aryl group, or L is a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl,
  • Trifluoromethanesulfonyl nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group
  • 0 is an integer from 1 to 4, preferably 2,
  • Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
  • Z are groups M 3 R 13 R 14 , in which M 3 is carbon, silicon, germanium or tin and R 13 and R 14 are identical or different and are a C 1 -C 20 -hydrocarbon-containing group such as d-Cio-alkyl, C 6 -Ci 4 aryl or trimethylsilyl.
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2) CH (C 4 H9) C (CH 3 ) 2 ,
  • Z can also form a mono- or potycyclic ring system with one or more radicals R 10 and / or R 11 .
  • Chiral bridged metallocene compounds of the formula (V) are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted such that they form 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 CrC 2 o-carbon-containing Groups such as CrCio-alkyl or C ⁇ -
  • Chiral bridged metallocene compounds of the formula (III) can be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also be used as pure racemic or pure meso compounds. But it can also
  • Mixtures of a racemic compound and a meso compound can be used.
  • metallocene compounds examples are:
  • Dimethyls landiylbis (indenyl) zirconium dichioride Dimethyls landiylbis (4-naphthyl-indenyi) zirconium dichloride Dimethyls landiylbis (2-methyl-benzo-indenyl) zirconium dichloride Dimethyls landiylbis (2-methyl-indenyl) 1- dimethyl (dichloride) zirconium dichloride naphthyl) -indenyl) zirconium dichloride Dimethyls iandiylbis (2-methyl-4- (2-naphthyl) -indenyl) zirconium dichloride Dimethyls landiylbis (2-methyl-4-phenyl-indenyl) zirconium dichioride Dimethyls iandiylbis (2-methyl-4-t- -indenyl) zirconium dichloride Dimethyls iandiylbis (2-methyl-4-isopropyl-in
  • Methylphenylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -ter-butylphenyl-indenyi) zirconium dichloride methylidene (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirconium dichloride
  • Dimethylsilanediyl 2-methyl-4-oxapentalen) (indenyl) zirconium dichloride Dimethylsilanediyl 2-methyl-5-oxapentalen) (indenyl) zirconium dichloride
  • zirconium dichloride are the meanings Z rkonium • monochloro-mono- (2,4-di-tert-butyl-phenolate)
  • Zirconium monochloro mono neopentyl has examples of the invention
  • corresponding zirconium dimethyl compounds the corresponding zirconium ⁇ -butadiene compounds, and the corresponding compounds with 1, 2- (1-methyl-ethanediyl) -, 1, 2- (1 J-dimethyl-ethanediyl) - and 1, 2 (1, 2-dimethyl-ethanediyl) bridge.
  • the catalyst system according to the invention can additionally contain an organometallic compound of the formula (IV)
  • M 4 is an element of I., II. And III.
  • Main group of the periodic table of the elements is, preferably lithium, magnesium and aluminum, in particular aluminum
  • R 9 is identical or different to a hydrogen atom, a halogen atom, a CrC 0 - carbon-containing group such as a C 1 -C 2 0 alkyl, C6-C 4 o-aryl, C 7 -C 4 o-aryl-alkyl or C 7 -C o-alkyl-aryl group, means p is an integer from 1 to 3 and q is an integer from 1 to 4, contain.
  • the organometallic compounds of the formula (IV) are also neutral Lewis acids
  • Examples of the preferred organometallic compounds of the formula (IV) are trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, trihexyl aluminum, trioctyl aluminum, tri-n-butylaium aluminum, tri-n-propyl aluminum, triisoprenaluminium, dimethylaluminium monochiorid, diethylaluminium aluminum chloride aluminum diethylaluminium aluminum chloride
  • Ethyliumsium sesquichloride dimethylaluminium hydride, diethylaluminium hydride, diisopropylaluminium hydride, dimethylaluminium (trimethylsiloxide), dimethylaluminium (triethylsiloxide), phenylalane, pentafluorophenylalane, o-tolylaian.
  • the catalyst system according to the invention can be obtained by reacting a
  • the activation of the catalyst system can be carried out either before it is introduced into the reactor or can only be carried out in the reactor.
  • a process for the production of polyolefins is also described.
  • the addition of a further chemical compound, which is added as an additive before the polymerization, can additionally be advantageous.
  • the carrier material is suspended in an organic solvent. Suitable solvents are aromatic or aliphatic solvents such as hexane, heptane, toluene or xylene or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.
  • the carrier can be pretreated beforehand with a compound of the formula (IV).
  • reaction time being between 1 minute and 48 hours, a reaction time between 10 minutes and 2 hours being preferred.
  • the reaction solution can be isolated and then resuspended, or it can also be reacted directly with a cocatalytically active organoboron compound according to formula (II) become.
  • the reaction time is between 1 minute and 48 hours, a reaction time of between 10 minutes and 2 hours being preferred.
  • one or more Lewis bases of the formula (I) can be reacted with one or more cocatalytically active organoboron compounds according to the formula (II).
  • the amount of 1 to 4 equivalents of a Lewis base of the formula (I) with one equivalent of a cocatalytically active compound is preferred.
  • the amount of one equivalent of a Lewis base of the formula (I) with one equivalent of a cocatalytically active compound is particularly preferred.
  • the reaction product of this reaction is a metallocenium-forming compound that is covalently attached to the carrier material. It is referred to below as a modified carrier material.
  • the reaction solution is then filtered and washed with one of the solvents mentioned above.
  • the modified carrier material is then dried in a high vacuum.
  • the individual components can also be added in any other order.
  • the application of one or more metallocene compounds, preferably of the formula (V) and one or more organometallic compounds of the formula (IV), to the modified support material is preferably such that one or more metallocene compounds of the formula (V) are dissolved or suspended in a solvent described above and then one or more
  • Carrier material are given.
  • the amount of modified carrier to a metallocene compound of formula (V) is preferably from 10g: 1 micromol to 10 "2 g. 1 .mu.mol
  • the stoichiometric ratio of metallocene compound of formula (V) is to the cocatalytically active chemical compound of the formula (II) 100: 1 to 10 "4 : 1, preferably 1: 1 to 10 " 2 : 1.
  • the supported catalyst system can be used directly for the polymerization. However, it can also be used resuspended for the polymerization after removal of the solvent.
  • the advantage of this activation method is that it offers the option of allowing the polymerization-active catalyst system to be formed only in the reactor. This prevents partial decomposition when the air-sensitive catalyst is introduced.
  • the polymerization can be a
  • olefins examples include 1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, cyclic olefins such as norbomene, vinyl norbornene, tetracyciododecene, ethylidene norbomene, dienes such as 1, 3-butadiene or 1, 4-hexadiene, biscyclopentadiene or methyl methacrylate.
  • propylene or ethylene are homopolymerized, ethylene with one or more Cs ⁇ cH-CHefins, in particular propylene, and / or one or several C4-C2o _ dienes, in particular 1, 3-butadiene, copolymerized or
  • the polymerization is preferably carried out at a temperature of from -60 to 300.degree. C., particularly preferably from 30 to 250.degree.
  • 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.
  • the supported catalyst system can either be formed directly in the polymerization system or it can be resuspended as a powder or solvent, and metered into the polymerization system as a suspension in an inert suspension medium.
  • a prepolymerization can be carried out with the aid of the catalyst system according to the invention.
  • catalyst systems are preferably used which contain two or more different transition metal compounds, e.g. B. contain metallocenes.
  • an aluminum alkyl for example trimethyl aluminum, triethyl aluminum or triisobutyl aluminum
  • This cleaning can take place both in the polymerization system itself or the olefin is brought into contact with the Al compound before the addition into the polymerization system and then separated again.
  • 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 used in a concentration, based on the transition metal, of preferably 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol Transition metal applied per dm 3 solvent or per dm 3 reactor volume.
  • Suitable 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 tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o- Dichlorobenzene.
  • an alkylaluminum compound such as trimethylaluminum, triethylaluminium, triisobutyliumiumium, trioctylaluminium or isoprenylaiumiumium can additionally be added to the reactor to render the polymerization system inert (for example to separate off existing catalyst poisons in the olefin). This is added to the polymerization system in a concentration of 200 to 0.001 mmol of AI per kg of reactor content.
  • Triisobutylaium aluminum and triethyl aluminum are preferably used in a concentration of 10 to 0.01 mmol Al per kg reactor content, so that the molar Al / M 1 ratio can be chosen to be small in the synthesis of a supported catalyst system.
  • an additive such as an antistatic, e.g. to improve the grain morphology of the polymer.
  • an antistatic e.g. to improve the grain morphology of the polymer.
  • all antistatic agents that are suitable for the polymerization can be used. Examples of these are salt mixtures of calcium salts of medialanic acid and chromium salts of N-stearyianthranilic acid, which are described in DE-A-3,543,360.
  • Other suitable antistatic agents are e.g. C ⁇ - to C22 fatty acid soaps from
  • a mixture of a metal salt can be used as an antistatic Medialan acid, a metal salt of anthranilic acid and a polyamine can be used, as described in EP-A-0,636,636.
  • ARU5R® 163 from ICI can also be used.
  • the antistatic is preferably used as a solution, in the preferred case of Stadis® 450 preferably 1 to 50% by weight of this solution, preferably 5 to
  • the result is 1,001 g of a light green, free-flowing powder.
  • a dry 16 dm 3 reactor is first flushed with nitrogen and then with propylene and filled with 10 dm 3 of liquid propene. Then 0.5 cm 3 of a 20% triisobutylaiumium solution in Varsol diluted with 30 cm 3 Exxol was added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes. The catalyst suspension was then added to the reactor. The reaction mixture was brought to the polymerization temperature of 60 ° C heated (4 ° C / min) and the polymerization system was kept at 60 ° C for 1 h by cooling. The polymerization was stopped by exhausting the remaining propylene. The polymer was dried in a vacuum drying cabinet. The result is 485 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 97 kg PP / g metallocene xh

Abstract

The invention relates to a catalyst system comprised of a metallocene, a co-catalyst, a supporting material and optionally of another organometallic compound. The catalyst system can be advantageously used for the polymerization of olefins. In doing this, the use of aluminoxanes such as methylaluminoxane (MAO) as a co-catalyst is foregone and yet a high catalytic activity and a good polymeric morphology are achieved.

Description

Beschreibungdescription
KatalysatorsystemCatalyst system
Die vorliegende Erfindung beschreibt ein Katalysatorsystem bestehen aus einemThe present invention describes a catalyst system consisting of a
Metallocen, einem Co-Katalysator, einem Trägermaterial und gegebenenfalls einer weiteren Organometallverbindung. Das Katalysatorsystem kann vorteilhaft zur Polymerisation von Olefinen eingesetzt werden. Hierbei wird auf die Verwendung von Aluminoxanen wie Methylaluminoxan (MAO) als Cokatalysator verzichtet und dennnoch eine hohe Katalysatoraktivität und gute Polymermorphologie erzielt .Metallocene, a co-catalyst, a support material and optionally another organometallic compound. The catalyst system can advantageously be used for the polymerization of olefins. The use of aluminoxanes such as methylaluminoxane (MAO) as a cocatalyst is dispensed with, and high catalyst activity and good polymer morphology are still achieved.
Die Rolle von kationischen Komplexen bei der Ziegler-Natta-Polymerisation mitThe role of cationic complexes in Ziegler-Natta polymerization
Metallocenen ist allgemein anerkannt (H.H. Brintzinger, D. Fischer, R. Mülhaupt, R.Metallocenes are generally recognized (H.H. Brintzinger, D. Fischer, R. Mülhaupt, R.
Rieger, R. Waymouth, Angew. Chem. 1995, 107, 1255-1283). MAO als wirksamer Co-Katalysator hat den Nachteil in hohem Überschuß eingesetzt werden zu müssen. Die Darstellung kationischer Alkylkomplexe eröffnet den WegRieger, R. Waymouth, Angew. Chem. 1995, 107, 1255-1283). MAO as an effective cocatalyst has the disadvantage of having to be used in a large excess. The representation of cationic alkyl complexes opens the way
MAO freier Katalysatoren mit vergleichbarer Aktivität, wobei der Co-Katalysator nahezu stöchiometrisch eingesetzt werden kann.MAO-free catalysts with comparable activity, whereby the co-catalyst can be used almost stoichiometrically.
Die Synthese von "Kationen-ähnlichen" Metallocen-Polymerisationskatalysatoren, wird im J. Am. Chem. Soc. 1991 , 113, 3623 beschrieben. Ein Verfahren zurThe synthesis of "cation-like" metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991, 113, 3623. A procedure for
Hersteilung von Salzen der allgemeinen Form LMX+ XA" nach dem oben beschriebenen Prinzip wird in EP-A-0 520 732 beansprucht.Production of salts of the general form LMX + XA " according to the principle described above is claimed in EP-A-0 520 732.
EP-A-0 558 158 beschreibt zwitterionische Katalysatorsysteme, die ausEP-A-0 558 158 describes zwitterionic catalyst systems which consist of
Metallocendialkyl-Verbindungen und Salzen der Form [R3NH]+ [B(CβH5)4]" dargestellt werden Die Umsetzung eines solchen Salzes mit z.B. Cp2ZrMe2 liefert durch Protolyse unter Methanabspaltung intermediär ein Zirkonocenmethyl-Kation.Metallocendialkyl compounds and salts of the form [R 3 NH] + [B (CβH 5 ) 4 ] " are shown. The reaction of such a salt with, for example, Cp 2 ZrMe 2 provides an intermediate zirconocenemethyl cation by protolysis with elimination of methane.
Dieses reagiert über C-H-Aktivierung zum Zwitterion Cp2Zr+-(m-C6H4)-BPh3 " ab. DasThis reacts via CH activation to the zwitterion Cp 2 Zr + - (mC 6 H 4 ) -BPh 3 "
Zr-Atom ist dabei kovalent an ein Kohlenstoffatom des Phenylrings gebunden und wird über agostische Wasserstoffbindungen stabilisiert. US-A-5, 348, 299 beschreibt zwitterionische Katalysatorsysteme, die ausThe Zr atom is covalently bound to a carbon atom of the phenyl ring and is stabilized via agostic hydrogen bonds. US-A-5, 348, 299 describes zwitterionic catalyst systems consisting of
Metallocendialkyl-Verbindungen und Salzen der Form [R3NH]+ [B(C6F5)4]" durch Protolyse dargestellt werden. Die C-H-Aktivierung als Folgereaktion unterbleibt dabei.Metallocendialkyl compounds and salts of the form [R 3 NH] + [B (C 6 F 5 ) 4 ] " by Protolysis are shown. The CH activation as a subsequent reaction does not occur.
EP-A-0 426 637 nutzt ein Verfahren in dem das Lewis-saure CPh3 + Kation zur Abstraktion der Methylgruppe vom Metallzentrum eingesetzt wird. Als schwach koordinierendes Anion fungiert ebenfalls B(C6F5)4 ".EP-A-0 426 637 uses a method in which the Lewis acidic CPh 3 + cation is used for the abstraction of the methyl group from the metal center. B (C 6 F 5 ) 4 " also acts as a weakly coordinating anion.
Eine industrielle Nutzung von Metallocen-Kataiysatoren fordert eine Heterogenisierung des Katalysatorsystems, um eine entsprechende Morphologie des resultierenden Polymers zu gewährleisten. Die Trägerung von kationischen Metallocen-Kataiysatoren auf Basis der oben genannten Borat-Anionen ist inIndustrial use of metallocene catalysts requires heterogenization of the catalyst system in order to ensure an appropriate morphology of the resulting polymer. The support of cationic metallocene catalysts based on the above borate anions is in
WO 91/09882 beschrieben. Dabei wird das Katalysatorsystem, durch Aufbringen einer Dialkylmetallocen-Verbindung und einer Brönsted sauren, quatären Ammonium-Verbindung, mit einem nichtkoordinierenden Anion wie Tetrakispentafluorphenylborat, auf einem anorganischen Träger, gebildet. Das Trägermaterial wird zuvor mit einer Triaikylaluminium-Verbindung modifiziert.WO 91/09882. The catalyst system is formed by applying a dialkyl metallocene compound and a Bronsted acidic, quaternary ammonium compound with a non-coordinating anion, such as tetrakispentafluorophenyl borate, on an inorganic support. The carrier material is modified beforehand with a triaikylaluminium compound.
Nachteil dieses Trägerungsverfahren ist, daß nur ein geringer Teil des eingesetzten Metallocens durch Physisorbtion an dem Trägermaterial fixiert ist. Bei der Dosierung des Katalysatorsystems in den Reaktor kann das Metallocen leicht von der Trägeroberfläche abgelöst werden. Dies führt zu einer teiiweisen homogen verlaufenden Polymerisation, was eine unbefriedigende Morphologie des Polymers zur Folge hat. Im WO96/04319 wird ein Katalysatorsystem beschrieben, in welchem der Cokatalysator kovalent an das Trägermaterial gebunden ist. Dieses Katalysatorsystem weist jedoch eine geringe Polymerisationsaktivität auf, zudem kann die hohe Empfindlichkeit der geträgerten kationischen Metallocen-The disadvantage of this carrier method is that only a small part of the metallocene used is fixed to the carrier material by physisorption. When the catalyst system is metered into the reactor, the metallocene can easily be detached from the support surface. This leads to a partially homogeneous polymerization, which results in an unsatisfactory morphology of the polymer. WO96 / 04319 describes a catalyst system in which the cocatalyst is covalently bound to the support material. However, this catalyst system has a low polymerization activity, and the high sensitivity of the supported cationic metallocene can
Kataiysatoren zu Problemen bei der Einschieusung in das Polymerisationssystem führen.Catalysts lead to problems with the injection into the polymerization system.
Es war daher wünschenswert ein Katalysatorsystem zu entwickeln, das wahlweise vor dem Einschleusen in den Reaktor bereits aktiviert ist oder erst im Polymerisationsautoklav aktiviert wird. Die Aufgabe bestand darin ein Katalysatorsystem zur Verfügung zu stellen, welches die Nachteile des Standes der Technik vermeidet und trotzdem hohe Polymersationsaktivitäten und eine gute Polymermorphologie garantiert. Zudem war ein Verfahren zur Herstellung dieses Katalysatorsystems zu entwickeln, das es ermöglicht die Aktivierung des Katalysatorsystems wahlweise vor dem Einschleusen oder aber erst im Polymerisationsautoklav durchzuführen.It was therefore desirable to develop a catalyst system that is either activated before it is introduced into the reactor or that is only activated in the polymerization autoclave. The object was to provide a catalyst system which avoids the disadvantages of the prior art and nevertheless guarantees high polymerization activities and good polymer morphology. In addition, a method had to be developed for the production of this catalyst system, which enables the activation of the catalyst system either before the introduction or only in the polymerization autoclave.
Die vorliegende Erfindung betrifft ein geträgertes Katalysatorsystem und ein Verfahren zur Herstellung von diesem. Weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung des erfindungsgemäßen Katalysatorsystems in derThe present invention relates to a supported catalyst system and a method for producing the same. The present invention furthermore relates to the use of the catalyst system according to the invention in
Hersteilung von Polyolefinen.Manufacture of polyolefins.
Das erfindungsgemäße Katalysatorsystem enthält A) mindestens ein Metallocen, B) mindestens eine Lewis Base der Formel IThe catalyst system according to the invention contains A) at least one metallocene, B) at least one Lewis base of the formula I.
M1 R3R4R5 ^ M 1 R 3 R 4 R 5 ^
worinwherein
R3, R4, R5 gleich oder verschieden sind und ein Wasserstoffatom, eine d- C2o Alkyi-, C-ι-C20 Halogenalkyl-, C6-C4o Aryl-, C6-C4o Halogenaryl-, C -C40 Alkylaryl- oder C7-C40 Arylalkyl-Gruppe ist und zwei Reste oder alle drei Reste R3, R4 und R5 über C2-C2o Kohlenstoffeinheiten miteinander verbunden sein können, M1 ist ein Element der V. Hauptgruppe des Periodensystems der Elemente, insbesondere Stickstoff oder Phosphor C) mindestens einen TrägerR 3 , R 4 , R 5 are the same or different and are a hydrogen atom, ad-C 2 o alkyl, C-ι-C 20 haloalkyl, C 6 -C 4 o aryl, C 6 -C 4 o haloaryl -, C -C 40 alkylaryl or C 7 -C 40 arylalkyl group and two radicals or all three radicals R 3 , R 4 and R 5 can be connected to one another via C 2 -C 2 o carbon units, M 1 is a Element of the 5th main group of the Periodic Table of the Elements, in particular nitrogen or phosphorus C) at least one carrier
D) und mindestens eine Organobor- oder Organoaluminium-Verbindung, die aus Einheiten der Formel IID) and at least one organoboron or organoaluminium compound which consists of units of the formula II
[R1 2M2-X-M2R2 23k worin R1,R2 gleich oder verschieden sind und ein Wasserstoffatom, ein[R 1 2 M 2 -XM 2 R 2 2 3 k wherein R 1 , R 2 are the same or different and a hydrogen atom
Halogenatom, eine borfreie Cι-C4o-kohienstoffhaltige Gruppe wie C C20-Alkyl, Cι-C2o-Halogenalkyl, Cι-C10-Alkoxy, C6-C2o-Aryl, C6-C2o- Halogenaryl, C6-C2o-Aryloxy, C7-C4o-Arylalkyl, C7-C4o-Halogenarylalkyl, C7-C4o-Alkylaryl, C7-C4o-Halogenalkylaryl sind oder R1 kann eine OSiRa 3-Gruppe sein, worin Ra gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, eine Cι-C4o-kohlenstoffhaltige Gruppe wie Cι-C2o-Aikyl, Cι-C2o-Haiogenalkyl, CrCio-Alkoxy, C6-C20-Halogen atom, a Cι-boron-free C 4 o-kohienstoffhaltige group such as CC 20 -alkyl, C 2 o-haloalkyl, Cι-C 10 alkoxy, C 6 -C 2 o-aryl, C 6 -C 2 o Haloaryl, C 6 -C 2 o-aryloxy, C 7 -C 4 o-arylalkyl, C 7 -C 4 o-Halogenarylalkyl, C 7 -C 4 o-alkylaryl, C 7 -C 4 o-haloalkylaryl or R 1 can be an OSiR a 3 group, in which R a are the same or different and a hydrogen atom, a halogen atom, a C 1 -C 4 -carbon-containing group such as C 1 -C 2 o -ikyl, C 1 -C 2 o-haiogenalkyl, CrCio -Alkoxy, C 6 -C 20 -
Aryl, C6-C2o-Haiogenaryl, C6-C2o-Aryloxy, C7-C4o-Arylalkyl, C7-C4o- Halogenarylalkyl, C7-C o-Alkyiaryl, C7-C4o-Halogenalkylaryl sind oder R1 kann eine CH(SiRb 3)2-Gruppe sein, worin Rb gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, eine d- C o-kohlenstoffhaltige Gruppe wie Cι-C2o-Alkyl, CrC2o-Halogenalkyl, d-Cio-Alkoxy, C6-C2o-Aryl, C6-C2o-Haiogenaryl, C6-C2o-Aryloxy, C7-C 0- Arylalkyl, C7-C40-Halogenaryialkyl, C7-C4o-Alkylaryl, C7-C40- Haiogenalkylaryl sein,Aryl, C 6 -C 2 o-Haiogenaryl, C 6 -C 2 o-aryloxy, C 7 -C 4 o-arylalkyl, C 7 -C 4 o- Halogenarylalkyl, C 7 -C o-Alkyiaryl, C 7 -C 4 are o-haloalkylaryl or R 1 can be a CH (SiR b 3 ) 2 group, in which R b are identical or different and are a hydrogen atom, a halogen atom, a d- C o -carbon-containing group such as C 1 -C 2 o- Alkyl, CrC 2 o-haloalkyl, d-Cio-alkoxy, C 6 -C 2 o-aryl, C 6 -C 2 o-haiogenaryl, C 6 -C 2 o-aryloxy, C 7 -C 0 - arylalkyl, C 7 -C 40 haloaryl alkyl, C 7 -C 4 o-alkylaryl, C 7 -C 40 - haiogenalkylaryl,
X gleich oder verschieden ein Element der Gruppe Via des Periodensystems der Elemente oder eine NH-Gruppe ist,X, identical or different, is an element of the Via group of the Periodic Table of the Elements or an NH group,
M2 ein Element der lila des Periodensystems der Elemente ist, und k eine natürliche Zahl von 1 bis 100 ist. aufgebaut ist und die kovalent an den Träger gebunden ist.M 2 is a purple element of the Periodic Table of the Elements, and k is a natural number from 1 to 100. is built up and is covalently bound to the carrier.
Bevorzugte Verbindungen der Formel (I) sind Triethylamin, Triisopropylamin,Preferred compounds of the formula (I) are triethylamine, triisopropylamine,
Triisobutylamin, Tri(n-butyl)amin, N,N-Dimethyianiiin, N,N-Diethylanilin, N,N-2,4,6-Pentamethylanilin, Dicyclohexylamin, Pyridin, Pyrazin, Triphenylphosphin, Tri(methylphenyl)phosphin, Tri(dimethylphenyl)phosphinTriisobutylamine, tri (n-butyl) amine, N, N-dimethyianiiin, N, N-diethylaniline, N, N-2,4,6-pentamethylaniline, dicyclohexylamine, pyridine, pyrazine, triphenylphosphine, tri (methylphenyl) phosphine, tri ( dimethylphenyl) phosphine
Die Verbindungen der Formel (II) können als Monomer oder als lineares, cyclisches oder käfigartiges Oligomer vorliegen. Außerdem können die erfindungsgemäßen Verbindungen der Formel (II) durch Lewis Säure-Base Wechselwirkung untereinander Dimere, Trimere oder höhere Oligomere bilden.The compounds of formula (II) can exist as a monomer or as a linear, cyclic or cage-like oligomer. In addition, the compounds of the formula (II) according to the invention can form dimers, trimers or higher oligomers by means of Lewis acid-base interaction with one another.
Bevorzugte cokatalytisch wirkende chemische Verbindung der Formel (II), sindPreferred cocatalytically active chemical compounds of the formula (II) are
Verbindungen in denen X ein Sauerstoff Atom oder eine NH-Gruppe ist und die Reste R1, R2 ein borfreier C1-C4o-Kohlenwasserstoffrest, der mit Halogenen wie Flour, Chlor, Brom oder Jod halogeniert, bevorzugt perhalogeniert, ist. Insbesondere bevorzugt ist R1, R2 eine halogenierte, insbesondere perhalogenierte Cι-C3u- Aikylgruppe wie Trifluormethyl-, Pentachlorethyl-, Heptafluorisopropyl oder Monofluorisobutyl oder eine halogenierte C6-C30-Arylgruppe wie Pentaflourphenyl-, 2,4,6-TrifIouφhenyl, Heptachlornaphtyl-, Heptaflournaphthyl, Heptaflourtolyl-, 3,5- bis(triflourmethyl)phenyl-, 2,4,6-tris(triflourmethyl)phenyl, Nonaflourbiphenyl- oder 4- (triflourmethyl)phenyl. Ebenfalls bevorzugt für R1 sind Reste wie Phenyl-, Naphtyl-, Anisyl-, Methyl-, Ethyl-, Isopropyl-, Butyl-, Tolyl-, Biphenyl oder 2,3-Dimethyl-phenyl. Besonders bevorzugt sind die Reste Pentaflourphenyl-, Phenyl-, Biphenyl, 3,5- bis(triflourmethyl)phenyl-, 4-triflourmethyl)phenyl, Nonafluorbiphenyl- und 4-Methyl- phenyl.Compounds in which X is an oxygen atom or an NH group and the radicals R 1 , R 2 are a boron-free C 1 -C 4 o-hydrocarbon radical which is associated with halogens such as Flour, chlorine, bromine or iodine is halogenated, preferably perhalogenated. R 1 , R 2 is particularly preferably a halogenated, in particular perhalogenated C 3 -C 3 -ikyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated C 6 -C 30 aryl group such as pentaflourphenyl, 2,4,6-triflourylhenyl , Heptachloronaphthyl-, Heptaflournaphthyl, Heptaflourtolyl-, 3,5- bis (triflourmethyl) phenyl-, 2,4,6-tris (triflourmethyl) phenyl, Nonaflourbiphenyl- or 4- (triflourmethyl) phenyl. Also preferred for R 1 are radicals such as phenyl, naphthyl, anisyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl or 2,3-dimethylphenyl. The radicals pentaflourphenyl, phenyl, biphenyl, 3,5- bis (triflourmethyl) phenyl-, 4-triflourmethyl) phenyl, nonafluorobiphenyl- and 4-methylphenyl are particularly preferred.
Ganz besonders bevorzugte cokataiytisch wirkende chemische Verbindungen der Formel (II) sind solchen, in denen X für Sauerstoff, M2 für Bor steht. Diese werden durch die Formel (III)Very particularly preferred cocatalyst chemical compounds of formula (II) are those in which X is oxygen, M 2 is boron. These are represented by the formula (III)
R ,RR, R
/ B — O— B \/ B - O— B \
1, R1, R
IIIIII
worin R1 für die unter Formel (II) angegebenen Reste steht, beschrieben.wherein R 1 represents the radicals specified under formula (II).
Bevorzugte Ausführungsformen der Formel (II) sind die nachfolgenden:Preferred embodiments of formula (II) are as follows:
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000007_0001
Figure imgf000008_0001
Die Trägerkomponente des erfindungsgemäßen Katalysatorsystems kann ein beliebiger organischer oder anorganischer, inerter Feststoff sein, insbesondere ein poröser Träger wie Talk, anorganische Oxide und feinteilige Poiymerpulver (z.B. Polyolefine).The carrier component of the catalyst system according to the invention 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).
Geeignete anorganische Oxide finden sich in den Gruppen 2, 3, 4, 5, 13, 14, 15 und 16 des Periodensystems der Elemente. Beispiele für als Träger bevorzugte Oxide umfassen Siliciumdioxid, Aluminiumoxid, sowie Mischoxide der beiden Elemente und entsprechende Oxid-Mischungen. Andere anorganische Oxide, die allein oder in Kombination mit den zuletzt genannten bevorzugten oxiden Trägern eingesetzt werden können, sind z.B. MgO, ZO2 , TiO2 oder B2O3 ,um nur einige zu nennen.Suitable inorganic oxides can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Examples of oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, ZO 2 , TiO 2 or B 2 O 3 , to name just a few.
Die verwendeten Trägermaterialien weisen eine spezifische Oberfläche im Bereich von 10 bis 1000 m2/g, ein Porenvolumen im Bereich von 0,1 bis 5 ml/g und eine mittlere Partikelgröße von 1 bis 500 μm auf. Bevorzugt sind Träger mit einer spezifischen Oberfläche im Bereich von 50 bis 500 μm , einem Porenvolumen im Bereich zwischen 0,5 und 3,5 ml/g und einer mittleren Partikelgröße im Bereich vonThe carrier materials used have a specific surface area in the range from 10 to 1000 m 2 / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 μm. Carriers with a specific surface area in the range from 50 to 500 μm, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from are preferred
5 bis 350 μm. Besonders bevorzugt sind Träger mit einer spezifischen Oberfläche im Bereich von 200 bis 400 m2/g, einem Porenvolumen im Bereich zwischen 0,8 bis 3,0 ml/g und einer mittleren Partikelgröße von 10 bis 200 μm. Wenn das verwendete Trägermaterial von Natur aus einen geringen Feuchtigkeitsgehalt oder Restlösemittelgehalt aufweist, kann eine Dehydratisierung oder Trocknung vor der Verwendung unterbleiben. Ist dies nicht der Fall, wie bei dem Einsatz von Siiicagel als Trägermaterial, ist eine Dehydratisierung oder Trocknung empfehlenswert. Die thermische Dehydratisierung oder Trocknung des Trägermaterials kann unter Vakuum und gleichzeitiger Inertgasüberlagerung (z.B. Stickstoff) erfolgen. Die Trocknungstemperatur liegt im Bereich zwischen 100 und 1000°C, vorzugsweise zwischen 200 und 800°C. Der Parameter Druck ist in diesem Fall nicht entscheidend. Die Dauer des Trocknungsprozesses kann zwischen 1 und 24 Stunden betragen. Kürzere oder längere Trocknungsdauern sind möglich, vorausgesetzt, daß unter den gewählten Bedingungen die Gleichgewichtseinstellung mit den Hydroxylgruppen auf der Trägeroberfläche erfolgen kann, was normalerweise zwischen 4 und 8 Stunden erfordert.5 to 350 μm. Carriers with a specific surface area in the range from 200 to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 μm are particularly preferred. If the carrier material used naturally has a low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as with the use of Siiicagel as a carrier material, dehydration or drying is recommended. The thermal dehydration or drying of the carrier material can be carried out under vacuum and at the same time inert gas blanket (e.g. Nitrogen). The drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical. The drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
Eine Dehydratisierung oder Trocknung des Trägermaterials ist auch auf chemischem Wege möglich, indem das adsorbierte Wasser und die Hydroxylgruppen auf der Oberfläche mit geeigneten inertisierungsmitteln zur Reaktion gebracht werden.Dehydration or drying of the carrier material is also possible chemically by reacting the adsorbed water and the hydroxyl groups on the surface with suitable inerting agents.
Durch die Umsetzung mit dem Inertisierungsreagenz können die Hydroxylgruppen vollständig oder auch teilweise in eine Form überführt werden, die zu keiner negativen Wechselwirkung mit den katalytisch aktiven Zentren führt. Geeignete Inertisierungsmittel sind beispielsweise Siliciumhalogenide und Silane, wie Siliciumtetrachlorid, Chlortrimethylsilan, Dimethylaminotrichlorsilan oder metallorganische Verbindungen von Aluminium- , Bor und Magnesium wie beispielsweise Trimethylaluminium, Triethylaluminium, Triisobutylaluminium, Triethylboran, Dibutylmagnesium. Die chemische Dehydratisierung oder Inertisierung des Trägermaterials erfolgt beispielsweise dadurch, daß man unter Luft- und Feuchtigkeitsausschluß eine Suspension des Trägermaterials in einem geeigneten Lösemittel mit dem Inertisierungsreagenz in reiner Form oder gelöst in einem geeigneten Lösemittel zur Reaktion bringt. Geeignete Lösemittel sind z.B. aliphatische oder aromatische Kohlenwasserstoffe wie Pentan, Hexan, Heptan, Toluol oder Xyiol. Die Inertisierung erfolgt bei Temperaturen zwischen 25°C und 120°C, bevorzugt zwischen 50 und 70°C. Höhere und niedrigere Temperaturen sind möglich. Die Dauer der Reaktion beträgt zwischen 30 Minuten und 20 Stunden, bevorzugt 1 bis 5 Stunden. Nach dem vollständigen Ablauf der chemischen Dehydratisierung wird das Trägermaterial durch Filtration unter Inertbedingungen isoliert, ein- oder mehrmals mit geeigneten inerten Lösemitteln wie sie bereits zuvor beschrieben worden sind gewaschen und anschließend im Inertgasstrom oder amThrough the reaction with the inerting reagent, the hydroxyl groups can be completely or partially converted into a form which does not lead to any negative interaction with the catalytically active centers. Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane or organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium. The chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture. Suitable solvents are e.g. aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xyiol. The inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible. The duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours. After the chemical dehydration has ended, the support material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then in an inert gas stream or on
Vakuum getrocknet. Organische Trägermaterialien wie feinteiiige Polyoiefinpulver (z.B. Polyethylen, Polypropylen oder Polystyrol) können auch verwendet werden und sollten ebenfalls vor dem Einsatz von anhaftender Feuchtigkeit, Lösemittelresten oder anderen Verunreinigungen durch entsprechende Reinigungs- und Trocknungsoperationen befreit werden.Vacuum dried. Organic carrier materials such as finely divided polyofin powder (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
Die erfindungsgemäßen chemische Verbindungen der Formel (II) kann zusammen mit einer Organometallübergangsverbindung als Katalysatorsystem verwendet werden. Als Organometallübergangsverbindung werden z.B. Metallocenverbindungen eingesetzt. Dies können z.B. verbrückte oder unverbrückteThe chemical compounds of formula (II) according to the invention can be used together with an organometallic transition compound as a catalyst system. As an organometallic transition compound, e.g. Metallocene compounds used. This can e.g. bridged or unbridged
Biscyciopentadienyikompiexe sein, wie sie z.B. in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 545 304 und EP-A-0 576 970 beschrieben sind,Biscyciopentadienyikompiexe, such as e.g. in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 545 304 and EP-A-0 576 970,
Monocyclopentadienylkomplexe, wie verbrückte Amidocyclopentadienylkomplexe die z.B in EP-A-0 416 815 beschrieben sind, mehrkernige Cyclopentadienylkomplexe wie in EP-A-0 632 063 beschrieben, π-Ligand substituierte Tetrahydropentalene wie in EP-A-0 659 758 beschrieben oder π-Ligand substituierte Tetrahydroindene wie in EP-A-0 661 300 beschrieben. Außerdem können Organometallverbindungen eingesetzt werden in denen der komplexierende Ligand kein Cyciopentadienyl- Liganden enthält. Beispiele hierfür sind Diamin-Komplexe der III. und IV. Nebengruppe des Periodensystems der Elemente, wie sie z.B. bei D.H. McConville, et al, Macromolecules, 1996, 29, 5241 und D.H. McConville, et ai, J. Am. Chem. Soo, 1996, 1 18, 10008 beschrieben werden. Außerdem können Diimin-Komplexe der VIII. Nebengruppe des Periodensystems der Elemente (z.B. Ni + oder Pd2+ Komplexe), wie sie bei Brookhart et al, J. Am. Chem. Soc. 1995, 117, 6414 und , Brookhart et al, J. Am. Chem. Soo, 1996, 118, 267 beschrieben werden, eingesetzt werden. Ferner lassen sich 2,6-bis(imino)pyridyl-Komplexe der VIII. Nebengruppe des Periodensystems der Elemente (z.B. Co2+ oder Fe2+ Komplexe), wie sie bei Brookhart et al, J. Am. Chem. Soc. 1998, 120, 4049 und Gibson et al, Chem. Commun. 1998, 849 beschrieben werden, einsetzen. Bevorzugte Metallocenverbindungen sind unverbrückte oder verbrückte Verbindungen der Formel (V),Monocyclopentadienyl complexes, such as bridged amidocyclopentadienyl complexes which are described, for example, in EP-A-0 416 815, multinuclear cyclopentadienyl complexes as described in EP-A-0 632 063, π-ligand-substituted tetrahydropentalenes as described in EP-A-0 659 758 or π substituted tetrahydroindenes as described in EP-A-0 661 300. Organometallic compounds can also be used in which the complexing ligand does not contain a cyciopentadienyl ligand. Examples of this are diamine complexes of III. and IV. Subgroup of the Periodic Table of the Elements, as described, for example, in DH McConville, et al, Macromolecules, 1996, 29, 5241 and DH McConville, et ai, J. Am. Chem. Soo, 1996, 1 18, 10008. In addition, diimine complexes of subgroup VIII of the Periodic Table of the Elements (eg Ni + or Pd 2+ complexes), as described by Brookhart et al, J. Am. Chem. Soc. 1995, 117, 6414 and, Brookhart et al, J. Am. Chem. Soo, 1996, 118, 267 are used. Furthermore, 2,6-bis (imino) pyridyl complexes of subgroup VIII of the Periodic Table of the Elements (eg Co 2+ or Fe 2+ complexes), as described by Brookhart et al, J. Am. Chem. Soc. 1998, 120, 4049 and Gibson et al, Chem. Commun. 1998, 849 are used. Preferred metallocene compounds are unbridged or bridged compounds of the formula (V)
R1°,R 1 °,
Figure imgf000011_0001
worin
Figure imgf000011_0001
wherein
M ein Metall der III., IV, V. oder VI. Nebengruppe des Periodensystems der Elemente ist, insbesondere Ti, Zr oder Hf,M is a metal of III., IV, V. or VI. Subgroup of the periodic table of the elements, in particular Ti, Zr or Hf,
R 10 gleich oder verschieden sind und ein Wasserstoffatom oder SiR3 12sind, worin R12 gleich oder verschieden ein Wasserstoffatom oder eine C1-C40- kohlenstoffhaltige Gruppe, bevorzugt Cι-C2o-Alkyl, Cι-Cι0-Fluoralkyl, C1-C10- Aikoxy, C6-C2o-Aryl, C6-Cιo-Fluoraryl, Cβ-C-io-Aryloxy, C2-Cιo-Alkenyl, C7-C40- Arylalkyl, C7-C40-Alkylaryl oder C8-C4o-Arylalkenyl, oder R10 eine C C3o - kohlenstoffhaltige Gruppe, bevorzugt Ct-C25-Alkyl, wie Methyl, Ethyl, tert.-Butyl, Cyclohexyl oder Octyl, C2-C25-Alkenyl, C3-Cι5-Alkylalkenyi, C6-C24-Aryl, C5-C24- Heteroaryl wie Pyridyl, Furyl oder Chinolyl, C7-C3o-Arylalkyl, C7-C30-Alkyiaryl, fluorhaltiges CrC25-Alkyl, fluorhaltiges C6-C24-Aryl, fluorhaltiges C7-C3o- Arylalkyl, fluorhaltiges C7-C3o-Alkylaryl oder C-ι-C-12-Aikoxy ist, oder zwei oder mehrere Reste R10 können so miteinander verbunden sein, daß die Reste R10 und die sie verbindenden Atome des Cyclopentadienylringes ein C4-C24- Ringsystem bilden, welches seinerseits substituiert sein kann,R 10 are identical or different and are a hydrogen atom or SiR 3 12, where R 12 are identical or different, represent a hydrogen atom or a C1-C 40 - carbon-containing group, preferably Cι-C 2 o-alkyl, Cι-Cι 0 fluoroalkyl, C 1 -C 10 - aikoxy, C 6 -C 2 o-aryl, C 6 -Cιo-fluoroaryl, Cβ-C-io-aryloxy, C 2 -Cιo-alkenyl, C7-C40-arylalkyl, C 7 -C 40 - Alkylaryl or C 8 -C 4 o-arylalkenyl, or R 10 is a CC 3 o - carbon-containing group, preferably C t -C 25 alkyl, such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 Alkenyl, C 3 -C 5 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 24 heteroaryl such as pyridyl, furyl or quinolyl, C 7 -C 3 o-arylalkyl, C 7 -C 30 alkylaryl, fluorine-containing CrC 25 alkyl, fluorine-containing C 6 -C 2 4-aryl, fluorine-containing C 7 -C 3 o-arylalkyl, fluorine-containing C 7 -C 3 o-alkylaryl or C 1 -C 12 -alkoxy, or two or a plurality of R 10 radicals can be bonded to one another in such a way that the R 10 radicals and the cyclopentadienylrin atoms connecting them form a C 4 -C 24 ring system, which in turn can be substituted,
>11 gleich oder verschieden sind und ein Wasserstoffatom oder SiR3 12 sind, worin R12 gleich oder verschieden ein Wasserstoffatom oder eine C1-C40- kohlenstoffhaltige Gruppe, bevorzugt Cι-C2o-Alkyi, CrCio-Fluoralkyl, C-rCio- Alkoxy, C6-Ci4-Aryl, C6-Cι0-Fluoraryl, C6-C10-Aryloxy, C2-Cι0-Alkenyl, C7-C40- Arylalkyl, C7-C4o-Alkylaryl oder C8-C4o-Arylalkenyl, oder R8 eine C1-C30 - kohlenstoffhaltige Gruppe, bevorzugt C-ι-C25-Alkyl, wie Methyl, Ethyl, tert.-Butyl, Cyclohexyl oder Octyl, C2-C25-Alkenyl, C3-Cι5-Alkylalkenyl, C6-C24-Aryl, C5-C24- Heteroaryl, wie. Pyridyl, Furyl oder Chinolyl, C7-C3o-Arylaikyl, C -C3o-Alkylaryl, fluorhaltiges CrC25-Alkyl, fluorhaltiges C6-C24-Aryl, fluorhaltiges C7-C30- Arylalkyl, fluorhaltiges C7-C3o-Alkylaryl oder CrCι2-Alkoxy ist, oder zwei oder mehrere Reste R11 können so miteinander verbunden sein, daß die Reste R11 und die sie verbindenden Atome des Cyciopentadienyiringes ein C4-C24- Ringsystem bilden, welches seinerseits substituiert sein kann,> 11 are the same or different and are a hydrogen atom or SiR 3 12 , in which R 12 is the same or different a hydrogen atom or a C1-C 40 - carbon-containing group, preferably C 1 -C 2 -alkyi, CrCio-fluoroalkyl, C-rCio- Alkoxy, C 6 -Ci 4 aryl, C 6 -Cι 0 fluoroaryl, C 6 -C 10 aryloxy, C 2 -Cι 0 alkenyl, C 7 -C 40 arylalkyl, C 7 -C 4 o-alkylaryl or C 8 -C 4 o-arylalkenyl, or R 8 is a C 1 -C 30 carbon-containing group, preferably C 1 -C 25 -alkyl, such as methyl, ethyl, tert-butyl, Cyclohexyl or octyl, C 2 -C 25 alkenyl, C 3 -C 5 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 24 - heteroaryl, such as. Pyridyl, furyl or quinolyl, C 7 -C 3 o-aryl-alkyl, C -C 3 o-alkylaryl, fluorine-containing CrC 25 -alkyl, fluorine-containing C 6 -C 24 -aryl, fluorine-containing C 7 -C 30 -arylalkyl, fluorine-containing C 7 -C 3 o-alkylaryl or CrCι 2 alkoxy, or two or more radicals R 11 can be linked together so that the radicals R 11 and the atoms connecting them of the cyciopentadienyiring form a C 4 -C 24 ring system, which in turn can be substituted
I gleich 5 für v = 0, und I gleich 4 für v = 1 ist, m gleich 5 für v = 0, und m gleich 4 für v = 1 ist, L1 gleich oder verschieden sein können und ein Wasserstoffatom, eine C1-C-10-I is 5 for v = 0, and I is 4 for v = 1, m is 5 for v = 0, and m is 4 for v = 1, L 1 can be the same or different and a hydrogen atom, a C 1 -C- 10 -
Kohlenwasserstoffgruppe wie CrCιo-Alkyi oder Cβ-Cio-Aryl, ein Halogenatom, oder OR16, SR16, OSiR3 16, SiR3 16, PR2 16 oder NR2 16bedeuten, worin R16 ein Halogenatom, eine C1-C10 Alkylgruppe, eine halogenierte C1-C10 Alkylgruppe, eine C6-C20 Arylgruppe oder eine halogenierte C6-C2o Arylgruppe sind, oder L sind eine Toluolsulfonyl-, Trifluoracetyl-, Trifluoracetoxyl-,Hydrocarbon group such as CrCιo-Alkyi or Cβ-Cio-aryl, a halogen atom, or OR 16 , SR 16 , OSiR 3 16 , SiR 3 16 , PR 2 16 or NR 2 16 , wherein R 16 is a halogen atom, a C 1 -C 10 is an alkyl group, a halogenated C 1 -C 10 alkyl group, a C 6 -C 20 aryl group or a halogenated C 6 -C 2 o aryl group, or L is a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl,
Trifluormethansulfonyl-, Nonafluorbutansulfonyl- oder 2,2,2- Trifluorethansulfonyl-Gruppe,Trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group,
0 eine ganze Zahl von 1 bis 4, bevorzugt 2 ist,0 is an integer from 1 to 4, preferably 2,
Z ein verbrückendes Strukturelement zwischen den beiden Cyclopentadienylringen bezeichnet und v ist 0 oder 1.Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
Beispiele für Z sind Gruppen M3R13R14, worin M3 Kohlenstoff, Silizium, Germanium oder Zinn ist und R13 und R14 gieich oder verschieden eine C1-C20- kohlenwasserstoffhaltige Gruppe wie d-Cio-Alkyl, C6-Ci4-Aryl oder Trimethylsilyl bedeuten. Bevorzugt ist Z gleich CH2, CH2CH2, CH(CH3)CH2) CH(C4H9)C(CH3)2,Examples of Z are groups M 3 R 13 R 14 , in which M 3 is carbon, silicon, germanium or tin and R 13 and R 14 are identical or different and are a C 1 -C 20 -hydrocarbon-containing group such as d-Cio-alkyl, C 6 -Ci 4 aryl or trimethylsilyl. Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2) CH (C 4 H9) C (CH 3 ) 2 ,
C(CH3)2, (CH3)2Si, (CH3)2Ge, (CH3)2Sn, (C6H5)2Si, (C6H5)(CH3)Si, Si(CH3)(SiR20R21R22), (C6H5)2Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2, o-C6H4 oder 2,2'-(CβH4)2. Wobei R20, R21, R22 gleich oder verschieden eine C C2o- kohlenwasserstoff-haltige Gruppe wie Ci-Cio-Alkyl oder Cβ-C -Aryl bedeuten. Z kann auch mit einem oder mehreren Resten R10 und/oder R11 ein mono- oder potycyclisches Ringsystem bilden. Bevorzugt sind chirale verbrückte Metallocenverbindungen der Formel (V), insbesondere solche in denen v gleich 1 ist und einer oder beide Cyclopentadienylringe so substituiert sind, daß sie einen Indenylring darsteilen. Der Indenylring ist bevorzugt substituiert, insbesondere in 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 oder 2,4,5,6-Stellung, mit CrC2o-kohlenstoffhaltigen Gruppen, wie CrCio-Alkyl oder CΘ-C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, Si (CH 3 ) (SiR 20 R 21 R 22 ), (C 6 H 5 ) 2 Ge, (C 6 H 5 ) 2 Sn, (CH 2 ) 4 Si, CH 2 Si (CH 3 ) 2 , oC 6 H 4 or 2,2 ' - (CβH 4 ) 2 . Where R 20 , R 21 , R 22, identically or differently, denote a group containing CC 2 o-hydrocarbon such as Ci-Cio-alkyl or Cβ-C-aryl. Z can also form a mono- or potycyclic ring system with one or more radicals R 10 and / or R 11 . Chiral bridged metallocene compounds of the formula (V) are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted such that they form 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 CrC 2 o-carbon-containing Groups such as CrCio-alkyl or CΘ-
C2o-Aryl, wobei auch zwei oder mehrere Substituenten des Indenylrings zusammen ein Ringsystem bilden können.C 2 o-aryl, where two or more substituents of the indenyl ring can together form a ring system.
Chirale verbrückte Metallocenverbindungen der Formel (III) können als reine racemische oder reine meso Verbindungen eingesetzt werden. Es können aber auchChiral bridged metallocene compounds of the formula (III) can be used as pure racemic or pure meso compounds. But it can also
Gemische aus einer racemischen Verbindung und einer meso Verbindung verwendet werden.Mixtures of a racemic compound and a meso compound can be used.
Beispiele für Metallocenverbindungen sind:Examples of metallocene compounds are:
Dimethyls landiylbis(indenyl)zirkoniumdichiorid Dimethyls landiylbis(4-naphthyl-indenyi)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-benzo-indenyl)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-indenyl)zirkoniumdichlorid Dimethyls landiyibis(2-methyl-4-(1-naphthyl)-indenyl)zirkoniumdichlorid Dimethyls iandiylbis(2-methyl-4-(2-naphthyl)-indenyl)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-4-phenyl-indenyl)zirkoniumdichiorid Dimethyls iandiylbis(2-methyl-4-t-butyl-indenyl)zirkoniumdichlorid Dimethyls iandiylbis(2-methyl-4-isopropyl-indenyl)zirkoniumdichiorid Dimethyls landiylbis(2-methyl-4-ethyl-indenyl)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-4- -acenaphth-indenyl)zirkoniumdichlorid Dimethyls landiyibis(2,4-dimethyl-indenyl)zirkoniumdichlorid Dimethyls landiylbis(2-ethyl-indenyl)zirkoniumdichlorid Dimethyls landiylbis(2-ethyl-4-ethyl-indenyl)zirkoniumdichiorid Dimethyls landiylbis(2-ethyl-4-phenyl-indenyl)zirkoniumdichlorid Dimethyls landiybis(2-methyl-4,5-benzo-indenyl)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-4,6 diisopropyl-indenyl)zirkoniumdichlorid Dimethyls !andiylbis(2-methyl-4,5 diisopropyl-indenyl)zirkoniumdichlorid Dimethylsilandiylbis(2,4,6-trimethyl-indenyl)zirkoniumdichioridDimethyls landiylbis (indenyl) zirconium dichioride Dimethyls landiylbis (4-naphthyl-indenyi) zirconium dichloride Dimethyls landiylbis (2-methyl-benzo-indenyl) zirconium dichloride Dimethyls landiylbis (2-methyl-indenyl) 1- dimethyl (dichloride) zirconium dichloride naphthyl) -indenyl) zirconium dichloride Dimethyls iandiylbis (2-methyl-4- (2-naphthyl) -indenyl) zirconium dichloride Dimethyls landiylbis (2-methyl-4-phenyl-indenyl) zirconium dichioride Dimethyls iandiylbis (2-methyl-4-t- -indenyl) zirconium dichloride Dimethyls iandiylbis (2-methyl-4-isopropyl-indenyl) zirconium dichioride Dimethyls landiylbis (2-methyl-4-ethyl-indenyl) zirconium dichloride Dimethyls landiylbis (2-methyl-4- -acenaphth-indenyliyidisidiryl) zirconium 2,4-dimethyl-indenyl) zirconium dichloride Dimethyls landiylbis (2-ethyl-indenyl) zirconium dichloride Dimethyls landiylbis (2-ethyl-4-ethyl-indenyl) zirconium dichioride Dimethyls landiylbis (2-ethyl-4-phenyl-indenyl) (zirconium dichloride) 2-methyl-4,5-benzo-indeny l) zirconium dichloride Dimethyls landiylbis (2-methyl-4,6 diisopropyl-indenyl) zirconium dichloride Dimethyls! andiylbis (2-methyl-4,5 diisopropyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2,4,6-trimethyl-indenyl) zirconium dichioride
Dimethylsiiandiylbis(2I5,6-trimethyl-indenyl)zirkoniumdichloridDimethylsiandiylbis (2 I 5,6-trimethyl-indenyl) zirconium dichloride
Dimethylsilandiylbis(2,4,7-trimethyl-indenyl)zirkoniumdichloridDimethylsilanediylbis (2,4,7-trimethyl-indenyl) zirconium dichloride
Dimethylsilandiylbis(2-methyl-5-isobutyl-indenyi)zirkoniumdichlorid Dimethylsilandiylbis(2-methyl-5-t-butyi-indenyl)zirkoniumdichloridDimethylsilanediylbis (2-methyl-5-isobutyl-indenyi) zirconium dichloride Dimethylsilanediylbis (2-methyl-5-t-butyi-indenyl) zirconium dichloride
Methyl(phenyl)silandiylbis(2-methyl-4-phenyl-indenyl)zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
Methyl(phenyl)silandiylbis(2-methyl-4,6 diisopropyl-indenyl)zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride
Methyl(phenyl)silandiylbis(2-methyl-4-isopropyi-indenyl)zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4-isopropyi-indenyl) zirconium dichloride
Methyi(phenyl)silandiylbis(2-methyl-4,5-benzo-indenyl)zirkoniumdichlorid Methyl(phenyl)silandiylbis(2-methyl-4,5-(methylbenzo)-indenyi)zirkoniumdi-chloridMethyl (phenyl) silanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-4,5- (methylbenzo) -indenyi) zirconium di-chloride
Methyl(phenyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-indenyl) zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4,5- (tetramethylbenzo) -indenyl) zirconium dichloride
Methyl(phenyl)silandiylbis(2-methyl-4- -acenaphth-indenyl)zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4- acenaphth-indenyl) zirconium dichloride
Methyl(phenyl)silandiylbis(2-methyl-indenyl)zirkoniumdichlorid Methyl(phenyl)silandiylbis(2-methyl-5-isobutyl-indenyl)zirkoniumdichioridMethyl (phenyl) silanediylbis (2-methyl-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-5-isobutyl-indenyl) zirconium dichioride
1 ,2-Ethandiylbis(2-methyl-4-phenyl-indenyl)zirkoniumdichlorid1,2-ethanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
1 ,4-Butandiylbis(2-methyl-4-phenyl-indenyl)zirkoniumdichlorid1,4-butanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
1 ,2-Ethandiylbis(2-methyl-4,6 diisopropyl-indenyl)zirkoniumdichlorid1,2-ethanediylbis (2-methyl-4,6 diisopropyl-indenyl) zirconium dichloride
1 ,4-Butandiylbis(2-methyl-4-isopropyi-indenyl)zirkoniumdichlorid 1 ,4-Butandiylbis(2-methyl-4,5-benzo-indenyl)zirkoniumdichlorid1,4-butanediylbis (2-methyl-4-isopropyi-indenyl) zirconium dichloride 1,4-butanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride
1 ,2-Ethandiylbis(2-methyl-4,5-benzo-indenyl)zirkoniumdichlorid1,2-ethanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride
1 ,2-Ethandiylbis(2,4,7-trimethyl-indenyl)zirkoniumdichlorid1,2-ethanediylbis (2,4,7-trimethyl-indenyl) zirconium dichloride
1 ,2-Ethandiylbis(2-methyl-indenyl)zirkoniumdichlorid1,2-ethanediylbis (2-methyl-indenyl) zirconium dichloride
1 ,4-Butandiylbis(2-methyi-indenyl)zirkoniumdichlorid [4-(η5-Cyclopentadienyl)-4,6,6-trimethyl-(η5-4,5-tetrahydropentalen)]- dichlorozirconium1,4-butanediylbis (2-methyl-indenyl) zirconium dichloride [4- (η 5 -cyclopentadienyl) -4,6,6-trimethyl- (η 5 -4,5-tetrahydropentalen)] - dichlorozirconium
[4-(η5-3'-Trimethylsilyi-cyclopentadienyl)-4,6,6-trimethyl-(η5-4I5-tetrahydropentalen)]- dichlorozirconium[4- (η 5 -3 ' -trimethylsilyi-cyclopentadienyl) -4,6,6-trimethyl- (η 5 -4 I 5-tetrahydropentalen)] - dichlorozirconium
[4-(η5-3'-lsopropyl-cyclopentadienyl)-4,6,6-trimethyl-(η5-4,5-tetrahydropentalen)]- dichlorozirconium[4- (η 5 -3 ' -isopropyl-cyclopentadienyl) -4,6,6-trimethyl- (η 5 -4,5-tetrahydropentalen)] - dichlorozirconium
[4-(η5-Cyclopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)]-dichlorotitan[4- (η 5 -cyclopentadienyl) -4,7,7-trimethyl- (η 5 -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
[4-(η5-Cyciopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)]- dichlorozirkonium[4- (η 5 -cyciopentadienyl) -4,7,7-trimethyl- (η 5 -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
[4-(η5-Cyclopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)]- dichlorohafnium[4- (η 5 -cyclopentadienyl) -4,7,7-trimethyl- (η 5 -4,5,6,7-tetrahydroindenyl)] - dichlorohafnium
[4-(η5-3'-tert.Butyl-cyclopentadienyl)-4,7,7-trimethyi-(η5-4,5,6,7-tetrahydroindenyl)]- dichlorotitan[4- (η 5 -3'-tert-butyl-cyclopentadienyl) -4,7,7-trimethyi- (η 5 -4,5,6,7-tetrahydroindenyl)] - dichlorotitanium
4-(η5-3'-lsopropylcyclopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)]- dichlorotitan4- (η 5 -3'-isopropylcyclopentadienyl) -4,7,7-trimethyl- (η 5 -4,5,6,7-tetrahydroindenyl)] - dichlorotitanium
4-(η5-3'-Methylcyclopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)]- dichlorotitan 4-(η5-3'-Trimethylsilyl-cyclopentadienyl)-2-trimethylsilyi-4,7,7-trimethyl-(η5-4, 5,6,7- tetrahydroindenyl)]-dichlorotitan4- (η 5 -3'-methylcyclopentadienyl) -4,7,7-trimethyl- (η 5 -4,5,6,7-tetrahydroindenyl)] - dichlorotitanium 4- (η 5 -3'-trimethylsilyl-cyclopentadienyl) -2-trimethylsilyi-4,7,7-trimethyl- (η 5 -4, 5,6,7-tetrahydroindenyl)] - dichlorotitan
4-(η5-3'-tert.Butyi-cyclopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)]- dichlorozirkonium4- (η 5 -3'-tert-buti-cyclopentadienyl) -4,7,7-trimethyl- (η 5 -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
(Tertbutylamido)-(tetramethyl-η5-cyclopentadienyl)-dimethylsilyl-dichlorotitan (Tertbutylamido)-(tetramethyl-η5-cyclopentadienyl)-1 ,2-ethandiyl-dichlorotitan- dichlorotitan(Tertbutylamido) - (tetramethyl-η 5 -cyclopentadienyl) -dimethylsilyl-dichlorotitan (Tertbutylamido) - (tetramethyl-η 5 -cyclopentadienyl) -1, 2-ethanediyl-dichlorotitan-dichlorotitan
(Methylamido)-(tetramethyl-η5-cyclopentadienyl)-dimethylsiiyl-dichlorotitan(Methylamido) - (tetramethyl-η 5 -cyclopentadienyl) -dimethylsiiyl-dichlorotitan
(Methylamido)-(tetramethyl-η5-cyclopentadienyl)-1 ,2-ethandiyl-dichlorotitan(Methylamido) - (tetramethyl-η 5 -cyclopentadienyl) -1, 2-ethanediyl dichlorotitanium
(Tertbutylamido)-(2,4-dimethyl-2,4-pentadien-1-yl)-dimethylsilyl-dichlorotitan Bis-(cyclopentadienyl)-zirkoniumdichlorid(Tertbutylamido) - (2,4-dimethyl-2,4-pentadien-1-yl) dimethylsilyl dichlorotitanium bis (cyclopentadienyl) zirconium dichloride
Bis-(n-butylcyclopentadienyl)-zirkoniumdichloridBis (n-butylcyclopentadienyl) zirconium dichloride
Bis-(1 ,3-dimethylcyclopentadienyl)-zirkoniumdichloridBis- (1,3-dimethylcyclopentadienyl) zirconium dichloride
Tetrachioro-[1-[bis(η5- H-inden-1-yliden)methylsilyl]-3-η5-cyclopenta-2,4-dien-1- yliden)-3-η5-9H-fiuoren-9-yiiden)butan]di-zirkonium Tetrachloro-[2-[bis(η5-2-methyl-1 H-inden-1 -yliden)methoxysilyl]-5-(η5-2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yliden)-5-(η5-9H-fluoren-9-yliden)hexan]di- zirkoniumTetrachioro- [1- [bis (η 5 - H-inden-1-ylidene) methylsilyl] -3-η 5 -cyclopenta-2,4-dien-1-ylidene) -3-η 5 -9H-fiuoren-9 -yiidene) butane] di-zirconium tetrachloro- [2- [bis (η 5 -2-methyl-1H-inden-1-ylidene) methoxysilyl] -5- (η 5 -2,3,4,5-tetramethylcyclopenta -2,4-dien-1-ylidene) -5- (η 5 -9H-fluorene-9-ylidene) hexane] dizirconium
Tetrachloro-[1-[bis(η5-1 H-inden-1-yliden)methylsilyl]-6-(η5-cyclopenta-2,4-dien-1- yliden)-6-(η5-9H-fluoren-9-yliden)-3-oxaheptan]di-zirkonium Dimethylsilandiylbis(2-methyl-4-(tert-butyl-phenyl-indenyl)-zirkoniumdichloridTetrachloro- [1- [bis (η 5 -1 H-inden-1-ylidene) methylsilyl] -6- (η 5 -cyclopenta-2,4-dien-1-ylidene) -6- (η 5 -9H- fluoren-9-ylidene) -3-oxaheptane] di-zirconium dimethylsilanediylbis (2-methyl-4- (tert-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiylbis(2-methyl-4-(4-methyl-phenyl-indenyl)zirkoniumdichloridDimethylsilanediylbis (2-methyl-4- (4-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiylbis(2-methyl-4-(4-ethyl-phenyi-indenyl)zirkoniumdichlorid Dimethyls iandiylb 2-methyl-4-(4-trifiuormethyl-phenyl-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4-methoxy-phenyl-indenyl)zirkoniumdichlorid Dimethyls Iandiylb 2-ethyl-4-(4-tert-butyl-phenyl-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4-methyl-phenyl-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4-ethyl-phenyl-indenyl)zirkoniumdichlorid Dimethyls iandiylb 2-ethyl-4-(4-trifluormethyl-phenyl-indenyi)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4-methoxy-phenyl-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4-tert-butyl-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-methyl-4-(4-methyl-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-methyl-4-(4-ethyl-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-methyl-4-(4-trifluormethyl-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-methyl-4-(4-methoxy-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-ethyl-4-(4-tert-butyl-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-ethyl-4-(4-methyi-phenyl-indenyl)zirkoniumdimethyl Dimethyls landiylb 2-ethyl-4-(4-ethyl-phenyl-indenyl)zirkoniumdiethyl Dimethyls iandiylb 2-ethyl-4-(4-trifluormethyl-phenyl-indenyl)zirkoniumdimethyl Dimethyls iandiylb 2-ethyl-4-(4-methoxy-phenyl-indenyl)zirkoniumdimethyl Dimethyls iandiylb 2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)hafnuimdichlorid Dimethyls landiylb 2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)titandichlorid Dimethyls landiylb 2-methyl-4-(4'-methyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4'-n-propyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4'-n-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4'-hexyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-methyl-4-(4'-sec-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4'-methyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4'-ethyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4'-n-propyl-phenyi)-indenyl)zirkoniumdichlorid Dimethyls iandiylb 2-ethyl-4-(4'-n-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls iandiylb 2-ethyl-4-(4'-hexyi-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb 2-ethyl-4-(4'-pentyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-ethyl-4-(4'-cyclohexyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls iandiylb s(2-ethyl-4-(4'-sec-butyl-phenyi)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls iandiylb s(2-n-propyl-4-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-propyl-4-(4'-methyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-propyl-4-(4'-ethyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-propyl-4-(4'-iso-propyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-propyl-4-(4'-n-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-propyl-4-(4'-hexyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls iandiylb s(2-n-propyl-4-(4'-cyclohexyl-phenyl)-indenyl)zirkoniumdichiorid Dimethyls landiylb s(2-n-propyl-4-(4'-sec-butyl-phenyl)-indenyi)zirkoniumdichlorid Dimethyls landiylb s(2-n-propyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-methyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-ethyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-n-propyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-iso-propyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-n-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-hexyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-cyclohexyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-sec-butyl-phenyi)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-n-butyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-methyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-ethyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-n-propyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-iso-propyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls iandiylb s(2-hexyl-4-(4'-n-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-hexyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-cyclohexyl-phenyl)-indenyl)zirkoniumdichiorid Dimethyls landiylb s(2-hexyl-4-(4'-sec-butyl-phenyl)-indenyl)zirkoniumdichlorid Dimethyls landiylb s(2-hexyl-4-(4'-tert.-butyi-phenyl)-indenyl)zirkoniumdichlorid Dimethylsilandiylbis(2-methyl-4-(4'-tert.-butyl-phenyl)- indenyl)zirkoniumbis(dimethylamid)Dimethylsilanediylbis (2-methyl-4- (4-ethylphenyi indenyl) zirconium dichloride Dimethyls iandiylb 2-methyl-4- (4-trifluoromethyl-phenyl-indenyl) zirconium dichloride Dimethyls landiylb 2-methyl-4- (4-methoxy-phenyl-indenyl) zirconium dichloride Dimethyls iandiylb 2-ethyl-4- (4-tert-butyl -phenyl-indenyl) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4-methyl-phenyl-indenyl) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4-ethyl-phenyl-indenyl) zirconium dichloride Dimethyls iandiylb 2-ethyl-4- (4-trifluoromethyl-phenyl-indenyi) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4-methoxy-phenyl-indenyl) zirconium dichloride Dimethyls landiylb 2-methyl-4- (4-tert-butyl-phenyl-indenyl) zirconiumdimethyl Dimethyls landiylb 2-methyl-4- (4-methyl-phenyl-indenyl) zirconium dimethyl dimethyls landiylb 2-methyl-4- (4-ethyl-phenyl-indenyl) zirconium dimethyl dimethyls landiylb 2-methyl-4- (4-trifluoromethyl-phenyl-indenyl ) zirconium dimethyl dimethyls landiylb 2-methyl-4- (4-methoxy-phenyl-indenyl) zirconium dimethyl dimethyls landiylb 2-ethyl-4- (4-tert-butyl-phenyl-indenyl) zirconium dimethyl dimethyls lan diylb 2-ethyl-4- (4-methylphenyl-indenyl) zirconium dimethyl dimethyls landiylb 2-ethyl-4- (4-ethylphenyl-indenyl) zirconium diethyl dimethyls iandiylb 2-ethyl-4- (4-trifluoromethyl-phenyl- indenyl) zirconium dimethyl dimethylsandiylb 2-ethyl-4- (4-methoxyphenyl-indenyl) zirconiumdimethyl dimethyls iandiylb 2-methyl-4- (4 ' -tert.-butylphenyl) -indenyl) zirconium dichloride dimethyls landiylb 2-methyl- 4- (4 '-tert-butyl-phenyl) -indenyl) hafnuimdichlorid Dimethyls landiylb 2-methyl-4- (4' -tert-butyl-phenyl) indenyl) titanium dichloride Dimethyls landiylb 2-methyl-4- (4 ' -methyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb 2-methyl-4- (4 ' -n-propyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb 2-methyl-4- (4 ' -n-butyl-phenyl) -indenyl) zirconium Dimethyls landiylb 2-methyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb 2-methyl-4- (4 '-sec-butyl-phenyl) indenyl) zirconium dichloride 2- Dimethyls landiylb ethyl-4-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4 '-methyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4' -ethyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4 '- n-propyl-phenyi) -indenyl) zirconium dichloride Dimethyls iandiylb 2-ethyl-4- (4 ' -n-butyl-phenyl) -indenyl) zirconium dichloride Dimethyls iandiylb 2-ethyl-4- (4 ' -hexyi-phenyl) -indenyl ) zirconium dichloride Dimethyls landiylb 2-ethyl-4- (4 ' -pentyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-ethyl-4- (4 ' -cyclohexyl-phenyl) -indenyl) zirconium dichloride Dimethyls iandiylb s (2-ethyl-4- (4 ' -sec-butyl-phenyi) -indenyl) zirconium dichloride Dimethyls landiylb s ( 2-ethyl-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride Dimethyls iandiylb s (2-n-propyl-4-phenyl) indenyl) zirconium dichloride Dimethyls landiylb s (2-n-propyl-4 - (4 '-methyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-propyl-4- (4' -ethyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-propyl-4- ( 4 '-iso-propyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-propyl-4- (4' -n-butyl-phenyl) indenyl) zirconium dichloride Dimethyls landiylb s (2-n-propyl-4 - (4 "-hexyl-phenyl) -indenyl) zirconium dichloride Dimethyls iandiylb s (2-n-propyl-4- (4 '-cyclohexyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-propyl-4- ( 4 '-sec-butyl-phenyl) -indenyi) zirconium Dimethyls landiylb s (2-n-propyl-4- (4' -tert-butyl-phenyl) indenyl) zirconium dichloride Dimethyls l andiylb s (2-n-butyl-4-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl-4- (4 ' -methyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl -4- (4 '-ethyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl-4- (4' -n-propyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl -4- (4 '-iso-propyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl-4- (4' -n-butyl-phenyl) indenyl) zirconium dichloride Dimethyls landiylb s (n-2 butyl-4- (4 '-hexyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl-4- (4' -cyclohexyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl -4- (4 '-sec-butyl-phenyl) indenyl) zirconium dichloride Dimethyls landiylb s (2-n-butyl-4- (4' -tert-butyl-phenyl) indenyl) zirconium dichloride Dimethyls landiylb s (2- hexyl-4-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-hexyl-4- (4 ' -methyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-hexyl-4- (4 ' -ethyl-phenyl) -i ndenyl) zirconium dichloride Dimethyls landiylb s (2-hexyl-4- (4 ' -n-propylphenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-hexyl-4- (4 ' -iso-propyl-phenyl) -indenyl) zirconium dichloride Dimethyls iandiylb s (2-hexyl-4- (4 '-n-butyl-phenyl) indenyl) zirconium dichloride Dimethyls landiylb s (2-hexyl-4- (4'-hexyl-phenyl) -indenyl) zirconium s Dimethyls landiylb (2-hexyl-4- (4 ' -cyclohexyl-phenyl) -indenyl) zirconium dichioride Dimethyls landiylb s (2-hexyl-4- (4 ' -sec-butyl-phenyl) -indenyl) zirconium dichloride Dimethyls landiylb s (2-hexyl -4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4- (4 '-tert-butyl-phenyl) - indenyl) zirconiumbis (dimethylamide)
Dimethylsilandiylbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdibenzyl Dimethylsilandiylbis(2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdimethyl Dimethylgermandiylbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyi)zirkoniumdichloridDimethylsilanediylbis (2-ethyl-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dibenzyl dimethylsilanediylbis (2-methyl-4- (4' -tert-butyl-phenyl) indenyl) zirconium dimethylgermandiylbis (2- ethyl-4- (4 '-tert-butyl-phenyl) -indenyi) zirconium dichloride
Dimethyigermandiylbis(2-ethyl-4-(4'-tert.-butyi-phenyl)-indenyl)hafniumdichlorid Dimethylgermandiylbis(2-propyl-4-(4'-tert.-butyi-phenyl)-indenyl)titandichlorid Dimethylgermandiylbis(2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Ethylidenbis(2-ethyl-4-phenyl)-indenyi)zirkoniumdichlorid Ethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichloridDimethyigermandiylbis (2-ethyl-4- (4 '-tert-butyl-phenyl) indenyl) hafnium dichloride dimethylgermandiylbis (2-propyl-4- (4' -tert-butyl-phenyl) indenyl) titanium dichloride dimethylgermandiylbis (2- methyl-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride ethylidenebis (2-ethyl-4-phenyl) -indenyi) zirconium dichloride ethylidenebis (2-ethyl-4- (4' -tert-butyl phenyl) -indenyl) zirconium dichloride
Ethylidenbis(2-n-propyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichiorid Ethyiidenbis(2-n-butyl-4-(4'-tert.-butyl-phenyl)-indenyl)titandichlorid Ethylidenbis(2-hexyi-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdibenzyl Ethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)hafniumdibenzyl Ethyiidenbis(2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)titandibenzylEthylidenebis (2-n-propyl-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride Ethyiidenbis (2-n-butyl-4- (4' -tert-butyl-phenyl) indenyl) titanium dichloride ethylidenebis (2-hexyi-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dibenzyl ethylidenebis- (2-ethyl-4- (4' -tert-butyl-phenyl) -indenyl) hafniumdibenzyl Ethyiidenbis (2- methyl-4- (4 '-tert-butyl-phenyl) indenyl) titanium dibenzyl
Ethylidenbis(2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Ethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)hafniumdimethyl Ethylidenbis(2-n-propyl-4-phenyl)-indenyl)titandimethyl Ethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumbis(dimethylamid) Ethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)hafniumbis(dimethylamid)Ethylidenebis (2-methyl-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) hafnium dimethyl ethylidenebis- (2- n-propyl-4-phenyl) -indenyl) titanium dimethyl ethylidenebis (2-ethyl-4- (4 ' -tert.-butyl-phenyl) -indenyl) zirconium bis (dimethylamide) ethylidenebis (2-ethyl-4- (4 ' - tert-butyl-phenyl) -indenyl) hafnium bis (dimethylamide)
Ethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)titanbis(dimethylamid) Methylethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Methylethylidenbis(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)hafniumdichlorid Phenylphosphandiyl(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl)zirkoniumdichlorid Phenylphosphandiyl(2-methyl-4-(4'-tert.-butyl-phenyl)-indenyl) zirkoniumdichloridEthylidenebis (2-ethyl-4- (4 '-tert-butyl-phenyl) indenyl) titanium bis (dimethylamide) Methylethylidenbis (2-ethyl-4- (4' -tert-butyl-phenyl) indenyl) zirconium dichloride Methylethylidenbis (2-ethyl-4- (4 '-tert-butyl-phenyl) indenyl) hafnium dichloride Phenylphosphandiyl (2-ethyl-4- (4' -tert-butyl-phenyl) indenyl) zirconium dichloride Phenylphosphandiyl (2-methyl -4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride
Phenylphosphandiyl(2-ethyl-4-(4'-tert.-butyl-phenyl)-indenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-methylphenyl-indenyl) zirkoniumdichloridPhenylphosphandiyl (2-ethyl-4- (4 '-tert-butyl-phenyl) indenyl) zirconium dichloride Dimethyisilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4' -methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-azapentalene) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4 '-methyiphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-methyiphenyl- indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4 '-methyiphenyl- indenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyi-N-phenyl-6-azapentalen)(2-methyl-4-(4 '-methyiphenyl- indenyl) zirkoniumdichloridDimethylsiandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -methyliphenyl-indenyl) zirconium dichloride Dimethyisilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4 - (4 '-methyiphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4 '-methyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-methyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - methylphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyi-4-thiapentalen)(2-methyl-4-(4'-methylphenyl- indenyl)zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyi-4-thiapentalen) (2-methyl-4- ( 4 '-methylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-methylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-methyiphenyl- indenyl)zirkoniumdichloridDimethyisilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4 '-methyiphenyl- indenyl) zirconium dichloride
Dimethylsilandiyi(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-methyiphenyl-indenyl) zirkoniumdichloridDimethylsilandiyi (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-methyiphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyi(2,5-dimethyi-6-thiapentalen)(2-methyi-4-(4 '-methyiphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-methylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyi (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-methyiphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -methylphenyl - indenyl) zirconium dichloride
Dimethyisilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-methylphenyl- indenyl)zirkoniumdichloridDimethyisilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirconium dichloride
Dimethyisiiandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-methylphenyl- indenyl)zirkoniumdichloridDimethyisiiandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyi-4-oxapentalen)(2-methyl-4-(4 '-methyiphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-methyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-methyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-methyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) ) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-ethyiphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -ethyiphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'-ethylphenyl- indenyl) zirkoniumdichloridDimethyisilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 '-ethylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-ethylphenyi- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-ethylphenyi-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -ethylphenyi- indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- ( 4 '-ethylphenyi-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentaien)(2-methyl-4-(4'-ethylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentaien) (2-methyl-4- (4 '-ethylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-ethylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-ethylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-ethyiphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-ethylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4 '-ethyiphenyl- indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4- (4' -ethylphenyl- indenyl ) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-ethylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyi-4-(4'-ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-ethylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyi-5-oxapentalen)(2-methyl-4-(4'-ethylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyi(2-methyl-6-oxapentalen)(2-methyi-4-(4'-ethyiphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyi-5-oxapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride Dimethylsilandiyi (2-methyl-6-oxapentalen) (2-methyi-4- (4 ' -ethyiphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4'-ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-n-propylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentaien)(2-methyl-4-(4 '-n-propylphenyl-indenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4 '-n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentaien) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride Dimethyisilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n -propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4 '-n-propylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-propylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'-n-propyiphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 '-n-propyiphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4 '-n-propylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-n-propylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4 '-n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- ( 4 '-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-n- propylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-n- propyiphenyi-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-n propyiphenyi-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-n-propyiphenyl- indenyi)zirkoniumdichlorid Dimethyisilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-n-propylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4 '-n-propyiphenyl- indenyi) zirconium dichloride Dimethyisilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4 '-n-propylphenyl indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-n-propylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-n-propylphenyl-indenyl) zirkoniumdichloridDimethylsiandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4 '-n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-n-propylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyi-5-oxapentalen)(2-methyl-4-(4'-n-propylphenyl- indenyl)zirkoniumdichioridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-n-propylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-n-propylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-n-propyIphenyl-inderiyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -n-propyIphenyl-inderiyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-oxapentaien)(2-methyl-4-(4 '-n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentaien) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-isopropyiphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -isopropyiphenyl-indenyl) zirconium dichloride
Dimethyisiiandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'-isopropyiphenyl- indenyl) zirkoniumdichloridDimethyisiiandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -isopropyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentaien)(2-methyl-4-(4'-isopropylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentaien) (2-methyl-4- (4 '-isopropylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyi(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl) zirkoniumdichloridDimethylsilandiyi (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyi-4-azapentalen)(2-methyl-4-(4'- isopropylphenyi-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- isopropyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyi-4-azapentalen) (2-methyl-4- (4 ' - isopropylphenyi-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2 -methyl-4- (4 ' - isopropyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyi)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyi) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyi)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyi) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyi-6-thiapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyi-6-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyi-5-oxapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl)zirkoniumdichioridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichioride
Dimethylsiiandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-isopropyiphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4'-isopropylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -isopropyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalene) (2-methyl-4- (4 '-n-butyl-phenyl-indenyl) zirconium dichloride
Dimethyisiiandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4 '-n-butylphenyl- indenyl) zirkoniumdichloridDimethyisiiandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4 '-n-butyl-phenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-butylphenyl indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4 '-n-butylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4 '-n-butylphenyl- indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl -4- (4 '-n-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4 '-n-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4'-n-butylphenyi-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-n-butylphenyi-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-n- butyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-butyiphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-n- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-n-butylphenyl- indenyl)zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2-methyl-4-thiapentalen) (2-methyl-4 - (4 ' -n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-n-butylphenyi- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-butylphenyi- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-n-butylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4- (4 '-n-butylphenyl indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-n-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4 '-n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-n-butylphenyi- indenyl)zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-butylphenyi- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-n-butylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-n-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-n-butylphenyl- indenyl)zirkoniumdichioridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirconium dichioride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-n-butyiphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-n-butyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-n-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methy!-4-azapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl! -4-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' - s-butylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentaien)(2-methyl-4-(4'-s-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentaien) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'-s-butylphenyl- indenyi) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyi) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-s-butylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4 - (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-s- butylphenyi-indenyl) zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -s-butylphenyi-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-s- butylphenyi-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -s-butylphenyi-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyi-4-(4'-s-butylphenyl- indenyl)zirkoniumdichlorid Dimethylsiiandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-s-butylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyi-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -s -butylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-s-butylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4'-s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-s-butylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyi(2-methyl-5-oxapentalen)(2-methyl-4-(4'-s-butylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-s-butylphenyi- indenyl)zirkoniumdichloridDimethylsilanediyi (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -s -butylphenyi- indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4 '-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' t-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' t-ter -butylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -ter-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- ( 4 '-tert-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-N-phenyl-6-azapentaien)(2-methyl-4-(4'-tert- butyiphenyl-indenyl) zirkoniumdichioridDimethyisilandiyl (2,5-dimethyl-N-phenyl-6-azapentaien) (2-methyl-4- (4 '-tert-butyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-thiapentaien)(2-methyl-4-(4'-tert-butyiphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' t-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentaien) (2-methyl-4- (4 '-tert-butyiphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' t-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' tert-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyi)zirkoniumdichloridDimethylsiiandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyi) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyi)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-tert-butylphenyl indenyi) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' tert-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methy!-4-(4'-n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalene) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyi-N-phenyl-4-azapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( 4 '-n-pentylphenyl indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyi-4-(4'-n-pentylphenyl- indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 '-n-pentylphenyl indenyl) zirconium dichloride
Dimethyisilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl) zirkoniumdichloridDimethyisilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-n-pentylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentaien)(2-methyl-4-(4'-n-pentyiphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4 '-n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentaien) (2-methyl-4- (4 '-n-pentyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-n- pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'-n- pentylphenyl-indenyl) zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentaien)(2-methyl-4-(4'-n-pentylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentaien) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4 '-n-pentylphenyl-indehyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- ( 4 '-n-pentylphenyl-indehyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-n-pentylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4 '-n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-oxapentaien)(2-methyl-4-(4'-n-pentyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-oxapentaien) (2-methyl-4- ( 4 '-n-pentyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-n-hexyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-6-azapentaien)(2-methyl-4-(4'-n-hexyiphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4 '-n-hexylphenyl- indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-6-azapentaien) (2-methyl-4- (4 ' -n-hexyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4 '-n-hexylphenyl- indenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4 '-n-hexylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride Dimethyisilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl -4- (4 '-n-hexylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-n-hexyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4 '-n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'-n- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentaien)(2-methyi-4-(4'-n- hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-thiapentaien)(2-methyl-4-(4'-n-hexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentaien) (2-methyi-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentaien) (2-methyl-4 - (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentaien)(2-methyl-4-(4'-n-hexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentaien) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-n-hexyiphenyl- indenyl)zirkoniumdichioridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-hexyiphenyl-indenyl) zirconium dichioride
Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'-n-hexyiphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-n-hexyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4 '-n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-n-hexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride Dimethyisilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-n-hexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-n-hexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-n-hexyiphenyi-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -n-hexyiphenyi-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4 '-cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4 '-cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl ) zirconium dichloride
Dimethylsiiandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4 '-cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsiandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyi-5-azapentalen)(2-methyl-4-(4'- cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyi-5-azapentalen) (2-methyl-4- (4 ' - cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-cyclohexylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- ( 4 '-cyclohexylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyi-4-(4 '-cyclohexylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-cyclohexylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyi(2-methyl-5-thiapentalen)(2-methyl-4-(4 '-cyclohexylphenyl- indenyl )zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilandiyi (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyi-4-(4'-cyclohexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'-cyclohexyiphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -cyclohexyiphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyi(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4'-cyciohexyiphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-cyclohexyiphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyi (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -cyciohexyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -cyclohexyiphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-cyclohexyiphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-cyclohexylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -cyclohexyiphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentaien)(2-methyi-4-(4 '-cyclohexylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentaien) (2-methyi-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyi-6-oxapentalen)(2-methyl-4-(4'-cyclohexylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyi-6-oxapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4'-trimethylsilylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4'-trimethylsiiylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4'-trimethylsilylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -trimethylsiiylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl ) zirconium dichloride
Dimethylsiiandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethyisiiandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'- trimethyisilylphenyl-indenyl) zirkoniumdichloridDimethyisiiandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' - trimethyisilylphenyl-indenyl) zirconium dichloride
Dimethyisiiandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethyisiiandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'-trimethylsilylphenyl- indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4 '-trimethyisilylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' trimethylsilylphenyl indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- trimethyisilylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - trimethyisilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-trimethylsilylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-trimethylsiiylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -trimethylsiiylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyi-4-(4'-trimethylsilylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-trimethyisilylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4- (4 '-trimethylsilylphenyl- indenyl) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4' -trimethyisilylphenyl - indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-thiapentaien)(2-methyl-4-(4 '-trimethyisilylphenyl- indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2-methyl-4-oxapentaien)(2-methyl-4-(4'-trimethylsilylphenyl- indenyi)zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentaien) (2-methyl-4- (4 '-trimethyisilylphenyl- indenyl) zirconium dichloride Dimethylsiiandiyl (2-methyl-4-oxapentaien) (2-methyl-4- (4' -trimethylsilylphenyl - indenyi) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'-trimethylsilylphenyi- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyi- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-trimethylsilylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4 '-trimethyisilylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -trimethyisilylphenyl - indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-trimethyisilylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-azapentalen)(2-methyl-4-(4 '-adamantylphenyi-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -trimethyisilylphenyl-indenyl) zirconium dichloride Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -adamantylphenyi -indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4-(4 '-adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4-(4 '-adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- adamantylphenyi-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'- adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - adamantylphenyi-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' - adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - adamantylphenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4 '-adamantylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-(4 '-adamantylphenyl- indenyl) zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4 '-adamantylphenyi- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- adamantylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4 ' -adamantylphenyidenidenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4 - (4 ' - adamantylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'-adamantylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - adamantylphenyl-indenyl) zirconium dichloride Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- ( 4 '-adamantylphenyl- indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-adamantylphenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyi(2-methyl-6-thiapentalen)(2-methyl-4-(4'-adamantylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-adamantylphenyl- indenyl) zirkoniumdichloridDimethylsilandiyi (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl - indenyl) zirconium dichloride
DimethylsiIandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4 '-adamantylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'-adamantylphenyl- indenyl)zirkoniumdichloridDimethylsilandiyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl - indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyi-5-oxapentalen)(2-methyl-4-(4'-adamantylphenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-(4'-adamaπtylphenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4 '-adamantylphenyl- indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -adamptylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl - indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-adamantylphenyi- indenyl) zirkoniumdichlorid Dimethyisiiandiyl(2-methyl-4-azapentaien)(2-methyi-4-(4'- tris(trifluormethyi)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyi- indenyl) zirconium dichloride Dimethyisiiandiyl (2-methyl-4-azapentaien) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl indenyl) zirconium dichloride
Dimethylsiiandiyi(2-methyl-5-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-6-azapentaien)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyi (2-methyl-5-azapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentaien) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyi-4-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyi) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyi-4-azapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyi) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2 -methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentaien)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentaien) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethyisiiandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethyisiiandiyl (2,5-dimethyl-N-phenyl-6- -6 azapentalene) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methyiphenyi-indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methyiphenyi-indenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyi) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyi) zirconium dichloride Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4 - (4 ' - tris (trifluoromethyl) methylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-5-oxapentalen)(2-methyl-4-(4'- tris(trifluoιmethyl)methylphenyl-indenyl)zirkoniumdichloridDimethylsiiandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-oxapentaien)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl)zirkoniumdichlorid Dimethyisilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyi-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4'- tris(trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-4-azapentalen)(2-ethyl-4-(4 '-tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentaien) (2-methyl-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethyisilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyi-4- (4 ' - tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4 - (4 '- tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-azapentalene) (2-ethyl-4- (4' -tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5,6-di-hydro-4-azapentalen)(2-ethyl-4-(4 '-tert-butylphenyl- indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2-methyl-4-azapentalen)(2-ethyl-4-(4'-tert-butylphenyi- tetrahydroindenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5,6-di-hydro-4-azapentalene) (2-ethyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride Dimethylsiiandiyl (2-methyl-4-azapentalene) (2-ethyl -4- (4 '-tert-butylphenyi- tetrahydroindenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-5-azapentalen)(2-n-butyl-4-(4 '-tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-5-azapentalen) (2-n-butyl-4- (4 ' t-butylphenyl indenyl) zirconium dichloride
Ethyliden(2-methyl-6-azapentalen)(2-methyl-4-(4 '-tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyl-N-trimethylsilyl-4-azapentalen)(2-methyi-4-(4 '-tert- butylphenyl-indenyl) zirkoniumdichloridEthylidene (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -ter-butylphenyl-indenyl) zirconium dichloride dimethyisilanediyl (2-methyl-N-trimethylsilyl-4-azapentalen) (2-methyi-4- ( 4 '-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyi-N-tolyl-5-azapentalen)(2-n-propyl-4-(4 '-tert-butylphenyl- indenyl) zirkoniumdichlorid Dimethylgermyldiyl(2-methyl-N-phenyl-6-azapentaien)(2-methyl-4-(4'-tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-tolyl-5-azapentalene) (2-n-propyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride Dimethylgermyldiyl (2-methyl-N-phenyl-6-azapentaien) (2 methyl-4- (4 '-tert-butylphenyl-indenyl) zirconium dichloride
Methylethyliden(2,5-dimethyl-4-azapentalen)(2-methyl-4-(4 '-tert-butylphenyl-indenyl) zirkoniumdichloridMethyl ethylidene (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' t-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-di-iso-propyl-6-azapentalen)(2-methyl-4-(4 '-tert-butylphenyl- indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentaien)(2,6-dimethyl-4-(4 '-tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-di-iso-propyl-6-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentaien) (2,6-dimethyl-4- (4 ' t-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(6'-tert- butylnaphthyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4-(6'-tert- butylanthracenyi-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (6 ' -ter-butylnaphthyl-indenyl) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (6 '-tert butylanthracenyi-indenyl) zirconium dichloride
Dimethyisiiandiyl(2-methyl-4-phosphapentalen)(2-methyl-4-(4'-tert-butyiphenyl- indenyl)zirkoniumdichlorid Diphenylsilandiyl(2-methyl-5-thiapentalen)(2-methyl-4-(4'-tert-butyiphenyl- indenyi)zirkoniumdichloridDimethysisandiyl (2-methyl-4-phosphapentalen) (2-methyl-4- (4 ' t-butyiphenyl-indenyl) zirconium dichloride Diphenylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4- (4 '-tert-butyiphenyl- indenyi) zirconium dichloride
Methylphenylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyi)zirkoniumdichlorid Methyliden(2,5-dimethyl-4-thiapentalen)(2-methyl-4-(4 '-tert-butylphenyl-indenyl) zirkoniumdichloridMethylphenylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -ter-butylphenyl-indenyi) zirconium dichloride methylidene (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirconium dichloride
Dimethylmethyliden(2,5-dimethyl-6-thiapentalen)(2-methyl-4-(4 '-tert-butylphenyl- indenyl) zirkoniumdichlorid Diphenylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-(4'-tert-butylphenyl- indenyl) zirkoniumdichloridDimethylmethylidene (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirconium dichloride Diphenylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- ( 4 '-tert-butylphenyl indenyl) zirconium dichloride
Diphenylsilandiyl(2,5-dimethyl-6-oxapentalen)(2-methyl-4-(4 '-tert-butylphenyl- indenyl) zirkoniumdichloridDiphenylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-tert-butylphenyl indenyl) zirconium dichloride
DimethylsilandiyI(2-methyl-4-azapentalen)(2-methyiindenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methylindenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methy!-6-azapentalen)(2-methyiindenyl) zirkoniumdichloridDimethylsilandiyI (2-methyl-4-azapentalen) (2-methyiindenyl) zirconium dichloride Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methylindenyl) zirconium dichloride Dimethyisilandiyl (2-methy! -6-azapentalenium) (2-methyidichiindi)
Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methylindenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methylindenyl) zirkoniumdichlorid Dimethyisilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methylindenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methylindenyl) zirconium dichloride Dimethyisilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-4-azapentalen)(2-methylindenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-6-azapentalen)(2-methylindenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methylindenyl) zirkoniumdichloridDimethylsiiandiyl (2,5-dimethyl-4-azapentalen) (2-methylindenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-6-azapentalen) (2-methylindenyl) zirconium dichloride Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-) azapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methylindenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methylindenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-5-thiapentalen)(2-methylindenyl)zirkoniumdichlorid Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methylindenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methylindenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methylindenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) zirconium dichloride
Dimethylsiiandiyl(2,5-dimethyl-4-thiapentalen)(2-methylindenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methylindenyl) zirkoniumdichlorid Dimethylsilandiyl 2-methyl-4-oxapentalen)(2-methylindenyl)zirkoniumdichlorid Dimethylsilandiyl 2-methyl-5-oxapentalen)(2-methylindenyl)zirkoniumdichlorid Dimethylsilandiyl 2-methyl-6-oxapentalen)(2-methylindenyl)zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-4-oxapentalen)(2-methyiindenyl) zirkoniumdichlorid Dimethylsilandiyl 2, 5-dimethyl-6-oxapentalen)(2-methylindenyl) zirkoniumdichloridDimethylsiandiyl (2,5-dimethyl-4-thiapentalen) (2-methylindenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methylindenyl) zirconium dichloride Dimethylsilanediyl 2-methyl-4-oxapentalen) (2-methylindenyl) zirconium dichloride dimethylsilanediyl 2-methyl-5-oxapentalen) (2-methylindenyl) zirconium dichloride dimethylsilanediyl 2-methyl-6-oxapentalen) (2-methylindenyl) zirconium dichloride dimethyl-4-oxapentalen) (2-methyindenyl) zirconium dichloride dimethylsilanediyl 2, 5-dimethyl-6-oxapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilandiyl 2-methyl-4-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2-methyl-5-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2-methyl-6-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2-methyl-N-phenyl-4-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl' 2-methyl-N-phenyl-5-azapentalen)(indenyl) zirkoniumdichloridDimethylsilanediyl 2-methyl-4-azapentalen) (indenyl) zirconium dichloride dimethylsilanediyl 2-methyl-5-azapentalen) (indenyl) zirconium dichloride dimethylsilanediyl 2-methyl-6-azapentalen) (indenyl) zirconium dichloride phenyl-methyldilloride phenyl-methyldilloride azapentalen) (indenyl) zirconium dichloride dimethylsilanediyl '2-methyl-N-phenyl-5-azapentalen) (indenyl) zirconium dichloride
Dimethylsilandiyl 2-methyl-N-phenyl-6-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-4-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-6-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2, 5-dimethyl-N-phenyl-4-azapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-N-phenyl-6-azapentalen)(indenyl) zirkoniumdichloridDimethylsilanediyl 2-methyl-N-phenyl-6-azapentalen) (indenyl) zirconium dichloride dimethylsilanediyl 2,5-dimethyl-4-azapentalen) (indenyl) zirconium dichloride dimethylsilanediyl 2,5-dimethyl-6-azapentalen) (indenyl) zirconiumdichloride 5-dimethyl-N-phenyl-4-azapentalen) (indenyl) zirconium dichloride Dimethylsilanediyl 2,5-dimethyl-N-phenyl-6-azapentalen) (indenyl) zirconium dichloride
Dimethylsilandiyl 2-methyl-4-thiapentalen)(indenyl)zirkoniumdichlorid Dimethylsilandiyl 2-methyl-5-thiapentalen)(indenyl)zirkoniumdichlorid Dimethylsilandiyl 2-methyi-6-thiapentalen)(indenyl)zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-4-thiapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-6-thiapentalen)(indenyl) zirkoniumdichloridDimethylsilanediyl 2-methyl-4-thiapentalen) (indenyl) zirconium dichloride dimethylsilanediyl 2-methyl-5-thiapentalen) (indenyl) zirconium dichloride dimethylsilanediyl 2-methyi-6-thiapentalen) (indenyl) zirconiumdiimidalidium (indenyl) zirconium dichloride dimethylsilanediyl 2,5-dimethyl-6-thiapentalen) (indenyl) zirconium dichloride
Dimethylsilandiyl 2-methyl-4-oxapentalen)(indenyl)zirkoniumdichlorid Dimethylsilandiyl 2-methyl-5-oxapentalen)(indenyl)zirkoniumdichlorid Dimethylsilandiyl' 2-methyl-6-oxapentalen)(indenyl)zirkoniumdichlorid Dimethylsilandiyl 2, 5-dimethyl-4-oxapentalen)(indenyl) zirkoniumdichlorid Dimethylsilandiyl 2,5-dimethyl-6-oxapentalen)(indenyl) zirkoniumdichloridDimethylsilanediyl 2-methyl-4-oxapentalen) (indenyl) zirconium dichloride Dimethylsilanediyl 2-methyl-5-oxapentalen) (indenyl) zirconium dichloride Dimethylsilanediyl '2-methyl-6-oxapentalen) (indenyl) zirconium dichloro-dimethyldilloro-dimethyl-5-oxapentalen ) (indenyl) zirconium dichloride dimethylsilanediyl 2,5-dimethyl-6-oxapentalen) (indenyl) zirconium dichloride
Dimethylsilandiyl 2-methyl-4-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichlorid i Dimethylsilandiyl 2-methyl-5-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichlorid i Dimethylsilandiyl 2-methyl-6-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl 2-methyl-N-phenyl-4-azapentalen)(2-methyl-4-phenyi-indenyl) zirkoniumdichloridDimethylsilanediyl 2-methyl-4-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride i Dimethylsilanediyl 2-methyl-5-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride i Dimethylsilanediyl 2-methyl-6 -azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride dimethylsilanediyl 2-methyl-N-phenyl-4-azapentalen) (2-methyl-4-phenyi-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichlorid Dimethylsiiandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4-phenyi-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride Dimethylsiiandiyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4-phenyi-indenyl ) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyi-6-azapentaien)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyi-6-azapentaien) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4-phenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-thiapentaien)(2-methyl-4-phenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentaien) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-thiapentalen)(2-methyl-4-phenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-thiapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethyisilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4-phenyl- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-5-oxapentalen)(2-methyl-4-phenyl- indenyl)zirkoniumdichloridDimethylsiiandiyl (2-methyl-5-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethyisilandiyl(2-methyl-6-oxapentalen)(2-methyl-4-phenyl- indenyl)zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-oxapentaien)(2-methyl-4-phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentaien) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-4-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsiiandiyl (2-methyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-6-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-4-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2-methyl-N-phenyl-5-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4,5 -benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-N-phenyl-6-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-4-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-6-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyl-N-phenyl-4-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichlorid Dimethylsilandiyi(2,5-dimethyl-N-phenyl-6-azapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride Dimethylsilandiyi (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl -4,5-benzo-indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-thiapentalen)(2-methyl-4,5-benzo- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilandiyl(2-methyi-5-thiapentalen)(2-methyl-4,5-benzo- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilandiyi(2-methyl-6-thiapentalen)(2-methyl-4,5-benzo- indenyl)zirkoniumdichloridDimethylsilandiyi (2-methyl-6-thiapentalene) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilandiyl(2,5-dimethyi-4-thiapentaien)(2-methyi-4,5-benzo-indenyl) zirkoniumdichlorid Dimethylsilandiyl(2,5-dimethyl-6-thiapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyi-4-thiapentaene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4,5-benzo-indenyl) ) zirconium dichloride
Dimethylsilandiyl(2-methyl-4-oxapentalen)(2-methyl-4,5-benzo- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4,5-benzo indenyl) zirconium dichloride
Dimethylsilandiyl(2-methyl-5-oxapentalen)(2-methyl-4,5-benzo- indenyl)zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsiiandiyl(2-methyl-6-oxapentalen)(2-methyi-4,5-benzo- indenyl)zirkoniumdichioridDimethylsiandiyl (2-methyl-6-oxapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichioride
Dimethylsilandiyl(2,5-dimethyl-4-oxapentalen)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethyisiiandiyl(2,5-dimethyl-6-oxapentaien)(2-methyl-4,5-benzo-indenyl) zirkoniumdichloridDimethyisiiandiyl (2,5-dimethyl-6-oxapentaien) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethyls landiylbis(2-methyl-4-azapentalen)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-5-azapentalen) zirkoniumdichlorid Dimethyls landiylbis(2-methyl-6-azapentaien) zirkoniumdichlorid Dimethyls landiylbis(2-methyl-N-phenyl-4-azapentalen) zirkoniumdichlorid Dimethyls landiylbis(2-methyl-N-phenyl-5-azapentalen) zirkoniumdichlorid Dimethyls landiylbis(2-methyl-N-phenyl-6-azapentaien) zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyi-4-azapentalen) zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyi-6-azapentalen) zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyl-N-phenyl-4-azapentalen) zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyl-N-phenyl-6-azapentaien) zirkoniumdichlorid Dimethyls landiylbis(2-methyl-4-thiapentalen)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-5-thiapentalen)zirkoniumdichlorid Dimethyls iandiylbis(2-methyl-6-thiapentalen)zirkoniumdichlorid Dimethyls iandiylbis(2,5-dimethyl-4-thiapentalen) zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyl-6-thiapentaien) zirkoniumdichlorid Dimethyls landiylbis(2-methyl-4-oxapentalen)zirkoniumdichlorid Dimethyls landiyibis(2-methyl-5-oxapentalen)zirkoniumdichlorid Dimethyls landiylbis(2-methyl-6-oxapentalen)zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyl-4-oxapentalen)zirkoniumdichlorid Dimethyls landiylbis(2,5-dimethyl-6-oxapentalen)zirkoniumdichloridDimethyls landiylbis (2-methyl-4-azapentalen) zirconium dichloride Dimethyls landiylbis (2-methyl-5-azapentalen) zirconium dichloride Dimethyls landiylbis (2-methyl-6-azapentaien) zirconium dichloride Dimethyls landiylbis (2-methyl-azapentalen) ) zirconium dichloride Dimethyls landiylbis (2-methyl-N-phenyl-5-azapentalen) zirconium dichloride Dimethyls landiylbis (2-methyl-N-phenyl-6-azapentaien) zirconium dichloride Dimethyls landiylbis (2,5-dimethyi-4-azapentiumchloride) (2,5-dimethyl-6-azapentalen) zirconium dichloride Dimethyls landiylbis (2,5-dimethyl-N-phenyl-4-azapentalen) zirconium dichloride Dimethyls landiylbis (2,5-dimethyl-N-phenyl-6-azapentaien) zirconium dichloride Dimethyls landiylbis (2-methyl-4-thiapentalen) zirconium dichloride Dimethyls landiylbis (2-methyl-5-thiapentalen) zirconium dichloride Dimethyls iandiylbis (2-methyl-6-thiapentalen) zirconium dichloride Dimethyls iandiylbis (2,5-dimethyl-4-thiidium di-dichloride) (2,5-dimethyl-6-thi apentaia) zirconium dichloride Dimethyls landiylbis (2-methyl-4-oxapentalen) zirconium dichloride Dimethyls landiyibis (2-methyl-5-oxapentalen) zirconium dichloride Dimethyls landiylbis (2-methyl-6-oxapentalen) zirconiumdichethylid (2,5) oxapentalen) zirconium dichloride Dimethyls landiylbis (2,5-dimethyl-6-oxapentalene) zirconium dichloride
Des weiteren sind die Metallocene, bei denen das Zirkoniumfragment „-zirkoniumdichlorid,, die Bedeutungen Z rkonium •monochloro -mono-(2,4-di-tert.-butyl-phenolat)Furthermore, the metallocenes in which the zirconium fragment “zirconium dichloride” are the meanings Z rkonium • monochloro-mono- (2,4-di-tert-butyl-phenolate)
Zi rkonium -monochioro -mono-(2,6-di-tert.-butyl-phenolat) z rkonium -monochloro -mono-(3,5-di-tert.-butyl-phenolat)Zirconium monochloro mono- (2,6-di-tert-butyl-phenolate) z rconium -monochloro-mono- (3,5-di-tert-butyl-phenolate)
Zi rkonium -monochloro- -mono-(2,6-di-sec.-butyl-phenolat) Zi rkonium- -monochloro- -mono-(2,4-di-methylphenolat) z rkonium- •monochloro- -mono-(2,3-di-methylphenolat) z rkonium- •monochloro- -mono-(2,5-di-methylphenolat) z rkonium- -monochloro- mono-(2,6-di-methylphenolat)Zirconium monochloro-mono- (2,6-di-sec-butyl-phenolate) Zirconium -monochloro- -mono- (2,4-dimethylphenolate) z rkonium- • monochloro- -mono- ( 2,3-dimethylphenolate) z rkonium- • monochloro- mono- (2,5-dimethylphenolate) z rkonium- monochloro- mono- (2,6-dimethylphenolate)
Zi rkonium- -monochloro- •mono-(3,4-di-methylphenolat) z rkonium- -monochloro- mono-(3,5-di-methylphenolat) z rkonium- monochloro- monophenolat z rkonium- monochloro- mono-(2-methylphenolat) z rkonium- monochioro- •mono-(3-methylphenolat)Zirconium monochloro- • mono- (3,4-di-methylphenolate) z rkonium- monochloro- mono- (3,5-dimethylphenolate) z rkonium- monochloro- monophenolate z rkonium- monochloro- mono- (2nd -methylphenolate) z rkonium- monochioro- • mono- (3-methylphenolate)
Zi rkonium- monochioro- •mono-(4-methylphenolat) Zi rkonium- monochloro- •mono-(2-ethylphenolat) Zi rkonium- monochloro- •mono-(3-ethylphenolat) Zi rkonium- monochloro- •mono-(4-ethylphenolat) Zi rkonium- monochloro- mono-(2-sec.-butylphenolat) z rkonium- monochloro- •mono-(2-tert.-butylphenolat) z rkonium- monochloro- mono-(3-tert.-butylphenolat) z rkonium- monochloro- •mono-(4-sec.-butylphenolat)Zirconium monochloro- • mono- (4-methylphenolate) zirconium monochloro- • mono- (2-ethylphenolate) zirconium monochloro- • mono- (3-ethylphenolate) zirconium monochloro- • mono- (4- ethylphenolate) zirconium monochloro mono- (2-sec.-butylphenolate) z rkonium monochloro- • mono- (2-tert.-butylphenolate) z rkonium monochloro mono- (3-tert.-butylphenolate) z rkonium - monochloro- • mono- (4-sec.-butylphenolate)
Zi rkonium- •monochloro- •mono-(4-tert.-butylphenolat) Zi rkonium- monochloro- mono-(2-isopropyl-5-methylphenolat) Zi rkonium- monochloro- mono-(4-isopropyl-3-methyiphenolat) Zi rkonium- -monochloro- mono-(5-isopropyl-2-methylphenolat) z rkonium- •monochloro- •mono-(5-isopropyl-3-methylphenolat) z rkonium- •monochloro- •mono-(2,4-bis-(2-methyl-2-butyl)-phenolat) z rkonium- •monochloro- mono-(2,6-di-tert.-butyl-4-methyl-phenolat) z rkonium- •monochloro- •mono-(4-nonylphenolat) z: rkonium- •monochloro- •mono-(l-naphthoiat) z rkonium- •monochloro- mono-(2-naphtholat)Zirconium • monochloro- • mono- (4-tert-butylphenolate) zirconium monochloro- mono- (2-isopropyl-5-methylphenolate) zirconium monochloro-mono- (4-isopropyl-3-methyiphenolate) zi rkonium- -monochloro-mono- (5-isopropyl-2-methylphenolate) z rkonium- • monochloro- • mono- (5-isopropyl-3-methylphenolate) z rkonium- • monochloro- • mono- (2,4-bis- (2-methyl-2-butyl) phenolate) z rkonium- • monochloro-mono- (2,6-di-tert-butyl-4-methyl-phenolate) z rkonium- • monochloro- • mono- (4- nonylphenolate) z: rkonium- • monochloro- • mono- (l-naphthoiate) z rkonium- • monochloro- mono- (2-naphtholate)
Z: rkonium- •monochloro- mono-(2-phenylphenolat) Zirkonium-monochioro-mono-(tert. butoxid)Z: rkonium- • monochloro-mono- (2-phenylphenolate) Zirconium monochloro mono- (tert.butoxide)
Zirkonium-monochloro-mono-(N-methylanilid)Zirconium monochloro mono- (N-methylanilide)
Zirkonium-monochloro-mono-(2-tert.-butylanilid)Zirconium monochloro-mono- (2-tert-butylanilide)
Zirkonium-moπochloro-mono-(tert.-butylamid)Zirconium-monochloro-mono- (tert-butylamide)
Zirkonium-monochloro-mono-(di-iso.-propylamid)Zirconium monochloro-mono- (di-iso-propylamide)
Zirkonium-monochloro-mono-methylZirconium monochloro mono methyl
Zirkonium-monochloro-mono-benzylZirconium monochloro mono benzyl
Zirkonium-monochloro-mono-neopentyl, hat, Beispiele für die erfindungsgemäßenZirconium monochloro mono neopentyl, has examples of the invention
Metallocene.Metallocenes.
Weiterhin bevorzugt sind die entsprechenden Zirkondimethyl-Verbindungen, die entsprechenden Zirkon-η -Butadien-Verbindungen, sowie die entsprechenden Verbindungen mit 1 ,2-(1-methyl-ethandiyl)-, 1 ,2-(1 J-dimethyl-ethandiyl)- und 1 ,2(1 ,2-dimethyl-ethandiyl)-Brücke.Also preferred are the corresponding zirconium dimethyl compounds, the corresponding zirconium η-butadiene compounds, and the corresponding compounds with 1, 2- (1-methyl-ethanediyl) -, 1, 2- (1 J-dimethyl-ethanediyl) - and 1, 2 (1, 2-dimethyl-ethanediyl) bridge.
Das erfindungsgemäße Kataiysatorsystem kann zusätzlich noch eine Organometallverbindung der Formel (IV)The catalyst system according to the invention can additionally contain an organometallic compound of the formula (IV)
[M4R9 p]q (IV) worin M4 ein Element der I., II. und III. Hauptgruppe des Periodensystems der Elemente ist, vorzugsweise Lithium, Magnesium und Aluminium, insbesondere Aluminium, ist R9 gleich oder verschieden ein Wasserstoffatom, ein Halogenatom, eine CrC 0- kohlenstoffhaltige Gruppe wie eine C1-C20- Alkyl-, C6-C4o-Aryl-, C7-C4o-Aryl-alkyl oder C7-C o-Alkyl-aryl-Gruppe, bedeutet, p eine ganze Zahl von 1 bis 3 und q eine ganze Zahl von 1 bis 4 ist, enthalten.[M 4 R 9 p ] q (IV) where M 4 is an element of I., II. And III. Main group of the periodic table of the elements is, preferably lithium, magnesium and aluminum, in particular aluminum, R 9 is identical or different to a hydrogen atom, a halogen atom, a CrC 0 - carbon-containing group such as a C 1 -C 2 0 alkyl, C6-C 4 o-aryl, C 7 -C 4 o-aryl-alkyl or C 7 -C o-alkyl-aryl group, means p is an integer from 1 to 3 and q is an integer from 1 to 4, contain.
Bei den Organometallverbindungen der Formel (IV) handelt es sich ebenfalls um neutrale Lewissäuren Beispiele für die bevorzugten Organometall- Verbindungen der Formel (IV) sind Trimethylaluminium, Triethylaluminium, Triisopropylaluminium, Trihexylaluminium, Trioctylaluminium, Tri-n-butylaiuminium, Tri-n-propylaluminium, Triisoprenaluminium, Dimethylaluminiummonochiorid, Diethylaluminiummonochlorid, Diisobutylaluminiummonochlorid, Methylaluminiumsesquichiorid,The organometallic compounds of the formula (IV) are also neutral Lewis acids Examples of the preferred organometallic compounds of the formula (IV) are trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, trihexyl aluminum, trioctyl aluminum, tri-n-butylaium aluminum, tri-n-propyl aluminum, triisoprenaluminium, dimethylaluminium monochiorid, diethylaluminium aluminum chloride aluminum diethylaluminium aluminum chloride
Ethyiaiuminiumsesquichlorid, Dimethylaluminiumhydrid, Diethylaluminiumhydrid, Diisopropylaluminiumhydrid, Dimethyialuminium(trimethylsiioxid), Dimethylaluminium(triethylsiloxid), Phenylalan, Pentafluorphenylalan, o-Tolylaian.Ethyliumsium sesquichloride, dimethylaluminium hydride, diethylaluminium hydride, diisopropylaluminium hydride, dimethylaluminium (trimethylsiloxide), dimethylaluminium (triethylsiloxide), phenylalane, pentafluorophenylalane, o-tolylaian.
Das erfindungsgemäße Katalysatorsystem ist erhältlich durch Umsetzung einerThe catalyst system according to the invention can be obtained by reacting a
Lewis Base der Formel (I) und einer Organobor- oder Organoaluminiumverbindung, die aus Einheiten der Formel (II) aufgebaut ist, mit einem Träger. Anschließend erfolgt die Umsetzung mit einer Lösung oder Suspension aus einem oder mehreren Metallocenverbindungen der Formel (V) und optional einer oder mehrerer Organometallverbindungen der Formel (IV).Lewis base of the formula (I) and an organoboron or organoaluminum compound which is composed of units of the formula (II) with a support. The reaction is then carried out with a solution or suspension of one or more metallocene compounds of the formula (V) and optionally one or more organometallic compounds of the formula (IV).
Die Aktivierung des Katalysatorsystems kann dadurch wahlweise vor dem Einschleusen in den Reaktor vorgenommen werden oder aber erst im Reaktor durchgeführt werden. Ferner wird ein Verfahren zur Herstellung von Polyolefinen beschrieben. Die Zugabe einer weiteren chemischen Verbindung, die als Additiv vor der Polymerisation zudosiert wird, kann zusätzlich von Vorteil sein. Zur Herstellung des erfindungsgemäßen Katalysatorsystems wird das Trägermeterial in einem organischen Lösemittel suspendiert. Geeignete Lösemittel sind aromatische oder aliphatische Lösemittel, wie beispielsweise Hexan, Heptan, Toluol oder Xylol oder halogenierte Kohlenwasserstoffe, wie Methylenchlorid oder halogenierte aromatische Kohlenwasserstoffe wie o-Dichlorbenzol. Der Träger kann zuvor mit einer Verbindung der Formel (IV) vorbehandelt werden. Anschließend wird eine oder mehrere Verbindungen der Formel (I) zu dieser Suspension gegeben, wobei die Reaktionszeit zwischen 1 Minute und 48 Stunden liegen kann, bevorzugt ist eine Reaktionszeit zwischen 10 Minuten und 2 Stunden. Die Reaktionslösung kann isoliert und anschließend resuspendiert werden oder aber auch direkt mit einer cokatalytisch wirkenden Organoborverbindung, gemäß der Formel (II), umgesetzt werden. Die Reaktionszeit liegt dabei zwischen 1 Minute und 48 Stunden, wobei eine Reaktionszeit von zwischen 10 Minuten und 2 Stunden bevorzugt ist. Zur Herstellung des erfindungsgemäßen Katalysatorsystems kann eine oder mehrere Lewis-Basen der Formel (I) mit einer oder mehrerem cokatalytisch wirksamen Organoborverbindungen, gemäß der Formel (II), umgesetzt werden. Bevorzugt ist die Menge von 1 bis 4 Äquivalenten einer Lewis-Base der Formel (I) mit einem Äquivalent einer cokatalytisch wirksamen Verbindung. Besonders bevorzugt ist die Menge von einem Äquivalent einer Lewis-Base der Formel (I) mit einem Äquivalent einer cokatalytisch wirksamen Verbindung. Das Reaktionsprodukt dieser Umsetzung ist eine metalloceniumbiidende Verbindung, die kovalent an das Trägermaterial fixiert ist. Es wird nachfolgend als modifiziertes Trägermaterial bezeichnet. Die Reaktionslösung wird anschließend filtriert und mit einem der oben genannten Lösemittel gewaschen. Danach wird das modifizierte Trägermaterial im Hochvakuum getrocknet. Die Zugabe der einzelnen Komponenten kann aber auch in jeder anderen Reihenfolge durchgeführt werden.As a result, the activation of the catalyst system can be carried out either before it is introduced into the reactor or can only be carried out in the reactor. A process for the production of polyolefins is also described. The addition of a further chemical compound, which is added as an additive before the polymerization, can additionally be advantageous. To produce the catalyst system according to the invention, the carrier material is suspended in an organic solvent. Suitable solvents are aromatic or aliphatic solvents such as hexane, heptane, toluene or xylene or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene. The carrier can be pretreated beforehand with a compound of the formula (IV). Then one or more compounds of the formula (I) are added to this suspension, the reaction time being between 1 minute and 48 hours, a reaction time between 10 minutes and 2 hours being preferred. The reaction solution can be isolated and then resuspended, or it can also be reacted directly with a cocatalytically active organoboron compound according to formula (II) become. The reaction time is between 1 minute and 48 hours, a reaction time of between 10 minutes and 2 hours being preferred. To prepare the catalyst system according to the invention, one or more Lewis bases of the formula (I) can be reacted with one or more cocatalytically active organoboron compounds according to the formula (II). The amount of 1 to 4 equivalents of a Lewis base of the formula (I) with one equivalent of a cocatalytically active compound is preferred. The amount of one equivalent of a Lewis base of the formula (I) with one equivalent of a cocatalytically active compound is particularly preferred. The reaction product of this reaction is a metallocenium-forming compound that is covalently attached to the carrier material. It is referred to below as a modified carrier material. The reaction solution is then filtered and washed with one of the solvents mentioned above. The modified carrier material is then dried in a high vacuum. However, the individual components can also be added in any other order.
Das Aufbringen einer oder mehrerer Metallocenverbindungen vorzugsweise der Formel (V) und einer oder mehrerer Organometallverbindungen der Formel (IV) auf das modifizierte Trägermaterial geht vorzugsweise so vonstatten, daß eine oder mehrere Metallocenverbindungen der Formel (V) in einem oben beschriebenen Lösemittel gelöst bzw. suspendiert wird und anschließend eine oder mehrereThe application of one or more metallocene compounds, preferably of the formula (V) and one or more organometallic compounds of the formula (IV), to the modified support material is preferably such that one or more metallocene compounds of the formula (V) are dissolved or suspended in a solvent described above and then one or more
Verbindungen der Formel (IV), die vorzugsweise ebenfalls gelöst bzw. suspendiert ist, umgesetzt werden. Das stöchiometrische Verhältnis an Metallocenverbindung der Formel (V) und einer Organometailverbindung der Formel (IV) beträgt 100 : 1 bis 10"4 : 1. Vorzugsweise beträgt das Verhältnis 1 : 1 bis 10"2 : 1. Das modifizierte Trägermaterial kann entweder direkt im Polymerisationsreaktor oder in einemCompounds of formula (IV), which is preferably also dissolved or suspended, are reacted. The stoichiometric ratio of metallocene compound of the formula (V) and an organometallic compound of the formula (IV) is 100: 1 to 10 "4 : 1. The ratio is preferably 1: 1 to 10 " 2 : 1. The modified carrier material can either be directly in the Polymerization reactor or in one
Reaktionskolben in einem oben genannten Lösemittel vorgelegt werden. Anschließend erfolgt die Zugabe der Mischung aus einer Metallocenverbindung der Formel (V) und einer Organometailverbindung der Formel (IV). Optional kann aber auch eine oder mehrere Metallocenverbindungen der Formel (V) ohne vorherige Zugabe einer Organometailverbindung der Formel (IV) zu dem modifiziertenReaction flasks are placed in a solvent mentioned above. The mixture of a metallocene compound of the formula (V) and an organometallic compound of the formula (IV) is then added. Optionally, however, one or more metallocene compounds of the formula (V) can also be added to the modified one without prior addition of an organometallic compound of the formula (IV)
Trägermaterial gegeben werden. Die Menge an modifizierten Träger zu einer Metallocenverbindung der Formel (V) beträgt vorzugsweise 10g : 1 μmol bis 10"2g : 1 μmol. Das stöchiometrische Verhältnis an Metallocenverbindung der Formel (V) zu der cokatalytisch wirkenden chemischen Verbindung der Formel (II) beträgt 100 : 1 bis 10"4 : 1 , vorzugsweise 1 : 1 bis 10"2 : 1.Carrier material are given. The amount of modified carrier to a metallocene compound of formula (V) is preferably from 10g: 1 micromol to 10 "2 g. 1 .mu.mol The stoichiometric ratio of metallocene compound of formula (V) is to the cocatalytically active chemical compound of the formula (II) 100: 1 to 10 "4 : 1, preferably 1: 1 to 10 " 2 : 1.
Das geträgerte Katalysatorsystem kann direkt zur Polymerisation eingesetzt werden. Es kann aber auch nach Entfernen des Lösemittels resuspendiert zur Polymerisation eingesetzt werden. Der Vorteil dieser Aktivierungsmethode liegt darin, daß es die Option bietet das polymerisationsaktive Kataiysatorsystem erst im Reaktor entstehen zu lassen. Dadurch wird verhindert, daß beim Einschleusen des luftempfindlichen Katalysators zum Teil Zersetzung eintritt.The supported catalyst system can be used directly for the polymerization. However, it can also be used resuspended for the polymerization after removal of the solvent. The advantage of this activation method is that it offers the option of allowing the polymerization-active catalyst system to be formed only in the reactor. This prevents partial decomposition when the air-sensitive catalyst is introduced.
Weiterhin wird ein Verfahren zur Herstellung eines Olefinpolymers in Gegenwart des erfindungsgemäßen Katalysatorsystems beschrieben. Die Polymerisation kann eineFurthermore, a method for producing an olefin polymer in the presence of the catalyst system according to the invention is described. The polymerization can be a
Homo- oder eine Copolymerisation sein.Homo- or a copolymerization.
Bevorzugt werden Olefine der Formel Rα-CH=CH-Rß polymerisiert, worin Rα und Rß gleich oder verschieden sind und ein Wasserstoffatom, ein Haiogenatom, eine Alkoxy-, Hydroxy-, Alkylhydroxy-, Aldehyd, Carbonsäure- oderPreferably olefins of the formula R α -CH = CH-Rß are polymerized, in which R α and Rß are the same or different and are a hydrogen atom, a halogen atom, an alkoxy, hydroxyl, alkylhydroxy, aldehyde, carboxylic acid or
Carbonsäureestergruppe oder einen gesättigten oder ungesättigten Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, insbesondere 1 bis 10 C-Atomen bedeuten, der mit einer Alkoxy-, Hydroxy-, Alkylhydroxy-, Aldehyd-, Carbonsäureoder Carbonsäureestergruppe substituiert sein kann, oder R und Rß mit den sie verbindenden Atomen einen oder mehrere Ringe bilden. Beispiele für solche Olefine sind 1 -Olefine wie Ethylen, Propylen, 1 -Buten, 1 -Hexen, 4-Methyl-1-penten, 1-Octen, Styrol, cyclische Olefine wie Norbomen, Vinylnorbornen, Tetracyciododecen, Ethylidennorbomen, Diene wie 1 ,3-Butadien oder 1 ,4-Hexadien, Biscyclopentadien oder Methacrylsäuremethylester.Carboxylate group or a saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms, in particular 1 to 10 carbon atoms, which can be substituted with an alkoxy, hydroxy, alkylhydroxy, aldehyde, carboxylic acid or carboxylic acid ester group, or R and Rß with the atoms connecting them form one or more rings. 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 norbomene, vinyl norbornene, tetracyciododecene, ethylidene norbomene, dienes such as 1, 3-butadiene or 1, 4-hexadiene, biscyclopentadiene or methyl methacrylate.
Insbesondere werden Propylen oder Ethylen homopolymerisiert, Ethylen mit einem oder mehreren Cs^cH-CHefinen, insbesondere Propyien, und /oder einem oder mehreren C4-C2o_Diene, insbesondere 1 ,3-Butadien, copolymerisiert oderIn particular, propylene or ethylene are homopolymerized, ethylene with one or more Cs ^ cH-CHefins, in particular propylene, and / or one or several C4-C2o _ dienes, in particular 1, 3-butadiene, copolymerized or
Norbornen und Ethylen copolymerisiert.Copolymerized norbornene and ethylene.
Die Polymerisation wird bevorzugt bei einer Temperatur von - 60 bis 300°C, besonders bevorzugt 30 bis 250°C, durchgeführt. Der Druck beträgt 0,5 bis 2500 bar, bevorzugt 2 bis 1500 bar. Die Polymerisation kann kontinuierlich oder diskontinuierlich, ein- oder mehrstufig, in Lösung, in Suspension, in der Gasphase oder in einem überkritischem Medium durchgeführt werden.The polymerization is preferably carried out at a temperature of from -60 to 300.degree. C., particularly preferably from 30 to 250.degree. 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.
Das geträgerte Katalysatorsystem kann entweder direkt im Polymerisationssystem gebildet werden oder es kann als Pulver oder noch Lösemittel behaftet wieder resuspendiert und als Suspension in einem inerten Suspensionsmittel in das Polymerisationssystem eindosiert werden.The supported catalyst system can either be formed directly in the polymerization system or it can be resuspended as a powder or solvent, and metered into the polymerization system as a suspension in an inert suspension medium.
Mit Hilfe des erfindungsgemäßen Katalysatorsystems kann eine Vorpolymerisation erfolgen. Zur Vorpolymerisation wird bevorzugt das (oder eines der) in derA prepolymerization can be carried out with the aid of the catalyst system according to the invention. For prepolymerization, preference is given to (or one of the) in the
Polymerisation eingesetzte(n) Olefin(e) verwendet.Polymerization used olefin (s) used.
Zur Herstellung von Olefinpolymeren mit breiter Molekuiargewichtsverteilung werden bevorzugt Katalysatorsysteme verwendet, die zwei oder mehr verschiedene Übergangsmetallverbindungen, z. B. Metallocene enthalten.For 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, e.g. B. contain metallocenes.
Zur Entfernung von im Olefin vorhandenen Katalysatorgiften ist eine Reinigung mit einem Aluminiumalkyl, beispielsweise Trimethylaluminium, Triethylaluminium oder Triisobutylaluminium vorteilhaft. Diese Reinigung kann sowohl im Poiymerisations- System selbst erfolgen oder das Olefin wird vor der Zugabe in das Poiymerisations- system mit der AI-Verbindung in Kontakt gebracht und anschließend wieder getrennt.To 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 the addition into the polymerization system and then separated again.
Ais Molmassenregler und/oder zur Steigerung der Aktivität wird, falls erforderlich, Wasserstoff zugegeben. Der Gesamtdruck im Polymerisationssystem beträgt 0,5 bis 2500 bar, bevorzugt 2 bis 1500 bar.If 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.
Dabei wird die erfindungsgemäße Verbindung in einer Konzentration, bezogen auf das Übergangsmetall von bevorzugt 10-3 bis 10-8, vorzugsweise 10-4 bis 10-7 mol Übergangsmetall pro dm3 Lösemittel bzw. pro dm3 Reaktorvolumen angewendet.The compound according to the invention is used in a concentration, based on the transition metal, of preferably 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol Transition metal applied per dm 3 solvent or per dm 3 reactor volume.
Geeignete Lösemittel zur Darstellung sowohl der erfindungsgemäßen geträgerten chemischen Verbindung als auch des erfindungsgemäßen Katalysatorsystems sind aliphatische oder aromatische Lösemittel, wie beispielsweise Hexan oder Toluol, etherische Lösemittel, wie beispielsweise Tetrahydrofuran oder Diethylether oder halogenierte Kohlenwasserstoffe, wie beispielsweise Methylenchlorid oder halogenierte aromatische Kohlenwasserstoffe wie beispielsweise o-Dichlorbenzol.Suitable 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 tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o- Dichlorobenzene.
Vor Zugabe des erfindungsgemäßen Katalysatorsystems bzw. vor Aktivierung des erfindungsgemäßen Katalysatorsystems im Polymerisationssystem kann zusätzlich eine Alkylalumiuniumverbindung wie beispielsweise Trimethylaluminium, Triethylaluminium, Triisobutylaiuminium, Trioctylaluminium oder Isoprenylaiuminium zur Inertisierung des Polymerisationssystems (beispielsweise zur Abtrennung vorhandener Katalysatorgifte im Olefin) in den Reaktor gegeben werden. Diese wird in einer Konzentration von 200 bis 0,001 mmol AI pro kg Reaktorinhalt dem Polymerisationssystem zugesetzt. Bevorzugt werden Triisobutylaiuminium und Triethylaluminium in einer Konzentration von 10 bis 0,01 mmol AI pro kg Reaktorinhalt eingesetzt, dadurch kann bei der Synthese eines geträgerten Katalysatorsystems das molare Al/M1-Verhäitnis klein gewählt werden.Before adding the catalyst system according to the invention or before activating the catalyst system according to the invention in the polymerization system, an alkylaluminum compound such as trimethylaluminum, triethylaluminium, triisobutyliumiumium, trioctylaluminium or isoprenylaiumiumium can additionally be added to the reactor to render the polymerization system inert (for example to separate off existing catalyst poisons in the olefin). This is added to the polymerization system in a concentration of 200 to 0.001 mmol of AI per kg of reactor content. Triisobutylaium aluminum and triethyl aluminum are preferably used in a concentration of 10 to 0.01 mmol Al per kg reactor content, so that the molar Al / M 1 ratio can be chosen to be small in the synthesis of a supported catalyst system.
Weiterhin kann beim erfindungsgemäßen Verfahren ein Additiv wie ein Antistatikum verwendet werden, z.B. zur Verbesserung der Kornmorphologie des Polymers. Generell können alle Antistatika, die für die Polymerisation geeignet sind, verwendet werden. Beispiele hierfür sind Salzgemische aus Calciumsalzen der Medialansäure und Chromsalze der N-Stearyianthranilsäure, die in DE-A-3,543,360 beschreiben werden. Weitere geeignete Antistatika sind z.B. C^- bis C22- Fettsäureseifen vonFurthermore, an additive such as an antistatic, e.g. to improve the grain morphology of the polymer. In general, all antistatic agents that are suitable for the polymerization can be used. Examples of these are salt mixtures of calcium salts of medialanic acid and chromium salts of N-stearyianthranilic acid, which are described in DE-A-3,543,360. Other suitable antistatic agents are e.g. C ^ - to C22 fatty acid soaps from
Alkali- oder Erdalkalimetallen, Salze von Sulfonsäureestern, Ester von Polyethylenglycolen mit Fettsäuren, Polyoxyethylenalkylether usw. Eine Übersicht über Antistatika wird in EP-A-0, 107,127 angegeben.Alkali or alkaline earth metals, salts of sulfonic acid esters, esters of polyethylene glycols with fatty acids, polyoxyethylene alkyl ethers etc. An overview of antistatic agents is given in EP-A-0, 107, 127.
Außerdem kann als Antistatikum eine Mischung aus einem Metallsalz der Medialansäure, einem Metallsalz der Anthranilsäure und einem Polyamin eingesetzt werden, wie in EP-A-0,636,636 beschrieben.In addition, a mixture of a metal salt can be used as an antistatic Medialan acid, a metal salt of anthranilic acid and a polyamine can be used, as described in EP-A-0,636,636.
Kommerziell erhältliche Produkte wie Stadis® 450 der Fa. DuPont, eine Mischung aus Toluol, Isopropanol, Dodecylbenzolsulfonsäure, einem Polyamin, einemCommercially available products such as Stadis® 450 from DuPont, a mixture of toluene, isopropanol, dodecylbenzenesulfonic acid, a polyamine, one
Copolymer aus Dec-1-en und SO2 sowie Dec-1-en oder ASA®-3 der Fa. Shell undCopolymer of dec-1-en and SO2 as well as dec-1-en or ASA®-3 from Shell and
ARU5R® 163 der Firma ICI können ebenfalls verwendet werden.ARU5R® 163 from ICI can also be used.
Vorzugsweise wird das Antistatikum als Lösung eingesetzt, im bevorzugten Fall von Stadis® 450 werden bevorzugt 1 bis 50 Gew.-% dieser Lösung, vorzugsweise 5 bisThe antistatic is preferably used as a solution, in the preferred case of Stadis® 450 preferably 1 to 50% by weight of this solution, preferably 5 to
25 Gew.-%, bezogen auf die Masse des eingesetzten Trägerkatalysators (Träger mit kovaleπt fixierter metalloceniumbildende Verbindung und eine oder mehrere Metallocenverbindungen z.B. der Formel IV) eingesetzt. Die benötigten Mengen an Antistatikum können jedoch, je nach Art des eingesetzten Antistatikums, in weiten. Bereichen schwanken.25% by weight, based on the mass of the supported catalyst used (support with covalently fixed metallocenium-forming compound and one or more metallocene compounds, for example of the formula IV). However, depending on the type of antistatic used, the required amounts of antistatic can vary widely. Areas fluctuate.
Die nachfolgenden Beispiele dienen zur näheren Erläuterung der ErfindungThe following examples serve to explain the invention in more detail
Allgemeine Angaben: Herstellung und Handhabung der Verbindungen erfolgten unter Ausschluß von Luft und Feuchtigkeit unter Argonschutz (Schlenk-Technik).General information: The connections were made and handled in the absence of air and moisture under argon protection (Schlenk technique).
Alle benötigten Lösemittel wurden vor Gebrauch durch mehrstündiges Sieden über geeignete Trockenmitte! und anschließende Destillation unter Argon absolutiert.All required solvents were boiled over a suitable drying agent for several hours before use! followed by distillation under argon.
Beispiel 1 : Synthese des AnhydridsExample 1: Synthesis of the anhydride
18J g (50mmol) Bis(pentafluorphenyl)borinsäure werden 8 Stunden lang im Hochvakuum bei 100°C getempert. Anschließend wird der verbleibende Rückstand in 500 ml Pentan aufgenommen und filtriert. Der Rückstand wird danach noch einmal mit 2 x 200 ml Pentan gewaschen und im Vakuum getrocknet. Man erhält 16.2 g des entsprechenden Anhydrid (92% Ausbeute).18J g (50mmol) bis (pentafluorophenyl) borinic acid are annealed for 8 hours in a high vacuum at 100 ° C. The remaining residue is then taken up in 500 ml of pentane and filtered. The residue is then washed again with 2 × 200 ml of pentane and dried in vacuo. 16.2 g of the corresponding anhydride (92% yield) are obtained.
19F-NMR (C6D6): -134ppm (m, 4F, o-B(C6F5)2); -146ppm (m, 2F, p-B(C6F5)2); 161 ppm (m, 4F, m-B(C6F5)2) Beispiel 2: Trägerung des Anhydrids 19 F NMR (C 6 D 6 ): -134ppm (m, 4F, oB (C 6 F 5 ) 2 ); -146ppm (m, 2F, pB (C 6 F 5 ) 2 ); 161 ppm (m, 4F, mB (C 6 F 5 ) 2 ) Example 2: Carrying the anhydride
14.0 g Si02 (MS3030, Fa. PQ, getrocknet bei 600°C im Argonstrom) werden in 20 ml Toluol vorgelegt, 2.6 ml N,N-Dimethyianilin (20.80 mmol) zugetropft und zwei Stunden bei Raumtemperatur gerührt. Anschließend werden bei 0°C 14.7 g14.0 g of SiO 2 (MS3030, PQ, dried at 600 ° C. in a stream of argon) are placed in 20 ml of toluene, 2.6 ml of N, N-dimethyianiline (20.80 mmol) are added dropwise and the mixture is stirred at room temperature for two hours. Then 14.7 g at 0 ° C
Borinsäureanhydrid (aus Beispiel 1 ) (20.80 mmol) gelöst in 40 ml Toluol zugegeben. Man läßt auf Raumtemperatur erwärmen und rührt die Suspension zwei Stunden bei dieser Temperatur. Die entstandene hellgrüne Suspension wird abfiltriert und der Rückstand mit 50 ml Toluol und anschließend mit dreimal 100 ml n-Pentan gewaschen. Danach wir der rückstand im Olpumpenvakuum getrocknet. Es resultieren 16.4 g des geträgerten Cokatalysatorsystems.Boric anhydride (from Example 1) (20.80 mmol) dissolved in 40 ml of toluene was added. The mixture is allowed to warm to room temperature and the suspension is stirred at this temperature for two hours. The resulting light green suspension is filtered off and the residue is washed with 50 ml of toluene and then with three times 100 ml of n-pentane. Then the residue is dried in an oil pump vacuum. 16.4 g of the supported cocatalyst system result.
Beispiel 3: Herstellung des KatalysatorsystemsExample 3: Preparation of the catalyst system
Zu einer Lösung von 5 mg (8 μmol) Dimethylsilandiylbis(2-methyl-4-phenyl-indenyl)- zirkoniumdichlorid in 5 ml Toluol werden 0.03 ml Trimethylaiuminium (20% ig in Exxol, 70 μmol) zugegeben und die Lösung 1.5 Stunden bei RT gerührt. Anschließend werden 996 mg (0J8 mmol/g) der unter Beispiel 2 hergestellten Verbindung portionsweise zugegeben. Die Lösung wird 30 Minuten bei Raumtemperatur gerührt. Danach entfernt man das Lösemittel im Olpumpenvakuum.To a solution of 5 mg (8 μmol) of dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride in 5 ml of toluene, 0.03 ml of trimethylamine (20% in Exxol, 70 μmol) are added and the solution for 1.5 hours at RT touched. Then 996 mg (0J8 mmol / g) of the compound prepared in Example 2 are added in portions. The solution is stirred for 30 minutes at room temperature. The solvent is then removed in an oil pump vacuum.
Es resultieren 1.001 g eines hellgrünen freifließenden Pulvers.The result is 1,001 g of a light green, free-flowing powder.
Beispiel 4: PolymerisationExample 4: Polymerization
Zum Einschleusen in das Polymerisationssystem wird 1 g des geträgertenTo infiltrate the polymerization system, 1 g of the supported
Katalysatorsystems in 30 ml Exxol resuspendiert.Resuspended catalyst system in 30 ml Exxol.
Parallel dazu wird ein trockener 16-dm3-Reaktor zunächst mit Stickstoff und anschließend mit Propylen gespült und mit 10 dm3 flüssigem Propen befüllt. Dann wurden 0.5 cm3 einer 20%igen Triisobutylaiuminiumlösung in Varsol mit 30 cm3 Exxol verdünnt in den Reaktor gegeben und der Ansatz bei 30°C 15 Minuten gerührt. Anschließend wurde die Katalysatorsuspension in den Reaktor gegeben. Das Reaktionsgemisch wurde auf die Polymerisationstemperatur von 60°C aufgeheizt (4°C/min) und das Polymerisationssystem 1 h durch Kühlung bei 60°C gehalten. Gestoppt wurde die Polymerisation durch Abgasen des restlichen Propyiens. Das Polymer wurde im Vakuumtrockenschrank getrocknet. Es resultieren 485 g Polypropylen-Pulver. Der Reaktor zeigte keine Beläge an der Innenwand oder Rührer. Die Katalysatoraktivität betrug 97 kg PP/g Metallocen x h In parallel, a dry 16 dm 3 reactor is first flushed with nitrogen and then with propylene and filled with 10 dm 3 of liquid propene. Then 0.5 cm 3 of a 20% triisobutylaiumium solution in Varsol diluted with 30 cm 3 Exxol was added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes. The catalyst suspension was then added to the reactor. The reaction mixture was brought to the polymerization temperature of 60 ° C heated (4 ° C / min) and the polymerization system was kept at 60 ° C for 1 h by cooling. The polymerization was stopped by exhausting the remaining propylene. The polymer was dried in a vacuum drying cabinet. The result is 485 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 97 kg PP / g metallocene xh

Claims

Patentansprüche: Claims:
1. Katalysatorsystem enthaltend1. Containing catalyst system
A) mindestens ein Metallocen,A) at least one metallocene,
B) mindestens eine Lewis Base der FormelB) at least one Lewis base of the formula
M1 R3R4R5 M 1 R 3 R 4 R 5
(I) worin(I) in which
R3, R4, R5 gleich oder verschieden sinR 3 , R 4 , R 5 are the same or different
C2o Alkyl-, C1-C20 Halogenalkyl-, C6-C40 Ar l-, C6-C 0 Halogenaryl-, C -C4o Alkylaryl- oder C7-C40 Arylalkyl-Gruppe ist und zwei Reste oder alle drei Reste R3, R4 und R5 über C2-C20 Kohienstoffeinheiten miteinander verbunden sein können, M1 ist ein Element der V. Hauptgruppe des Periodensystems der Elemente, insbesondere Stickstoff oder Phosphor C) mindestens einen TrägerC 2 o alkyl, C 1 -C 20 haloalkyl, C6-C40 Ar l, C 6 -C 0 haloaryl, C -C 4 o alkylaryl or C7-C40 arylalkyl group and two radicals or all three Residues R 3 , R 4 and R 5 can be connected to one another via C 2 -C 20 carbon units, M 1 is an element of the V. main group of the Periodic Table of the Elements, in particular nitrogen or phosphorus C), at least one carrier
D) und mindestens eine Organobor- oder Organoaluminium-Verbindung, die aus Einheiten der Formel IID) and at least one organoboron or organoaluminium compound which consists of units of the formula II
[R1 2M2-X-M2R2 2]k worin R1,R2 gleich oder verschieden sind und ein Wasserstoffatom, ein[R 1 2 M 2 -XM 2 R 2 2 ] k wherein R 1 , R 2 are the same or different and a hydrogen atom
Halogenatom, eine borfreie CrC4o-kohlenstoffhaltige Gruppe wie C-r C2o-Alkyl, d-C2o-Halogenaikyl, C Cιo-Alkoxy, C6-C2o-Aryi, C6-C2o- Halogenaryl, C6-C-2o-Aryloxy, C7-C4o-Arylalkyl, C7-C4o-Halogenaryla!kyl, C7-C4o-Alkylaryl, C7-C4o-Halogenalkylaryl sind oder R1 kann eine OSiRa 3-Gruppe sein, worin Ra gleich oder verschieden sind und einHalogen atom, a boron-free CrC 4 o carbon-containing group such as Cr C 2 o -alkyl, dC 2 o-haloalkyl, C Cιo-alkoxy, C 6 -C 2 o-Aryi, C 6 -C 2 o-haloaryl, C 6 - C- 2 o-aryloxy, C 7 -C 4 o-arylalkyl, C7-C 4 o-haloarylaalkyl, C 7 -C 4 o-alkylaryl, C 7 -C 4 o-haloalkylaryl or R 1 can be an OSiR a 3 group in which R a are the same or different and a
Wasserstoffatom, ein Halogenatom, eine CrC^o-kohlenstoffhaltige Gruppe wie Cι-C2o-Alkyl, CrC2o-Halogenalkyi, Cι-Cιo-Alkoxy, C6-C20- Aryl, C6-C2o-Haiogenaryl, C6-C2o-Aryloxy, C7-C o-Arylalkyl, C7-C40- Halogenarylaikyl, C7-C4o-Alkylaryl, C7-C4o-Halogenalkylaryl sind oder R1 kann eine CH(SiRb 3)2-Gruppe sein, worin Rb gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, eine C C o-kohlenstoffhaltige Gruppe wie Cι-C2o-Alkyl, d^o-Halogenalkyl, CrCio-Alkoxy, C6-C o-Aryl, C6-C2o-Halogenaryl, C6-C2o-Aryloxy, C7-C40- Arylalkyl, C7-C40-Halogenarylalkyl, C7-C4o-Alkylaryl, C7-C40- Halogenalkylaryl sein,Hydrogen atom, a halogen atom, a CrC ^ o-carbon-containing group such as -C-C 2 o-alkyl, CrC 2 o-haloalkyl, -C-Cιo-alkoxy, C 6 -C 20 aryl, C 6 -C 2 o-haiogenaryl, C 6 -C 2 o-aryloxy, C 7 -C o-arylalkyl, C 7 -C 40 -haloarylaikyl, C 7 -C 4 o-alkylaryl, C 7 -C 4 o-haloalkylaryl or R 1 can be a CH ( SiR b 3 ) 2 group, in which R b are the same or different and a hydrogen atom, a halogen atom, a CC o-carbon-containing group such as -CC 2 o-alkyl, d ^ o-haloalkyl, CrCio-alkoxy, C6 -aryl, C 6 -C2o-haloaryl, C 6 -C 2 o-aryloxy, C 7 -C 40 - aralkyl, C 7 -C 40 -Halogenarylalkyl, C7 -C4o -alkylaryl , C 7 -C 40 - haloalkylaryl,
X gleich oder verschieden ein Element der Gruppe Via des Periodensystems der Elemente oder eine NH-Gruppe ist,X, identical or different, is an element of the Via group of the Periodic Table of the Elements or an NH group,
M2 ein Element der lila des Periodensystems der Elemente ist, und k eine natürliche Zahl von 1 bis 100 ist. aufgebaut ist und die kovalent an den Träger gebunden ist.M 2 is a purple element of the Periodic Table of the Elements, and k is a natural number from 1 to 100. is built up and is covalently bound to the carrier.
2. Katalysatorsystem gemäß Anspruch 1 , dadurch gekennzeichnet, daß es zusätzlich noch eine Organometailverbindung der Formel (IV)2. Catalyst system according to claim 1, characterized in that it additionally contains an organometallic compound of the formula (IV)
[M4R9 p]q (IV) worin[M 4 R 9 p ] q (IV) wherein
M4 ein Element der I., II. und III. Hauptgruppe des Periodensystems der Elemente ist, vorzugsweise Lithium, Magnesium und Aluminium, insbesondere Aluminium, ist R9 gleich oder verschieden ein Wasserstoffatom, ein Haiogenatom, eine C1-C40- kohlenstoffhaltige Gruppe wie eine C1-C2o- Alkyl-, C6-C40-Aryl-, C7-C4o-Aryl- alkyl oder C7-C4o-Alkyl-aryl-Gruppe, bedeutet, p eine ganze Zahl von 1 bis 3 und q eine ganze Zahl von 1 bis 4 ist, enthält.M 4 is an element of I., II. And III. Main group of the Periodic Table of the Elements is, preferably lithium, magnesium and aluminum, in particular aluminum, R 9 is the same or different is a hydrogen atom, a haiogen atom, a C 1 -C 40 carbon-containing group such as a C 1 -C 2 o-alkyl, C 6 -C 4 0 aryl, C 7 -C 4 o-aryl alkyl or C 7 -C 4 -alkyl-aryl group, p is an integer from 1 to 3 and q is an integer of 1 to 4 contains.
3. Verfahren zur Herstellung eines Polyolefins durch Polymerisation eines oder mehrerer Olefine in Gegenwart eines Katalysatorsystems nach einem der Ansprüche 1 oder 2.3. A process for the preparation of a polyolefin by polymerizing one or more olefins in the presence of a catalyst system as claimed in claim 1 or 2.
4. Verwendung eines Katalysatorsystems gemäß einem der Ansprüche 1 oder 2 zur Herstellung eines Polyolefins. 4. Use of a catalyst system according to one of claims 1 or 2 for the production of a polyolefin.
PCT/EP1999/007087 1998-10-01 1999-09-23 Catalyst system WO2000020466A1 (en)

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DE1998145240 DE19845240A1 (en) 1998-10-01 1998-10-01 Supported catalyst system, useful for the production of polyolefins comprises a metallocene, a Lewis base and an organoboron or organoaluminium compound.
DE19845240.3 1998-10-01
DE19903306A DE19903306A1 (en) 1999-01-28 1999-01-28 Organometallic compound, catalyst system containing this organometallic compound and its use
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG83828A1 (en) * 1999-12-27 2001-10-16 Sumitomo Chemical Co Catalyst for addition polymerization, and process for producing addition polymer with the same
US8058200B2 (en) 2007-05-17 2011-11-15 Chevron Phillips Chemical Company, L.P. Catalysts for olefin polymerization
US9951089B2 (en) 2010-02-03 2018-04-24 Infinity Pharmaceuticals, Inc. Methods of treating a fatty acid amide hydrolase-mediated condition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JO3598B1 (en) 2006-10-10 2020-07-05 Infinity Discovery Inc Boronic acids and esters as inhibitors of fatty acid amide hydrolase
TW201000107A (en) 2008-04-09 2010-01-01 Infinity Pharmaceuticals Inc Inhibitors of fatty acid amide hydrolase

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495099A1 (en) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Olefin copolymer and production thereof
DE19733017A1 (en) * 1997-07-31 1999-02-04 Hoechst Ag Chemical compound
DE19757540A1 (en) * 1997-12-23 1999-06-24 Hoechst Ag Supported olefin polymerization catalyst system, particularly for propylene or ethylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495099A1 (en) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Olefin copolymer and production thereof
DE19733017A1 (en) * 1997-07-31 1999-02-04 Hoechst Ag Chemical compound
DE19757540A1 (en) * 1997-12-23 1999-06-24 Hoechst Ag Supported olefin polymerization catalyst system, particularly for propylene or ethylene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG83828A1 (en) * 1999-12-27 2001-10-16 Sumitomo Chemical Co Catalyst for addition polymerization, and process for producing addition polymer with the same
US6894130B2 (en) 1999-12-27 2005-05-17 Sumitomo Chemical Company, Limited Catalyst for addition polymerization, and process for producing addition polymer with the same
US7005486B2 (en) 1999-12-27 2006-02-28 Sumitomo Chemical Company, Limited Catalyst for addition polymerization, and process for producing addition polymer with the same
US8058200B2 (en) 2007-05-17 2011-11-15 Chevron Phillips Chemical Company, L.P. Catalysts for olefin polymerization
US9951089B2 (en) 2010-02-03 2018-04-24 Infinity Pharmaceuticals, Inc. Methods of treating a fatty acid amide hydrolase-mediated condition

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