EP1082363A1 - Organometallverbindung, katalysatorsystem enthaltend diese organometallverbindung und seine verwendung - Google Patents

Organometallverbindung, katalysatorsystem enthaltend diese organometallverbindung und seine verwendung

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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Withdrawn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)
English (en)
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/de
Withdrawn legal-status Critical Current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.

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