EP1082363A1 - Organometal compound, catalyst system containing said organometal compound and its use - Google Patents

Organometal compound, catalyst system containing said organometal compound and its use

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Publication number
EP1082363A1
EP1082363A1 EP00910601A EP00910601A EP1082363A1 EP 1082363 A1 EP1082363 A1 EP 1082363A1 EP 00910601 A EP00910601 A EP 00910601A EP 00910601 A EP00910601 A EP 00910601A EP 1082363 A1 EP1082363 A1 EP 1082363A1
Authority
EP
European Patent Office
Prior art keywords
methyl
indenyl
zirconium dichloride
dichloride dimethylsilanediyl
azapentalen
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00910601A
Other languages
German (de)
French (fr)
Inventor
Jörg SCHOTTEK
Roland Kratzer
Andreas Winter
Volker Fraaije
Michael-Joachim Brekner
Markus Oberhoff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Targor GmbH
Basell Polyolefine 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
Application filed by Targor GmbH, Basell Polyolefine GmbH filed Critical Targor GmbH
Publication of EP1082363A1 publication Critical patent/EP1082363A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • Organometallic compound Organometallic compound, catalyst system containing this organometallic compound and its use.
  • the present invention relates to specially substituted metal ocenes and corresponding highly active supported catalyst systems which can advantageously be used in olefin polymerization and to a process for their preparation and to polymers which are prepared using the supported catalyst systems.
  • Processes for the production of polyolefins using soluble, homogeneous catalyst systems, consisting of a transition metal component of the metallocene type and a cocatalyst component of the aluminoxane type, a Lewis acid or an ionic compound, are known. With high activity, these catalysts deliver polymers and copolymers with a narrow molecular weight distribution.
  • Catalyst systems form heavy deposits on the reactor walls and stirrer when the polymer is obtained as a solid. These deposits always arise from agglomeration of the polymer particles when metallocene and / or cocatalyst are present in solution in the suspension. Such deposits in the reactor systems must be removed regularly, since these quickly reach considerable strengths, have high strength and prevent heat exchange with the cooling medium. Such homogeneous catalyst systems cannot be used industrially in modern polymerization processes, for example in liquid monomer or in the gas phase.
  • supported catalyst systems have been proposed in which the metallocene and / or the aluminum compound serving as cocatalyst are fixed on an inorganic support material.
  • the catalyst activities can be increased by increasing the loading of the support with active substances (metallocene component (s), cocatalyst (s) and optionally additives), but at the same time such catalysts tend to form large amounts of deposits and cannot be used industrially.
  • active substances metallicocene component (s), cocatalyst (s) and optionally additives
  • the object on which the present invention is based is achieved by a specially substituted metallocene, a supported catalyst system which contains at least one specially substituted metallocene, at least one cocatalyst, at least one carrier and, if appropriate, at least one further additive component.
  • the catalyst system is produced according to the invention by mixing at least one specially substituted metallocene, at least one cocatalyst and at least one carrier and, if appropriate, at least one further additive component.
  • the metallocene according to the invention which is also used as a metallocene component in the catalyst system according to the invention, is a compound of the formula I below
  • M 1 is a metal from group IVb of the Periodic Table of the Elements
  • R 1 and R 2 are the same or different and a hydrogen atom, a C ⁇ -C ⁇ o-alkyl group, a C ⁇ -C ⁇ o alkoxy group, a
  • R 3 , R 4 , R 6 , R 7 and R 8 and R 3 'and R 4 ' are the same or different and are a hydrogen atom, a hydrocarbon group which can be partially halogenated, alo "-generated, linear, cyclic or branched, for example a -C-C ⁇ o-alkyl group, C 2 -C ⁇ 0 alkenyl group, C 6 -C 2 rj-aryl group, a C -C 4 o-arylalkyl group, a C 7 -C 4 o-alkyl aryl group, a C 8th -C 4 o-arylalkenyl group, an Si (R 13 ) 3 -, N (R 13 ) 2 -, SR 13 - or OR 13 group, with R 13 as R 4 , with the proviso that R 3 is different from hydrogen, R 3 'and R 4 ' can also be cyclically linked, and R 5 is a C 6 to C 40 aryl
  • R 14 is a halogen atom F, Cl or Br, a Ci to C o -alkyl radical, a C 2 to C 2 o-alkenyl radical, a C 6 to C 24 aryl radical, a C 7 to C 4 o-arylalkyl radical, a C 7 to C 4 o -alkylaryl, a Cs to C 4 o-arylalkenyl radical where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine, chlorine or bromine, -N (R 15 ) 2 , - ⁇ > (R 15 ) 2 , -SR 15 , -0R 15 , -Si (R 15 ) 3 ,
  • radicals R 16 can be the same or different despite the same indexing and the meaning of R 14 or hydrogen and adjacent R 16 radicals can also be cyclically linked, or one or more of the R 16 radicals form a cyclic linkage with the R 6 or R 4 and / or R 14 radicals, with the proviso that R 14 also Can be hydrogen if at least one of the radicals R16 is different from hydrogen,
  • R 9 means a bridge
  • R 10 , R 11 can also be the same or different with the same indexing and denote a hydrogen atom, a halogen atom, a C 1 -C 4 o-hetero atom-containing hydrocarbon group or a C 1 -C 4 o -carbon-containing group, such as a C 1 -C 20 -alkyl, a C ⁇ -C 10 fluoroalkyl, a C ⁇ -C ⁇ o alkoxy, a C 6 -C 14 aryl, a C ⁇ -Cio-fluoroaryl group, a C 6 -aryloxy -C ⁇ 0 , a C 2 -C ⁇ o alkenyl, a C 7 -C 4 o-arylalkyl, a C 7 -C 40 alkylaryl, a C 8 -C 40 arylalkenyl group, a -N (Rl 7 ) 2 , - P (Rl 7 ) 2 , -SR 17
  • x means an integer from 0 to 18,
  • M 2 means silicon, germanium or tin, and heteroatom-containing hydrocarbon groups are understood to mean hydrocarbons which contain at least one element from groups 13 to 16 of the Periodic Table of the Elements.
  • R 9 can also link two units of the formula I to one another.
  • R a denotes a saturated or unsaturated hydrocarbon group, preferably with 1 to 40 carbon atoms, in particular with 1 to 30 carbon atoms, which can also be substituted by one or more radicals with the meaning of R 3 , the radical R as such contains at least one heteroatom from groups 13, 14, 15 or 16 of the Periodic Table of the Elements. In the above meaning R a , this means that the heteroatom is present as such in the ring system. If the ring system already contains at least one heteroatom, one or more radicals R 3 can also contain a heteroatom.
  • M 1 is zirconium, hafnium or titanium
  • R 1 and R 2 are the same and represent methyl, dimethylamide, dibenzyl or chlorine,
  • R 3 and R 3 ' are the same or different and are a hydrocarbon group which can be partially halogenated, halogenated, linear, cyclic or branched, for example a -C 1 -C ⁇ alkyl group, C -C 1o alkenyl group, a C -C 4 o- Alkylaryl group mean
  • R 5 is a C 6 to C 2 o aryl group having a substituent R contributes in para-position to the binding site on the indenyl ring 14, and R 14 is a Ci to C ⁇ o _ alkyl, C 2 to Cio-alkenyl radical, a C 6 to C ⁇ 8 aryl, a C to
  • R a denotes a saturated or unsaturated hydrocarbon group with 2 to 40 carbon atoms, which can also be substituted with radicals as R 3 , and which has at least one heteroatom selected from the group B, Al, Si, Sn, N , P, O or S contains.
  • R 3 radicals as R 3
  • R 3 has at least one heteroatom selected from the group B, Al, Si, Sn, N , P, O or S contains.
  • M 1 is zirconium
  • R 1 and R 2 are the same and represent methyl or chlorine
  • R 3 and R 3 ' are the same or different and are a hydrocarbon group which can be halogenated, linear, cyclic or branched, for example a -C-C ⁇ o-alkyl group, C 2 -C ⁇ 0 -alkenyl group, a C 7 -C 40 -alkylaryl group ,
  • R 9 or - is in which R 10 and R 11 are identical or different and denote hydrogen, phenyl, methyl or ethyl, the radicals, R 4 , R 6 , R 7 and R 8 and R 4 'are hydrogen,
  • R 5 is a C 6 to C 20 aryl group, in particular a phenyl group,
  • Naphthyl or anthracenyl group mean one in the para position to the binding site to the indenyl ring
  • R 14 carries substituents, where R 14 is a Si (R 15 ) 3 radical, with R 15 as R 4 , or a linear Ci to C ⁇ o alkyl radical, a branched C 3 to C 10 alkyl radical C 2 to Cin-alkenyl radical or a branched C to C o ⁇ alkylaryl radical, where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine or chlorine, and
  • R a is a saturated or unsaturated hydrocarbon group with 1 to 30 carbon atoms, which can also be substituted with radicals as R 3 , and which has at least one
  • Heteroatom selected from the group N, P, 0 or S contains.
  • the fragment R a together with the cyclopentadienyl base to which it is attached very particularly preferably forms the following molecular fragments of the formula I (for reasons of clarity, the hydrogen atoms in the heteroatom-containing rings have been omitted in the rings). Only residues R were taken into account and indicated, which can also be different from hydrogen):
  • the heteroatom functions X are the same or different and have the meaning NR ⁇ , PR ⁇ , N, 0 or S, the radicals R ⁇ , R ⁇ , R ⁇ and R are hydrogen or the meaning of R 3 , the radicals R ⁇ the meaning of R 3 'and the radicals RP have the meaning of R 4 '.
  • Examples of preferred metallocene components of the catalyst system according to the invention are combinations of the following molecule fragments of the compound I:
  • R 3 , R 3 ' methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, s-butyl,
  • R 6, R 7 hydrogen, Ci to C 4 alkyl, C 6 to C ⁇ 0 aryl,
  • R 5 p-methyl-phenyl, p-ethyl-phenyl, pn-propyl-phenyl, p-isopropyl-phenyl, pn-butyl-phenyl, p-tert-butyl-phenyl, ps-butyl- phenyl, p-pentyl-phenyl, p-hexyl-phenyl, p-cyclohexyl-phenyl, p-trimethylsilyl-phenyl, p-adamantyl-phenyl, p- (F 3 C) 3 C-phenyl,
  • R 9 dimethylsilanediyl, phenyl (methyl) silanediyl, diphenylsilanedyl, dirnethylgermandiyl, ethylidene, 1-methylethylidene, 1,1-dimethylethylidene, 1,2-dirnethylethylidene, 1, 1, 2, 2-tetramethylethylidene, dimethylmethylidene, phenyl (methyl) methylidene, diphenylmethylidene,
  • R a 2-alkyl-4-azapentalene, 2-alkyl-5-azapentalene,
  • 2-alkyl-6-azapentalenes 2-alkyl-N-aryl-4-azapentalenes, 2-A1-alkyl-N-aryl-5-azapentalenes, 2-alkyl-N-aryl-6-azapentalenes, 2, 5- Dialkyl-4-azapentalene, 2,5-dialkyl-6-azapentalene,
  • Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -isopropylphenyl -indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- ( 4 'isopropylphenyl indenyl) zirconium dichloride
  • Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirconium dichloride
  • dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
  • preferred metallocene components are furthermore the corresponding homologues of the abovementioned compounds which are substituted in the 2- and / or in the 2,5-position with ethyl, n-propyl, isopropyl, isobutyl, n-butyl and s-butyl.
  • the metallocenes of the formula I can be used as a mixture of isomers or as one of the possible racemic isomers in pure or enriched form.
  • the catalyst system according to the invention preferably additionally contains at least one cocatalyst.
  • the cocatalyst component which can be present in the catalyst system according to the invention contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound, which converts this into a cationic compound by reaction with a metallocene.
  • the usable in the inventive method aluminoxanes Kgs ⁇ NEN example, cyclic as in formula II
  • the radicals R in the formulas (II), (III) or (IV) can be the same or different and a C ⁇ -C o hydrocarbon group such as a Ci-Ce alkyl group, a C 6 -Ci 8 aryl group, benzyl or hydrogen mean, and p is an integer from 2 to 50, preferably 10 to 35.
  • the radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen or isobutyl or n-butyl preferably containing 0.01-40% (number of the radicals R).
  • the aluminoxane can be produced in various ways by known processes.
  • One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
  • an inert solvent such as toluene
  • AIR 3 + AIR ' 3 two different aluminum trialkyls (AIR 3 + AIR ' 3 ) are reacted with water according to the desired composition and reactivity (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 20 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated Groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) henyl.
  • organoboron or organoaluminum compound which contains C 1 -C 20 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluor
  • Preferred Lewis acids are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (p - fluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyljborane, tris (3,5-difluorophenyl) borane and / or
  • Tris (3, 4, 5-trifluorophenyl) borane Tris (pentafluorophenyl) borane is particularly preferred.
  • Compounds which contain a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenyl borates, SbFg-, CF 3 S0 3 - or C10 4 -, are preferably used as ionic cocatalysts.
  • a cationic counterion Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N -dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetra-hydrothiophene and triphenylcarbenium are used.
  • Triethylammonium tetr (phenyl) borate Triethylammonium tetr (phenyl) borate
  • Trimethylammonium tetra (tolyl) borate Trimethylammonium tetra (tolyl) borate
  • Triphenylcarbenium tetrakis (phenyl) aluminate Triphenylcarbenium tetrakis (phenyl) aluminate
  • N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate.
  • Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
  • Borane or carborane compounds such as e.g.
  • 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, Zr0 2 , Ti0 or B0 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 2 / g, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 ⁇ m 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.
  • 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 silica gel 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 / or inert gas overlay (eg nitrogen).
  • the drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C.
  • the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the selected conditions
  • Equilibrium can be done with the hydroxyl groups on the support surface, which normally takes 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 As a result of 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 trimethylaluminium, triethylaluminum, triisobutylaluminum, methylaluminoxane, triethylborane, dibutylmagnesium.
  • 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 xylene.
  • the inerting takes place at temperatures between 0 ° C and 120 ° C, preferably between 20 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 carrier material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then dried in an inert gas stream or under vacuum.
  • the supported catalyst system can also contain more than one metallocene.
  • metallocenes which can be used in this context are described, for example, in EP-A-0 485 821, DE 195 44 828 AI or EP-A-0 576 970. These are preferably bridged bisindenyl metallocenes which are in the 2-; 2.4-; 2.5-; 2,4,5-; 2,4,6-; 2,4,7-; 2,4,5,6- or 2, 5, 6-position are substituted.
  • At least one of the metallocene components of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
  • the preparation thus obtained is then mixed with the dehydrated or rendered inert carrier material, the solvent is removed and the resulting supported metallocene catalyst system is dried to ensure that the solvent is completely or largely removed from the pores of the carrier material.
  • the supported catalyst is obtained as a free-flowing powder.
  • a possible method for producing a free-flowing and optionally prepolymerized supported catalyst system comprises the following steps:
  • Process steps a) and b) can also be combined, where
  • Preferred solvents for the production of the metallocene / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
  • the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of metallocene and cocatalyst components is soluble in the chosen solvent.
  • suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Toluene is very particularly preferred.
  • a molar ratio of aluminum to transition metal in the metallocene of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1.
  • the metallocene can be dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the metallocene separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used. If several metallocenes are used, the dissolving process can be carried out separately or with the previously mixed metallocenes.
  • the preactivation time can be 1 minute to 200 hours.
  • the pre-activation can take place at room temperature (20 ° C). In individual cases, the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity. In this case, a higher temperature means a range between 20 and 150 ° C.
  • the preactivated solution (s) or the metallocene / cocatalyst mixture (s) can / can subsequently be mixed with an inert carrier material, preferably silica gel, in the form of a dry powder or as a suspension in one of the above mentioned solvents are present.
  • the carrier material is preferably used as a powder.
  • the order of addition is arbitrary. If several solutions or metallocene / cocatalyst mixtures are used, intermediate drying can also take place between the individual addition steps (sequential support).
  • the preactivated metallocene-cocatalyst solution (s) or the metallocene-cocatalyst mixture (s) can be metered into the support material or the support material can be introduced into the solution (s) .
  • the volume (or the sum of the individual volumes) of the preactivated solution (s) or of the metallocene / cocatalyst mixture (s) can exceed 100% of the total pore volume of the support material used or can be up to 100% of the total pore volume.
  • the temperature at which the preactivated solution (s) or the metallocene / cocatalyst mixture (s) is / are brought into contact with the support material can vary in the range between 0 and 100 ° C. However, lower or higher temperatures are also possible.
  • the solvent or solvent mixture is then completely or for the most part removed from the supported catalyst system, the mixture being able to be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed.
  • the solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C.
  • the free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores.
  • the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely.
  • the supported catalyst system can then be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
  • the supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before being used in a polymerization process.
  • the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
  • an olefin preferably an ⁇ -olefin (for example styrene or phenyldimethylvinylsilane) as an activity-increasing component or for example an antistatic agent (as in US patent application Serial No. 08/365280)
  • ⁇ -olefin for example styrene or phenyldimethylvinylsilane
  • an antistatic agent as in US patent application Serial No. 08/365280
  • the molar ratio of additive to metallocene is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
  • the present invention also relates to a process for the preparation of a polyolefin by polymerization of one or more olefins in the presence of the catalyst system according to the invention, comprising at least one transition metal component of the formula I.
  • polymerization is understood to mean homopolymerization and also copolymerization.
  • olefins examples include 1-olefins having 2 to 40, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene, ethyl - norbornadiene and cyclic olefins such as norbornene, tetracyclododecenes or methylnorbornene.
  • 1-olefins having 2 to 40, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norborna
  • propene or ethene are preferably homopolymerized, or Propene with ethene and / or with one or more 1-01efins with 4 to 20 C atoms, such as hexene, and / or one or more dienes with 4 to 20 C atoms, such as 1, 4-butadiene, norbornadiene, ethylidene copolymerized norbones or ethyl norbornadiene.
  • Examples of such copolymers are ethene / propene copolymers or ethene / propene / 1,4-hexadiene terpolymers.
  • the polymerization is carried out at a temperature of from -60 to 300 ° C., preferably from 50 to 200 ° C., very particularly preferably from 50 to 100 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 5 to 100 bar.
  • the catalyst system can be metered into the polymerization system in any manner.
  • the catalyst system is preferably metered in in the form of a powder, a suspension or a paste with an adapted viscosity.
  • Two or more catalyst systems according to the invention or mixtures of catalyst system (s) according to the invention with at least one further catalyst system can also be separated into the polymerization or metered in as a mixture.
  • the polymerization can be carried out in solution, in bulk, in suspension, in the gas phase or in a supercritical medium continuously or batchwise, in one or more stages.
  • the catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one alkyl compound of the elements from I. to III.
  • Main group of the periodic table e.g. an aluminum, magnesium or lithium alkyl or an aluminoxane can be used.
  • the alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances that can impair the catalyst activity. The amount of alkyl compound added depends on the quality of the monomers used.
  • hydrogen is added as a molecular weight regulator and / or to increase the activity.
  • an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used.
  • the addition of an antistatic can also be carried out after the polymerization Process step may be useful to improve the processing of the polymer.
  • the catalyst systems according to the invention are highly active and no deposits or caking occur during the polymerization.
  • polymers such as polypropylene
  • polypropylene can be obtained with extremely high stereo and region specificity.
  • copolymers which can be prepared using the catalyst system according to the invention are notable for high molar masses. At the same time, such copolymers can be produced by using the catalyst system according to the invention with high productivity with technically relevant process parameters without formation of deposits.
  • the polymers obtainable by the process according to the invention are particularly suitable for the production of tear-resistant, hard and rigid moldings such as fibers, filaments, injection molded parts, foils, sheets or large hollow bodies (e.g. pipes), as well as for the production of copolymers with high rigidity, toughness, low white breakage and transparency.
  • organometallic compounds were produced and handled with the exclusion of air and moisture under an argon protective gas (Schlenk technique or glove box). All required solvents were flushed with argon before use and absoluteized using a molecular sieve.
  • the metallocenes used were analyzed by iH-NMR, 13 C-NMR and IR
  • Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 't-butyl-phenyl) -indene) and Dimethylsilanediyl (2, 5-dimethyl-N-phe-5 nyl-4-azapentalen ) (2-methyl-4- (4 '- tert -butyl-phenyl-indene) were analogous to the ligand synthesis in WO 98/22486 from 2-methyl-4- (4'-tert. -Butyl-phenyl) -indene and the corresponding dimethylchlorosilanediylpentalene derivative.
  • Example la 45 Representation of the supported catalyst system: 62 mg (0.09 mmol) of dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were dissolved in 4.3 cm 3 (20 mmol AI) 30% toluene solution of methylaluminoxane 1 * was dissolved, the solution was diluted with 3.7 cm 3 of toluene and protected from light for 1 hour at 25 ° C. This solution was added in portions to 4 g of SiO 2 2) and the mixture was mixed at the end of the addition, stirring was continued for 10 min.
  • the ratio of the volume of the solution to the total pore volume of the carrier material was 1.25.
  • the mixture was then dried at 40 ° C. and 10 -3 mbar within 4 h. 5.6 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.17% by weight of Zr and 9.7% by weight of Al.
  • the catalyst activity was 1.7 kg PP / (g cat x h).
  • the polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor showed no deposits.
  • Carrier The carrier example la was repeated, but it was
  • the result was 3.1 kg of polypropylene powder with a bulk density of 462 g / dm 3 .
  • the catalyst activity was 3.1 kg PP / (g cat x h).
  • the polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor showed no deposits.
  • Carrier example 1a was repeated, but 55 mg (0.09 mmol) of dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride were used.
  • the catalyst activity was 1.3 kg PP / (g cat x h).
  • the polymer was a free flowing powder and contained neither
  • Carrier example 1a was repeated, but 110 mg (0.18 mmol) of dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used.
  • the result was 2.4 kg of polypropylene powder with a bulk density of 432 g / dm 3 .
  • the catalyst activity was 2.4 kg PP / (g cat x h).
  • the polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor showed no deposits.
  • Solution A was added a little at a time to 4 g of SiO 2) . After the addition had ended, the mixture was stirred for 10 min. Then solution B was also added in portions with stirring. After the addition had ended, the mixture was also stirred for a further 10 min. The ratio of the total volume of solution A plus volume of solution B to the total pore volume of the carrier material was 1.25. The mixture was then dried at 40 ° C. and 10 -3 mbar within 4 h. 5.7 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.36% by weight of Zr and 9.9% by weight of Al.
  • Example 1 a The procedure was as in Example 1 a because of the high catalyst activity, the polymerization was terminated after 30 minutes. The result was 1.8 kg of polypropylene powder with a bulk density of 450 g / dm 3 .
  • the catalyst activity was 3.6 kg PP / (g cat x h).
  • the polymer was a free flowing powder and contained neither fine grain fractions nor agglomerates. The inspection of the reactor showed that there was no coating.
  • the polymerization was stopped by degassing and the copolymer obtained was dried in vacuo.
  • the result was 1.35 kg of free-flowing, agglomerate-free powder with a bulk density of 445 g / dm 3 .
  • the copolymer contained 3.5% by weight of statistically incorporated ethylene.
  • the catalyst activity was 2.7 kg copolymer / (g cat x h). The inspection of the reactor showed no deposits.
  • a dry 24 dm 3 reactor which had first been flushed with nitrogen and then with propene, was filled with 12 dm 3 of liquid propene, 0.25 Ndm 3 of hydrogen and 50 g of ethylene. 4 cm 3 of a 20% strength triethylaluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 5 min. A suspension of 1 g of the supported metallocene catalyst from Example 3 (support) in 20 cm 3 of Exxsol was then added to the reactor, heated to the polymerization temperature of 60 ° C. and the polymerization system was kept at 60 ° C. for 30 minutes.
  • the polymerization was stopped by degassing and the copolymer obtained was dried in vacuo.
  • the result was 1.4 kg of free-flowing, agglomerate-free powder with a bulk density of 430 g / dm 3 .
  • the copolymer contained 3.3% by weight of statistically incorporated ethylene.
  • the catalyst activity was 2.8 kg copolymer / (g cat x h). The inspection of the reactor showed no deposits.
  • a dry 24 dm 3 reactor which had first been flushed with nitrogen and then with propene, was filled with 10 dm 3 of liquid propene and 5 Ndm 3 of hydrogen. 6 cm 3 of a 20% strength triisobutylaluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 5 min.
  • a suspension of 0.5 g of the supported metallocene catalyst from Example 3 (support) was then rinsed into the reactor via a pressure lock with 2 dm 3 of liquid propene. It was then heated to the polymerization temperature of 75 ° C (7.5 ° C / min, in situ prepolymerization) and the polymerization system was kept at this temperature for 1 h.
  • the reactor was then let down to 10 bar and 25 bar of ethylene were applied.
  • the batch was polymerized further at 60 ° C. for 1 h.
  • the polymerization was stopped by degassing and the block copolymer obtained was dried in vacuo.
  • the result was 3.2 kg of free-flowing, agglomerate-free powder with a bulk density of 440 g / dm 3 .
  • the rubber (ethylene-propylene copolymer) produced in the second polymerization stage contained 39% by weight of ethylene and had a glass transition temperature of ⁇ 50 ° C. The inspection of the reactor showed no deposits.
  • Carrier example 1a was repeated, but 57 mg (0.09 mmol) of dimethylsilanediylbis (2, 5-dimethyl-N-phenyl-4-aza-pentalen) zirconium dichloride were used. 5.6 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.18% by weight of Zr and 9.8% by weight of Al.
  • Carrier example 1a was repeated, but 114 mg (0.18 mmol) of dimethylsilanediylbis (2, 5-dimethyl-N-phenyl-4-aza-pentalen) zirconium dichloride were used. 5-.5-g of a free-flowing powder were obtained, which according to elemental analysis contained 0.38% by weight of Zr and 9.4% by weight of Al.
  • Carrier example 1a was repeated, but 55 mg (0.09 mmol) of dimethylsilanediyl (2-methyl-indenyl) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used.
  • the catalyst activity was 1.4 kg PP / (g Kat xh).
  • the polymer was a free-flowing powder and contained neither fine-grain fractions nor agglomerates. The inspection of the reactor revealed that there was no deposit.
  • Carrier example 1a was repeated, except that 110 mg (0.18 mmol) of dimethylsilanediyl (2-methyl-indenyl) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used. 5.5 g of a free-flowing solution were used Powder obtained, which according to elemental analysis contained 0.40 wt% Zr and 10.1 wt% AI.
  • the result was 2.5 kg of polypropylene powder with a bulk density of 400 g / dm 3 .
  • the catalyst activity was 2.5 kg PP / (g cat x h).
  • the polymer contained 9.5% by weight of agglomerates.
  • the inspection of the reactor showed deposits on the reactor wall and on the stirrer blades.
  • Carrier example Ia was repeated, but 67 mg (0.09 mmol) of rac-dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used. 5.8 g of a free-flowing powder were obtained, which, according to Elemental analysis contained 0.18 wt% Zr and 9.6 wt% AI. Polymerization:
  • the result was 1.7 kg of polypropylene powder with a bulk density of 475 g / dm 3 .
  • the catalyst activity was 1.7 kg PP / (g Kat xh).
  • the polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor revealed that there was no deposit.
  • Carrier example 1a was repeated, but 134 mg (0.18 mmol) of rac-dimethylsilanediylbis (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride were used. 5.6 g of a free-flowing powder were obtained, which according to elemental analysis contained 0.37% by weight of Zr and 9.9% by weight of Al.
  • the result was 3.2 kg of polypropylene powder with a bulk density of 440 g / dm 3 .
  • the catalyst activity was 3.2 kg PP / (g cat x h).
  • the polymer contained about 5% by weight of agglomerates.
  • the inspection of the reactor showed deposits on the reactor wall and on the stirrer blades.
  • Carrier example 1a was repeated, but 44 mg (0.09 mmol) of dimethylsilanediylbis (2-methyl-4-thiapentalene) zirconium dichloride were used. 5.6 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.16% by weight of Zr and 9.5% by weight of Al.
  • Carrier example 1a was repeated, but 88 mg (0.18 mmol) of dimethylsilanediylbis (2-4-thiapentalene) zirconium dichloride were used. 5.7 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.39% by weight of Zr and 9.7% by weight of Al.

Abstract

The invention relates to specifically substituted metallocenes and to corresponding highly active supported catalyst systems. According to the invention, said catalyst systems are used for olefin polymerization. The invention also relates to a method for producing said systems and to polymers produced with said supported catalyst systems.

Description

Organometallverbindung, Katalysatorsystem enthaltend diese Organo etallverbindung und seine Verwendung.Organometallic compound, catalyst system containing this organometallic compound and its use.
Beschreibungdescription
Die vorliegende Erfindung betrifft speziell substituierte Metall - ocene und entsprechende hochaktive geträgerte Katalysatorsysteme, die vorteilhaft bei der Olefinpolymerisation eingesetzt werden können und ein Verfahren zu ihrer Herstellung sowie Polymere, die mit den geträgerten KatalysatorSystemen hergestellt werden. Verfahren zur Herstellung von Polyolefinen mit Hilfe von löslichen, homogenen Katalysatorsystemen, bestehend aus einer Über- gangsmetallkomponente vom Typ eines Metallocens und einer Cokata- lysator-Komponente vom Typ eines Aluminoxans, einer Lewis-Säure oder einer ionischen Verbindung sind bekannt. Diese Katalysatoren liefern bei hoher Aktivität Polymere und Copolymere mit enger Molmassenverteilung .The present invention relates to specially substituted metal ocenes and corresponding highly active supported catalyst systems which can advantageously be used in olefin polymerization and to a process for their preparation and to polymers which are prepared using the supported catalyst systems. Processes for the production of polyolefins using soluble, homogeneous catalyst systems, consisting of a transition metal component of the metallocene type and a cocatalyst component of the aluminoxane type, a Lewis acid or an ionic compound, are known. With high activity, these catalysts deliver polymers and copolymers with a narrow molecular weight distribution.
Bei Polymerisationsverfahren mit löslichen, homogenenIn polymerization processes with soluble, homogeneous
Katalysatorsystemen bilden sich starke Beläge an Reaktorwänden und Rührer aus, wenn das Polymer als Feststoff anfällt. Diese Beläge entstehen immer dann durch Agglomeration der Polymer- partikel, wenn Metallocen und/oder Cokatalysator gelöst in der Suspension vorliegen. Derartige Beläge in den Reaktorsystemen müssen regelmäßig entfernt werden, da diese rasch erhebliche Stärken erreichen, eine hohe Festigkeit besitzen und den Wärmeaustausch zum Kühlmedium verhindern. Industriell in modernen Polymerisationsverfahren, beispielsweise in flüssigem Monomer oder in der Gasphase, sind solche homogenen Katalysatorsysteme nicht einsetzbar.Catalyst systems form heavy deposits on the reactor walls and stirrer when the polymer is obtained as a solid. These deposits always arise from agglomeration of the polymer particles when metallocene and / or cocatalyst are present in solution in the suspension. Such deposits in the reactor systems must be removed regularly, since these quickly reach considerable strengths, have high strength and prevent heat exchange with the cooling medium. Such homogeneous catalyst systems cannot be used industrially in modern polymerization processes, for example in liquid monomer or in the gas phase.
Zur Vermeidung von Belagsbildung im Reaktor sind geträgerte Katalysatorsysteme vorgeschlagen worden, bei denen das Metallocen und/oder die als Cokatalysator dienende Aluminiumverbindung auf einem anorganischen Trägermaterial fixiert werden.To avoid the formation of deposits in the reactor, supported catalyst systems have been proposed in which the metallocene and / or the aluminum compound serving as cocatalyst are fixed on an inorganic support material.
Aus EP-A 0 576 970, EP-A 0 659 756 und EP-A 0 659 757 sind Metallocene und entsprechende geträgerte Katalysatorsysteme be- kannt.Metallocenes and corresponding supported catalyst systems are known from EP-A 0 576 970, EP-A 0 659 756 and EP-A 0 659 757.
Zur Absenkung von Katalysatorrestgehalten im Polymer und aus Kostengründen ist eine Verbesserung der Katalysatoraktivitäten wünschenswe t . Durch eine Erhöhung der Beladung des Trägers mit Wirksubstanzen (Metallocenkomponente (n) , Cokatalysator (en) und gegebenenfalls Additive) lassen sich die Katalysatoraktivitäten erhöhen, gleichzeitig neigen solche Katalysatoren aber zu starker Belagsbildung und sind industriell nicht einsetzbar.In order to reduce residual catalyst contents in the polymer and for reasons of cost, an improvement in the catalyst activities is desirable. The catalyst activities can be increased by increasing the loading of the support with active substances (metallocene component (s), cocatalyst (s) and optionally additives), but at the same time such catalysts tend to form large amounts of deposits and cannot be used industrially.
Es bestand somit die Aufgabe, spezielle Metallocene sowie geträgerte Metallocenkatalysatorsysteme bereitzustellen, die auch bei hoher Katalysatoraktivität, entsprechend hoher Belegung mit Wirksubstanzen, unter technisch relevanten Polymerisationsbedingungen eine belagsfreie Polymerisation ermöglichen und Polymere mit hohem Schmelzpunkt und hoher Molmasse liefern.It was therefore the task of providing special metallocenes and supported metallocene catalyst systems which, even with high catalyst activity, correspondingly high occupancy of active substances, enable polymerisation without deposits under technically relevant polymerization conditions and deliver polymers with a high melting point and high molar mass.
Die der vorliegenden Erfindung zugrundeliegende Aufgabe wird durch ein speziell substituiertes Metallocen, ein geträgertes Katalysatorsystem, das mindestens ein speziell substituiertes Metallocen, mindestens einen Cokatalysator, mindestens einen Träger und gegebenenfalls mindestens eine weitere Additivkomponente enthält, gelöst.The object on which the present invention is based is achieved by a specially substituted metallocene, a supported catalyst system which contains at least one specially substituted metallocene, at least one cocatalyst, at least one carrier and, if appropriate, at least one further additive component.
Das Katalysatorsystem wird erfindungsgemäß hergestellt, indem mindestens ein speziell substituiertes Metallocen, mindestens ein Cokatalysator und mindestens ein Träger und gegebenenfalls mindestens eine weitere Additivkomponente gemischt werden.The catalyst system is produced according to the invention by mixing at least one specially substituted metallocene, at least one cocatalyst and at least one carrier and, if appropriate, at least one further additive component.
Bei dem erfindungsgemäßen Metallocen, welches auch als Metallocenkomponente im erfindungsgemäßen Katalysatorsystem eingesetzt wird, handelt es sich um eine Verbindung der nachstehenden Formel I The metallocene according to the invention, which is also used as a metallocene component in the catalyst system according to the invention, is a compound of the formula I below
worinwherein
M1 ein Metall der Gruppe IVb des Periodensystems der Elemente ist,M 1 is a metal from group IVb of the Periodic Table of the Elements,
R1 und R2 gleich oder verschieden sind und ein Wasserstoffatom, eine Cι-Cιo-Alkylgruppe, eine Cχ-Cιo-Alkoxygruppe, eineR 1 and R 2 are the same or different and a hydrogen atom, a Cι-Cιo-alkyl group, a Cχ-Cιo alkoxy group, a
C6-C2o-Arylgruppe, eine C6-Cιo-Aryloxygruppe, eine C2-Cι0-Alkenylgruppe, eine OH-Gruppe, eine NR12 2-Gruppe, wobei R12 eine Cj bis Cio -Alkylgruppe oder C6 bis Cχ4-Arylgruppe ist, oder ein Halogenatom bedeuten,C 6 -C 2 o-aryl group, a C 6 -Cιo aryloxy group, a C 2 -Cι 0 alkenyl group, an OH group, an NR 12 2 group, where R 12 is a Cj to Cio alkyl group or C 6 to Cχ 4 aryl group, or a halogen atom,
R3, R4, R6, R7 und R8 sowie R3' und R4' gleich oder verschieden sind und ein Wasserstoffatom, eine Kohlenwasserstoffgruppe, die teilhalogeniert, alo"- geniert, linear, cyclisch oder verzweigt sein kann, z.B. eine Cι-Cιo-Alkylgruppe, C2-Cι0-Alkenylgruppe, C6-C2rj-Aryl- gruppe, eine C -C4o-Arylalkylgruppe, eine C7-C4o-Alkyl- arylgruppe, eine C8-C4o-Arylalkenylgruppe, eine Si(R13)3-, N(R13)2-, SR13- oder OR13-Gruppe bedeuten, mit R13 in der Bedeutung von R4 , mit der Maßgabe, daß R3 von Wasser- stoff verschieden ist, R3' und R4' auch cyclisch verbunden sein können, und R5 eine C6 bis C40 -Arylgruppe die in para-Position zur Bindungs- stelle an den Indenylring einen Substituenten R14 trägt, bedeutet,R 3 , R 4 , R 6 , R 7 and R 8 and R 3 'and R 4 ' are the same or different and are a hydrogen atom, a hydrocarbon group which can be partially halogenated, alo "-generated, linear, cyclic or branched, for example a -C-Cιo-alkyl group, C 2 -Cι 0 alkenyl group, C 6 -C 2 rj-aryl group, a C -C 4 o-arylalkyl group, a C 7 -C 4 o-alkyl aryl group, a C 8th -C 4 o-arylalkenyl group, an Si (R 13 ) 3 -, N (R 13 ) 2 -, SR 13 - or OR 13 group, with R 13 as R 4 , with the proviso that R 3 is different from hydrogen, R 3 'and R 4 ' can also be cyclically linked, and R 5 is a C 6 to C 40 aryl group which has a substituent R 14 in the para position to the point of attachment to the indenyl ring,
wobeiin which
R14 ein Halogenatom F, Cl oder Br, ein Ci bis C o-Alkylrest, ein C2 bis C2o-Alkenylrest , ein C6 bis C24-Arylrest, ein C7 bis C4o-Arylalkylrest, ein C7 bis C4o-Alkylarylrest, ein Cs bis C4o-Arylalkenylrest wobei die Kohlenwasserstoffreste auch mit Fluor, Chlor oder Brom halogeniert oder teilhalogeniert sein können, -N(R15)2 , -Ε> (R15) 2 , -SR15, -0R15, -Si(R15)3,R 14 is a halogen atom F, Cl or Br, a Ci to C o -alkyl radical, a C 2 to C 2 o-alkenyl radical, a C 6 to C 24 aryl radical, a C 7 to C 4 o-arylalkyl radical, a C 7 to C 4 o -alkylaryl, a Cs to C 4 o-arylalkenyl radical where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine, chlorine or bromine, -N (R 15 ) 2 , -Ε> (R 15 ) 2 , -SR 15 , -0R 15 , -Si (R 15 ) 3 ,
-[N(R15)3]+ oder -[P(R15)3]+ bedeutet mit R15 in der Bedeutung von R4, die Reste R16 trotz gleicher Indizierung gleich oder verschieden sein können und die Bedeutung von R14 oder Wasserstoff haben und jeweils benachbarte Reste R16 auch cyclisch verbunden sein können, oder einer oder mehrere der Reste R16 bilden mit den Resten R6 oder R4 und/oder R14 eine cyclische Verknüpfung, mit der Maßgabe, daß R14 auch Wasserstoff sein kann, wenn mindestens einer der Reste R16 von Wasserstoff verschieden ist,- [N (R 1 5) 3 ] + or - [P (R 15 ) 3 ] + means with R 15 in the meaning of R 4 , the radicals R 16 can be the same or different despite the same indexing and the meaning of R 14 or hydrogen and adjacent R 16 radicals can also be cyclically linked, or one or more of the R 16 radicals form a cyclic linkage with the R 6 or R 4 and / or R 14 radicals, with the proviso that R 14 also Can be hydrogen if at least one of the radicals R16 is different from hydrogen,
R9 bedeutet eine VerbrückungR 9 means a bridge
R 1 0 R 1 0 R 1 0 1 0R 1 0 R 1 0 R 1 0 1 0
R 1 0 RR 1 0 R
I II I
0 — - 0 - - c - 0 M - C M0 - - 0 - - c - 0 M - C M
1 1 I 1 1 1 1 R " , R R R 1 1 R1 1 I 1 1 1 1 R ", RRR 1 1 R
R 1 0 R 1 0 R 1 0 R 1 0 R 1 0 R 1 0
I I I — c — c — c —I I I - c - c - c -
I I I R 1 1 R 1 1 R 1 1 ,IIIR 1 1 R 1 1 R 1 1 ,
/BR1 0 ,/A I R1 0 , -Ge- , -0- , -S- , ode r P ( 0 ) R ' ° , wobei/ BR 1 0 , / AIR 1 0 , -Ge-, -0-, -S-, or P (0) R '°, in which
R10, R11 auch bei gleicher Indizierung, gleich oder verschieden sein können und ein Wasserstoffatom, ein Halogenatom, eine Cι-C4o-heteroatomhaltige Kohlenwasserstoff-Gruppe oder eine Cι-C4o-kohlenstoffhaltige Gruppe bedeuten, wie eine Cι-C20-Alkyl-, eine Cι-C10-Fluoralkyl-, eine Cι-Cιo-Alkoxy-, eine C6-C14-Aryl-, eine Cδ-Cio-Fluoraryl-, eine C6-Cι0-Aryloxy-, eine C2-Cιo-Alkenyl-, eine C7-C4o-Arylalkyl-, eine C7-C40-Alkylaryl-, eine C8-C40-Arylalkenylgruppe, eine -N(Rl7)2 , -P(Rl7)2, -SR17, -ORi7, -SiR3 17, -[N(Ri7)3]-*- oder -[P(R17)3]+ bedeuten mit R17 in der Bedeutung von R4, oder R10 und R11 bilden jeweils mit den sie verbindenden Atomen einen oder mehrere Ringe,R 10 , R 11 can also be the same or different with the same indexing and denote a hydrogen atom, a halogen atom, a C 1 -C 4 o-hetero atom-containing hydrocarbon group or a C 1 -C 4 o -carbon-containing group, such as a C 1 -C 20 -alkyl, a Cι-C 10 fluoroalkyl, a Cι-Cιo alkoxy, a C 6 -C 14 aryl, a C δ -Cio-fluoroaryl group, a C 6 -aryloxy -Cι 0 , a C 2 -Cιo alkenyl, a C 7 -C 4 o-arylalkyl, a C 7 -C 40 alkylaryl, a C 8 -C 40 arylalkenyl group, a -N (Rl 7 ) 2 , - P (Rl 7 ) 2 , -SR 17 , -OR i7 , -SiR 3 17 , - [N (R i7 ) 3 ] - * - or - [P (R 17 ) 3 ] + mean with R 17 in meaning of R 4 , or R 10 and R 11 each form one or more rings with the atoms connecting them,
x bedeutet eine ganze Zahl von 0 bis 18,x means an integer from 0 to 18,
M2 bedeutet Silizium, Germanium oder Zinn, und unter heteroatom- haltigen Kohlenwasserstoffgruppen sind Kohlenwasserstoffe zu verstehen, die mindestens ein Element der Gruppen 13 bis 16 des Periodensystems der Elemente enthalten.M 2 means silicon, germanium or tin, and heteroatom-containing hydrocarbon groups are understood to mean hydrocarbons which contain at least one element from groups 13 to 16 of the Periodic Table of the Elements.
R9 kann auch zwei Einheiten der Formel I miteinander verknüpfen.R 9 can also link two units of the formula I to one another.
Ra bedeutet eine gesättigte oder ungesättigte Kohlenwasserstoff- gruppe, vorzugsweise mit 1 bis 40 Kohlenstoffatomen, ins - besondere mit 1 bis 30 Kohlenstoffatomen, die auch mit einem oder mehreren Resten in der Bedeutung von R3 substituiert sein können, wobei der Rest R als solcher mindestens ein Heteroatom aus den Gruppen 13, 14, 15 oder 16 des Periodensystems der Elemente enthält. In der vorstehenden Bedeutung Ra bedeutet dies, daß das Heteroatom in dem Ringsystem als solches eingebaut vorliegt. Sollte das Ringsystem bereits mindestens ein Heteroatom beinhalten, so können auch ein oder mehrere Reste R3 ein Heteroatom enthalten.R a denotes a saturated or unsaturated hydrocarbon group, preferably with 1 to 40 carbon atoms, in particular with 1 to 30 carbon atoms, which can also be substituted by one or more radicals with the meaning of R 3 , the radical R as such contains at least one heteroatom from groups 13, 14, 15 or 16 of the Periodic Table of the Elements. In the above meaning R a , this means that the heteroatom is present as such in the ring system. If the ring system already contains at least one heteroatom, one or more radicals R 3 can also contain a heteroatom.
Die den Verbindungen der Formel I entsprechenden 4, 5, 6, 7-Tetra- hydroindenyl-analoga sind ebenfalls von Bedeutung.The 4, 5, 6, 7-tetrahydroindenyl analogs corresponding to the compounds of the formula I are also important.
In Formel I gilt bevorzugt, daßIn formula I it is preferred that
M1 Zirkonium, Hafnium oder Titan ist,M 1 is zirconium, hafnium or titanium,
R1 und R2 gleich sind und für Methyl, Dimethylamid, Dibenzyl oder Chlor stehen,R 1 and R 2 are the same and represent methyl, dimethylamide, dibenzyl or chlorine,
R3 und R3' gleich oder verschieden sind und eine Kohlenwasserstoffgruppe, die teilhalogeniert, halogeniert, linear, cyclisch oder verzweigt sein kann, z.B. eine Cι-Cιo~Alkylgruppe, C -Cιo-Alkenyl- gruppe, eine C -C4o-Alkylarylgruppe bedeuten,R 3 and R 3 'are the same or different and are a hydrocarbon group which can be partially halogenated, halogenated, linear, cyclic or branched, for example a -C 1 -C ~ alkyl group, C -C 1o alkenyl group, a C -C 4 o- Alkylaryl group mean
R9 Ri°R"Si=, R10R1:LGe=, RiθR11C= oder - (RioRιιc_CRιoRιi) - bedeutet, wobei R10 und R11 gleich oder verschieden sind und Wasserstoff, eine Cι-C2o~Kohlenwasserstoffgruppe, insbesondere Cι-Cιo-Alkyl oder C6-Cι4-Aryl bedeuten,R 9 Ri ° R "Si =, R 10 R 1: L Ge =, RiθR 11 C = or - (Rio R ιι c _ CR ιo R ιi) - means, where R 10 and R 11 are the same or different and are hydrogen , a C 2 -C ~ hydrocarbon group, in particular C 1 -C 4 alkyl or C 6 -C 4 aryl,
R5 eine C6 bis C2o -Arylgruppe bedeutet, die in para-Position zur Bindungsstelle an den Indenylring einen Substituenten R14 trägt, und R14 ein Ci bis Cιo_Alkylrest, ein C2 bis Cio-Alkenylrest , ein C6 bis Cχ8-Arylrest, ein C bisR 5 is a C 6 to C 2 o aryl group having a substituent R contributes in para-position to the binding site on the indenyl ring 14, and R 14 is a Ci to Cιo _ alkyl, C 2 to Cio-alkenyl radical, a C 6 to Cχ 8 aryl, a C to
C2o-Arylalkylrest, ein C bis C2o~Alkylarylrest, ein Cs bis C20-Arylalkenylrest wobei die Kohlenwasserstoffreste auch mit Fluor oder Chlor halogeniert oder teilhalogeniert sein können, -N(R15)2 , _p(Rl5)2 -SR15, -Si(Rl5)3 _[N(R15)3] + oder -[P(R15)3]+ bedeuten, mit R15 in der Bedeutung von R4, und die Reste R16 gleich oder verschieden sind und Fluor, Chlor, Wasserstoff, einen Ci bis Cιo_Alkylrest, der auch mit Fluor oder Chlor halogeniert oder teilhalogeniert sein kann, einen C6 bis Ci8~Arylrest oder einen C2 bis Cio-Alkenylrest bedeuten, oder benachbarte Reste R16 cyclisch verbunden sind.C 2 o-arylalkyl, a C to C 2 ~ alkylaryl, a Cs to C 20 -arylalkenyl radical, where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine or chlorine, - N (R15) 2 , _p (Rl5) 2 -SR15 , -Si ( R 15) 3 _ [ N ( R 15) 3 ] + or - [P (R 15 ) 3 ] + mean, with R 15 as R 4 , and the radicals R 16 are the same or different and fluorine, chlorine, hydrogen, a Ci to Cιo _ alkyl radical, which can also be halogenated or partially halogenated with fluorine or chlorine, a C 6 to Ci 8 ~ aryl radical or a C 2 to Cio-alkenyl radical, or neighboring radicals R 16 cyclically are connected.
Ra bedeutet eine gesättigte oder ungesättigte Kohlenwasserstoff- gruppe mit 2 bis 40 Kohlenstoff tomen die auch mit Resten in der Bedeutung von R3 substituiert sein kann, und die minde- stens ein Heteroatom ausgewählt aus der Gruppe B, AI, Si, Sn, N, P, O oder S enthält. In Formel I gilt ganz besonders bevorzugt, daßR a denotes a saturated or unsaturated hydrocarbon group with 2 to 40 carbon atoms, which can also be substituted with radicals as R 3 , and which has at least one heteroatom selected from the group B, Al, Si, Sn, N , P, O or S contains. In formula I it is particularly preferred that
M1 Zirkonium ist,M 1 is zirconium,
R1 und R2 gleich sind und für Methyl oder Chlor stehen,R 1 and R 2 are the same and represent methyl or chlorine,
R3 und R3' gleich oder verschieden sind und eine Kohlenwasserstoffgruppe, die halogeniert, linear, cyclisch oder verzweigt sein kann, z.B. eine Cι-Cιo-Alkylgruppe, C2-Cι0-Alkenylgruppe, eine C7-C40-Alkylarylgruppe bedeuten,R 3 and R 3 'are the same or different and are a hydrocarbon group which can be halogenated, linear, cyclic or branched, for example a -C-Cιo-alkyl group, C 2 -Cι 0 -alkenyl group, a C 7 -C 40 -alkylaryl group ,
R9 oder - - ist, worin R10 und R11 gleich oder verschieden sind und Wasserstoff, Phenyl, Methyl oder Ethyl bedeuten, die Reste, R4,R6,R7 und R8 sowie R4' Wasserstoff sind, R 9 or - is in which R 10 and R 11 are identical or different and denote hydrogen, phenyl, methyl or ethyl, the radicals, R 4 , R 6 , R 7 and R 8 and R 4 'are hydrogen,
R5 eine C6 bis C20 -Arylgruppe, insbesondere eine Phenyl-,R 5 is a C 6 to C 20 aryl group, in particular a phenyl group,
Naphthyl- oder Anthracenyl-Gruppe bedeuten, die in para-Posi- tion zur Bindungsstelle an den Indenylring einenNaphthyl or anthracenyl group mean one in the para position to the binding site to the indenyl ring
Substituenten R14 trägt, wobei R14 ein Si(R15)3 -Rest , mit R15 in der Bedeutung von R4 , oder ein linearer Ci bis Cχo- Alkyl- rest, ein verzweigter C3 bis C10- Alkylrest, ein C2 bis Cin- Alkenylrest oder ein verzweigter C bis C o~ Alkylarylrest ist, wobei die Kohlenwasserstoffreste auch mit Fluor oder Chlor halogeniert oder teilhalogeniert sein können, undR 14 carries substituents, where R 14 is a Si (R 15 ) 3 radical, with R 15 as R 4 , or a linear Ci to Cχo alkyl radical, a branched C 3 to C 10 alkyl radical C 2 to Cin-alkenyl radical or a branched C to C o ~ alkylaryl radical, where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine or chlorine, and
Ra eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen, die auch mit Resten in der Bedeu- tung von R3 substituiert sein kann, und die mindestens einR a is a saturated or unsaturated hydrocarbon group with 1 to 30 carbon atoms, which can also be substituted with radicals as R 3 , and which has at least one
Heteroatom ausgewählt aus der Gruppe N, P, 0 oder S enthält.Heteroatom selected from the group N, P, 0 or S contains.
Das Fragment Ra bildet zusammen mit dem Cyclopentadienyl-Grundkör- per, an den es gebunden ist ganz besonders bevorzugt folgende Mo- lekülfragmente der Formel I ( in den Molekülfragmenten wurde aus Gründen der Übersichtlichkeit in den heteroatomhaltigen Ringen auf das Einzeichnen der Wasserstoff tome verzichtet. Es wurden nur Reste R berücksichtigt und indiziert, die auch von Wasserstoff verschieden sein können) : The fragment R a together with the cyclopentadienyl base to which it is attached very particularly preferably forms the following molecular fragments of the formula I (for reasons of clarity, the hydrogen atoms in the heteroatom-containing rings have been omitted in the rings). Only residues R were taken into account and indicated, which can also be different from hydrogen):
Wobei die Heteroatomfunktionen X gleich oder verschieden sind und die Bedeutung NRλ, PRλ, N, 0 oder S haben, die Reste Rδ, Rε, R^ und R Wasserstoff sind oder die Bedeutung von R3 haben, die Reste Rα die Bedeutung von R3' und die Reste RP die Bedeutung von R4' ha- ben. The heteroatom functions X are the same or different and have the meaning NR λ , PR λ , N, 0 or S, the radicals R δ , R ε , R ^ and R are hydrogen or the meaning of R 3 , the radicals R α the meaning of R 3 'and the radicals RP have the meaning of R 4 '.
Beispiele für bevorzugte Metallocenkomponenten des erfindungs- gemäßen Katalysatorsystems sind Kombinationen folgender Molekül - fragmente der Verbindung I:Examples of preferred metallocene components of the catalyst system according to the invention are combinations of the following molecule fragments of the compound I:
M^R2: ZrCl2, Zr(CH3)2,M ^ R 2 : ZrCl 2 , Zr (CH 3 ) 2 ,
R3, R3': Methyl, Ethyl, n-Propyl, Isopropyl, Isobutyl, n-Bu- tyl, s-Butyl,R 3 , R 3 ': methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, s-butyl,
R4, R8, R4': WasserstoffR 4 , R 8 , R 4 ': hydrogen
R6, R7: Wasserstoff, Ci- bis C4-Alkyl, C6 bis Cι0-Aryl,R 6, R 7: hydrogen, Ci to C 4 alkyl, C 6 to Cι 0 aryl,
R5 : p-methyl-phenyl, p-ethyl-phenyl , p-n-propyl-phenyl, p-Isopro- pyl-phenyl, p-n-Butyl-phenyl, p-tert.-Butyl-phenyl, p-s-bu- tyl-phenyl, p-Pentyl-phenyl, p-Hexyl-phenyl, p-Cyclohexyl- phenyl, p-Trimethylsilyl-phenyl, p-Adamantyl-phenyl, p-(F3C)3C-phenyl,R 5 : p-methyl-phenyl, p-ethyl-phenyl, pn-propyl-phenyl, p-isopropyl-phenyl, pn-butyl-phenyl, p-tert-butyl-phenyl, ps-butyl- phenyl, p-pentyl-phenyl, p-hexyl-phenyl, p-cyclohexyl-phenyl, p-trimethylsilyl-phenyl, p-adamantyl-phenyl, p- (F 3 C) 3 C-phenyl,
R9: Dimethylsilandiyl, Phenyl (methyl) silandiyl , Diphenylsilan- diyl, Dirnethylgermandiyl, Ethyliden, 1-Methylethyliden, 1,1-Dimethylethyliden, 1,2-Dirnethylethyliden, 1, 1, 2 , 2-Tetrame- thylethyliden, Dimethylmethyliden, Phenyl (methyl)methyliden, Diphenylmethyliden,R 9 : dimethylsilanediyl, phenyl (methyl) silanediyl, diphenylsilanedyl, dirnethylgermandiyl, ethylidene, 1-methylethylidene, 1,1-dimethylethylidene, 1,2-dirnethylethylidene, 1, 1, 2, 2-tetramethylethylidene, dimethylmethylidene, phenyl (methyl) methylidene, diphenylmethylidene,
Ra: 2-Alkyl-4-azapentalene, 2-Alkyl-5-azapentalene,R a : 2-alkyl-4-azapentalene, 2-alkyl-5-azapentalene,
2-Alkyl-6-azapentalene, 2-Alkyl-N-aryl-4-azapentalene, 2-A1- kyl-N-aryl-5-azapentalene, 2-Alkyl-N-aryl-6-azapentalene, 2, 5-Dialkyl-4-azapentalene, 2 , 5-Dialkyl-6-azapentalene,2-alkyl-6-azapentalenes, 2-alkyl-N-aryl-4-azapentalenes, 2-A1-alkyl-N-aryl-5-azapentalenes, 2-alkyl-N-aryl-6-azapentalenes, 2, 5- Dialkyl-4-azapentalene, 2,5-dialkyl-6-azapentalene,
2 , 5-Dialkyl-N-aryl-4-azapentalene, 2, 5-Dialkyl-N-aryl-6-aza- pentalene, 2-Alkyl-4-phosphapentalene, 2-Alkyl-5-phosphapenta- lene, 2-Alkyl-6-phosphapentalene, 2-Alkyl-P-aryl-4-phospha- pentalene, 2-Alkyl-P-aryl-5-phosphapentalene, 2-Alkyl-P- aryl-6-phosphapentalene, 2, 5-Dialkyl-4-phosphapentalene,2,5-dialkyl-N-aryl-4-azapentalenes, 2,5-dialkyl-N-aryl-6-azapentalenes, 2-alkyl-4-phosphapentalenes, 2-alkyl-5-phosphapentalenes, 2- Alkyl-6-phosphapentalenes, 2-alkyl-P-aryl-4-phosphapentalenes, 2-alkyl-P-aryl-5-phosphapentalenes, 2-alkyl-P-aryl-6-phosphapentalenes, 2, 5-dialkyl- 4-phosphapentalene,
2,5-Dialkyl-6-phosphapentalene, 2, 5-Dialkyl-P-aryl-4-phospha- pentalene, 2 , 5-Dialkyl-P-aryl-6-phosphapentalene, 2-Alkyl-4-thiapentalene, 2-Alkyl-5-thiapentalene, 2-Alkyl-6-thiapentalene, 2 , 5-Dialkyl-4-thiapentalene, 2, 5-Dialkyl-6-thiaρentalene, 2-Alkyl-4-oxapentalene, 2-Alkyl-5-oxapentalene, 2-Alkyl-6-oxapentalene,2,5-dialkyl-6-phosphapentalenes, 2,5-dialkyl-P-aryl-4-phosphapentalenes, 2,5-dialkyl-P-aryl-6-phosphapentalenes, 2-alkyl-4-thiapentalenes, 2- Alkyl-5-thiapentalenes, 2-alkyl-6-thiapentalenes, 2, 5-dialkyl-4-thiapentalenes, 2, 5-dialkyl-6-thiaρentalenes, 2-alkyl-4-oxapentalenes, 2-alkyl-5-oxapentalenes, 2-alkyl-6-oxapentalenes,
2, 5-Dialkyl-4-oxapentalene oder 2 , 5-Dialkyl-6-oxapentalene.2, 5-dialkyl-4-oxapentalenes or 2, 5-dialkyl-6-oxapentalenes.
Konkrete Beispiele für bevorzugte Metallocenkomponenten des erfindungsgemäßen Katalysatorsystems sind somit folgende Verbindungen I :The following compounds I are thus concrete examples of preferred metallocene components of the catalyst system according to the invention:
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -methyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -methylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -methyl- phenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-methyl-phenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen)) (2-methyl-4 - (4'-Methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N- phenyl-6-azapentalene) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-θ-azapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-θ-azapentalene) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl -4- (4'-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2- methyl-4-thiapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -me- thylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -me - thylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid , .Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride, .Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-methylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -me- thylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -me - thylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-ethyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapenta- len) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- 0 len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) ) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4' -ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl ( 2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-6-azapentalen)) (2-methyl-4- ( 4'-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl- N-phenyl-6-azapenta-len) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid 5 Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-thiapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapenta- 0 len) {2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride 5 dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -ethylphenyl- indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-thiapentalena)) (2 -methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid 5 Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-oxapenta- len) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-oxapenta- Q -len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride 5 dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -ethylphenyl- indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-oxapenta- Q -len) ( 2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-pro- pylpheny1-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-propylpheny1-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -n-pro- pylphenyl-indenyl) zirkoniumdichlorid 5 Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n-pro- pylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride 5 Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4th '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (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
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapentalen) (2- methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapentalen) (2- methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-pro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -n propylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n- propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n- propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n-pro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n propylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -n- propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -n- propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -isopro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -isopro- pylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -isopro- -pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -isopro - -pylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -iso¬ propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4 - (4'-Isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-iso ¬ propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -isopro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl -4- (4'-isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2- methyl-4-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -isopro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -isopropylphenyl -indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- ( 4 'isopropylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-isopropylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-butyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -n -butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -n-butyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-n-butylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -n-butyl- phenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4 - (4 '-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (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) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (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-azapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -n- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2nd -methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl -4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -s-butyl- phenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -s-butyl- phenyl-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-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -s-butyl- phenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-s-butyl-phenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4 - (4 '-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) 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) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2nd -methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-s-butylphenyl-indenyl ) zirconium dichloride dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -s- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- ( 4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -s-butyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -s -butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -s- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -s- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- ( 4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -tert-bu- tylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -tert-bu- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '- tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -tert-bu- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapenta- len) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -tert- -butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl -4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-azapentalen)) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5- dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-tert- -butyl phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4'- tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-tert-bu¬ tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- ( 4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-tert-bu ¬ tylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -tert-bu¬ tylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-tert-bu ¬ tylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' - tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '- tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- ( 4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-pen- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -n-pen- tylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -n-pen- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl -4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -n- pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -n- pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- ( 4'-n-pentylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- ( 4'-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -n -pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-n- pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n- -pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- ( 4'-n- -pentylphenyl-indenyl) 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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n- pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n -pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n- pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -n-hexyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-n-hexylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n-hexyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-n-hexylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4-Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4-
(4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid(4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4-Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4-
(4' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4-(4'-n-hexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4-
(4 ' -h-hexylphenyl-indenyl) zirkoniumdichlorid(4'-h-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -n- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-n-hexylphenyl-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-azapenta- len) (2-methyl-4- (4' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl -4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-he- xylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -n- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n- hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (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 Dimethylsilanediyl (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-hexyl- phenyl-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- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n- hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-cyclohe- xylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -cyclohe- xylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -cyclohe- xylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( 4'-cyclohexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6- azapentalene) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4' -cyclo- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl -4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2- methyl-4-thiapentalen) (2-methyl-4- (4 '-cyclo-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -cyclohexylphenyl -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -cyclohe- xylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -cyclohe - xylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -trime- -thylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4') trime - -thylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -trime- thylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -trime- thylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( 4'-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4 - (4'-Trimethylsilylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl -4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4 - (4'-Trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5~thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -trime- thylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5 ~ thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -trimethylsilylphenyl -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -trime- thylsilylpheny1-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -trime- thylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-trimethylsilylpheny1-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -trime - thylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -adaman- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -adaman - tylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -adaman- tylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -adaman- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -adaman) - tylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-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) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-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 Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N- phenyl-6-azapentalene) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4-Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl ) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4-
(4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid(4'-Adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -ada- mantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4-Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4-
(4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4-(4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4-
(4'-tris (trifluorrαethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4-(4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4-
(4 '-tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4-(4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4-
(4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-pheny1-5-azapentalen) (2-methyl-4- (4 '-tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4-(4'-Tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-pheny1-5-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2 -methyl-N-phenyl-6-azapentalen) (2-methyl-4-
(4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4-(4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4-
(4 '-tris (trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4-(4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4-
(4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid(4'-tris (trifluoromethyl) methylphenyl indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4~ (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4-Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4- thiapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4-
(4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4-(4'-Tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5 oxapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -tris (trifluoromethyl) methylphenyl- indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5, 6-di-hydro-4-azapentalen) (2-ethyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid(4'-Tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-azapentalen) (2-ethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5, 6 -di-hydro-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-ethyl-4- (4 ' -tert-bu- tylphenyl-tetrahydroindenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-ethyl-4- (4 't-butylphenyl tetrahydroindenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-n-butyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichlorid Ethyliden (2-methyl-6-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-n-butyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride ethylidene (2-methyl-6-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-trimethylsilyl-4-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-tolyl-5-azapentalen) (2-n-pro- pyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-trimethylsilyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-tolyl-5-azapentalen) (2-n -propyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dirnethylgermyldiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichloridDirnethylgermyldiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Methylethyliden (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-di-iso-propyl-6-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2 , 6- dimethyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid 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-butylanthracenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-phosphapentalen) (2-methyl-4-Methylethylidene (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2,5-di-iso-propyl-6-azapentalene) (2-methyl -4- (4 'tert-butylphenyl indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2, 6-dimethyl-4- (4 '-ter-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6--6 azapentalen) (2-methyl-4- (6'-tert-butylnaphthyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (6 '-tert-butylanthracenyl -indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-phosphapentalen) (2-methyl-4-
(4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid(4'-tert-butylphenyl-indenyl) zirconium dichloride
Diphenylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -tert- butylphenyl-indenyl) zirkoniumdichloridDiphenylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride
Methylphenylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4-Methylphenylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4-
(4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Methyliden(2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylmethylide (2, 5-dimethyl-6-thiapentalen) (2-methyl-4-(4'-tert-Butylphenyl-indenyl) zirconium dichloride methylidene (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylmethylide (2,5-dimethyl-6 -thiapentalene) (2-methyl-4-
(4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Diphenylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4-(4'-tert-butylphenyl-indenyl) zirconium dichloride diphenylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4-
(4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Diphenylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid.(4'-tert-butylphenyl-indenyl) zirconium dichloride Diphenylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride.
Weitere konkrete Beispiele für bevorzugte Metallocen-Komponenten sind ferner die entsprechenden in 2- und/oder in 2,5-Position mit Ethyl, n-Propyl, Isopropyl, Isobutyl, n-Butyl und s-Butyl substituierten Homologen der vorstehend genannten Verbindungen.Further specific examples of preferred metallocene components are furthermore the corresponding homologues of the abovementioned compounds which are substituted in the 2- and / or in the 2,5-position with ethyl, n-propyl, isopropyl, isobutyl, n-butyl and s-butyl.
In den Polymerisationen kann das Metallocene der Formel I als Isomerengemisch oder als eines der möglichen racemischen Isomere in reiner oder angereicherter Form eingesetzt werden.In the polymerizations, the metallocenes of the formula I can be used as a mixture of isomers or as one of the possible racemic isomers in pure or enriched form.
Mögliche Herstellungsverfahren für Metallocene der Formel I sind beispielsweise in Journal of Organometallic Chemistry 288 (1985) 63 - 67 und in den dort zitierten Dokumenten, sowie in WO 98/22486, EPA 0 659 757 oder EP 0 576 970 prinzipiell- beschrie- ben.Possible production processes for metallocenes of the formula I are described in principle, for example, in Journal of Organometallic Chemistry 288 (1985) 63-67 and in the documents cited therein, as well as in WO 98/22486, EPA 0 659 757 or EP 0 576 970.
Das erfindungsgemäße Katalysatorsystem enthält vorzugsweise zusätzlich mindestens einen Cokatalysator.The catalyst system according to the invention preferably additionally contains at least one cocatalyst.
Die Cokatalysatorkomponente, die erfindungsgemäß im Katalysator- system enthalten sein kann, enthält mindestens eine Verbindung vom Typ eines Aluminoxans oder einer Lewis-Säure oder einer ionischen Verbindung, die durch Reaktion mit einem Metallocen dieses in eine kationische Verbindung überführt. Die im erfindungsgemäßen Verfahren einsetzbaren Aluminoxane kön¬ nen z.B. cyclisch wie in Formel IIThe cocatalyst component which can be present in the catalyst system according to the invention contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound, which converts this into a cationic compound by reaction with a metallocene. The usable in the inventive method aluminoxanes Kgs ¬ NEN example, cyclic as in formula II
oder linear wie in Formel IIIor linear as in Formula III
mit p = 0 bis 100,with p = 0 to 100,
oder vom Cluster-Typ wie in Formel IV sein,or be of the cluster type as in Formula IV,
wie sie in neuerer Literatur beschrieben werden; vgl. JACS 117 (1995), 6465-74 beziehungsweise Organometallics 13(1994), 2957-2969.as described in recent literature; see. JACS 117 (1995), 6465-74 or Organometallics 13 (1994), 2957-2969.
Die Reste R in den Formeln (II) , (III) oder (IV) können gleich oder verschieden sein und eine Cχ-C o-Kohlenwasserstoffgruppe wie eine Ci-Ce-Alkylgruppe, eine C6-Ci8-Arylgruppe, Benzyl oder Wasserstoff bedeuten, und p eine ganze Zahl von 2 bis 50, bevorzugt 10 bis 35 bedeuten. Bevorzugt sind die Reste R gleich und bedeuten Methyl, Isobutyl, n-Butyl, Phenyl oder Benzyl, besonders bevorzugt Methyl.The radicals R in the formulas (II), (III) or (IV) can be the same or different and a Cχ-C o hydrocarbon group such as a Ci-Ce alkyl group, a C 6 -Ci 8 aryl group, benzyl or hydrogen mean, and p is an integer from 2 to 50, preferably 10 to 35. The radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
Sind die Reste R unterschiedlich, so sind sie bevorzugt Methyl und Wasserstoff, Methyl und Isobutyl oder Methyl und n-Butyl, wobei Wasserstoff bzw. Isobutyl oder n-Butyl bevorzugt zu 0,01 - 40 % (Zahl der Reste R) enthalten sind.If the radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen or isobutyl or n-butyl preferably containing 0.01-40% (number of the radicals R).
Das Aluminoxan kann auf verschiedene Arten nach bekannten Verfah- ren hergestellt werden. Eine der Methoden ist beispielsweise, daß eine AluminiumkohlenwasserstoffVerbindung und/oder eine Hydridoa- luminiumkohlenwasserstoffVerbindung mit Wasser (gasförmig, fest, flüssig oder gebunden - beispielsweise als Kristallwasser) in einem inerten Lösungsmittel (wie z. B. Toluol) umgesetzt wird. Zur Herstellung eines Aluminoxans mit verschiedenen Alkylgruppen R werden entsprechend der gewünschten Zusammensetzung und Reaktivität zwei verschiedene Aluminiumtrialkyle (AIR3 + AIR'3) mit Wasser umgesetzt (vgl. S. Pasynkiewicz, Polyhedron 9 (1990) 429 und EP-A 302 424) .The aluminoxane can be produced in various ways by known processes. One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene). To produce an aluminoxane with different alkyl groups R, two different aluminum trialkyls (AIR 3 + AIR ' 3 ) are reacted with water according to the desired composition and reactivity (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
Unabhängig von der Art der Herstellung ist allen Aluminoxan- lösungen ein wechselnder Gehalt an nicht umgesetzter Aluminiumausgangsverbindung, die in freier Form oder als Addukt vorliegt, gemeinsam.Regardless of the type of production, all aluminoxane solutions have in common a changing content of unreacted aluminum starting compound, which is present in free form or as an adduct.
Als Lewis-Säure werden bevorzugt mindestens eine bor- oder aluminiumorganische Verbindung eingesetzt, die Cι-C2o-kohlenstoff - haltige Gruppen enthalten, wie verzweigte oder unverzweigte Alkyl- oder Halogenalkyl , wie z.B. Methyl, Propyl , Isopropyl, Isobutyl, Trifluormethyl, ungesättigte Gruppen, wie Aryl oder Halogenaryl, wie Phenyl, Tolyl, Benzylgruppen, p-Fluorophenyl , 3 , 5-Difluorophenyl, Pentachlorophenyl , Pentafluorophenyl, 3,4,5 Trifluorophenyl und 3,5 Di (trifluoromethyl) henyl .The Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 20 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated Groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) henyl.
Bevorzugte Lewis-Säuren sind Trimethylaluminium, Triethyl- aluminium, Triisobutylaluminium, Tributylaluminium, Trifluorobo- ran, Triphenylboran, Tris (4-fluorophenyl) boran, Tris (3 , 5-difluorophenyl)boran, Tris (4-fluoromethylphenyl)boran, Tris(penta- fluorophenyl) boran, Tris (tolyl) boran, Tris (3 , 5-dimethyl- phenyljboran, Tris (3 , 5-difluorophenyl) boran und/oderPreferred Lewis acids are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (p - fluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyljborane, tris (3,5-difluorophenyl) borane and / or
Tris (3 ,4 , 5-trifluorophenyl) boran. Insbesondere bevorzugt ist Tris (pentafluorophenyl) boran.Tris (3, 4, 5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
Als ionische Cokatalysatoren werden bevorzugt Verbindungen einge- setzt, die ein nicht koordinierendes Anion enthalten, wie beispielsweise Tetrakis (pentafluorophenyl)borate, Tetraphenyl- borate, SbFg-, CF3S03— oder C104-. Als kationisches Gegenion werden Lewis-Basen wie z.B. Metyhlamin, Anilin, Dimethylamin, Diethyl- amin, N-Methylanilin, Diphenylamin, N,N-Dimethylanilin, Tri- methylamin, Triethylamin, Tri-n-butylamin, Methyldiphenylamin, Pyridin, p-Bromo-N,N-dimethylanilin, p-Nitro-N,N-dimethylanilin, Triethylphosphin, Triphenylphosphin, Diphenylphosphin, Tetra - hydrothiophen und Triphenylcarbenium eingesetzt.Compounds which contain a non-coordinating anion, such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenyl borates, SbFg-, CF 3 S0 3 - or C10 4 -, are preferably used as ionic cocatalysts. As a cationic counterion Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N -dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetra-hydrothiophene and triphenylcarbenium are used.
Beispiele für solche erfindungsgemäßen ionischen Verbindungen sind . Triethylammoniumtetr (phenyl) borat,Examples of such ionic compounds according to the invention are. Triethylammonium tetr (phenyl) borate,
Tributylammoniumtetra (phenyl) borat,Tributylammonium tetra (phenyl) borate,
Trimethylammoniumtetra (tolyl) borat,Trimethylammonium tetra (tolyl) borate,
Tributylammoniumtetra (tolyl) borat,Tributylammonium tetra (tolyl) borate,
Tributylammoniumtetra (pentafluorophenyl) borat, Tributylammoniumtetra (pentafluorophenyl) luminat,Tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (pentafluorophenyl) luminate,
Tripropylammoniumtetra (dimethylphenyl) borat,Tripropylammonium tetra (dimethylphenyl) borate,
Tributylammoniumtetra (trifluoromethylphenyl) borat,Tributylammonium tetra (trifluoromethylphenyl) borate,
Tributylammoniumtetra (4-fluorophenyl)borat,Tributylammonium tetra (4-fluorophenyl) borate,
N, N-Dimethylaniliniumtetra (phenyl) borat, N,N-Diethylaniliniumtetra (phenyl) borat,N, N-dimethylanilinium tetra (phenyl) borate, N, N-diethylanilinium tetra (phenyl) borate,
N, N-Dimethylaniliniumtetrakis (pentafluorophenyl) borate,N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N,N-Dimethylaniliniumtetrakis (pentafluorophenyl) aluminat,N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,
Di (propyl) ammoniumtetrakis (pentafluorophenyl) borat,Di (propyl) ammonium tetrakis (pentafluorophenyl) borate,
Di (cyclohexyl) ammoniumtetrakis (pentafluorophenyl) borat, Triphenylphosphoniumtetrakis (phenyl) borat,Di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (phenyl) borate,
Triethylphosphoniumtetrakis (phenyl) borat,Triethylphosphonium tetrakis (phenyl) borate,
Diphenylphosphoniu tetrakis (phenyl)borat,Diphenylphosphoniu tetrakis (phenyl) borate,
Tri (methylphenyl)phosphoniumtetrakis (phenyl) borat,Tri (methylphenyl) phosphonium tetrakis (phenyl) borate,
Tri (dimethylphenyl)phosphoniumtetrakis (phenyl) borat, Triphenylcarbeniumtetrakis (pentafluorophenyl) borat,Tri (dimethylphenyl) phosphonium tetrakis (phenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbeniumtetrakis (pentafluorophenyl) aluminat,Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,
Triphenylcarbeniumtetrakis (phenyl) aluminat,Triphenylcarbenium tetrakis (phenyl) aluminate,
Ferroceniumtetrakis (pentafluorophenyl) borat und/oderFerrocenium tetrakis (pentafluorophenyl) borate and / or
Ferroceniumtetrakis (pentafluorophenyl) aluminat. Bevorzugt sind Triphenylcarbeniumtetrakis (pentafluorophenyl) borat und/oderFerrocenium tetrakis (pentafluorophenyl) aluminate. Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or are preferred
N, N-Dimethylaniliniumtetrakis (pentafluorophenyl) borat .N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate.
Es können auch Gemische mindestens einer Lewis-Säure und minde- istens einer ionischen Verbindung eingesetzt werden.Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
Als Cokatalysatorkomponenten sind ebenfalls Boran- oder Carboran- Verbindungen wie z.B.Borane or carborane compounds such as e.g.
7 , 8-Dicarbaundecaboran (13 ) ,7, 8-dicarbaundecaboran (13),
Undecahydrid-7, 8-dimethyl-7, 8-dicarbaundecaboran, Dodecahydrid-l-phenyl-1 , 3-dicarbanonaboran, Tri (butyl) ammoniumundecahydrid-8-ethyl-7 , 9-dicarbaundecaborat, 4-Carbanonaboran (14) Bis (tri (butyl) ammonium)nonaborat, Bis (tri (butyl) mmonium) undecaborat, Bis (tri (butyl) ammonium) dodecaborat, Bis (tri (butyl) mmonium) decachlorodecaborat, Tri (butyl) ammonium-1-carbadecaborate, Tri (butyl) ammonium-1-carbadodecaborate, Tri (butyl) ammonium-1-trimethylsilyl-l-carbadecaborate, Tri (buyl) ammoniumbis (nonahydrid-1, 3-dicarbonnonaborat) cobal- täte (III) ,Undecahydrid-7, 8-dimethyl-7, 8-dicarbaundecaboran, dodecahydrid-l-phenyl-1, 3-dicarbanonaboran, Tri (butyl) ammonium undecahydrid-8-ethyl-7, 9-dicarbaundecaborate, 4-carbanonaborane (14) bis (tri (butyl) ammonium) nonaborate, bis (tri (butyl) mmonium) undecaborate, bis (tri (butyl) ammonium) dodecaborate, bis (tri (butyl) mmonium) decachlorodecaborate, tri (butyl) ammonium-1-carbadecaborate, tri (butyl) ammonium-1-carbadodecaborate, tri (butyl) ammonium-1-trimethylsilyl-l-carbadecaborate, tri (buyl) ammonium bis (nonahydrid-1, 3-dicarbonnonaborate) cobaltates (III),
Tri (butyl) ammoniumbis (undecahydrid-7, 8-dicarbaundecaborat) fer- rat(III)Tri (butyl) ammonium bis (undecahydrid-7, 8-dicarbaundecaborate) ferrat (III)
von Bedeutung .significant .
Die Trägerkomponente des erfindungsgemäßen Katalysatorsystems kann ein beliebiger organischer oder anorganischer, inerter Feststoff sein, insbesondere ein poröser Träger wie Talk, anorganische Oxide und feinteilige Polymerpulver (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 ent- sprechende Oxid-Mischungen. Andere anorganische Oxide, die allein oder in Kombination mit den zuletzt genannten bevorzugten oxiden Trägern eingesetzt werden können, sind z.B. MgO, Zr02 , Ti0 oder B03 ,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, Zr0 2 , Ti0 or B0 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 m2/g, einem Porenvolumen im Bereich zwischen 0,5 und 3,5 ml/g und einer mittleren Partikel - große im Bereich von 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.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 μm. Carriers with a specific surface area in the range from 50 to 500 m 2 / g, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 μm 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 μm are particularly preferred.
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 Silicagel als Trägermaterial, ist eine Dehydratisierung oder Trocknung empfehlenswert. Die thermische Dehydratisierung oder Trocknung des Trägermaterials kann unter Vakuum und/oder Inertgasüberlagerung (z.B. Stickstoff) erfolgen. Die Trocknungstemperatur liegt im Bereich zwischen 100 und 1000°C, vorzugsweise zwischen 200 und 800°C. Die Dauer des Trocknungsprozesses kann zwischen 1 und 24 Stunden betragen. Kürzere oder längere Trocknungsdauern sind mög- lieh, vorausgesetzt, daß unter den gewählten Bedingungen dieIf 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 silica gel 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 / or inert gas overlay (eg nitrogen). The drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. The drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the selected conditions
Gleichgewichtseinstellung mit den Hydroxylgruppen auf der Träger- Oberfläche erfolgen kann, was normalerweise zwischen 4 und 8 Stunden erfordert.Equilibrium can be done with the hydroxyl groups on the support surface, which normally takes 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 Inertisierungs- mitteln zur Reaktion gebracht werden. 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 führen. Geeignete Inertisierungsmittel sind beispielsweise Silicium- halogenide und Silane, wie Siliciumtetrachlorid, Chlortrimethyl- silan, Dimethylaminotrichlorsilan oder metallorganische Verbindungen von Aluminium- , Bor und Magnesium wie beispielsweise Trimethylaluminium, Triethylaluminium, Triisobutyl- aluminium, Methylaluminoxan, Triethylboran, Dibutylmagnesium. Die chemische Dehydratisierung oder Inertisierung des Trägermaterials erfolgt beispielsweise dadurch, daß man unter Luft- und Feuchtig - keitsausschluß 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 Xylol. Die Inertisierung erfolgt bei Temperaturen zwischen 0 °C und 120 °C, bevorzugt zwischen 20 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 Träger- material 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 am Vakuum getrocknet.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. As a result of 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 trimethylaluminium, triethylaluminum, triisobutylaluminum, methylaluminoxane, triethylborane, dibutylmagnesium. 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 xylene. The inerting takes place at temperatures between 0 ° C and 120 ° C, preferably between 20 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 carrier material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then dried in an inert gas stream or under vacuum.
-Organische Trägermaterialien wie feinteilige Polyolefinpulver (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 be- freit werden. Das geträgerte Katalysatorsystem kann auch definitionsgemäß mehr als ein Metallocen enthalten. In diesem Fall werden entweder zwei oder mehr der erfindungsgemäßen Metallocene der Formel I verwendet, oder mindestens ein erfindungsgemäßes Metallocen der Formel I und mindestens ein weiteres Metallocen. In diesem Zusammenhang verwendbare Metallocene sind beispielsweise in EP-A-0 485 821, DE 195 44 828 AI oder EP-A-0 576 970 beschrieben. Bevorzugt handelt es sich dabei um verbrückte Bisindenyl-Metallocene, die am Indenylliganden in 2- ; 2,4- ; 2,5- ; 2,4,5- ; 2,4,6- ; 2,4,7-; 2,4,5,6- oder 2 , 5, 6-Stellung substituiert sind.-Organic carrier materials such as finely divided polyolefin powders (eg polyethylene, polypropylene or polystyrene) can also be used and should also be removed by appropriate cleaning and drying operations before the use of adhering moisture, solvent residues or other contaminants. By definition, the supported catalyst system can also contain more than one metallocene. In this case, either two or more of the metallocenes of the formula I according to the invention are used, or at least one metallocene of the formula I according to the invention and at least one further metallocene. Metallocenes which can be used in this context are described, for example, in EP-A-0 485 821, DE 195 44 828 AI or EP-A-0 576 970. These are preferably bridged bisindenyl metallocenes which are in the 2-; 2.4-; 2.5-; 2,4,5-; 2,4,6-; 2,4,7-; 2,4,5,6- or 2, 5, 6-position are substituted.
Zur Darstellung des geträgerten Katalysatorsystems wird beispielsweise mindestens eine der oben beschriebenen Metallocen- Komponenten der Formel I in einem geeigneten Lösemittel mit min- destens einer Cokatalysatorkomponente in Kontakt gebracht, wobei bevorzugt ein lösliches Reaktionsprodukt , ein Addukt oder ein Gemisch erhalten wird.To prepare the supported catalyst system, for example, at least one of the metallocene components of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
Die so erhaltene Zubereitung wird dann mit dem dehydratisierten oder inertisierten Trägermaterial vermischt, das Lösemittel entfernt und das resultierende geträgerte Metallocen-Katalysatorsy- stem getrocknet, um sicherzustellen, daß das Lösemittel vollständig oder zum größten Teil aus den Poren des Trägermaterials entfernt wird. Der geträgerte Katalysator wird als frei fließendes Pulver erhalten.The preparation thus obtained is then mixed with the dehydrated or rendered inert carrier material, the solvent is removed and the resulting supported metallocene catalyst system is dried to ensure that the solvent is completely or largely removed from the pores of the carrier material. The supported catalyst is obtained as a free-flowing powder.
Ein mögliches Verfahren zur Darstellung eines frei fließenden und gegebenenfalls vorpolymerisierten geträgerten Katalysatorsystems umfaßt die folgenden Schritte:A possible method for producing a free-flowing and optionally prepolymerized supported catalyst system comprises the following steps:
a) Herstellung einer Metallocen-/Cokatalysator-Mischung in einem geeigneten Löse- oder Suspensionsmittel, wobei mindestens eine Metallocen-Komponente eine der zuvor beschriebenena) Preparation of a metallocene / cocatalyst mixture in a suitable solvent or suspending agent, at least one metallocene component being one of those described above
Strukturen der Formel I besitzt. b) Aufbringen der Metallocen-/Cokatalysator-Mischung auf einen porösen, bevorzugt anorganischen dehydratisierten Träger c) Entfernen des Hauptanteils an Lösemittel von der resultierenden Mischung d) Isolierung des geträgerten Katalysatorsystems "e) Gegebenenfalls eine Vorpolymerisation des erhaltenen geträgerten Katalysatorsystems mit einem oder mehreren olefinischen Monomer (en), um ein vorpolymerisiertes geträgertes Katalysatorsystem zu erhalten. Die Verfahrensschritte a) und b) können auch zusammengefaßt sein, wobeiHas structures of formula I. b) application of the metallocene / cocatalyst mixture to a porous, preferably inorganic, dehydrated support c) removal of the main proportion of solvent from the resulting mixture d) isolation of the supported catalyst system "e) if necessary, a prepolymerization of the supported catalyst system obtained with one or more olefinic ones Monomer (s) to obtain a prepolymerized supported catalyst system. Process steps a) and b) can also be combined, where
alle möglichen Permutationen der Zugabereihenfolge der Katalysatorkomponenten möglich sind. Darüber hinaus ist es auch möglich, die Komponenten gleichzeitig zu vermischen.all possible permutations of the order of addition of the catalyst components are possible. In addition, it is also possible to mix the components at the same time.
Bevorzugte Lösemittel für die Herstellung der Metallocen-/Cokata- lysator-Mischung sind Kohlenwasserstoffe und Kohlenwasserstoff- gemische, die bei der gewählten Reaktionstemperatur flüssig sind und in denen sich die Einzelkomponenten bevorzugt lösen. Die Löslichkeit der Ξinzelkomponenten ist aber keine Voraussetzung, wenn sichergestellt ist, daß das Reaktionsprodukt aus Metallocen- und Cokatalysatorkomponenten in dem gewählten Lösemittel löslich ist. Beispiele für geeignete Lösemittel umfassen Alkane wie Pentan, Isopentan, Hexan, Heptan, Octan, und Nonan; Cycloalkane wie Cyclopentan und Cyclohexan; und Aromaten wie Benzol, Toluol. Ethylbenzol und Diethylbenzol . Ganz besonders bevorzugt ist Toluol.Preferred solvents for the production of the metallocene / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve. However, the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of metallocene and cocatalyst components is soluble in the chosen solvent. Examples of suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Toluene is very particularly preferred.
Die bei der Präparation des geträgerten Katalysatorsystems eingesetzten Mengen an Aluminoxan und Metallocen können über einen weiten Bereich variiert werden. Bevorzugt wird ein molares Verhältnis von Aluminium zum Übergangsmetall im Metallocen von 10 : 1 bis 1000 : 1 eingestellt, ganz besonders bevorzugt ein Verhältnis von 50 : 1 bis 500 : 1.The amounts of aluminoxane and metallocene used in the preparation of the supported catalyst system can be varied over a wide range. A molar ratio of aluminum to transition metal in the metallocene of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1.
Im Fall von Methylaluminoxan werden bevorzugt 30 %ige toluolische Lösungen eingesetzt; die Verwendung von 10 %igen Lösungen ist aber auch möglich.In the case of methylaluminoxane, 30% toluene solutions are preferably used; the use of 10% solutions is also possible.
Zur Voraktivierung kann das Metallocen in Form eines Feststoffes in einer Lösung des Aluminoxans in einem geeigneten Lösemittel aufgelöst werden. Es ist auch möglich, das Metallocen.getrennt in einem geeigneten Lösemittel aufzulösen und diese Lösung anschließend mit der Aluminoxan-Lösung zu vereinigen. Bevorzugt wird Toluol verwendet. Bei Verwendung mehrerer Metallocene kann der Lösungsvorgang getrennt oder mit den zuvor gemischten Metalloce- nen durchgeführt werden. Die Voraktivierungszeit kann 1 Minute - -bis 200 Stunden betragen. Die Voraktivierung kann bei Raumtemperatur (20 °C) stattfinden. Die Anwendung höherer Temperaturen kann im Einzelfall die erforderliche Dauer der Voraktivierung verkürzen und eine zusätzliche Aktivitätssteigerung bewirken. Höhere Temperatur bedeutet in diesem Fall ein Bereich zwischen 20 und 150 °C. Die voraktivierte (n) Lösung (en) bzw. das/die Metallocen-/Cokata- lysator-Gemisch (e) kann/können anschließend mit einem inerten Trägermaterial, bevorzugt Kieselgel, das in Form eines trockenen Pulvers oder als Suspension in einem der oben genannten Löse- mittel vorliegt, vereinigt werden. Bevorzugt wird das Trägermaterial als Pulver eingesetzt. Die Reihenfolge der Zugabe ist dabei beliebig. Bei Verwendung mehrerer Lösungen bzw. Metallocen/ Cokatalysator-Gemischen kann zwischen den einzelnen Zugabeschritten auch eine Zwischentrocknung erfolgen (sequentielle Trägerung) . Die voraktivierte (n) Metallocen-Cokatalysator-Lö- sung(en) bzw. das/die Metallocen-Cokatalysatorgemisch(e) kann/ können zum vorgelegten Trägermaterial dosiert, oder aber das Trägermaterial in die vorgelegte (n) Lösung (n) eingetragen werden.For preactivation, the metallocene can be dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the metallocene separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used. If several metallocenes are used, the dissolving process can be carried out separately or with the previously mixed metallocenes. The preactivation time can be 1 minute to 200 hours. The pre-activation can take place at room temperature (20 ° C). In individual cases, the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity. In this case, a higher temperature means a range between 20 and 150 ° C. The preactivated solution (s) or the metallocene / cocatalyst mixture (s) can / can subsequently be mixed with an inert carrier material, preferably silica gel, in the form of a dry powder or as a suspension in one of the above mentioned solvents are present. The carrier material is preferably used as a powder. The order of addition is arbitrary. If several solutions or metallocene / cocatalyst mixtures are used, intermediate drying can also take place between the individual addition steps (sequential support). The preactivated metallocene-cocatalyst solution (s) or the metallocene-cocatalyst mixture (s) can be metered into the support material or the support material can be introduced into the solution (s) .
Das Volumen (bzw. die Summe der Einzelvolumina) der vor- aktivierten Lösung (en) bzw. der/des Metallocen-Cokatalysatorgemi- sche(s) kann 100 % des Gesamtporenvolumens des eingesetzten Trägermaterials überschreiten oder aber bis zu 100 % des Gesamtporenvolumens betragen.The volume (or the sum of the individual volumes) of the preactivated solution (s) or of the metallocene / cocatalyst mixture (s) can exceed 100% of the total pore volume of the support material used or can be up to 100% of the total pore volume.
Die Temperatur, bei der die voraktivierte (n) Lösung (en) bzw. das/ die Metallocen-Cokatalysatorgemisch(e) mit dem Trägermaterial in Kontakt gebracht wird/werden, kann im Bereich zwischen 0 und 100°C variieren. Niedrigere oder höhere Temperaturen sind aber auch möglich.The temperature at which the preactivated solution (s) or the metallocene / cocatalyst mixture (s) is / are brought into contact with the support material can vary in the range between 0 and 100 ° C. However, lower or higher temperatures are also possible.
Bei Verwendung mehrerer Metallocene ist bevorzugt, zuerst die Lösung (en) des/der nicht erfindungsgemäßen Metallocens/Metall- ocene auf den Träger aufzubringen und dann die Lösung (en) des/der erfindungsgemäßen Metallocens/Metallocene aufzubringen.When using several metallocenes, it is preferred to first apply the solution (s) of the metallocene / metallocene not according to the invention to the support and then to apply the solution (s) of the metallocene / metallocene according to the invention.
Anschließend wird das Lösemittel oder Lösemittelgemisch vollständig oder zum größten Teil vom geträgerten Katalysatorsystem entfernt, wobei die Mischung gerührt und gegebenenfalls auch erhitzt werden kann. Bevorzugt wird sowohl der sichtbare Anteil des Lösemittels als auch der Anteil in den Poren des Trägermaterials entfernt. Das Entfernen des Lösemittels kann in konventioneller Art und Weise unter Anwendung von Vakuum und/oder Spülen mit Inertgas erfolgen. Beim Trocknungsvorgang kann die Mischung erwärmt wer- -den, bis das freie Lösemittel entfernt worden ist, was üblicherweise 1 bis 3 Stunden bei einer vorzugsweise gewählten Temperatur zwischen 30 und 60 °C erfordert. Das freie Lösemittel ist der sichtbare Anteil an Lösemittel in der Mischung. Unter Restlösemittel versteht man den Anteil, der in den Poren eingeschlossen ist. Alternativ zu einer vollständigen Entfernung des Lösemittels kann das geträgerte Katalysatorsystem auch nur bis zu einem gewissen Restlösemittelgehalt getrocknet werden, wobei das freie Lösemittel vollständig entfernt worden ist. Anschließend kann das geträgerte Katalysatorsystem mit einem niedrig siedenden Kohlenwasserstoff wie Pentan oder Hexan gewaschen und erneut getrocknet werden.The solvent or solvent mixture is then completely or for the most part removed from the supported catalyst system, the mixture being able to be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed. The solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C. The free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores. As an alternative to a complete removal of the solvent, the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely. The supported catalyst system can then be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
Das erfindungsgemäß dargestellte geträgerte Katalysatorsystem kann entweder direkt zur Polymerisation von Olefinen eingesetzt oder vor seiner Verwendung in einem Polymerisationsprozeß mit einem oder mehreren olefinischen Monomeren vorpolymerisiert werden. Die Ausführung der Vorpolymerisation von geträgerten Katalysatorsystemen ist beispielsweise in WO 94/28034 beschrie- ben.The supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before being used in a polymerization process. The prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
Als Additiv kann während oder nach der Herstellung des geträgerten Katalysatorsystems eine geringe Menge eines Olefins bevorzugt eines α-Olefins (beispielsweise Styrol oder Phenyldime- thylvinylsilan) als aktivitätssteigernde Komponente oder beispielsweise eines Antistatikums (wie in US-Patentanmeldung mit der Serial No. 08/365280 beschrieben) zugesetzt werden. Das molare Verhältnis von Additiv zu Metallocen beträgt dabei bevorzugt zwischen 1 : 1000 bis 1000 : 1, ganz besonders bevorzugt 1 : 20 bis 20 : 1.As an additive, a small amount of an olefin, preferably an α-olefin (for example styrene or phenyldimethylvinylsilane) as an activity-increasing component or for example an antistatic agent (as in US patent application Serial No. 08/365280) can be used as an additive during or after the preparation of the supported catalyst system described) are added. The molar ratio of additive to metallocene is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung eines Polyolefins durch Polymerisation einer oder mehrerer Olefine in Gegenwart des erfindungsgemäßen Katalysator- Systems, enthaltend mindestens eine Übergangsmetallkomponente der Formel I. Unter dem Begriff Polymerisation wird eine Homopoly- merisation wie auch eine Copolymerisation verstanden.The present invention also relates to a process for the preparation of a polyolefin by polymerization of one or more olefins in the presence of the catalyst system according to the invention, comprising at least one transition metal component of the formula I. The term polymerization is understood to mean homopolymerization and also copolymerization.
Bevorzugt werden Olefine der Formel Rm-CH=CH-Rn polymexisiert, wo- rin Rm und Rn gleich oder verschieden sind und ein Wasserstoffatom oder einen kohlenstoffhaltigen Rest mit 1 bis 20 C-Atomen, insbesondere 1 bis 10 C-Atome, bedeuten, und Rm und Rn zusammen mit den sie verbindenden Atomen einen oder mehrere Ringe bilden können.Olefins of the formula R m -CH = CH-R n are preferably polymexized, where R m and R n are identical or different and a hydrogen atom or a carbon-containing radical having 1 to 20 C atoms, in particular 1 to 10 C atoms , mean, and R m and R n together with the atoms connecting them can form one or more rings.
Beispiele für solche Olefine sind 1-Olefine mit 2 - 40, vorzugsweise 2 bis 10 C-Atomen, wie Ethen, Propen, 1-Buten, 1-Penten, 1-Hexen, 4-Methyl-l-penten oder 1-Octen, Styrol, Diene wie 1, 3-Butadien, 1, 4-Hexadien, Vinylnorbornen, Norbornadien, Ethyl - norbornadien und cyclische Olefine wie Norbornen, Tetracyclodode- cen oder Methylnorbornen. Bevorzugt werden in dem erfindungs- gemäßen Verfahren Propen oder Ethen homopolymerisiert, oder Propen mit Ethen und/oder mit einem oder mehreren l-01efinen mit 4 bis 20 C-Atomen, wie Hexen, und/oder einem oder mehreren Dienen mit 4 bis 20 C-Atomen, wie 1, 4-Butadien, Norbornadien, Ethyliden- norbonen oder Ethylnorbornadien, copolymerisiert . Beispiele sol- eher Copolymere sind Ethen/Propen-Copolymere oder Ethen/Pro- pen/1, 4-Hexadien-Terpolymere.Examples of such olefins are 1-olefins having 2 to 40, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene, ethyl - norbornadiene and cyclic olefins such as norbornene, tetracyclododecenes or methylnorbornene. In the process according to the invention, propene or ethene are preferably homopolymerized, or Propene with ethene and / or with one or more 1-01efins with 4 to 20 C atoms, such as hexene, and / or one or more dienes with 4 to 20 C atoms, such as 1, 4-butadiene, norbornadiene, ethylidene copolymerized norbones or ethyl norbornadiene. Examples of such copolymers are ethene / propene copolymers or ethene / propene / 1,4-hexadiene terpolymers.
Die Polymerisation wird bei einer Temperatur von - 60 bis 300°C , bevorzugt 50 bis 200°C, ganz besonders bevorzugt 50 - 100°C durch- geführt. Der Druck beträgt 0,5 bis 2000 bar, bevorzugt 5 bis 100 bar.The polymerization is carried out at a temperature of from -60 to 300 ° C., preferably from 50 to 200 ° C., very particularly preferably from 50 to 100 ° C. The pressure is 0.5 to 2000 bar, preferably 5 to 100 bar.
Die Dosierung des Katalysatorsystems in das Polymerisationssystem kann in beliebiger Weise erfolgen. Bevorzugt wird das Katalysatorsystem in Form eines Pulvers, einer Suspension oder einer Paste mit angepaßter Viskosität zudosiert.The catalyst system can be metered into the polymerization system in any manner. The catalyst system is preferably metered in in the form of a powder, a suspension or a paste with an adapted viscosity.
Es können auch zwei oder mehr erfindungsgemäße Katalysatorsysteme oder Mischungen aus erfindungsgemäßem/erfindungsgemäßen Katalysatorsystem(en) mit mindestens einem weiteren Katalysatorsystem in die Polymerisation getrennt oder als Mischung dosiert werden.Two or more catalyst systems according to the invention or mixtures of catalyst system (s) according to the invention with at least one further catalyst system can also be separated into the polymerization or metered in as a mixture.
Die Polymerisation kann in Lösung, in Masse, in Suspension, in der Gasphase oder in einem überkritischen Medium kontinuierlich oder diskontinuierlich, ein- oder mehrstufig durchgeführt werden.The polymerization can be carried out in solution, in bulk, in suspension, in the gas phase or in a supercritical medium continuously or batchwise, in one or more stages.
Das erfindungsgemäß dargestellte Katalysatorsystem kann als einzige Katalysatorkomponente für die Polymerisation von Olefinen mit 2 bis 20 C-Atomen eingesetzt werden, oder bevorzugt in Kombination mit mindestens einer AIkylVerbindung der Elemente aus der I. bis III. Hauptgruppe des Periodensystems, wie z.B. einem Aluminium-, Magnesium- oder Lithiumalkyl oder einem Aluminoxan eingesetzt werden. Die AlkylVerbindung wird dem Monomeren oder Suspensionsmittel zugesetzt und dient zur Reinigung des Monomeren von Substanzen, die die Katalysatoraktivität beeinträchtigen können. Die Menge der zugesetzten Alkylverbindung hängt von der Qualität der eingesetzten Monomere ab.The catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one alkyl compound of the elements from I. to III. Main group of the periodic table, e.g. an aluminum, magnesium or lithium alkyl or an aluminoxane can be used. The alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances that can impair the catalyst activity. The amount of alkyl compound added depends on the quality of the monomers used.
Als Molmassenregler und/oder zur Steigerung der Aktivität wird, falls erforderlich, Wasserstoff zugegeben.If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity.
Bei der Polymerisation kann außerdem ein Antistatikum zusammen mit oder getrennt von dem eingesetzten Katalysatorsystem in das Polymerisationssystem eindosiert werden. Der Zusatz eines Anti- statikums kann auch in einem der Polymerisation nachgeordneten Verfahrensschritt sinnvoll sein, um die Aufarbeitung des Polymers zu verbessern.In the polymerization, an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used. The addition of an antistatic can also be carried out after the polymerization Process step may be useful to improve the processing of the polymer.
Mit dem erfindungsgemäßen Katalysatorsystem können Polymerpulver mit gleichmäßiger Kornmorphologie und ohne Feinkornanteile hergestellt werden.With the catalyst system according to the invention, polymer powders with a uniform grain morphology and without fine grain fractions can be produced.
Die erfindungsgemäßen Katalysatorsysteme sind hochaktiv und bei der Polymerisation treten keine Beläge oder Verbackungen auf .The catalyst systems according to the invention are highly active and no deposits or caking occur during the polymerization.
Mit dem erfindungsgemäßen Katalysatorsystem können Polymere, wie Polypropylen, mit außerordentlich hoher Stereo- und Regiospezifi- tät erhalten werden.With the catalyst system according to the invention, polymers, such as polypropylene, can be obtained with extremely high stereo and region specificity.
Die mit dem erfindungsgemäßen Katalysatorsystem herstellbaren Copolymere zeichnen sich durch hohe Molmassen aus. Gleichzeitig sind solche Copolymere durch Einsatz des erfindungsgemäßen Katalysatorsystems mit hoher Produktivität bei technisch relevanten Prozessparametern ohne Belagsbildung herstellbar.The copolymers which can be prepared using the catalyst system according to the invention are notable for high molar masses. At the same time, such copolymers can be produced by using the catalyst system according to the invention with high productivity with technically relevant process parameters without formation of deposits.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Polymere sind insbesondere zur Herstellung reißfester, harter und steifer Formkörper wie Fasern, Filamente, Spritzgußteile, Folien, Platten oder Großhohlkörpern (z.B. Rohre), sowie zur Herstellung von Copolymeren mit hoher Steifigkeit, Zähigkeit, Weißbrucharmut und Transparenz geeignet.The polymers obtainable by the process according to the invention are particularly suitable for the production of tear-resistant, hard and rigid moldings such as fibers, filaments, injection molded parts, foils, sheets or large hollow bodies (e.g. pipes), as well as for the production of copolymers with high rigidity, toughness, low white breakage and transparency.
Beispiele:Examples:
Allgemeine Angaben:General Information:
Die Herstellung und Handhabung der organometallischen Verbindungen erfolgte unter Ausschluß von Luft und Feuchtigkeit unter Argon-Schutzgas (Schlenk-Technik bzw. Glove-Box) . Alle be- nötigten Lösemittel wurden vor Gebrauch mit Argon gespült und über Molsieb absolutiert.The production and handling of the organometallic compounds was carried out with the exclusion of air and moisture under an argon protective gas (Schlenk technique or glove box). All required solvents were flushed with argon before use and absoluteized using a molecular sieve.
Die eingesetzten Metallocene wurden mit iH-NMR, 13C-NMR und IR-The metallocenes used were analyzed by iH-NMR, 13 C-NMR and IR
Spektroskopie charakterisiert.Characterized spectroscopy.
Es bedeutenMean it
PP = PolypropylenPP = polypropylene
MC = MetallocenMC = metallocene
Kat = geträgertes Katalysatorsystem h = Stunde KomplexsynthesenKat = supported catalyst system h = hour Complex syntheses
Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4' -tert. - butyl-phenyl) -inden) und Dimethylsilandiyl (2, 5-dimethyl-N-phe- 5 nyl-4-azapentalen) (2-methyl-4- (4' - tert . -butyl-phenyl-inden) wurden analog der Ligandensynthese in WO 98/22486 aus 2-Methyl-4- (4 ' -tert. -butyl-phenyl) -inden und dem entsprechenden Dimethylchlorsilandiylpentalenderivat synthetisiert .Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 't-butyl-phenyl) -indene) and Dimethylsilanediyl (2, 5-dimethyl-N-phe-5 nyl-4-azapentalen ) (2-methyl-4- (4 '- tert -butyl-phenyl-indene) were analogous to the ligand synthesis in WO 98/22486 from 2-methyl-4- (4'-tert. -Butyl-phenyl) -indene and the corresponding dimethylchlorosilanediylpentalene derivative.
10 14 mmol des Liganden wurden in 70 ml Diethylether gelöst, bei Raumtemperatur mit 10.5 ml einer 20%igen Lösung von Butyllithium in Toluol versetzt und anschließend 3 Stunden zum Rückfluß erhitzt. Das Lösungsmittel wurde im Vakuum entfernt und der Rückstand mit 50 ml Hexan über eine G3-Schlenkfritte filtriert, mit10 14 mmol of the ligand were dissolved in 70 ml of diethyl ether, 10.5 ml of a 20% solution of butyllithium in toluene were added at room temperature and the mixture was then heated under reflux for 3 hours. The solvent was removed in vacuo and the residue was filtered through a G3 Schlenk frit with 50 ml of hexane
15 50 ml Hexan nachgewaschen und getrocknet (0.1 mbar, 20°C) . Das Dilithiumsalz wurde bei -78°C zu einer Suspension von 3.2 g (14 mmol) Zirkoniumtetrachlorid in 80 ml Methylenchlorid gegeben und im Verlauf von 18 h unter Rühren auf Raumtemperatur erwärmt. Der Ansatz wurde über eine G3-Fritte filtriert und der Rückstand15 Wash 50 ml of hexane and dry (0.1 mbar, 20 ° C). The dilithium salt was added to a suspension of 3.2 g (14 mmol) of zirconium tetrachloride in 80 ml of methylene chloride at -78 ° C. and warmed to room temperature in the course of 18 h with stirring. The mixture was filtered through a G3 frit and the residue
20 portionsweise mit insgesamt 400 ml Methylenchlorid nachextrahiert. Die vereinigten Filtrate wurden im Vakuum vom Lösungsmittel weitestgehend befreit. Der ausgefallene orange-braune Niederschlag aus Methylenchlorid wurde isoliert. Der Niederschlag besteht aus racemischen Isomeren, die durch weitere Umkristalli-20 extracted in portions with a total of 400 ml of methylene chloride. The combined filtrates were largely freed from the solvent in vacuo. The precipitated orange-brown precipitate from methylene chloride was isolated. The precipitate consists of racemic isomers, which are further recrystallized
25 sation isoliert werden können. Der Einfachheit halber wurde in den Polymerisationsbeispielen das Isomerengemisch eingesetzt.25 sation can be isolated. For the sake of simplicity, the isomer mixture was used in the polymerization examples.
Ausbeute Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -tert . -butyl-phenyl) -indenyl) zirkonium- 30 dichlorid 2,0 g (21 %)Yield dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-ter. -Butyl-phenyl) -indenyl) zirconium-30 dichloride 2.0 g (21 %)
Elementaranalyse: H 6.07 (5.71) C 62.93 (64.60) N 2.04 (2.37) 1H-NMR (C6D6) , in ppm: 7.73-6.80 (m, 15H) , 2.48-2.02 (m, 9H) , 1.50-1.25 (m, 15H)Elemental analysis: H 6.07 (5.71) C 62.93 (64.60) N 2.04 (2.37) 1H-NMR (C6D6), in ppm: 7.73-6.80 (m, 15H), 2.48-2.02 (m, 9H), 1.50-1.25 (m , 15H)
35 Ausbeute Dimethylsilandiyl (2-methyl-4-thiapenta- len) (2-methyl-4- (4 ' -tert .-butyl-phenyl) -indenyl) zirkoniumdichlorid 2,3 g (27 %)35 Yield of dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4 't-butylphenyl) -indenyl) zirconium dichloride 2.3 g (27%)
Elementaranalyse: H 5.45 (5.35) C 59.50 (57.78) 1H-NMR (C6D6) in ppm: 7.81-6.79 (m, 11H) , 2.45-2.15 (m, 6H) ,Elemental analysis: H 5.45 (5.35) C 59.50 (57.78) 1H-NMR (C6D6) in ppm: 7.81-6.79 (m, 11H), 2.45-2.15 (m, 6H),
40- *1.50-1.22 (m, 15H)40- * 1.50-1.22 (m, 15H)
Trägerungsbeispiele und Polymerisationsbeispiele:Carrier examples and polymerization examples:
Beispiel la 45 Darstellung des geträgerten Katalysatorsystems: 62 mg (0.09 mmol) Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid wurden bei Raumtemperatur in 4.3 cm3 (20 mmol AI) 30 %iger toluolischer Methylaluminoxan-Lösung1* gelöst. Die Lösung wurde mit 3.7 cm3 Toluol verdünnt und lichtgeschützt bei 25 °C 1 h gerührt. Diese Lösung wurde portionsweise unter Rühren zu 4 g Si02 2) gegeben und der Ansatz nach beendeter Zugabe 10 min nachgerührt. Das Verhältnis Volumen der Lösung zum Gesamtporenvolumen des Trägermaterials betrug 1.25. Anschließend wurde der Ansatz innerhalb von 4 h bei 40 °C und 10~3 mbar getrocknet. Es wurden 5.6 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.17 Gew% Zr und 9.7 Gew% AI enthielt.Example la 45 Representation of the supported catalyst system: 62 mg (0.09 mmol) of dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were dissolved in 4.3 cm 3 (20 mmol AI) 30% toluene solution of methylaluminoxane 1 * was dissolved, the solution was diluted with 3.7 cm 3 of toluene and protected from light for 1 hour at 25 ° C. This solution was added in portions to 4 g of SiO 2 2) and the mixture was mixed at the end of the addition, stirring was continued for 10 min. The ratio of the volume of the solution to the total pore volume of the carrier material was 1.25. The mixture was then dried at 40 ° C. and 10 -3 mbar within 4 h. 5.6 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.17% by weight of Zr and 9.7% by weight of Al.
1) Albemarle Corporation, Baton Rouge, Louisiana, USA 2) Silica Typ MS 948 , W.R. Grace, Davison Chemical Devision, Baltimore, Maryland, USA, Porenvolumen 1.6 ml/g, calciniert bei 600 °C 1 ) Albemarle Corporation, Baton Rouge, Louisiana, USA 2 ) Silica type MS 948, WR Grace, Davison Chemical Division, Baltimore, Maryland, USA, pore volume 1.6 ml / g, calcined at 600 ° C
Polymerisation: Ein trockener 16 dm3 -Reaktor, der zunächst mit Stickstoff und anschließend mit Propen gespült worden war, wurde mit 10 dm3 flüssigem Propen gefüllt. Als Scavenger wurden 8 cm3 20 %iger Triethyla- luminium-Lösung in Varsol (Witco) zugesetzt und der Ansatz 15 min bei 30 °C gerührt. Anschließend wurde eine Suspension von 1 g des geträgerten Metallocen-Katalysators in 20 cm3 Exxsol in den Reaktor gegeben, auf die Polymerisationstemperatur von 65 °C aufgeheizt und das Polymerisationssystem 1 h bei 65 °C gehalten. Die Polymerisation wurde durch Entgasen gestoppt und das erhaltene Polymer im Vakuum getrocknet. Es resultierten 1.7 kg Polypropy- len-Pulver mit einer Schüttdichte von 460 g/dm3.Polymerization: A dry 16 dm 3 reactor, which had first been flushed with nitrogen and then with propene, was filled with 10 dm 3 of liquid propene. 8 cm 3 of 20% triethylaluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 15 min. A suspension of 1 g of the supported metallocene catalyst in 20 cm 3 of Exxsol was then added to the reactor, heated to the polymerization temperature of 65 ° C. and the polymerization system was kept at 65 ° C. for 1 hour. The polymerization was stopped by degassing and the polymer obtained was dried in vacuo. The result was 1.7 kg of polypropylene powder with a bulk density of 460 g / dm 3 .
Die Katalysatoraktivität betrug 1.7 kg PP/ (g Kat x h) . Das Polymer war ein frei fließendes Pulver und enthielt weder Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors ergab Be- lagsfreiheit.The catalyst activity was 1.7 kg PP / (g cat x h). The polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor showed no deposits.
Beispiel lbExample lb
Trägerung : Das Trägerungsbeispiel la wurde wiederholt, es wurden jedochCarrier: The carrier example la was repeated, but it was
124 mg (0.18 mmol) Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-aza- pentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid verwendet. Es wurden 5.7 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.31 Gew% Zr und 9.6 Gew% AI enthielt.124 mg (0.18 mmol) of dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used. 5.7 g of one was released flowing powder obtained, which according to elemental analysis contained 0.31% by weight of Zr and 9.6% by weight of Al.
Polymerisation: Es wurde verfahren wie in Beispiel la.Polymerization: The procedure was as in example la.
Es resultierten 3.1 kg Polypropylen-Pulver mit einer Schüttdichte von 462 g/dm3.The result was 3.1 kg of polypropylene powder with a bulk density of 462 g / dm 3 .
Die Katalysatoraktivität betrug 3.1 kg PP/ (g Kat x h) . Das Polymer war ein frei fließendes Pulver und enthielt weder Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors ergab Belagsfreiheit.The catalyst activity was 3.1 kg PP / (g cat x h). The polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor showed no deposits.
Beispiel 2aExample 2a
Trägerung :Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 55 mg (0.09 mmol) Dimethylsilandiyl (2-methyl-4-thiapenta- len) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid verwendet.Carrier example 1a was repeated, but 55 mg (0.09 mmol) of dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride were used.
Es wurden 5.4 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.18 Gew% Zr und 10.1 Gew% AI enthielt.5.4 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.18% by weight of Zr and 10.1% by weight of Al.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la.The procedure was as in example la.
Es resultierten 1.3 kg Polypropylen-Pulver mit einer Schüttdichte von 432 g/dm3.The result was 1.3 kg of polypropylene powder with a bulk density of 432 g / dm 3 .
Die Katalysatoraktivität betrug 1.3 kg PP/ (g Kat x h) . Das Polymer war ein frei fließendes Pulver und enthielt wederThe catalyst activity was 1.3 kg PP / (g cat x h). The polymer was a free flowing powder and contained neither
Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors ergab Belagsfreiheit.Fine grain fractions or agglomerates. The inspection of the reactor showed no deposits.
Beispiel 2bExample 2b
Trägerung:Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 110 mg (0.18 mmol) Dimethylsilandiyl (2-methyl-4-thiapenta- len) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid verwendet.Carrier example 1a was repeated, but 110 mg (0.18 mmol) of dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used.
Es wurden 5.7 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.35 Gew% Zr und 9.4 Gew% AI enthielt.5.7 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.35% by weight of Zr and 9.4% by weight of Al.
Polymerisation: Es wurde verfahren wie in Beispiel la.Polymerization: The procedure was as in Example la.
Es resultierten 2.4 kg Polypropylen-Pulver mit einer Schüttdichte von 432 g/dm3.The result was 2.4 kg of polypropylene powder with a bulk density of 432 g / dm 3 .
Die Katalysatoraktivität betrug 2.4 kg PP/ (g Kat x h) .The catalyst activity was 2.4 kg PP / (g cat x h).
Das Polymer war ein frei fließendes Pulver und enthielt weder Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors ergab Belagsfreiheit. Beispiel 3The polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor showed no deposits. Example 3
Trägerung:Carrier:
126 mg (0.17 mmol) des Metallocens rac-Dimethylsilandiylbis (2- methyl-4- (4' -tert-butyl-phenyl-indenyl) zirkoniumdichlorid, wurden bei Raumtemperatur in 3.0 cm3 (14 mmol AI) 30 %iger toluolischer Methylaluminoxan-Lösung1' gelöst, mit 2.5 cm3 Toluol verdünnt und lichtgeschützt bei 25 °C 1 h gerührt (Lösung A) . Parallel dazu wurden 21 mg (0.03 mmol) des Metallocens Dimethylsilandiyl (2, 5- dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkonium-dichlorid bei Raumtemperatur in 1.5 cm3 (7 mmol AI) 30 %iger toluolischer Methylaluminoxan-Lösung1' gelöst, mit 1.0 cm3 Toluol verdünnt und lichtgeschützt bei 25 °C 1 h gerührt (Lösung B) .126 mg (0.17 mmol) of the metallocene rac-dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl-indenyl) zirconium dichloride) were at room temperature in 3.0 cm 3 (14 mmol Al) 30% toluene methylaluminoxane Solution 1 'was dissolved, diluted with 2.5 cm 3 of toluene and stirred for 1 h (solution A) at 25 ° C. In parallel, 21 mg (0.03 mmol) of the metallocene dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4- azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride at room temperature dissolved in 1.5 cm 3 (7 mmol Al) 30% toluene methylaluminoxane solution 1 ', diluted with 1.0 cm 3 toluene and stirred protected from light at 25 ° C. for 1 h (solution B).
Lösung A wurde portionsweise unter Rühren zu 4 g Si02). Nach beendeter Zugabe wurde der Ansatz 10 min nachgerührt. Anschließend wurde Lösung B ebenfalls portionsweise unter Rühren zugegeben. Nach beendeter Zugabe wurde der Ansatz ebenfalls 10 min nach- gerührt. Das Verhältnis der Summe Volumen der Lösung A plus Volumen der Lösung B zum Gesamtporenvolumen des Trägermaterials betrug 1.25. Anschließend wurde der Ansatz innerhalb von 4 h bei 40 °C und 10~3 mbar getrocknet. Es wurden 5.7 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.36 Gew% Zr und 9.9 Gew% AI enthielt.Solution A was added a little at a time to 4 g of SiO 2) . After the addition had ended, the mixture was stirred for 10 min. Then solution B was also added in portions with stirring. After the addition had ended, the mixture was also stirred for a further 10 min. The ratio of the total volume of solution A plus volume of solution B to the total pore volume of the carrier material was 1.25. The mixture was then dried at 40 ° C. and 10 -3 mbar within 4 h. 5.7 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.36% by weight of Zr and 9.9% by weight of Al.
1) Albemarle Corporation, Baton Rouge, Louisiana, USA 1 ) Albemarle Corporation, Baton Rouge, Louisiana, USA
2) Silica Typ MS 948 , W.R. Grace, Davison Chemical Devision, Baltimore, Maryland, USA, Porenvolumen 1.6 ml/g, calciniert bei 600 °C 2 ) Silica type MS 948, WR Grace, Davison Chemical Division, Baltimore, Maryland, USA, pore volume 1.6 ml / g, calcined at 600 ° C
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la aufgrund der hohen Katalysatoraktivität wurde die Polymerisation nach 30 min abgebrochen. Es resultierten 1.8 kg Polypropylen-Pulver mit einer Schüttdichte von 450 g/dm3.The procedure was as in Example 1 a because of the high catalyst activity, the polymerization was terminated after 30 minutes. The result was 1.8 kg of polypropylene powder with a bulk density of 450 g / dm 3 .
Die Katalysatoraktivität betrug 3.6 kg PP/ (g Kat x h) . Das Polymer war ein frei fließendes Pulver und enthielt weder Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors er- 'gab Belagsfreiheit.The catalyst activity was 3.6 kg PP / (g cat x h). The polymer was a free flowing powder and contained neither fine grain fractions nor agglomerates. The inspection of the reactor showed that there was no coating.
Beispiel 4Example 4
Polymerisation: Ein trockener 24 dm3-Reaktor, der zunächst mit Stickstoff und anschließend mit Propen gespült worden war, wurde mit 12 dm3 flüssigem Propen, 0.25 Ndm3 Wasserstoff und 50 g Ethylen gefüllt. Als Scavenger wurden 4 cm3 einer 20 %igen Triethylaluminium-Lösung in Varsol (Witco) zugesetzt und der Ansatz 5 min bei 30 °C gerührt. Anschließend wurde eine Suspension von 1 g des geträgerten Metallocen-Katalysators aus Beispiel 2b (Trägerung) in 20 cm3 Ex- xsol in den Reaktor gegeben, auf die Polymerisationstemperatur von 65 °C aufgeheizt und das Polymerisationssystem 30 min bei 65 °C gehalten. Die Polymerisation wurde durch Entgasen gestoppt und das erhaltene Copolymer im Vakuum getrocknet. Es resultierten 1.35 kg frei fließendes, agglomeratfreies Pulver mit einer Schüttdichte von 445 g/dm3. Das Copolymer enthielt 3.5 Gew.-% statistisch eingebautes Ethylen.Polymerization: A dry 24 dm 3 reactor, which had first been flushed with nitrogen and then with propene, was filled with 12 dm 3 of liquid propene, 0.25 Ndm 3 of hydrogen and 50 g of ethylene. As Scavengers were added 4 cm 3 of a 20% triethylaluminum solution in Varsol (Witco) and the mixture was stirred at 30 ° C. for 5 min. A suspension of 1 g of the supported metallocene catalyst from Example 2b (support) in 20 cm 3 Exxsol was then added to the reactor, heated to the polymerization temperature of 65 ° C. and the polymerization system was kept at 65 ° C. for 30 minutes. The polymerization was stopped by degassing and the copolymer obtained was dried in vacuo. The result was 1.35 kg of free-flowing, agglomerate-free powder with a bulk density of 445 g / dm 3 . The copolymer contained 3.5% by weight of statistically incorporated ethylene.
Die Katalysatoraktivität betrug 2.7 kg Copolymer/ (g Kat x h) . Die Inspektion des Reaktors ergab Belagsfreiheit.The catalyst activity was 2.7 kg copolymer / (g cat x h). The inspection of the reactor showed no deposits.
Beispiel 5Example 5
Polymerisation:Polymerization:
Ein trockener 24 dm3-Reaktor, der zunächst mit Stickstoff und an- schließend mit Propen gespült worden war, wurde mit 12 dm3 flüssigem Propen, 0.25 Ndm3 Wasserstoff und 50 g Ethylen gefüllt. Als Scavenger wurden 4 cm3 einer 20 %igen Triethylaluminium-Lösung in Varsol (Witco) zugesetzt und der Ansatz 5 min bei 30°C gerührt. Anschließend wurde eine Suspension von 1 g des geträgerten Metallocen-Katalysators aus Beispiel 3 (Trägerung) in 20 cm3 Exxsol in den Reaktor gegeben, auf die Polymerisationstemperatur von 60 °C aufgeheizt und das Polymerisationssystem 30 min bei 60 °C gehalten. Die Polymerisation wurde durch Entgasen gestoppt und das erhaltene Copolymer im Vakuum getrocknet. Es re- sultierten 1.4 kg frei fließendes, agglomeratfreies Pulver mit einer Schüttdichte von 430 g/dm3. Das Copolymer enthielt 3.3 Gew.-% statistisch eingebautes Ethylen.A dry 24 dm 3 reactor, which had first been flushed with nitrogen and then with propene, was filled with 12 dm 3 of liquid propene, 0.25 Ndm 3 of hydrogen and 50 g of ethylene. 4 cm 3 of a 20% strength triethylaluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 5 min. A suspension of 1 g of the supported metallocene catalyst from Example 3 (support) in 20 cm 3 of Exxsol was then added to the reactor, heated to the polymerization temperature of 60 ° C. and the polymerization system was kept at 60 ° C. for 30 minutes. The polymerization was stopped by degassing and the copolymer obtained was dried in vacuo. The result was 1.4 kg of free-flowing, agglomerate-free powder with a bulk density of 430 g / dm 3 . The copolymer contained 3.3% by weight of statistically incorporated ethylene.
Die Katalysatoraktivität betrug 2.8 kg Copolymer/ (g Kat x h) . Die Inspektion des Reaktors ergab Belagsfreiheit.The catalyst activity was 2.8 kg copolymer / (g cat x h). The inspection of the reactor showed no deposits.
Beispiel 6Example 6
Polymerisation:Polymerization:
Ein trockener 24 dm3-Reaktor, der zunächst mit Stickstoff und an- schließend mit Propen gespült worden war, wurde mit 10 dm3 flüssigem Propen und 5 Ndm3 Wasserstoff befüllt. Als Scavenger wurden 6 cm3 einer 20 %igen Triisobutylaluminium-Lösung in Varsol (Witco) zugesetzt und der Ansatz 5 min bei 30 °C gerührt. Anschließend wurde eine Suspension von 0.5 g des geträgerten Metallocen-Kata- lysators aus Beispiel 3 (Trägerung) über eine Druckschleuse mit 2 dm3 flüssigem Propen in den Reaktor gespült. Es wurde dann auf die Polymerisationstemperatur von 75 °C aufgeheizt (7.5 °C/min, in situ Vorpolymerisation) und das Polymerisationssystem 1 h bei dieser Temperatur gehalten.A dry 24 dm 3 reactor, which had first been flushed with nitrogen and then with propene, was filled with 10 dm 3 of liquid propene and 5 Ndm 3 of hydrogen. 6 cm 3 of a 20% strength triisobutylaluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 5 min. A suspension of 0.5 g of the supported metallocene catalyst from Example 3 (support) was then rinsed into the reactor via a pressure lock with 2 dm 3 of liquid propene. It was then heated to the polymerization temperature of 75 ° C (7.5 ° C / min, in situ prepolymerization) and the polymerization system was kept at this temperature for 1 h.
Anschließend wurde der Reaktor auf 10 bar entspannt und mit 25 bar Ethylen beaufschlagt. Der Ansatz wurde bei 60 °C 1 h weiter- polymerisiert. Die Polymerisation wurde durch Entgasen gestoppt und das erhaltene Blockopolymer im Vakuum getrocknet. Es resultierten 3.2 kg frei fließendes, agglomeratfreies Pulver mit einer Schüttdichte von 440 g/dm3. Der in der zweiten Polymerisations - stufe hergestellte Kautschuk (Ethylen-Propylen-Copolymer) enthielt 39 Gew.-% Ethylen und zeigte eine Glastemperatur von - 50 °C. Die Inspektion des Reaktors ergab Belagsfreiheit.The reactor was then let down to 10 bar and 25 bar of ethylene were applied. The batch was polymerized further at 60 ° C. for 1 h. The polymerization was stopped by degassing and the block copolymer obtained was dried in vacuo. The result was 3.2 kg of free-flowing, agglomerate-free powder with a bulk density of 440 g / dm 3 . The rubber (ethylene-propylene copolymer) produced in the second polymerization stage contained 39% by weight of ethylene and had a glass transition temperature of −50 ° C. The inspection of the reactor showed no deposits.
Vergleichsbeispiel laComparative example la
Trägerung :Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 57 mg (0.09 mmol) Dimethylsilandiylbis (2 , 5-dimethyl-N-phenyl-4-aza- pentalen) -zirkoniumdichlorid verwendet. Es wurden 5.6 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.18 Gew% Zr und 9.8 Gew% AI enthielt.Carrier example 1a was repeated, but 57 mg (0.09 mmol) of dimethylsilanediylbis (2, 5-dimethyl-N-phenyl-4-aza-pentalen) zirconium dichloride were used. 5.6 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.18% by weight of Zr and 9.8% by weight of Al.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la. Es resultierte eine wachs - artige Polymermasse, die teilweise an Rührerblättern und Reaktor- wänden haften blieb. Auf eine Bestimmung der Polymerisationsaktivität wurde verzichtet.The procedure was as in example la. The result was a wax-like polymer mass that partially stuck to the stirrer blades and reactor walls. The polymerization activity was not determined.
Vergleichsbeispiel lbComparative Example Ib
Trägerung:Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 114 mg (0.18 mmol) Dimethylsilandiylbis (2, 5-dimethyl-N-phenyl-4-aza- pentalen) -zirkoniumdichlorid verwendet. Es wurden 5-.5-g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.38 Gew% Zr und 9.4 Gew% AI enthielt.Carrier example 1a was repeated, but 114 mg (0.18 mmol) of dimethylsilanediylbis (2, 5-dimethyl-N-phenyl-4-aza-pentalen) zirconium dichloride were used. 5-.5-g of a free-flowing powder were obtained, which according to elemental analysis contained 0.38% by weight of Zr and 9.4% by weight of Al.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la. Es resultierte eine wachs - artige Polymermasse, die teilweise an Rührerblättern und Reaktor- wänden haften blieb. Auf eine Bestimmung der Polymerisationsaktivität wurde verzichtet. Vergleichsbeispiel 2aThe procedure was as in example la. The result was a wax-like polymer mass that partially stuck to the stirrer blades and reactor walls. The polymerization activity was not determined. Comparative Example 2a
Trägerung :Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 55 mg (0.09 mmol) Dimethylsilandiyl (2-methyl-indenyl) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid verwendet.Carrier example 1a was repeated, but 55 mg (0.09 mmol) of dimethylsilanediyl (2-methyl-indenyl) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used.
Es wurden 5.7 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.17 Gew% Zr und 10.0 Gew% AI enthielt.5.7 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.17% by weight of Zr and 10.0% by weight of Al.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la.The procedure was as in example la.
Es resultierten 1.4 kg Polypropylen-Pulver mit einer Schüttdichte von 445 g/dm3.The result was 1.4 kg of polypropylene powder with a bulk density of 445 g / dm 3 .
Die Katalysatoraktivität betrug 1.4 kg PP/(g Kat x h) . Das Poly¬ mer war ein frei fließendes Pulver und enthielt weder Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors ergab Belags - freiheit.The catalyst activity was 1.4 kg PP / (g Kat xh). The polymer was a free-flowing powder and contained neither fine-grain fractions nor agglomerates. The inspection of the reactor revealed that there was no deposit.
Vergleichsbeispiel 2bComparative Example 2b
Trägerung :Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 110 mg (0.18 mmol) Dimethylsilandiyl (2-methyl-indenyl) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid verwendet. Es wurden 5.5 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.40 Gew% Zr und 10.1 Gew% AI enthielt.Carrier example 1a was repeated, except that 110 mg (0.18 mmol) of dimethylsilanediyl (2-methyl-indenyl) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used. 5.5 g of a free-flowing solution were used Powder obtained, which according to elemental analysis contained 0.40 wt% Zr and 10.1 wt% AI.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la.The procedure was as in example la.
Es resultierten 2.5 kg Polypropylen-Pulver mit einer Schüttdichte von 400 g/dm3.The result was 2.5 kg of polypropylene powder with a bulk density of 400 g / dm 3 .
Die Katalysatoraktivität betrug 2.5 kg PP/(g Kat x h) , Das Polymer enthielt 9.5 Gew.-% Agglomerate. Die Inspektion des Reaktors zeigte Beläge an der Reaktorwand und auf den Rührerblättern.The catalyst activity was 2.5 kg PP / (g cat x h). The polymer contained 9.5% by weight of agglomerates. The inspection of the reactor showed deposits on the reactor wall and on the stirrer blades.
Vergleichsbeispiel 3a *Comparative Example 3a *
Trägerung:Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 67 mg (0.09 mmol) rac-Dimethylsilandiylbis (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid verwendet. Es wurden 5.8 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.18 Gew% Zr und 9.6 Gew% AI enthielt. Polymerisation:Carrier example Ia was repeated, but 67 mg (0.09 mmol) of rac-dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride were used. 5.8 g of a free-flowing powder were obtained, which, according to Elemental analysis contained 0.18 wt% Zr and 9.6 wt% AI. Polymerization:
Es wurde verfahren wie in Beispiel la.The procedure was as in example la.
Es resultierten 1.7 kg Polypropylen-Pulver mit einer Schüttdichte von 475 g/dm3. Die Katalysatoraktivität betrug 1.7 kg PP/ (g Kat x h) . Das Polymer war ein frei fließendes Pulver und enthielt weder Feinkornanteile noch Agglomerate. Die Inspektion des Reaktors ergab Belags - freiheit.The result was 1.7 kg of polypropylene powder with a bulk density of 475 g / dm 3 . The catalyst activity was 1.7 kg PP / (g Kat xh). The polymer was a free-flowing powder and contained neither fine-grained fractions nor agglomerates. The inspection of the reactor revealed that there was no deposit.
Vergleichsbeispiel 3bComparative Example 3b
Trägerung :Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 134 mg (0.18 mmol) rac-Dimethylsilandiylbis (2-methyl-4- (4 ' -tert-bu- tylphenyl-indenyl) zirkoniumdichlorid verwendet. Es wurden 5.6 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.37 Gew% Zr und 9.9 Gew% AI enthielt.Carrier example 1a was repeated, but 134 mg (0.18 mmol) of rac-dimethylsilanediylbis (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride were used. 5.6 g of a free-flowing powder were obtained, which according to elemental analysis contained 0.37% by weight of Zr and 9.9% by weight of Al.
Polymerisation: Es wurde verfahren wie in Beispiel la.Polymerization: The procedure was as in Example la.
Es resultierten 3.2 kg Polypropylen-Pulver mit einer Schüttdichte von 440 g/dm3.The result was 3.2 kg of polypropylene powder with a bulk density of 440 g / dm 3 .
Die Katalysatoraktivität betrug 3.2 kg PP/ (g Kat x h) .The catalyst activity was 3.2 kg PP / (g cat x h).
Das Polymer enthielt ca. 5 Gew.-% Agglomerate. Die Inspektion des Reaktors zeigte Beläge an der Reaktorwand und auf den Rührerblättern.The polymer contained about 5% by weight of agglomerates. The inspection of the reactor showed deposits on the reactor wall and on the stirrer blades.
Vergleichsbeispiel 4aComparative Example 4a
Trägerung:Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 44 mg (0.09 mmol) Dimethylsilandiylbis (2-methyl-4-thiapenta- len) -zirkoniumdichlorid verwendet. Es wurden 5.6 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.16 Gew% Zr und 9.5 Gew% AI enthielt.Carrier example 1a was repeated, but 44 mg (0.09 mmol) of dimethylsilanediylbis (2-methyl-4-thiapentalene) zirconium dichloride were used. 5.6 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.16% by weight of Zr and 9.5% by weight of Al.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la. Es resultierte eine wachs - artige Polymermasse, die teilweise an Rührerblättern und Reaktor- "Vänden haften blieb. Auf eine Bestimmung der Polymerisationsaktivität wurde verzichtet. Vergleichsbeispiel 4bThe procedure was as in example la. The result was a wax-like polymer mass which partially adhered to the stirrer blades and reactor walls. The polymerization activity was not determined. Comparative Example 4b
Trägerung :Carrier:
Das Trägerungsbeispiel la wurde wiederholt, es wurden jedoch 88 mg (0.18 mmol) Dimethylsilandiylbis (2-4-thiapentalen) zirkoniumdichlorid verwendet. Es wurden 5.7 g eines frei fließenden Pulvers erhalten, das laut Elementaranalyse 0.39 Gew% Zr und 9.7 Gew% AI enthielt.Carrier example 1a was repeated, but 88 mg (0.18 mmol) of dimethylsilanediylbis (2-4-thiapentalene) zirconium dichloride were used. 5.7 g of a free-flowing powder were obtained which, according to elemental analysis, contained 0.39% by weight of Zr and 9.7% by weight of Al.
Polymerisation:Polymerization:
Es wurde verfahren wie in Beispiel la. Es resultierte eine wachs - artige Polymermasse, die teilweise an Rührerblättern und Reaktorwänden haften blieb. Auf eine Bestimmung der Polymerisationsaktivität wurde verzichtet.The procedure was as in example la. The result was a wax - like polymer mass that partially stuck to the stirrer blades and reactor walls. The polymerization activity was not determined.
Die in den Beispielen la bis 3 und den Vergleichsbeispielen bei der Trägerung eingesetzten Metallocen-Mengen, die Polymerisationsaktivitäten der Katalysatoren, die Morphologie der erhaltenen Polymere und das jeweilige Ergebnis der Belagsinspektion sind in Tabelle zusammengefaßt.The amounts of metallocene used in the support in Examples 1a to 3 and the comparative examples, the polymerization activities of the catalysts, the morphology of the polymers obtained and the respective result of the coating inspection are summarized in the table.
Zur Beurteilung des Immobilisierungsgrades der Metallocene auf dem Trägermaterial wurde folgendes Extraktionsexperiment durchgeführt :The following extraction experiment was carried out to assess the degree of immobilization of the metallocenes on the support material:
Jeweils lg der Katalysatoren aus den Beispielen la, lb und den Vergleichsbeispielen 2a, 2b, 3a und 3b wurde jeweils in 20 ml Toluol suspendiert, der Ansatz 30 min bei 50 °C gerührt und anschließend über eine G3-Fritte filtriert. Die jeweilige Farbe des Filtrats ist in Tabelle 1 aufgeführt.In each case 1 g of the catalysts from examples 1 a, 1 b and comparative examples 2 a, 2 b, 3 a and 3 b was suspended in 20 ml of toluene, the mixture was stirred at 50 ° C. for 30 minutes and then filtered through a G3 frit. The respective color of the filtrate is listed in Table 1.
Das Filtrat aus Vergleichsbeispiel 2b wurde analog zu Beispiel la in der Polymerisation eingesetzt. Die anschließende Inspektion des Reaktors ergab einen dünnen, weißen Belag an Rührer und Reak- torwänden. Eine Probe des Belags wurde getrocknet und mittels IR- Spektroskopie untersucht. Es handelte sich um isotaktisches Polypropylen.The filtrate from comparative example 2b was used in the polymerization analogously to example la. Subsequent inspection of the reactor revealed a thin, white coating on the stirrer and reactor walls. A sample of the coating was dried and examined by means of IR spectroscopy. It was isotactic polypropylene.
Die Filtrate aus den Beispielen la und lb und dem Vergleichs - * -beispiel 2a wurden ebenfalls zur Polymerisation eingesetzt. Sie erwiesen sich als polymerisationsinaktiv, die Inspektion des Reaktors zeigte keine Beläge. Tabelle 1The filtrates from Examples la and lb and the comparison - * -Example 2a have also been used for the polymerization. They proved to be inactive for polymerization, the inspection of the reactor showed no deposits. Table 1
VB Vergleichsbeispiel e.g. erfindungsgemäß n-e-<?- nicht erfindungsgemäß VB comparative example eg according to the invention n - e - < ? - not according to the invention

Claims

Patentansprüche claims
1 . Verbindung der Formel I ,1 . Compound of formula I,
worinwherein
M1 ein Metall der Gruppe IVb des Periodensystems der Elemente ist,M 1 is a metal from group IVb of the Periodic Table of the Elements,
R1, R2 gleich oder verschieden sind und ein Wasserstoffatom, eine Cι-Cιo-Alkylgruppe, eine Cι-Cιo-Alkoxygxuppe, eine C6-C o-Arylgruppe, eine Cg-Cι0-Aryloxygruppe, eineR 1 , R 2 are the same or different and are a hydrogen atom, a Cι-Cιo-alkyl group, a Cι-Cιo-Alkoxygxuppe, a C 6 -C o-aryl group, a Cg-Cι 0 aryloxy group, a
C-Cιo-Alkenylgruppe, eine OH-Gruppe, eine N(R12) 2-Gruppe, wobei R12 eine Ci bis Cχo -Alkylgruppe oder Cg bis C14-Arylgruppe ist, oder ein Halogenatom bedeuten,C-Cιo-alkenyl group, an OH group, an N (R 12 ) 2 group, where R 12 is a Ci to Cχo alkyl group or Cg to C 14 aryl group, or a halogen atom,
-R3, R4, R6, 7, R87 R3', R4- gleich oder verschieden sind und ein Wasserstoffatom, eine Kohlenwasserstoffgruppe mit 1 bis 40 Kohlenstoff - atomen, die teilhalogeniert, halogeniert, linear, cyclisch oder verzweigt sein kann, eine Si(R13)3-, N(R13) -, SR13- oder OR13-Gruppe bedeuten, mit R13 in der Bedeutung von R4, mit der Maßgabe, daß R3 von Wasserstoff verschie- den ist, R3' und R4' auch cyclisch verbunden sein können, und-R 3 , R 4 , R6, 7, R8 7 R 3 ', R 4- are identical or different and are a hydrogen atom, a hydrocarbon group with 1 to 40 carbon atoms, which can be partially halogenated, halogenated, linear, cyclic or branched , a Si (R 13 ) 3 , N (R 13 ), SR 13 or OR 13 group, with R 13 as R 4 , with the proviso that R 3 is different from hydrogen that is, R 3 'and R 4 ' can also be cyclically linked, and
R5 eine C6 bis C40 -Arylgruppe die in para-Position zur Bin- dungsstelle an den Indenylring einen Substituenten R14 trägt, bedeutet,R 5 is a C 6 to C 40 aryl group which has a substituent R 14 in the para position to the binding site on the indenyl ring,
wobeiin which
R14 ein Halogenatom F,C1 oder Br, ein Ci bis C20-Alkylrest, ein C2 bis C 0-Alkenylrest , ein Cg bis C2 -Arylrest, ein C7 bis C4o-Arylalkylrest, ein C7 bis C4o-Alkylarylrest , ein Cs bisR 14 is a halogen atom F, C1 or Br, a Ci to C 20 alkyl radical, a C 2 to C 0 alkenyl radical, a Cg to C 2 aryl radical, a C 7 to C 4 o-arylalkyl radical, a C 7 to C 4 o-alkylaryl, a Cs bis
C40-Arylalkenylrest wobei die Kohlenwasserstoffreste auch mit Fluor, Chlor und/oder Brom halogeniert oder teilhalogeniert sein können, - (Ri5)2 , -P(R15)2 f -SR15 _0R15, _si(Ri5)3 C 40 arylalkenyl radical where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine, chlorine and / or bromine, - ( R i5) 2 , - P ( R 15) 2 f - SR 15 _ 0 R15, _ s i ( R i5 ) 3
-[N(R15)3]+ oder -[P(R15)3]+ bedeutet mit R1^ in der Bedeutung von R4,- [N (R 15 ) 3 ] + or - [P (R 15 ) 3 ] + means with R 1 ^ in the meaning of R 4 ,
R16 trotz gleicher Indizierung gleich oder verschieden sein können und die Bedeutung von R14 oder Wasserstoff haben und jeweils benachbarte Reste R16 auch cyclisch verbunden sein kön- nen, oder einer oder mehrere der Reste R16 bilden mit den Resten R6 oder R4 und/oder R14 eine cyclische Verknüpfung, mit der Maßgabe, daß R14 auch Wasserstoff sein kann, wenn mindestens einer der Reste R16 von Wasserstoff verschieden ist,In spite of the same indexing, R 16 can be the same or different and have the meaning of R 14 or hydrogen and adjacent radicals R 16 can also be cyclically linked, or one or more of the radicals R 16 form with the radicals R 6 or R 4 and / or R 14 is a cyclic linkage, with the proviso that R 14 can also be hydrogen if at least one of the radicals R 16 is different from hydrogen,
R9 eine Verbrückung R 9 is a bridge
10 10 10 1010 10 10 10
R R R10 RRRR 10 R
-0 M 0 c 0 M - C - M --0 M 0 c 0 M - C - M -
I II I
11 11 11 R 11 R R R11 R11 11 11 R 11 RRR 11 R
1010
R 10R 10
R10 RR 10 R
C — CC - C
11 1111 11
R11 R RR 11 RR
\. \. \.. \ \„ \„« \. V.\. \. \ .. \ \ "\" «\. V.
/BR1β./AIR10.-ββ-. -0-, -S-, ^SO, ^S02, /NR10, ^CO. ^PR10 o e r^ (0)Rto,/ BR 1β ./AIR 10. -Ββ-. -0-, -S-, ^ SO, ^ S0 2 , / NR 10 , ^ CO. ^ PR 10 oer ^ (0) R to ,
wobeiin which
R10, Rlα auch bei gleicher Indizierung, gleich oder verschieden sein können und ein Wasserstoffatom, ein Halogenatom, eine Cι-C4o-heteroatomhaltige Kohlenwasserstoffruppe, eine Cι-C4o_kohlenstoffhaltige Gruppe,R 10, R lα even with the same index, can be identical or different and are a hydrogen atom, a halogen atom, a Cι-C 4 o-hetero atom-containing hydrocarbon Ruppe, a Cι-C 4 o _ carbon-containing group,
-N(R17)2 , -P(Rl7)2/ -SRI7, -OR17, -Si(Rl )3, -[N(Rl )3] + oder -[P(R17)3]+ bedeuten mit R17 in der Bedeutung von R4, oder R10 und R11 bilden jeweils mit den sie verbindenden Atomen einen oder mehrere Ringe, x bedeutet eine ganze Zahl von 0 bis 18, -M2 bedeutet Silizium, Germanium oder Zinn, und-N (R 17 ) 2 , -P (R 17 ) 2 / -SRI 7 , -OR 17 , -Si (Rl) 3 , - [N (Rl) 3 ] + or - [P (R 17 ) 3 ] + mean with R 17 in the meaning of R 4 , or R 10 and R 11 each form one or more rings with the atoms connecting them, x means an integer from 0 to 18, -M 2 means silicon, germanium or tin, and
R9 auch zwei Einheiten der Formel I miteinander verknüpfen kann,R 9 can also link two units of the formula I to one another,
Ra bedeutet eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe, die auch mit Resten in der Bedeutung von R3 substituiert sein kann, und die mindestens ein Heteroatom aus den Gruppen 13, 14, 15 oder 16 des Periodensystems der Elemente enthält.R a denotes a saturated or unsaturated hydrocarbon group, which can also be substituted by radicals as R 3 , and which has at least one hetero atom from groups 13, 14, 15 or 16 of the Periodic Table of the Elements.
2. Verbindung der Formel I gemäß Anspruch 1, dadurch gekenn- zeichnet, daß die bei R3, R4, R6, R7, R8, R3', R4' beschriebene Kohlenwasserstoffgruppe eine Cι-Cιo-Alkylgruppe, C2-Cιo-Alkenylgruppe, Cg-C2o~Arylgruppe, eine C -C4o-Arylalkyl- gruppe, eine C7-C4o~Alkylarylgruppe oder eine C8-C4o-Aryl- alkenylgruppe ist.2. Compound of formula I according to claim 1, characterized in that the hydrocarbon group described in R 3 , R 4 , R 6 , R 7 , R 8 , R 3 ', R 4 ' is a C 1 -C 8 alkyl group, C 2 -Cιo-alkenyl group, Cg-C 2 o ~ aryl group, a C -C 4 o-arylalkyl group, a C 7 -C 4 o ~ alkylaryl group or a C 8 -C 4 o-aryl alkenyl group.
3. Verbindung der Formel I gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die bei R10, R11 beschriebene kohlenstoffhaltige Gruppe eine Cι-C20-Alkyl-, eine Cι-Cιo-Fluoralkyl-, eine Cι-Cιo-Alkoxy-, eine Cg-Cι4-Aryl-, eine Cg-Cio-Fluoraryl-, eine Cg-Cio-Aryloxy-, eine C2-Cι0-Alkenyl-, eine C7-C4o-Aryl- alkyl-, eine C7-C4o-Alkylaryl- oder eine C8-C40-Arylalkenyl- gruppe ist.3. A compound of formula I according to claim 1 or 2, characterized in that the carbon-containing group described in R 10 , R 11 is a C 1 -C 20 alkyl, a C 1 -C 2 -fluoroalkyl, a C 1 -C 1 -alkoxy- a Cg-Cι 4 -aryl, a Cg-Cio-fluoroaryl, a Cg-Cio-aryloxy, C 2 -Cι 0 alkenyl, a C 7 -C 4 o-aryl alkyl, Is C 7 -C 4 o-alkylaryl or a C 8 -C 40 arylalkenyl group.
4. Verbindung der Formel I gemäß Anspruch 1 bis 3, dadurch ge- kennzeichnet, daß die heteroatomhaltigen Kohlenwasserstoff - gruppen mindestens ein Element der Gruppen 13 bis 16 des Periodensystems der Elemente enthalten.4. Compound of formula I according to claim 1 to 3, characterized in that the heteroatom-containing hydrocarbon groups contain at least one element from groups 13 to 16 of the periodic table of the elements.
5. Verbindung der Formel I gemäß Anspruch 1 bis 4, dadurch ge- kennzeichnet, daß5. Compound of formula I according to claim 1 to 4, characterized in that
M1 Zirkonium, Hafnium oder Titan ist,M 1 is zirconium, hafnium or titanium,
R1, R2 gleich sind und für Methyl, Dimethylamid, Dibenzyl oder Chlor stehen, R3, R3' gleich oder verschieden sind und eine Cχ-Cιo-Alkylgruppe, C2~Gιo-Alkenylgruppe oder eine C7-C4o-Alkylarylgruppe bedeuten, R 9 RioRιιSi= Ri0RnGe=, R10R1:LC= oder - (Ri°RiiC-CR10R1:l) - bedeutet, wobei R10 und R11 gleich oder verschieden sind und Wasser- stoff, eine Cι-C2o-Kohlenwasserstoffgruppe, insbesondere Cl-Cirj-Alkyl oder Cg-Ci4~Aryl bedeuten, R5 eine Cg bis C 0 -Arylgruppe bedeutet, die in para-Position zur Bindungsstelle an den Indenylring einen Substituenten R14 trägt, und R14 ein Ci bis Cio-Alkylrest, ein C bis Cio-Alkenylrest , ein Cg bis Cis-Arylrest, ein C bis C2o-Arylalkylrest, ein C bis C2o-Alkylarylrest, ein Cs bis C20-Arylalkenylrest wobei die Kohlenwasserstoffreste auch mit Fluor und/oder Chlor halogeniert oder teilhalogeniert sein können, -NR2 15 , -P(R15)2/ -SR15, -Si(R15)3, -[N(Ri5)3]+ oder -[P(R15)3]+ bedeuten, mit R15 in der Bedeutung von R4 , R16 gleich oder verschieden sind und Fluor, Chlor, Wasserstoff, einen Ci bis Cio-Alkylrest, der auch mit Fluor und/oder Chlor halogeniert oder teilhalogeniert sein kann, einen Cg bis Ci8~Arylrest oder einen C bis Cio-Alkenylrest bedeuten, oder benachbarte Reste R16 cyclisch verbunden sind,R 1 , R 2 are the same and represent methyl, dimethylamide, dibenzyl or chlorine, R 3 , R 3 'are the same or different and a Cχ-Cιo-alkyl group, C 2 ~ Gιo-alkenyl group or a C 7 -C 4 o -Alkylarylgruppe mean, R 9 R i o R ιι S i = R i0 R n Ge =, R 10 R 1: L C = or - (Ri ° RiiC-CR 10 R 1: l ) - means, where R 10 and R 11 are the same or different and represent hydrogen, a C 1 -C 2 -hydrocarbon group, in particular Cl-Cirj-alkyl or Cg-Ci 4 ~ aryl, R 5 represents a Cg to C 0 aryl group which in para- Position to the binding site on the indenyl ring carries a substituent R 14 , and R 14 is a Ci to Cio-alkyl radical, a C to Cio-alkenyl radical, a Cg to Cis-aryl radical, a C to C 2 o-arylalkyl radical, a C to C 2 o-alkylaryl radical, a Cs to C 20 arylalkenyl radical where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine and / or chlorine, -NR 2 15 , -P (R 15 ) 2 / -SR 15 , -Si (R 15 ) 3 , - [N (R i 5) 3 ] + or - [P (R 15 ) 3 ] + be indicate, with R 15 as R 4 , R 16 are the same or different and are fluorine, chlorine, hydrogen, a Ci to Cio-alkyl radical, which can also be halogenated or partially halogenated with fluorine and / or chlorine, a Cg to Ci 8 ~ aryl radical or a C to Cio-alkenyl radical, or adjacent R 16 radicals are cyclically linked,
Ra bedeutet eine gesättigte oder ungesättigte Kohlenwasserstoff- gruppe mit 1 bis 40 Kohlenstoffatomen, die auch mit Resten in der Bedeutung von R3 substituiert sein kann, und .die mindestens ein Heteroatom ausgewählt aus der Gruppe B, AI, Si, Sn, N, P, 0 oder S enthält.R a denotes a saturated or unsaturated hydrocarbon group with 1 to 40 carbon atoms, which can also be substituted with radicals meaning R 3 , and. The at least one hetero atom selected from the group B, Al, Si, Sn, N, Contains P, 0 or S.
6. Verbindung der Formel I gemäß Anspruch 5, dadurch gekennzeichnet, daß6. A compound of formula I according to claim 5, characterized in that
M1 Zirkonium ist,M 1 is zirconium,
R1, R2 gleich sind und für Methyl oder Chlor stehen, R9 0 er - (RioRιιc_CRιoRii) _ ist, worin R10 und R11 gleich oder verschieden sind und Wasserstoff, Phenyl, Methyl oder Ethyl bedeuten, die Reste, R4,R6,R7 und R8 sowie R4' Wasserstoff sind,R 1 , R 2 are the same and represent methyl or chlorine, R 9 0 er - (Rio R ιι c _ CR ιo R ii) _ i st , wherein R 10 and R 11 are the same or different and are hydrogen, phenyl, methyl or ethyl, the radicals, R 4 , R 6 , R 7 and R 8 and R 4 'are hydrogen,
R5 eine C6 bis C20 -Arylgruppe, insbesondere eine Phenyl-,R 5 is a C 6 to C 20 aryl group, in particular a phenyl group,
Naphthyl- oder Anthracenyl-Gruppe bedeuten, die in paraPosition zur Bindungsstelle an den Indenylring einen Substituenten R14 trägt, wobei R14 ein SiR3 15 -Rest , mit R15 in der Bedeutung von R4 , oder ein linearer Ci bisNaphthyl or anthracenyl group, which bears a substituent R 14 in position to the binding site on the indenyl ring, wherein R 14 is a SiR 3 15 radical, with R 15 as R 4 , or a linear Ci bis
Cio- Alkylrest, ein verzweigter C3 bis Cirj- Alkylrest, ein C2 bis Cio- Alkenylrest oder ein verzweigter C7 bis C2o~ Alkylarylrest ist, wobei die Kohlenwasserstoffreste auch mit Fluor und/oder Chlor halogeniert oder teilhalogeniert sein können,Cio-alkyl radical, a branched C 3 to Cirj alkyl radical, a C 2 to Cio alkenyl radical or a branched C 7 to C 2 o alkylaryl radical, where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine and / or chlorine,
Ra eine gesättigte oder ungesättigte Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen, die auch mit Resten in der Bedeutung von R3 substituiert sein kann, und die mindestens ein Heteroatom ausgewählt aus der Gruppe N, P, 0 oder S enthält.R a is a saturated or unsaturated hydrocarbon group with 1 to 30 carbon atoms, which can also be substituted with radicals with the meaning of R 3 , and which contains at least one heteroatom selected from the group N, P, 0 or S.
7. Verbindung der Formel I gemäß Anspruch 1 bis 6, dadurch gekennzeichnet, daß der Rest Ra zusammen mit dem Cyclopentadie- nyl-Grundkörper, an den es gebunden ist, folgende Molekül - fragmente bildet 7. Compound of formula I according to claim 1 to 6, characterized in that the radical R a together with the cyclopentadienyl base body to which it is bound forms the following molecule fragments
wobei die Heteroatomfunktionen X gleich oder verschieden sind und die Bedeutung NRλ, PRλ, N, 0 oder S haben, die Reste Rδ, Rε, Rζ und Rλ Wasserstoff sind oder die Bedeutung von R3 haben, die Reste Rα die Bedeutung von R3' und die Reste Rß die Bedeutung von R4' ha- ben. where the heteroatom functions X are identical or different and have the meaning NR λ , PR λ , N, 0 or S, the radicals R δ , R ε , R ζ and R λ are hydrogen or have the meaning of R 3 , the radicals R α has the meaning of R 3 'and the Rß radicals have the meaning of R 4 '.
8. Verbindung der Formel I gemäß Anspruch 1 bis 7, worin8. A compound of formula I according to claim 1 to 7, wherein
M^-RiR2: ZrCl2, Zr(CH3)2, R3, R3' : Methyl, Ethyl, n-Propyl, Isopropyl, Isobutyl, n-Butyl, s-Butyl, R4, R8, R4': WasserstoffM ^ -RiR 2 : ZrCl 2 , Zr (CH 3 ) 2 , R 3 , R 3 ': methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, s-butyl, R 4 , R 8 , R 4 ': hydrogen
R6, R7: Wasserstoff, Cι~ bis C4~Alkyl, C6 bis Cι0-Aryl, R5 : p-methyl-phenyl, p-ethyl-phenyl, p-n-propyl-phenyl, p- Isopropyl-phenyl, p-n-Butyl-phenyl, p-tert. -Butyl-phenyl, p-s-butyl-phenyl, p-Pentyl-phenyl, p-Hexyl-phenyl, p-Cyclohexyl-phenyl, p-Trimethylsilyl- phenyl, p-Adamantyl-phenyl, p- (F3C) 3C-phenyl, R9 : Dimethylsilandiyl, Phenyl (methyl) silandiyl , Diphenylsilandiyl, Dimethylgermandiyl, Ethyliden, 1-Methylethyli- den, 1, 1-Dimethylethyliden,R 6, R 7 are hydrogen, C ~ to ~ 4 alkyl, C 6 to Cι 0 aryl, R 5: p-methylphenyl, p-ethylphenyl, p-propylphenyl, p-isopropyl-phenyl , pn-butylphenyl, p-tert. -Butyl-phenyl, ps-butyl-phenyl, p-pentyl-phenyl, p-hexyl-phenyl, p-cyclohexyl-phenyl, p-trimethylsilyl-phenyl, p-adamantyl-phenyl, p- (F 3 C) 3 C -phenyl, R 9 : dimethylsilanediyl, phenyl (methyl) silanediyl, diphenylsilanediyl, dimethylgermandiyl, ethylidene, 1-methylethylidene, 1, 1-dimethylethylidene,
1,2-Dimethylethyliden, 1, 1, 2, 2-Tetramethylethyliden, Dirnethylmethyliden, Phenyl (methyl) methyliden, Diphenylme- thyliden,1,2-dimethylethylidene, 1, 1, 2, 2-tetramethylethylidene, dimethylmethylidene, phenyl (methyl) methylidene, diphenylmethylidene,
Ra: 2-Alkyl-4-azapentalene, 2-Alkyl-5-azapentalene, 2-Alkyl-6-azapentalene,R a : 2-alkyl-4-azapentalene, 2-alkyl-5-azapentalene, 2-alkyl-6-azapentalene,
2-Alkyl-N-aryl-4-azapentalene, 2-Alkyl-N-aryl-5-azapenta- lene, 2-Alkyl-N-aryl-6-azapentalene, 2, 5-Dialkyl-4-aza- pentalene, 2, 5-Dialkyl-6-azapentalene,2-alkyl-N-aryl-4-azapentalenes, 2-alkyl-N-aryl-5-azapentalenes, 2-alkyl-N-aryl-6-azapentalenes, 2, 5-dialkyl-4-azapentalenes, 2,5-dialkyl-6-azapentalene,
2,5-Dialkyl-N-aryl-4-azapentalene, 2, 5-Dialkyl-N- aryl-6-azapentalene, 2-Alkyl-4-phosphapentalene, 2-Alkyl-5-phosphapentalene, 2-Alkyl-6-phosphapentalene, 2-Alkyl-P-aryl-4-phosphapentalene, 2-Alkyl-P- aryl-5-phosphapentalene, 2-Alkyl-P-aryl-6-phosphapenta- lene, 2, 5-Dialkyl-4-phosphapentalene, 2, 5-Dialkyl-6-phosphapentalene, 2, 5-Dialkyl-P- aryl-4-phosphapentalene, 2, 5-Dialkyl-P-aryl-6-phosphapen- talene, 2-Alkyl-4-thiapentalene, 2-Alkyl-5-thiapenta- lene, 2-Alkyl-6-thiapentalene, 2, 5-Dialkyl-4-thiapenta- lene, 2, 5-Dialkyl-6-thiapentalene, 2-Alkyl-4-oxapenta- lene, 2-Alkyl-5-oxapentalene, 2-Alkyl-6-oxapentalene, 2, 5-Dialkyl-4-oxapentalene oder 2, 5-Dialkyl-6-oxapentalene, bedeuten. 2,5-dialkyl-N-aryl-4-azapentalenes, 2,5-dialkyl-N-aryl-6-azapentalenes, 2-alkyl-4-phosphapentalenes, 2-alkyl-5-phosphapentalenes, 2-alkyl-6- phosphapentalenes, 2-alkyl-P-aryl-4-phosphapentalenes, 2-alkyl-P-aryl-5-phosphapentalenes, 2-alkyl-P-aryl-6-phosphapentalenes, 2, 5-dialkyl-4-phosphapentalenes, 2,5-dialkyl-6-phosphapentalenes, 2,5-dialkyl-P-aryl-4-phosphapentalenes, 2,5-dialkyl-P-aryl-6-phosphapentalenes, 2-alkyl-4-thiapentalenes, 2- Alkyl-5-thiapentalenes, 2-alkyl-6-thiapentalenes, 2,5-dialkyl-4-thiapentalenes, 2,5-dialkyl-6-thiapentalenes, 2-alkyl-4-oxapentenalenes, 2- Alkyl-5-oxapentalenes, 2-alkyl-6-oxapentalenes, 2, 5-dialkyl-4-oxapentalenes or 2, 5-dialkyl-6-oxapentalenes.
9. Verbindung der Formel I gemäß Anspruch 1 bis 8, in der Bedeutung von9. A compound of formula I according to claim 1 to 8, in the meaning of
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -methyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (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-azapenta- len) (2-methyl-4- (4 '-methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen)) (2-methyl-4- ( 4'-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6- azapentalene) (2-methyl-4- (4'-methylphenyl-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 ' -methylphenyl-indenyl) zirkoniumdichlorid 0 Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl- 4- (4' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride 0 Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl- 4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2- methyl- 4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -methyl- 5 phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl- 4- (4'-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- ( 4'-methyl-5 phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid 0 Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride 0 Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' - methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4-.(4' -methyl- 5 phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- . (4' - methyl 5 phenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Q Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Q Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' - methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -ethyl- 5 phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -ethyl - 5 phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -ethyl¬ phenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapenta- len) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -ethyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-ethyl ¬ phenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen)) (2-methyl-4 - (4'-Ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N- phenyl-6-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen)) (2-methyl-4- (4' -ethylphenyl-indenyl ) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen)) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride Dim ethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4~ (4' -ethylphenyl-indenyl ) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-thiapenta- len) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -ethyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4 ~ (4 '-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen)) (2-methyl-4- (4' -ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (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 Dimethylsilanediyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-oxapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-oxapenta- len) (2-methyl-4- (4 ' -ethylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -n-pro- , ^pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen)) (2-methyl-4- (4' -ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-ethylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl -4- (4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-n-pro-, ^ pylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( 4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (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- propylpheny1-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (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-propylpheny1-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- ( 4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -n -propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n- propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -n- propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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-methyl-5-oxapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -n-propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-n -propylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -n- propylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -n- propylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-n-propylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) ) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl- 4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl- 4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4 - (4'-Isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (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 Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl- 4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2 -methyl- 4- (4'-isopropylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -isopro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -isopropylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -isopro- pylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-isopropylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -isopropylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -isopropylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-isopropylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n-butyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -n -butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (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) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl -4- (4'-n-Butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4'-n- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4'-n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- ( 4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapentalen) (2- methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl- 4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -n-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-butyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -n-butyl-phenyl-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) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -n- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -s-butyl- phenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-n-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -s-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( 4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (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-5-azapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapentalen) (2- methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -s-bu- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2-methyl -4- (4'-s-Butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -s- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -s- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -s -butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -s-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -s- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-s-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -s- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4' t-ter -butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( 4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl -4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5- dimethyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- ( 4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2- methyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) ) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapenta- len) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 '-ter-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-4-thiapentalen)) (2-methyl-4- ( 4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-tert-bu¬ tylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-oxapenta- len) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-oxapenta- len) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -n-pen- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' t-ters -butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-tert-bu ¬ tylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4 - (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl- 4-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- ( ' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4 ' -n-pentyiphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-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- ( '-n-pentylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -n-pentiphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N -phenyl-6-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -n- pentylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -n- pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-pen- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6--6 azapentalene) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalen) (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-thiapentalene) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4' -n- pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4' -n- pentylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- ( 4 '-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-pentylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -n-pen- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -n -pen- phenyl-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-oxapentalen) (2-methyl-4- (4' -n- pentylphenyl-indenyl ) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- ( 4 '-n-pentylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-pheny1-4-azapentalen) (2-methyl-4- (4' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-pheny1-6-azapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -n- hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -n- hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -n -hexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-pheny1-4-azapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-5- azapentalene) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-pheny1-6-azapentalene) (2-methyl-4- (4 '-n-hexylphenyl -indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl -4- (4'-n-Hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium d Iloride Dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -n -hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -n- hexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -n- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- ( 4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -n-hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-n-hexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -n -hexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -n- hexylphenyl-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-hexylphenyl-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) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl ) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4 - (4'-Cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -cy- clohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4' -cy- clohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -cyclo- hexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -cyclohexylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl -indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -cyclohe- xylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl) -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -cyclohexylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 '-cyclohexylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl -indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4' -trime- thylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -trime- thylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-trime - thylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4 - (4'-Trimethylsilylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-azapentalene) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen)) (2-methyl -4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkonium- dichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -trime- thy1silylpheny1-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -trime-thy1silylpheny1 -indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-thiapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -trimethylsilylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl ) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -trimethylsilylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -tri- methylsilylpheny1-indenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-trimethylsilylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -trimethylsilylpheny1-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-5-azapenta- len) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-azapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -adaman- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl ) zirconium dichloride dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-adamantylphenyl-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 dimethylsilanediyl (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 Dimethylsilanediyl (2, 5-dimethyl-4-azapentalene) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl -4- (4'-adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2- methyl-4-thiapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-4-thiapenta- len) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-6-thiapenta- len) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4' -adaman- tylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (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 dimethylsilanediyl (2, 5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl -4- (4'-Adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4 ' -adamantylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4 '-tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4 ' -tris (trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl- 4- (4' -tris (trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-oxapentalen) (2-methyl-4- (4 '-adamantylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -adamantylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl -4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2- methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl- 4- (4' -tris (trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (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) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4- (4 '-tris (trifluormethyl)methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-4-azapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-6-azapentalen) (2-methyl-4 - (4'-Tris (trifluoromethyl) methylphenyl indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (4' -tris (trifluormethyl)methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-thiapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-thiapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4 - (4'-Tris (trifluoromethyl) methylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-thiapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl)methylphenyl-inde- nyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-inde- nyl) zirconium dichloride
Dimethylsilandiyl (2, 5-dimethyl-4-thiapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-4-thiapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-6-thiapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-dimethyl-6-thiapentalene) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-oxapenta- len) (2-methyl-4- (4' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5-oxapenta- len) (2-methyl-4- (4 ' -tris (trifluormethyl) methylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-5-oxapentalen)) (2-methyl-4 - (4'-Tris (trifluoromethyl) methylphenyl indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-6-oxapenta- len) (2-methyl-4- (4 '-tris (trifluormethyl)methylphenyl-inde- nyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4 '-tris (trifluoromethyl) methylphenyl-inde- nyl) zirconium dichloride
Dimethylsilandiyl (2 , 5-dimethyl-4-oxapentalen) (2-methyl-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) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-5, 6-di-hydro-4-azapenta- len) (2-ethyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-4-azapentalen) (2-ethyl-4- (4' -tert-bu- tylphenyl-tetrahydroindenyl) zirkoniumdichloridDimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-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-azapentalen) (2-ethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-5, 6-di-hydro-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-4-azapentalen) (2-ethyl-4- (4 ' -tert-butylphenyl-tetrahydroindenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-5-azapentalen) (2-n-butyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-5-azapentalen) (2-n-butyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Ethyliden (2-methyl-6-azapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-trimethylsilyl-4-azapenta- len) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2-methyl-N-tolyl-5-azapentalen) (2-n-pro- pyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dirnethylgermyldiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Methylethyliden (2, 5-dimethyl-4-azapentalen) (2-methyl-4- (4' -tert- butylphenyl-indenyl) zirkoniumdichloridEthylidene (2-methyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2-methyl-N-trimethylsilyl-4-azapentalen)) (2-methyl-4 - (4 't-Butylphenyl indenyl) zirconium dichloride Dimethylsilanediyl (2-methyl-N-tolyl-5-azapentalen) (2-n-propyl-4- (4 '-ter-butylphenyl-indenyl) zirconium dichloride, direthyl-methyl-diyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride methylethylidene (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tert-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-azapentalen) (2,6- dimethyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2, 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (6' -tert-butylnaphthyl-indenyl) zirkoniumdichlorid Dimethylsilandiyl (2 , 5-dimethyl-N-phenyl-6-azapenta- len) (2-methyl-4- (6' -tert-butylanthracenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2, 5-di-iso-propyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-4-azapentalen) (2,6-dimethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (6 '-ter -butylnaphthyl-indenyl) zirconium dichloride Dimethylsilanediyl (2, 5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (6'-tert-butylanthracenyl-indenyl) zirconium dichloride
Dimethylsilandiyl (2-methyl-4-phσsphapentalen) (2-methyl-4- (4 ' -tert-butylphenyl-indenyl) zirkoniumdichlorid Diphenylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4 ' -tert- butylphenyl-indenyl) zirkoniumdichloridDimethylsilanediyl (2-methyl-4-phσsphapental) (2-methyl-4- (4 '-ter-butylphenyl-indenyl) zirconium dichloride Diphenylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4' tert - butylphenyl indenyl) zirconium dichloride
Methylphenylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichloridMethylphenylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4 't-butylphenyl-indenyl) zirconium dichloride
Methyliden (2, 5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-tert-bu- tylpheny1-indenyl) zirkoniumdichlorid 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) zirkoniumdichlorid Diphenylsilandiyl (2, 5-dimethyl-6-oxapentalen) (2-methyl-4- (4' -tert-butylphenyl-indenyl) zirkoniumdichloridMethylidene (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-tert-butylpheny1-indenyl) zirconium dichloride Dimethylmethyliden (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 diphenylsilanediyl (2, 5-dimethyl- 6-oxapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
und die entsprechenden in 2- und / oder in 2,5-Position mit Ethyl, n-Propyl, Isopropyl, Isobutyl, n-Butyl und s-Butyl substituierten Homologen der vorstehend genannten Verbindungen.and the corresponding homologues of the abovementioned compounds which are substituted in the 2- and / or in the 2,5-position by ethyl, n-propyl, isopropyl, isobutyl, n-butyl and s-butyl.
10. Verwendung einer Verbindung der Formel I gemäß einem der Ansprüche 1 bis 9 zur Herstellung von Polyolefinen.10. Use of a compound of formula I according to one of claims 1 to 9 for the production of polyolefins.
11. Katalysatorsystem enthaltend mindestens ein Metallocen der Formel I gemäß einem der Ansprüche 1 bis 9, mindestens einen11. A catalyst system containing at least one metallocene of the formula I according to one of claims 1 to 9, at least one
Cokatalysator, mindestens einen Träger.Cocatalyst, at least one carrier.
12. Katalysatorsystem gemäß Anspruch 11, zusätzlich enthaltend mindestens eine weitere Additivkomponente. 12. A catalyst system according to claim 11, additionally containing at least one further additive component.
13. Verwendung einer Verbindung der Formel I gemäß einem der Ansprüche 1 bis 9 zur Herstellung eines Katalysatorsystems gemäß einem der Ansprüche 11 oder 12.13. Use of a compound of formula I according to one of claims 1 to 9 for the preparation of a catalyst system according to one of claims 11 or 12.
14. Verwendung des Katalysatorsystems gemäß Anspruch 11 oder 12 in der Herstellung von Polyolefinen.14. Use of the catalyst system according to claim 11 or 12 in the production of polyolefins.
15. Verfahren zur Herstellung von Polyolefinen durch Polymerisation von einem oder mehreren Olefinen in Gegenwart eines Katalysatorsystems gemäß Anspruch 11 oder 12. 15. A process for the preparation of polyolefins by polymerizing one or more olefins in the presence of a catalyst system according to claim 11 or 12.
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BR0004493A (en) 2000-12-19

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