WO1998040419A1 - Method for producing olefin polymers with a higher melting point - Google Patents

Method for producing olefin polymers with a higher melting point Download PDF

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Publication number
WO1998040419A1
WO1998040419A1 PCT/EP1998/001231 EP9801231W WO9840419A1 WO 1998040419 A1 WO1998040419 A1 WO 1998040419A1 EP 9801231 W EP9801231 W EP 9801231W WO 9840419 A1 WO9840419 A1 WO 9840419A1
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WO
WIPO (PCT)
Prior art keywords
group
methyl
indenyl
cιo
aryl
Prior art date
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PCT/EP1998/001231
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German (de)
French (fr)
Inventor
Carsten Bingel
Markus Goeres
Volker Fraaije
Andreas Winter
Wolfgang Bidell
Heike Gregorius
Roland Hingmann
David Fischer
Carsten SÜLING
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Targor Gmbh
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Publication date
Priority claimed from DE19713546A external-priority patent/DE19713546A1/en
Priority claimed from DE19757563A external-priority patent/DE19757563A1/en
Priority claimed from DE1997157262 external-priority patent/DE19757262A1/en
Application filed by Targor Gmbh filed Critical Targor Gmbh
Priority to EP98920472A priority Critical patent/EP0931099A1/en
Priority to AU73323/98A priority patent/AU7332398A/en
Publication of WO1998040419A1 publication Critical patent/WO1998040419A1/en
Priority to NO991113A priority patent/NO991113L/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to an improved process for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C. in the presence of a metallocene support catalyst, and to the use of polymers of olefins thus obtainable for the production of fibers, films and moldings.
  • Metallocene catalysts are increasingly being used in carrier-fixed form, for example for the polymerization of olefins, since this has process engineering advantages.
  • catalysts which are obtainable from metallocene and aluminoxanes provide polymers, in particular propylene polymers, in a fixed form with a lower polymer melting point than the analogous soluble catalyst system (see EP-A 0 576 970 compared to EP-A 0 780 402) ).
  • a reduced melting point means reduced crystallinity of the polymer and deteriorates mechanical properties, such as rigidity.
  • the object of the present invention was therefore to find a polymerization process using a supported catalyst system, which polymers with an increased melting point, similar to those with the analog solution
  • Catalyst systems are available, accessible, the other properties of the polymer, such as high molecular weight M w narrow molecular weight distribution M w / M n and low xylene-soluble fractions remain practically unchanged during the transition from the soluble to the supported catalyst.
  • a process for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C in the presence of a supported metallocene catalyst characterized in that a supported metallocene catalyst containing active ingredients A) a metallocene complex
  • a metallocenium ion-forming compound selected from the group consisting of Lewis acids and ionic compounds with non-coordinating anions
  • any metallocene can serve as the metallocene component A) of the process according to the invention.
  • the metallocene can be both bridged and unbridged and have the same or different ligands.
  • Highly suitable metallocene components A are those which are described, for example, in DE-A 196 06 167, to which reference is expressly made here, with particular reference to the disclosure on page 3, line 28 to page 6, line 48 of the DE- A 196 06 167 is pointed out.
  • Preferred metallocene components A) are those 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 are a hydrogen atom, a C ⁇ -C ⁇ o-alkyl group, a C ⁇ -C ⁇ o-alkoxy group, a C 6 -C 0 aryl group, a C 6 -C ⁇ o-aryloxy group, a C 2 -C ⁇ o -Alkenyl group, an OH group, an NR 12 group, where R 12 is a C 1 -C 2 -alkyl group or C 6 -C 4 -aryl group, or a halogen atom,
  • R 3 to R 8 and R 3 'to R 8 ' are the same or different and a hydrogen atom is a C ⁇ -C4o-hydrocarbon group, which can be linear, cyclic or branched, for example a C ⁇ -C ⁇ o-alkyl group, C 2 - C ⁇ o-alkenyl group, C 6 -C o-aryl group, a C 7 -C 4 o-arylalkyl group, a C 7 -C 4 o-alkylaryl group or a C 8 -C 40 -arylalkenyl group, or adjacent radicals R 4 to R 8 and / or R 4 'to R 8 ' form a ring system with the atoms connecting them, R 9 signifies a bridge, preferably Rio R ⁇ o R ⁇ o R ⁇ o R ⁇ o R ⁇ o
  • R i ° and R U are the same or different and is a hydrogen atom, a halogen atom or a -C-C 4 o-carbon-containing group such as a C ⁇ -C o-alkyl, a C ⁇ -C ⁇ rj-fluoroalkyl, a C ⁇ -C ⁇ o- Alkoxy, a C 6 -C 4 aryl -, a C ⁇ -Cio-fluoroaryl-, a C- 6 -C ⁇ o-aryloxy-, a C -C ⁇ 0 alkenyl-, a C -C 4 o-aralkyl-, a C 7 -C 4 o "alkylaryl or a Cs-Cirj-arylalkenyl group or R 10 and R 11 each form one or more rings with the atoms connecting them and x is an integer from zero to 18,
  • M 2 is silicon, germanium or tin, and rings A and B are the same or different, saturated, unsaturated or partially saturated.
  • R 9 can also link two units of the formula I to one another.
  • M x is zirconium or hafnium
  • the indenyl or tetrahydroindenyl ligands of the metallocenes of the formula I are preferably in 2-, 2,4-, 4,7-, 2,6-, 2,4,6-, 2,5,6-, 2,4, 5,6- and 2, 4, 5, 6, 7 position, in particular in the 2, 4 position, substituted.
  • Preferred substituents are a C 1 -C alkyl group such as methyl, ethyl or isopropyl or a C 6 -Cio aryl group such as phenyl, naphthyl or mesityl.
  • the 2 position is preferably substituted by a C 1 -C 4 alkyl group, such as methyl or ethyl. If substituted in the 2,4-position, the following applies:
  • R 5 and R 5 ' are preferably the same or different and one
  • Highly suitable metallocenes of the general formula I are those which are described in DE application 197 094 02.3 on page 78, line 21 to page 100, line 22 and in DE application 197 135 46.3 on page 78, line 14 to page 103, Line 22 are disclosed, to which express reference is made here; the dimethylsilanediylbis- [1- (2-methyl-4- (4-tert. -butylphenyl) indenyl)] zirconium dichloride being particularly suitable.
  • metallocenes of the formula I in which the substituents in the 4- and 5-position of the indenyl radicals (R 5 and R 6 and R 5 'and R 6 ') together with the atoms connecting them form a ring system, preferably one Six-ring.
  • This condensed ring system can also be substituted by radicals with the meaning of R 3 -R 8 .
  • Examples of such compounds I include dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride.
  • An example of such compounds of the formula I is dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride.
  • Examples of the metallocene component A of the process according to the invention are:
  • Dimethylsilanediylbis indenyl) zirconium dichloride Dimethylsilanediylbis -naphthyl- indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl -benzo- indenyl) zirconium dichloride Dimethylsilanediylbis-2 -methyl-indenyl) zirconyldichloro-1-methyldichloride
  • Dimethylsilanediylbis 2 -methyl-4- (2-naphthyl) indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl -4 -phenyl -indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2,4,6 -trimethyl -indenyl) zirconium dichloride Dimethylsilanediylbis (2,5,6 -trimethyl -indenyl) zirconiumdichloride Dimethylsilanediylbis (2,4,7 -trimethyl -indenyl) zirconiumdichloride Dimethylsilanediylbis (2 -mutyl- 5-is ) zirconium dichloride dimethylsilanediylbis (2 -methyl- 5- t -butyl-indenyl) zirconium dichloride
  • the catalyst system according to the invention contains compounds B) forming metallocenium ions. These can be Lewis acids and / or ionic compounds with non-coordinated anions.
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 2 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) phenyl.
  • organoboron or organoaluminum compound which contains C 1 -C 2 carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluor
  • Organoboron compounds are particularly preferred.
  • Lewis acids examples include trifluoroborane, triphenylborane, tris (4-fluorophenyl) orane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tis (pentafluorophenyl) borane, tris (tolyl) borane, tris ( 3, 5 -dimethylphenyl) borane, tris (3, 5-dime- thylfluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
  • Well-suited ionic compounds which contain a non-coordinating anion are, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 " , CF 3 SO 3 " or CIO 4 ".
  • Lewis bases such as methylamine are generally used as the cationic counterion , 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-dimehylaniline, tri-ethylphosphine, tri-phenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium are used.
  • Tributylammonium tetra (phenyl) borate Trimethylammonium tetra (tolyl) borate
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate Triphenylcarbenium tetrakis (pentafluorophenyl) borate
  • Ferrocenium tetrakis (pentafluorophenyl) aluminate Ferrocenium tetrakis (pentafluorophenyl) aluminate.
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred.
  • 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.
  • Tri (butyl) mmonium-1-carbadecec. Tri (butyl) mmonium-1-carbadecec.
  • 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 oxidic supports are, for example, MgO, Zr0, Ti0 2 or B0 3 , to name just a few.
  • the carrier materials used generally 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 of 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 of 200 are particularly preferred up 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.
  • 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 is the case when using silica gel as the carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the carrier material can take place under vacuum and at the same time inert gas blanket (e.g. nitrogen).
  • the drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical.
  • the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
  • Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane and organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium.
  • the chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture.
  • suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene.
  • the inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible.
  • the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
  • the carrier material is isolated by filtration under inert conditions, one or more times with suitable ten inert solvents, as described above, washed and then dried with an inert gas stream or in vacuo.
  • Organic carrier materials such as finely divided polyolefin powders (e.g. 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.
  • polyolefin powders e.g. polyethylene, polypropylene or polystyrene
  • the preparation of the supported catalyst is generally not critical.
  • Well-suited variants are the following:
  • At least one metallocene component A) is generally brought into contact with the compound B) forming metallocenium ions in an organic solvent, in order to obtain a dissolved or partially suspended product.
  • This product is then generally added to the support material, preferably porous silicon dioxide (silica gel), if appropriate pretreated as described above, the solvent is removed and the supported catalyst is obtained as a free-flowing solid.
  • the supported catalyst can then be prepolymerized, for example with C 2 - to C 1 -C 1 -enes.
  • the metallocene supported catalyst is generally obtained by the following process steps
  • an inorganic support material preferably porous silicon dioxide as described above
  • an inerting agent as described above, preferably an aluminum tri-C ⁇ -C ⁇ o-alkyl, such as trimethylaluminium, triethylaluminium, triisobutylaluminum,
  • an alkali metal, alkaline earth metal or main group -III- organometallic compound preferably aluminum tri- C ⁇ -C ⁇ o-alkyl, such as trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
  • 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, tetracyclododecene or methyl norbornene.
  • 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
  • Ethene or propene are preferably homopolymerized in the process according to the invention, or ethene with one or more 1-olefins with 3 to 20 C atoms, such as propene, and / or one or more dienes with 4 to 20 C atoms, such as 1, 4 -Butadiene, norbornadiene or ethylnorbornadiene, copolymerized.
  • Examples of such copolymers are ethene / propene copolymers or ethene / propene / 1,4-hexadiene terpolymers.
  • the polymerization is carried out at a temperature of -60 to 300 ° C, preferably 50 to 200 ° C.
  • the pressure is 0.5 to 3000 bar, preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • the polyolefins according to the invention are distinguished, inter alia, by the fact that they have a high crystallinity, expressed, inter alia, by a high DSC melting point, and high rigidity. Based on current knowledge, this property profile can be traced back to a special microstructure of the polymer chains.
  • Example 2 the metallocene used was rac-dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride.
  • Example 2 the metallocene used was rac-dimethylsilanediylbis (2 -methyl -4 (1-naphthyl) indenyl) zirconium dichloride.
  • the melting points of the corresponding polymers can be found in the table.

Abstract

The invention relates to a method for producing polyolefins by polymerizing olefins at pressures ranging from 0.5 to 3,000 bars and at temperatures ranging from -60 to 300 °C in the presence of a metallocene carrier catalyst. To this end, a metallocene carrier catalyst is used containing the following active constituents: a) a metallocene complex and b) a metallocenium ion forming compound selected from the group consisting of Lewis acids and ionic compounds with non-coordinating anions.

Description

Verfahren zur Herstellung von Olefinpolymerisaten mit erhöhtem SchmelzpunktProcess for the preparation of olefin polymers with an increased melting point
Beschreibungdescription
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung von Polyolefinen durch Polymerisation von Olefinen bei Drücken im Bereich von 0,5 bis 3000 bar und Temperaturen im Bereich von -60 bis 300°C in Gegenwart eines Metallocen-Trägerka- talysators, sowie die Verwendung der so erhältlichen Polymerisate von Olefinen zur Herstellung von Fasern, Folien und Formkörpern.The present invention relates to an improved process for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C. in the presence of a metallocene support catalyst, and to the use of polymers of olefins thus obtainable for the production of fibers, films and moldings.
Metallocenkatalysatoren werden immer häufiger in trägerfixierter Form beispielsweise zur Polymerisation von Olefinen eingesetzt, da dies verfahrenstechnische Vorteile hat.Metallocene catalysts are increasingly being used in carrier-fixed form, for example for the polymerization of olefins, since this has process engineering advantages.
Katalysatoren, die aus Metallocen und Aluminoxanen erhältlich sind, liefern jedoch in trägerfixierter Form Polymere, ins- besondere Propylenpolymerisate, mit, im Vergleich zum analogen löslichen Katalysatorsystem, abgesenktem Polymerschmelzpunkt (siehe EP-A 0 576 970 im Vergleich zu EP-A 0 780 402). Ein abgesenkter Schmelzpunkt bedeutet abgesenkte Kristallinität des Polymeren und verschlechtert mechanische Eigenschaften, wie Steifig- keit.However, catalysts which are obtainable from metallocene and aluminoxanes provide polymers, in particular propylene polymers, in a fixed form with a lower polymer melting point than the analogous soluble catalyst system (see EP-A 0 576 970 compared to EP-A 0 780 402) ). A reduced melting point means reduced crystallinity of the polymer and deteriorates mechanical properties, such as rigidity.
Aufgabe der vorliegenden Erfindung war es daher, ein Polymerisationsverfahren unter Verwendung eines trägerfixierten Katalysatorsystem zu finden, welches Polymere mit erhöhtem Schmelzpunkt, ähnlich jenen, die mit den analogen gelöstenThe object of the present invention was therefore to find a polymerization process using a supported catalyst system, which polymers with an increased melting point, similar to those with the analog solution
Katalysatorsystemen erhältlich sind, zugänglich machen, wobei die sonstigen Eigenschaften des Polymeren, wie hohes Molekulargewicht Mw enge Molekulargewichtsverteilung Mw/Mn und geringe xylol- lösliche Anteile praktisch unverändert bleiben beim Übergang vom löslichen zum trägerfixierten Katalysator.Catalyst systems are available, accessible, the other properties of the polymer, such as high molecular weight M w narrow molecular weight distribution M w / M n and low xylene-soluble fractions remain practically unchanged during the transition from the soluble to the supported catalyst.
Demgemäß wurde ein Verfahren zur Herstellung von Polyolefinen durch Polymerisation von Olefinen bei Drücken im Bereich von 0,5 bis 3000 bar und Temperaturen im Bereich von -60 bis 300°C in Gegenwart eines Metallocen-Trägerkatalysators, dadurch gekennzeichnet, daß man einen Metallocen-Trägerkatalysator, enthaltend als aktive Bestandteile A) einen MetallocenkomplexAccordingly, a process for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C in the presence of a supported metallocene catalyst, characterized in that a supported metallocene catalyst containing active ingredients A) a metallocene complex
B) eine metalloceniumionenbildende Verbindung, ausgewählt aus der Gruppe, bestehend aus Lewissäuren und ionischen Verbindungen mit nicht-koordinierenden AnionenB) a metallocenium ion-forming compound selected from the group consisting of Lewis acids and ionic compounds with non-coordinating anions
verwendet, sowie die gemäß den Verfahrensmerkmalen erhältlichen Polymerisate von Olefinen und deren Verwendung zur Herstellung von Fasern, Folien und Formkörpern gefunden.used, and the polymers of olefins obtainable according to the process features and their use for the production of fibers, films and moldings found.
Als Metallocenkomponente A) des erfindungsgemäßen Verfahrens kann grundsätzlich jedes Metallocen dienen. Das Metallocen kann sowohl verbrückt als auch unverbrückt sein und gleiche oder verschiedene Liganden aufweisen. Bevorzugt sind Metallocene der Gruppe IVb des Periodensystems der Elemente, wie Titan, Zirkonium oder Hafnium.In principle, any metallocene can serve as the metallocene component A) of the process according to the invention. The metallocene can be both bridged and unbridged and have the same or different ligands. Metallocenes of group IVb of the periodic table of the elements, such as titanium, zirconium or hafnium, are preferred.
Es können selbstverständlich auch Mischungen unterschielicher Metallocene als Komponente A) dienen.Mixtures of different metallocenes can of course also serve as component A).
Gut geeignete Metallocenkomponenten A) sind solche, die bei- spielsweise in DE-A 196 06 167 auf die hier ausdrücklich Bezug genommen wird, beschrieben sind, wobei besonders auf die Offenbarung auf Seite 3, Zeile 28 bis Seite 6, Zeile 48 der DE-A 196 06 167 hingewiesen wird.Highly suitable metallocene components A) are those which are described, for example, in DE-A 196 06 167, to which reference is expressly made here, with particular reference to the disclosure on page 3, line 28 to page 6, line 48 of the DE- A 196 06 167 is pointed out.
Bevorzugte Metallocenkomponenten A) sind solche der nachstehenden Formel (I) .Preferred metallocene components A) are those of the formula (I) below.
Figure imgf000004_0001
worin
Figure imgf000004_0001
wherein
M1 ein Metall der Gruppe IVb des Periodensystems der Elemente ist, R1 und R2 gleich oder verschieden sind und ein Wasserstoff atom, eine Cι-Cιo-Alkylgruppe, eine Cχ-Cιo-Alkoxygruppe, eine C6-C 0-Arylgruppe, eine C6 -Cχo-Aryloxygruppe, eine C2-Cιo-Alkenyl- gruppe, eine OH -Gruppe, eine NR12 -Gruppe, wobei R12 eine Ci- bis C2-Alkylgruppe oder C6- bis Cι4-Arylgruppe ist, oder ein Halogenatom bedeuten,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 are a hydrogen atom, a Cι-Cιo-alkyl group, a Cχ-Cιo-alkoxy group, a C 6 -C 0 aryl group, a C 6 -Cχo-aryloxy group, a C 2 -Cιo -Alkenyl group, an OH group, an NR 12 group, where R 12 is a C 1 -C 2 -alkyl group or C 6 -C 4 -aryl group, or a halogen atom,
R3 bis R8 und R3' bis R8' gleich oder verschieden sind und ein Wasserstoff atom eine Cχ-C4o-Kohlenwasserstof f gruppe, die linear, cyclisch oder verzweigt sein kann, z.B. eine Cχ-Cιo-Alkylgruppe, C2-Cχo-Alkenylgruppe, C6 -C o-Arylgruppe, eine C7-C4o-Arylalkyl- gruppe, eine C7-C4o-Alkylarylgruppe oder eine C8-C4o-Arylalkenyl- gruppe, bedeuten, oder benachbarte Reste R4 bis R8 und/oder R4' bis R8' mit den sie verbindenden Atomen ein Ringsystem bilden, R9 eine Verbrückung bedeutet, bevorzugt Rio Rιo Rιo Rιo RιoR 3 to R 8 and R 3 'to R 8 ' are the same or different and a hydrogen atom is a Cχ-C4o-hydrocarbon group, which can be linear, cyclic or branched, for example a Cχ-Cιo-alkyl group, C 2 - Cχo-alkenyl group, C 6 -C o-aryl group, a C 7 -C 4 o-arylalkyl group, a C 7 -C 4 o-alkylaryl group or a C 8 -C 40 -arylalkenyl group, or adjacent radicals R 4 to R 8 and / or R 4 'to R 8 ' form a ring system with the atoms connecting them, R 9 signifies a bridge, preferably Rio R ιo R ιo R ιo R ιo
.0 — M — 0 — •0- M2- C M2-.0 - M - 0 - • 0- M 2 - CM 2 -
R11 , RU , Rll R11 RllR 11 , RU, Rll R 11 Rll
R10 R10 R10 RIO RIO R 10 R 10 R 10 RIO RIO
M2- M2- M2 CM 2 - M 2 - M 2 C
Rll Rll Rll Rll RllRll Rl l Rll R ll Rll
Figure imgf000005_0001
Figure imgf000005_0001
^BRl°, AIR10, Ge , Q- -S , so, S02, ^ BRl °, AIR 10 , Ge, Q- -S, so, S0 2 ,
NRl°, CO, PRl° oder R(0)Ri°,NRl °, CO, PRl ° or R (0) Ri °,
bedeutet, wobeimeans where
Ri° und RU gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom oder eine Cι-C4o-kohlenstoffhaltige Gruppe ist wie eine Cχ-C o-Alkyl- , eine Cι-Cιrj-Fluoralkyl- , eine Cι-Cιo-Alkoxy- , eine C6-Cι4-Aryl - , eine Cδ-Cio-Fluoraryl- , eine C-6-Cιo-Aryloxy- , eine C -Cι0-Alkenyl- , eine C -C4o-Aralkyl- , eine C7 -C4o"Alkylaryl- oder eine Cs-Cirj-Arylalkenylgruppe oder R10 und R11 jeweils mit den sie verbindenden Atomen einen oder mehrere Ringe bilden und x eine ganze Zahl von Null bis 18 ist,R i ° and R U are the same or different and is a hydrogen atom, a halogen atom or a -C-C 4 o-carbon-containing group such as a Cχ-C o-alkyl, a Cι-Cιrj-fluoroalkyl, a Cι-Cιo- Alkoxy, a C 6 -C 4 aryl -, a C δ -Cio-fluoroaryl-, a C- 6 -Cιo-aryloxy-, a C -Cι 0 alkenyl-, a C -C 4 o-aralkyl-, a C 7 -C 4 o "alkylaryl or a Cs-Cirj-arylalkenyl group or R 10 and R 11 each form one or more rings with the atoms connecting them and x is an integer from zero to 18,
M2 Silizium, Germanium oder Zinn ist, und die Ringe A und B gleich oder verschieden, gesättigt, ungesättigt oder teilweise gesättigt sind.M 2 is silicon, germanium or tin, and rings A and B are the same or different, saturated, unsaturated or partially saturated.
R9 kann auch zwei Einheiten der Formel I miteinander verknüpfen.R 9 can also link two units of the formula I to one another.
In Formel I gilt besonders bevorzugt, daßIn formula I it is particularly preferred that
Mx Zirkonium oder Hafnium ist,M x is zirconium or hafnium,
Ri und R2 gleich sind und für Methyl oder Chlor, insbesondere Chlor, stehen und R9 = M2Ri°RH ist, worin M2 Silizium oder Germanium ist und Ri° sowie R1X eine Cι-C20-Kohlenwasserstoffgruppe, wie Cι-Cιo-Alkyl oder C6-C14-Aryl ist.R i and R 2 are the same and represent methyl or chlorine, in particular chlorine, and R 9 = M 2 R i ° R H , where M 2 is silicon or germanium and R i ° and R 1X is a C 1 -C 20 - Hydrocarbon group, such as -CC-alkyl or C 6 -C 14 aryl.
Die Indenyl- bzw. Tetrahydroindenylliganden der Metallocene der Formel I sind bevorzugt in 2-, 2,4-, 4,7-, 2,6-, 2,4,6-, 2,5,6-, 2,4,5,6- und 2, 4, 5, 6, 7 -Stellung, insbesondere in 2 , 4 -Stellung, substituiert. Bevorzugte Substituenten sind eine C1-C -Alkylgruppe wie z.B. Methyl, Ethyl oder Isopropyl oder eine C6 -Cio-Arylgruppe wie Phenyl, Naphthyl oder Mesityl. Die 2 -Stellung ist bevorzugt durch eine C1-C4 -Alkylgruppe, wie z.B. Methyl oder Ethyl substituiert. Wenn in 2,4-Stellung substituiert ist, so gilt, daßThe indenyl or tetrahydroindenyl ligands of the metallocenes of the formula I are preferably in 2-, 2,4-, 4,7-, 2,6-, 2,4,6-, 2,5,6-, 2,4, 5,6- and 2, 4, 5, 6, 7 position, in particular in the 2, 4 position, substituted. Preferred substituents are a C 1 -C alkyl group such as methyl, ethyl or isopropyl or a C 6 -Cio aryl group such as phenyl, naphthyl or mesityl. The 2 position is preferably substituted by a C 1 -C 4 alkyl group, such as methyl or ethyl. If substituted in the 2,4-position, the following applies:
R5 und R5' bevorzugt gleich oder verschieden sind und eineR 5 and R 5 'are preferably the same or different and one
Cß -Cio-Arylgruppe, eine C7-Cιo-Arylalkylgruppe, eine C7 -C40"Alkyl- arylgruppe oder eine
Figure imgf000006_0001
bedeuten.C ß -Cio aryl group, a C 7 -Cιo arylalkyl group, a C 7 -C 40 "alkyl aryl group or one
Figure imgf000006_0001
mean.
Gut geeignete Metallocene der allgemeinen Formel I sind jene, die in der DE-Anmeldung 197 094 02.3 auf Seite 78, Zeile 21 bis Seite 100, Zeile 22 und in der DE-Anmeldung 197 135 46.3 auf Seite 78, Zeile 14 bis Seite 103, Zeile 22 offenbart sind, auf die hier ausdrücklich Bezug genommen wird; wobei das Dimethyl- silandiylbis- [1- (2 -methyl-4- (4 -tert. -butyl-phenyl) indenyl) ] zirco- niumdichlorid besonders gut geeignet ist.Highly suitable metallocenes of the general formula I are those which are described in DE application 197 094 02.3 on page 78, line 21 to page 100, line 22 and in DE application 197 135 46.3 on page 78, line 14 to page 103, Line 22 are disclosed, to which express reference is made here; the dimethylsilanediylbis- [1- (2-methyl-4- (4-tert. -butylphenyl) indenyl)] zirconium dichloride being particularly suitable.
Für den Substitutionsort gilt dabei die folgende Nomenklatur:
Figure imgf000007_0001
The following nomenclature applies to the place of substitution:
Figure imgf000007_0001
Von besonderer Bedeutung sind weiterhin Metallocene der Formel I, bei denen die Substituenten in 4- und 5 -Stellung der Indenylreste (R5 und R6 sowie R5' und R6') zusammen mit den sie verbindenden Atomen ein Ringsystem bilden, bevorzugt einen Sechsring. Dieses kondensierte Ringsystem kann ebenfalls durch Reste in der Bedeutung von R3-R8 substituiert sein. Beispielhaft für solche Verbindungen I ist DimetylsilandiyIbis (2 -methyl-4, 5 -benzoinde- nyl) zirkoniumdichlorid zu nennen.Also of particular importance are metallocenes of the formula I in which the substituents in the 4- and 5-position of the indenyl radicals (R 5 and R 6 and R 5 'and R 6 ') together with the atoms connecting them form a ring system, preferably one Six-ring. This condensed ring system can also be substituted by radicals with the meaning of R 3 -R 8 . Examples of such compounds I include dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride.
Insbesondere bevorzugt sind solche Verbindungen der Formel I, die in 4 -Stellung eine Cδ -C o-Arylgruppe und in 2 -Stellung eine C1-C4-Alkylgruppe tragen. Beispielhaft für solche Verbindungen er Formel I ist Dimethylsilandiylbis (2 -methyl-4 -phenylinde- nyl) zirkoniumdichlorid.Particularly preferred are those compounds of the formula I which carry a C δ -C o aryl group in the 4 position and a C 1 -C 4 alkyl group in the 2 position. An example of such compounds of the formula I is dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride.
Beispiele für die Metallocenkomponente A des erfindungsgemäßen Verfahrens sind:Examples of the metallocene component A of the process according to the invention are:
Dimethylsilandiylbis indenyl) zirkoniumdichlorid Dimethylsilandiylbis -naphthyl- indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -methyl -benzo- indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -methyl- indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -methyl-4- (1 -naphthyl) -indenyl) zirkonium- dichloridDimethylsilanediylbis indenyl) zirconium dichloride Dimethylsilanediylbis -naphthyl- indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl -benzo- indenyl) zirconium dichloride Dimethylsilanediylbis-2 -methyl-indenyl) zirconyldichloro-1-methyldichloride
Dimethylsilandiylbis 2 -methyl-4- (2 -naphthyl) indenyl) zirkonium- dichlorid Dimethylsilandiylbis 2 -methyl -4 -phenyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -methyl - 4 - t-butyl - indenylzirkoniumdiChlorid Dimethylsilandiylbis 2 -methyl- 4 -isopropyl- indenyl) zirkonium- dichloridDimethylsilanediylbis 2 -methyl-4- (2-naphthyl) indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl -4 -phenyl -indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl - 4 - t-butyl - indenylzirconiumdiChloridyldisilyl-4 indenyl) zirconium dichloride
Dimethylsilandiylbis 2 -methyl- 4 -ethyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -methyl- 4 -a-acenaphth- indenyl) zirkonium- dichloridDimethylsilanediylbis 2 -methyl- 4 -ethyl -indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl- 4-a-acenaphth-indenyl) zirconium dichloride
Dimethylsilandiylbis 2 , 4 -dimethyl- indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -ethyl - indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -ethyl -4 -ethyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -ethyl -4 -phenyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis 2 -methyl-4, 5 -benzo-indenyl) zirkonium- dichlorid Dimethylsilandiylbis (2 -methyl-4, 6 -diisopropyl- indenyl) Zirkonium- dichloridDimethylsilanediylbis 2, 4 -dimethyl-indenyl) zirconium dichloride Dimethylsilanediylbis 2 -ethyl - indenyl) zirconium dichloride Dimethylsilanediylbis 2 -ethyl -4 -ethyl -indenyl) zirconium dichloride Dimethylsilanediylbis 2 -ethyl -4 -phenyl-ethyldichloro-5-di-5-yl-2-di-5-yl-2-di-5-yl-5-di-5-yl-2-di-5-yl-2-dimethyl-2-di-5-yl-2-yl -benzo-indenyl) zirconium dichloride dimethylsilanediylbis (2 -methyl-4, 6 -diisopropyl-indenyl) zirconium- dichloride
Dimethylsilandiylbis (2 -methyl-4, 5-diisopropyl- indenyl) zirkoniumdichloridDimethylsilanediylbis (2 -methyl-4,5-diisopropyl-indenyl) zirconium dichloride
Dimethylsilandiylbis (2,4,6 -trimethyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2,5,6 -trimethyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2,4,7 -trimethyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2 -methyl- 5 - isobutyl - indenyl ) zirkoniumdichlorid Dimethylsilandiylbis (2 -methyl- 5- t-butyl- indenyl) zirkonium- dichloridDimethylsilanediylbis (2,4,6 -trimethyl -indenyl) zirconium dichloride Dimethylsilanediylbis (2,5,6 -trimethyl -indenyl) zirconiumdichloride Dimethylsilanediylbis (2,4,7 -trimethyl -indenyl) zirconiumdichloride Dimethylsilanediylbis (2 -mutyl- 5-is ) zirconium dichloride dimethylsilanediylbis (2 -methyl- 5- t -butyl-indenyl) zirconium dichloride
Dimethylsilandiylbis (2 -methyl- 4 -phenanthrylinden) zirkoniumdichloridDimethylsilanediylbis (2 -methyl-4-phenanthrylindene) zirconium dichloride
Dimethylsilandiylbis (2 -ethyl -4 -phenanthylindenyl) zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -methyl - -phenyl -indenyl) zirkoniumdichloridDimethylsilanediylbis (2-ethyl -4-phenanthylindenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl - phenyl -indenyl) zirconium dichloride
Methyl (phenyl) silandiylbis (2 -methyl-4, 6 -diisopropyl- indenyl) - zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -methyl-4 -isopropyl -indenyl) - zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-4-isopropylindenyl) zirconium dichloride
Methyl (phenyl) silandiylbis (2 -methyl-4, 5 -benzo- indenyl) zirkoniumdichloridMethyl (phenyl) silanediylbis (2 -methyl-4,5-benzo-indenyl) zirconium dichloride
Methyl (phenyl) silandiylbis (2 -methyl -4, 5- (methylbenzo) -indenyl) - zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -methyl-4, 5- (tetramethylbenzo) - indenyl) zirkoniumdichloridMethyl (phenyl) silanediylbis (2 -methyl -4, 5- (methylbenzo) -indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2 -methyl-4, 5- (tetramethylbenzo) indenyl) zirconium dichloride
Methyl (phenyl) silandiylbis (2 -methyl- 4 -a-acenaphth- indenyl) - zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -methyl- indenyl) zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -methyl- 5- isobutyl - indenyl) zirkoniumdichloridMethyl (phenyl) silanediylbis (2-methyl-4-a-acenaphth-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-5-isobutyl-indenylchloride) zirconium
Methyl (phenyl) silandiylbis (2 -methyl- 4 -phenanthrylindenyl) - zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -ethyl -4 -phenanthrylindenyl) - zirkoniumdichloridMethyl (phenyl) silanediylbis (2 -methyl- 4 -phenanthrylindenyl) - zirconium dichloride Methyl (phenyl) silanediylbis (2 -ethyl -4 -phenanthrylindenyl) - zirconium dichloride
1, 2-Ethandiylbis (2 -methyl -4 -phenyl -indenyl) zirkoniumdichlorid 1, 4-Butandiylbis (2 -methyl -4 -phenyl -indenyl) zirkoniumdichlorid 1, 2-Ethandiylbis (2 -methyl-4, 6 -diisopropyl -indenyl) zirkoniumdichlorid 1, 4-Butandiylbis (2 -methyl-4 -isopropyl- indenyl) zirkoniumdichlorid 1, 4-Butandiylbis (2 -methyl-4, 5 -benzo- indenyl) zirkoniumdichlorid 1, 2 -Ethandiylbis (2 -methyl-4, 5 -benzo- indenyl) zirkoniumdichlorid 1 , 2 -Ethandiylbis (2,4,7- trimethyl - indenyl ) zirkoniumdichlorid 1, 2 -Ethandiylbis (2 -methyl-indenyl) zirkoniumdichlorid 1, 4-Butandiylbis (2 -methyl -indenyl) zirkoniumdichlorid Bis (butylcyclopentadienyl) Zr+CH2CHCHCH2B- (C6F5) 3 Bis (methylindenyl) Zr+CH2CHCHCH2B- (C6F5) 3 Dimethylsilandiybis (2 -methyl -4,5 -benzo -indenyl) - Zr+CH2CHCHCHB' (C6F5)3 1, 2-ethanediylbis (2 -methyl -4 -phenyl -indenyl) zirconium dichloride 1, 4-butanediylbis (2 -methyl -4 -phenyl -indenyl) zirconium dichloride 1, 2-ethanediylbis (2 -methyl-4, 6 -diisopropyl - indenyl) zirconium dichloride 1, 4-butanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride 1, 4-butanediylbis (2-methyl-4, 5 -benzo-indenyl) zirconium dichloride 1, 2 -ethanediylbis (2-methyl-4 , 5-benzo-indenyl) zirconium dichloride 1,2-ethanediylbis (2,4,7-trimethyl-indenyl) zirconium dichloride 1,2-ethanediylbis (2-methyl-indenyl) zirconium dichloride 1,4-butanediylbis (2-methyl -indenyl) zirconium dichloride bis (butylcyclopentadienyl) Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3 bis (methylindenyl) Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3 Dimethylsilandiybis (2 -methyl -4,5 -benzo -indenyl) - Zr + CH 2 CHCHCHB '(C 6 F 5 ) 3
1,2 -Ethandiylbis (2 -methyl -indenyl) -Zr+CHCHCHCH2B- (C5F5)3 1, 4 -Butandiylbis (2 -methyl -indenyl) -Zr+CH2CHCHCH2B- (C6F5)3 Dimethylsilandiylbis (2 -methyl-4, 6- diisopropyl- indenyl) - Zr+CH2CHCHCH2B- (C6F5)3 1,2-ethanediylbis (2 -methyl -indenyl) -Zr + CHCHCHCH 2 B- (C 5 F 5 ) 3 1, 4 -butanediylbis (2 -methyl -indenyl) -Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3 dimethylsilanediylbis (2 -methyl-4, 6-diisopropyl-indenyl) - Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3
Dimethylsilandiylbis (2 -ethyl -4 -phenyl - indenyl) - Zr+CH2CHCHCH2B- (C6F5) 3 Dimethylsilanediylbis (2-ethyl -4-phenyl-indenyl) - Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3
Dimethylsilandiylbis (2 -methyl-4 -phenyl -indenyl) - Zr+CH2CHCHCH2B- (C6F5)3 Dimethylsilanediylbis (2 -methyl-4-phenylindenyl) - Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3
Methyl (phenyl) silandiylbis (2 -methyl -4 -phenyl -indenyl) - Zr+CH2CHCHCH2B- (C5F5)3 Methyl (phenyl) silanediylbis (2 -methyl -4 -phenyl -indenyl) - Zr + CH 2 CHCHCH 2 B- (C 5 F 5 ) 3
Dimethylsilandiylbis (2 -methyl-4 -phenyl -indenyl) - Zr+CH2CHCHCH2B- (C6F5)3 Dimethylsilandiylbis (indenyl) -Zr+CH2CHCHCH2B- (C5F5)3 Dimethylsilanediylbis (2 -methyl-4-phenylindenyl) - Zr + CH 2 CHCHCH 2 B- (C 6 F 5 ) 3 Dimethylsilanediylbis (indenyl) -Zr + CH 2 CHCHCH 2 B- (C 5 F 5 ) 3
Dimethylsilandiyl (tert. -Butylamino) (tetramethylcyclopentadienyl) ■ zirkoniumdichloridDimethylsilanediyl (tert-butylamino) (tetramethylcyclopentadienyl) ■ zirconium dichloride
[Tris (pentafluorophenyl) (cyclopentadienyliden)borato] (cyclopenta- dienyl) -1,2,3,4 - tetraphenylbuta- 1, 3 -dienylZirkonium Dimethylsilandiyl- [tris (pentafluorophenyl) (2 -methyl-4 -phenylinde- nyliden)borato] (2 -methyl -4 -phenylindenyl) -1,2,3, 4- tetraphenyl- buta-1, 3 -dienylzirkonium[Tris (pentafluorophenyl) (cyclopentadienylidene) borato] (cyclopentadienyl) -1,2,3,4 - tetraphenylbuta- 1,3 -dienylzirconium dimethylsilanediyl- [tris (pentafluorophenyl) (2-methyl-4-phenylindenylnylidene) borato ] (2-methyl -4-phenylindenyl) -1,2,3, 4-tetraphenyl-buta-1,3-dienylzirconium
Dimethylsilandiyl- [tris (trifluoromethyl) (2 -methylbenzindenyl- iden)borato] (2 -methylbenzindenyl) -1,2,3, 4 - tetraphenylbuta- 1, 3- dienylzirkoniumDimethylsilanediyl- [tris (trifluoromethyl) (2 -methylbenzindenylidene) borato] (2 -methylbenzindenyl) -1,2,3,4-tetraphenylbuta- 1,3-dienylzirconium
Dimethylsilandiyl- [tris (pentafluorophethyl) (2 -methyl - indenyl- iden)borato] (2 -methyl- indenyl) -1,2,3,4 - tetraphenylbuta- 1, 3 -dienylzirkoniumDimethylsilanediyl- [tris (pentafluorophethyl) (2-methyl-indenyl-idene) borato] (2-methyl-indenyl) -1,2,3,4-tetraphenylbuta- 1,3-dienylzirconium
Dimethylsilandiylbis (indenyl) zirkoniumdimethyl Dimethylsilandiylbis (4 -naphthyl- indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2 -methyl-benzo-indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2 -methyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis [2-methyl-4- (1-naphthyl) -indenyl) zirkoniumdi- methyl Dimethylsilandiylbis 2 -methyl-4- (2 -naphthyl) -indenyl) zirkoniumdi- methylDimethylsilanediylbis (indenyl) zirconiumdimethyldimethylsilanediylbis (4 -naphthyl-indenyl) zirconiumdimethyldimethylsilanediylbis (2 -methyl-benzo-indenyl) zirconiumdimethyldimethylsilanediylbis (2 -methyl -indenyl-methyl-1-methyl-1-nyl-methyl-1-nyl-methyl-zirconiumdimethyl zirconium dimethyl dimethylsilanediylbis 2 -methyl-4- (2-naphthyl) -indenyl) zirconium dimethyl
Dimethylsilandiylbis 2 -methyl -4 -phenyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis 2 -methyl-4 - t-butyl - indenyl) zirkoniumdimethyl Dimethylsilandiylbis 2 -methyl - 4 - isopropyl - indenyl) zirkoniumdi- methylDimethylsilanediylbis 2 -methyl -4 -phenyl -indenyl) zirconiumdimethyl Dimethylsilanediylbis 2 -methyl-4 - t-butyl - indenyl) zirconiumdimethyl Dimethylsilanediylbis 2 -methyl - 4 - isopropyl - indenyl) zirconiumdimethyl
Dimethylsilandiylbis 2 -methyl -4 -ethyl -indenyl) zirkoniumdimethylDimethylsilanediylbis 2 -methyl -4 -ethyl -indenyl) zirconiumdimethyl
Dimethylsilandiylbis 2 -methyl- 4 -a-acenaphth- indenyl) zirkoniumdi- methylDimethylsilanediylbis 2 -methyl-4-a-acenaphth-indenyl) zirconium dimethyl
DirnethylsilandiyIbis 2,4-dimethyl- indenyl) zirkoniumdimethyl Dimethylsilandiylbis 2 -ethyl - indenyl ) zirkoniumdimethyl Dimethylsilandiylbis 2 -ethyl - 4 -ethyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis 2 -ethyl -4 -phenyl- indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2 -methyl-4, 5 -benzo- indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2 -methyl-4, 6 -diisopropyl -indenyl) zirkoniumdimethylDirnethylsilandiyIbis 2,4-dimethyl-indenyl) zirconium dimethyl dimethylsilanediylbis 2 -ethyl - indenyl) zirconium dimethyl dimethylsilanediylbis 2 -ethyl - 4 -ethyl -indenyl) zirconiumdimethyl dimethylsilanediylbis 2 -ethyl -4-phenyl-indimethyl) zirconium Dimethylsilanediylbis (2 -methyl-4, 5 -benzo-indenyl) zirconiumdimethylDimethylsilanediylbis (2 -methyl-4, 6 -diisopropyl -indenyl) zirconiumdimethyl
Dimethylsilandiylbis (2 -methyl-4, 5 -diisopropyl -indenyl) zirkonium- dimethylDimethylsilanediylbis (2 -methyl-4,5-diisopropylindenyl) zirconium dimethyl
Dimethylsilandiylbis (2,4,6 -trimethyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2,5,6 -trimethyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2,4,7 -trimethyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2 -methyl- 5- isobutyl -indenyl) zirkoniumdi- methylDimethylsilanediylbis (2,4,6 -trimethyl -indenyl) zirconium dimethyldimethylsilanediylbis (2,5,6 -trimethyl -indenyl) zirconiumdimethyldimethylsilanediylbis (2,4,7 -trimethyl -indenyl) zirconiumdimethyldimethylsilanediylbis (2 -methyl-5-isobutyl) ) zirconium dimethyl
Dimethylsilandiylbis (2 -methyl- 5- t-butyl -indenyl) zirkoniumdimethyl Dimethylsilandiylbis (2 -methyl-4 -phenanthrylindenyl) zirkoniumdimethylDimethylsilanediylbis (2 -methyl-5-t-butyl -indenyl) zirconiumdimethylDimethylsilanediylbis (2 -methyl-4-phenanthrylindenyl) zirconiumdimethyl
Dimethylsilandiylbis (2 -ethyl -4 -phenanthrylindenyl) zirkoniumdi- methylDimethylsilanediylbis (2-ethyl -4-phenanthrylindenyl) zirconium dimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4 -phenyl -indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4, 6 -diisopropyl- indenyl) zirkoniumdimethyl Methyl (phenyl) silandiylbis (2 -methyl- 4 -isopropyl -indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2 -methyl-4, 6 -diisopropyl-indenyl) zirconiumdimethylMethyl (phenyl) silanediylbis (2 -methyl-4 -isopropyl -indenyl) zirconiumdimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4, 5 -benzo-indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2 -methyl-4,5-benzo-indenyl) zirconium dimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4, 5- (methylbenzo) - indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2 -methyl-4, 5- (methylbenzo) indenyl) zirconium dimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4, 5- (tetramethylbenzo) - indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2 -methyl-4, 5- (tetramethylbenzo) indenyl) zirconium dimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4 -a-acenaphth- indenyl) zirkoniumdimethyl Methyl (phenyl) silandiylbis (2 -methyl- indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2 -methyl-4-a-acenaphth-indenyl) zirconiumdimethylMethyl (phenyl) silanediylbis (2 -methyl-indenyl) zirconiumdimethyl
Methyl (phenyl) silandiylbis (2 -methyl -5- isobutyl -indenyl) zirkoniumdimethylMethyl (phenyl) silanediylbis (2 -methyl -5-isobutyl -indenyl) zirconium dimethyl
Methyl (phenyl) silandiylbis (2 -methyl-4 -phenanthrylindenyl) - zirkoniumdimethyl Methyl (phenyl) silandiylbis (2 -ethyl - -phenanthrylindenyl) - zirkoniumdimethylMethyl (phenyl) silanediylbis (2-methyl-4-phenanthrylindenyl) - zirconium dimethyl Methyl (phenyl) silanediylbis (2 -ethyl - phenanthrylindenyl) - zirconium dimethyl
1, 2 -Ethandiylbis (2 -methyl -4 -phenyl -indenyl) zirkoniumdimethyl 1, 2-Butandiylbis (2 -methyl-4 -phenyl -indenyl) zirkoniumdimethyl 1, 2 -Ethandiylbis (2 -methyl-4, 6 -diisopropyl -indenyl) zirkoniumdi- methyl1,2-ethanediylbis (2 -methyl -4 -phenyl -indenyl) zirconiumdimethyl 1,2-butanediylbis (2 -methyl-4 -phenyl -indenyl) zirconiumdimethyl 1,2, -ethanediylbis (2 -methyl-4,6-diisopropyl - indenyl) zirconium dimethyl
1, 4-Butandiylbis (2 -methyl-4 -isopropyl- indenyl) zirkoniumdimethyl 1, 4-Butandiylbis (2 -methyl-4 , 5 -benzo- indenyl) zirkoniumdimethyl 1, 2 -Ethandiylbis (2 -methyl-4 , 5 -benzo- indenyl) zirkoniumdimethyl 1, 2 -Ethandiylbis (2,4,7 -trimethyl -indenyl) zirkoniumdimethyl 1, 4-Butandiylbis (2 -methyl -indenyl) zirkoniumdimethyl Besonders bevorzugt sind:1, 4-Butanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dimethyl 1, 4-butanediylbis (2-methyl-4, 5-benzo-indenyl) zirconium dimethyl 1, 2 -ethanediylbis (2-methyl-4, 5 - benzo-indenyl) zirconium dimethyl 1,2-ethanediylbis (2,4,7-trimethyl -indenyl) zirconium dimethyl 1,4-butanediylbis (2-methyl -indenyl) zirconium dimethyl The following are particularly preferred:
Dimethylsilandiylbis (2 -methyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2 -methyl-4- (1 -naphthyl) -indenyl) zirkonium- dichloridDimethylsilanediylbis (2 -methyl -indenyl) zirconium dichloride Dimethylsilanediylbis (2 -methyl-4- (1-naphthyl) -indenyl) zirconium dichloride
Dimethylsilandiylbis (2 -methyl - 4 -phenyl -indenyl ) zirkoniumdichlorid Dimethylsilandiylbis (2 -methyl-4 -a-acenaphth- indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2 -ethyl -4 -phenyl -indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2 -methyl -4, 5 -benzo- indenyl) zirkoniumdichloridDimethylsilanediylbis (2 -methyl - 4 -phenyl -indenyl) zirconium dichloride Dimethylsilanediylbis (2 -methyl-4-a-acenaphth-indenyl) zirconium dichloride Dimethylsilanediylbis (2 -ethyl -4 -phenyl -indenyl) zirconiumdichloryldimethyl (2-methyldisloride) -benzo- indenyl) zirconium dichloride
Dimethylsilandiylbis (2 -methyl - 4 , 6 -diisopropyl - indenyl) zirkoniumdichlorid Dimethylsilandiylbis (2 -methyl -4 -phenanthryl -indenyl) zirkonium- dichloridDimethylsilanediylbis (2 -methyl-4, 6 -diisopropyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2 -methyl -4 -phenanthryl -indenyl) zirconium dichloride
Dimethylsilandiylbis (2 -ethyl -4 -phenanthryl -indenyl) zirkoniumdichloridDimethylsilanediylbis (2-ethyl -4-phenanthryl -indenyl) zirconium dichloride
Methyl (phenyl) silandiylbis (2 -methyl -4 -phenanthryl- indenyl) - zirkoniumdichlorid Methyl (phenyl) silandiylbis (2 -ethyl -4 -phenanthryl -indenyl) - zirkoniumdichloridMethyl (phenyl) silanediylbis (2 -methyl -4 -phenanthryl-indenyl) - zirconium dichloride Methyl (phenyl) silanediylbis (2 -ethyl -4 -phenanthryl -indenyl) - zirconium dichloride
Herstellungsverfahren für Metallocene der Formel I sind z.B. in Journal of Organometallic Chem. 288 (1985) 63-67 und den dort zi- tierten Dokumenten beschrieben.Manufacturing processes for metallocenes of formula I are e.g. in Journal of Organometallic Chem. 288 (1985) 63-67 and the documents cited therein.
Als Komponente B) enthält das erfindungsgemäße Katalysatorsystem metalloceniumionenbildende Verbindungen B) . Dies können Lewis - säuren und/oder ionische Verbindungen mit nicht-koordinierten An- ionen sein.As component B), the catalyst system according to the invention contains compounds B) forming metallocenium ions. These can be Lewis acids and / or ionic compounds with non-coordinated anions.
Als Lewis- Säure werden bevorzugt mindestens eine bor- oder aluminiumorganische Verbindung eingesetzt, die Cι-C2o"kohlenstoffhaltige 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) phenyl .The Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 2 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) phenyl.
Besonders bevorzugt sind bororganische Verbindungen.Organoboron compounds are particularly preferred.
Beispiele für Lewis -Säuren sind Trifluorboran, Triphenylboran, Tris (4-fluorophenyl) oran, Tris (3, 5 -difluorophenyl) boran, Tris (4-fluoromethylphenyl) boran, Tis (pentafluorophenyl)boran, Tris (tolyl)boran, Tris (3, 5 -dimethylphenyl) boran, Tris (3, 5-dime- thylfluorophenyl) boran und/oder Tris (3,4, 5- trifluorophenyl) boran. Insbesondere bevorzugt ist Tris (pentafluorophenyl)boran.Examples of Lewis acids are trifluoroborane, triphenylborane, tris (4-fluorophenyl) orane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tis (pentafluorophenyl) borane, tris (tolyl) borane, tris ( 3, 5 -dimethylphenyl) borane, tris (3, 5-dime- thylfluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
Gut geeignete ionische Verbindungen, die ein nicht koordinieren- des Anion enthalten, sind beispielsweise Tetrakis (pentafluorophenyl)borate, Tetraphenylborate, SbF6 ", CF3SO3 " oder CIO4". Als kationisches Gegenion werden im allgemeinen Lewis -Basen wie z.B. Methylamin, Anilin, Dimethylamin, Diethylamin, N-Methylanilin, Diphenylamin, N,N-Dimethylanilin, Trimethylamin, Triethylamin, Tri-n-butylamin, Methyldiphenylamin, Pyridin, p-Bromo-N,N-dime- thylanilin, p-Nitro-N,N-dimehylanilin, Tri_ethylphosphin, Tri - phenylphosphin, Diphenylphosphin, Tetrahydrothiophen und Triphe- nylcarbenium eingesetzt.Well-suited ionic compounds which contain a non-coordinating anion are, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 " , CF 3 SO 3 " or CIO 4 ". Lewis bases such as methylamine are generally used as the cationic counterion , 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-dimehylaniline, tri-ethylphosphine, tri-phenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium are used.
Beispiele für solche erfindungsgemäßen ionischen Verbindungen mit nicht-koordinierenden Anionen sindExamples of such ionic compounds according to the invention with non-coordinating anions are
Triethylammoniumtetra (phenyl)borat,Triethylammonium tetra (phenyl) borate,
Tributylammoniumtetra (phenyl )borat , Trimethylammoniumtetra (tolyl)borat,Tributylammonium tetra (phenyl) borate, trimethylammonium tetra (tolyl) borate,
Tributylammoniumtetra (tolyl) borat,Tributylammonium tetra (tolyl) borate,
Tributylammoniumtetra (pentafluorophenyl) borat,Tributylammonium tetra (pentafluorophenyl) borate,
Tributylammoniumtetra (pentafluorophenyl) aluminat,Tributylammonium tetra (pentafluorophenyl) aluminate,
Tripropylammoniumtetra (dimethylphenyl) borat, Tributylammoniumtetra (trifluoromethylphenyl) borat,Tripropylammonium tetra (dimethylphenyl) borate, tributylammonium tetra (trifluoromethylphenyl) borate,
Tributylammoniumtetra (4 - fluorophenyl) borat,Tributylammonium tetra (4-fluorophenyl) borate,
N,N-Dimethylaniliniumtetra (phenyl) orat,N, N-dimethylanilinium tetra (phenyl) orate,
N, -Diethylaniliniumtetra (phenyl ) orat,N, -diethylanilinium tetra (phenyl) orate,
N,N-Dirnethylaniliniumtetrakis (pentafluorophenyl)borate, N,N-Dimethylaniliniumtetrakis (pentafluorophenyl) aluminat,N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,
Di (propyl) ammoniumtetrakis (pentafluorophenyl)borat,Di (propyl) ammonium tetrakis (pentafluorophenyl) borate,
Di (cyclohexyl) ammoniumtetrakis (pentafluorophenyl) borat,Di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate,
Triphenylphosphoniumtetrakis (phenyl)borat,Triphenylphosphonium tetrakis (phenyl) borate,
Triethylphosphoniumtetrakis (phenyl)borat, Diphenylphosphoniumtetrakis (phenyl) borat,Triethylphosphonium tetrakis (phenyl) borate, diphenylphosphonium tetrakis (phenyl) borate,
Tri (methylphenyl)phosphoniumtetrakis (phenyl) borat,Tri (methylphenyl) phosphonium tetrakis (phenyl) borate,
Tri (dimethylphenyl)phosphoniumtetrakis (phenyl) borat,Tri (dimethylphenyl) phosphonium tetrakis (phenyl) borate,
Triphenylcarbeniumtetrakis (pentafluorophenyl)borat,Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbeniumtetrakis (pentafluorophenyl) aluminat, Triphenylcarbeniumtetrakis (phenyl) aluminat,Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis (phenyl) aluminate,
Ferroceniumtetrakis (pentafluorophenyl)borat und/oderFerrocenium tetrakis (pentafluorophenyl) borate and / or
Ferroceniumtetrakis (pentafluorophenyl) aluminat .Ferrocenium tetrakis (pentafluorophenyl) aluminate.
Bevorzugt sind Triphenylcarbeniumtetrakis (pentafluorophenyl) borat und/oder N,N-Dimethylaniliniumtetrakis (pentafluorophenyl)borat . Es können auch Gemische mindestens einer Lewis -Säure und mindestens einer ionischen Verbindung eingesetzt werden.Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred. 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,Undecahydrid-7, 8-dimethyl-7, 8-dicarbaundecaboran,
Dodecahydrid-1 -phenyl- 1, 3 -dicarbaundecaboran,Dodecahydrid-1-phenyl-1, 3 -dicarbaundecaboran,
Tri (butyl) ammoniumdecahydrid-8 -ethyl -7 , -dicarbaundecaborat, 4 -Carbanonaboran (14) Bis (tri (butyl) ammonium)nonaborat,Tri (butyl) ammonium decahydrid-8-ethyl-7, -dicarbaundecaborat, 4-carbanonaboran (14) bis (tri (butyl) ammonium) nonaborate,
Bis (tri (butyl) ammonium)undecaborat,Bis (tri (butyl) ammonium) undecaborate,
Bis (tri (butyl) ammonium) dodecaborat,Bis (tri (butyl) ammonium) dodecaborate,
Bis (tri (butyl) ammonium) decachlorodecaborat,Bis (tri (butyl) ammonium) decachlorodecaborate,
Tri (butyl) mmonium- 1-carbadecaborate, Tri (butyl) mmonium- 1-carbadodecaborate,Tri (butyl) mmonium-1-carbadecec., Tri (butyl) mmonium-1-carbadecec.,
Tri (butyl) ammonium-1 - trimethylsilyl-1-carbadecaborate,Tri (butyl) ammonium-1-trimethylsilyl-1-carbadecaborate,
Tri (butyl) ammoniumbis (nonahydrid-1, 3 -dicarbonnonaborat) cobal- tat(III) ,Tri (butyl) ammonium bis (nonahydrid-1,3-dicarbonnonaborate) cobalt (III),
Tri (butyl) mmoniumbis (undecahydrid-7 , 8 -dicarbaundecaborat) fer- rat(IH) ,Tri (butyl) ammonium bis (undecahydrid-7, 8-dicarbaundecaborate) ferrat (IH),
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 entsprechende Oxid-Mischungen. Andere anorganische Oxide, die allein oder in Kombination mit den zuletzt genannten bevorzugten oxidischen Trägern eingesetzt werden können, sind z.B. MgO, Zr0 , Ti02 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 oxidic supports are, for example, MgO, Zr0, Ti0 2 or B0 3 , to name just a few.
Die verwendeten Trägermaterialien weisen im allgemeinen eine spezifische Oberfläche im Bereich von 10 bis 1000 m2/g, ein Poren- volumen im Bereich von 0,1 bis 5 ml/g und eine mittlere Partikel - große 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 Partikelgröße 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 generally 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 of 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 of 200 are particularly preferred up 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.
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. Der Gewichtsverlust beim Glühen (LOI = Loss on igni- tion) sollte 1 % oder weniger betragen. Die thermische Dehydratisierung oder Trocknung des Trägermaterials kann unter Vakuum und gleichzeitiger Inertgasüberlagerung (z.B. Stickstoff) erfolgen. Die Trocknungstemperatur liegt im Bereich zwischen 100 und 1000°C, vorzugsweise zwischen 200 und 800°C. Der Parameter Druck ist in diesem Fall nicht entscheidend. Die Dauer des Trocknungsprozesses kann zwischen 1 und 24 Stunden betragen. Kürzere oder längere Trocknungsdauern sind möglich, vorausgesetzt, daß unter den gewählten Bedingungen die Gleichgewichtseinstellung mit den Hydroxylgruppen auf der Trägeroberfläche erfolgen kann, was normalerweise zwischen 4 und 8 Stunden erfordert.If the carrier material used naturally has a low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as is the case when using silica gel as the carrier material, dehydration or drying is recommended. The weight loss during glow (LOI = loss on ignition) should be 1% or less. The thermal dehydration or drying of the carrier material can take place under vacuum and at the same time inert gas blanket (e.g. nitrogen). The drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical. The drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
Eine Dehydratisierung oder Trocknung des Trägermaterials ist auch auf chemischem Wege möglich, indem das adsorbierte Wasser und die Hydroxylgruppen auf der Oberfläche mit geeigneten Inertisierungs- mittein 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 und metallorganische Verbindung von Aluminium, Bor und Magnesium wie beispielsweise Trimethyl - aluminium, Triethylaluminium, Triisobutylaluminium, Triethyl- boran, Dibutylmagnesium. Die chemische Dehydratisierung oder Inertisierung des Trägermaterials erfolgt beispielsweise dadurch, daß man unter Luft- und Feuchtigkeitsausschluß eine Suspension des Trägermaterials in einem geeigneten Lösemittel mit dem Inertisierungsreagenz in reiner Form oder gelöst in einem geeigneten Lösemittel zur Reaktion bringt. Geeignete Lösemittel sind z.B. aliphatische oder aromatische Kohlenwasserstoffe wie Pentan, Hexan, Heptan, Toluol oder Xylol . Die Inertisierung erfolgt bei Temperaturen zwischen 25°C und 120°C, bevorzugt zwischen 50 und 70°C. Höhere und niedrigere Temperaturen sind möglich. Die Dauer der Reaktion beträgt zwischen 30 Minuten und 20 Stunden, bevor- zugt 1 bis 5 Stunden. Nach dem vollständigen Ablauf der chemischen Dehydratisierung wird das Trägermaterial durch Filtration unter Inertbedingungen isoliert, ein- oder mehrmals mit geeigne- ten inerten Lösemitteln, wie sie bereits zuvor beschrieben worden sind, gewaschen und anschließend mit 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 and organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium. The chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture. Suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene. The inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible. The duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours. After the chemical dehydration is complete, the carrier material is isolated by filtration under inert conditions, one or more times with suitable ten inert solvents, as described above, washed and then dried with an inert gas stream or in vacuo.
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.Organic carrier materials such as finely divided polyolefin powders (e.g. 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.
Die Herstellung des Trägerkatalysators ist im allgemeinen nicht kritisch. Gut geeignete Varianten sind die folgenden:The preparation of the supported catalyst is generally not critical. Well-suited variants are the following:
Bei Variante I wird im allgemeinen mindestens eine Metallocenkomponente A) üblicherweise in einem organischen Lösungsmittel mit der metalloceniumionenbildenden Verbindung B) in Kontakt gebracht, um ein gelöstes oder teilsuspendiertes Produkt zu erhalten. Dieses Produkt wird dann in der Regel zum, gegebenenfalls wie vorher beschrieben, vorbehandelten Trägermaterial, vorzugsweise poröses Siliciumdioxid (Silicagel) gegeben, das Lösemittel entfernt und den Trägerkatalysator als frei fließender Feststoff erhalten. Der Trägerkatalysator kann dann noch zum Beispiel mit C2- bis Cιo-Alk-1-enen vorpolymerisiert werden.In variant I, at least one metallocene component A) is generally brought into contact with the compound B) forming metallocenium ions in an organic solvent, in order to obtain a dissolved or partially suspended product. This product is then generally added to the support material, preferably porous silicon dioxide (silica gel), if appropriate pretreated as described above, the solvent is removed and the supported catalyst is obtained as a free-flowing solid. The supported catalyst can then be prepolymerized, for example with C 2 - to C 1 -C 1 -enes.
Nach Variante 2 erhält man den Metallocen-Trägerkatalysator im allgemeinen durch folgende VerfahrensschritteAccording to variant 2, the metallocene supported catalyst is generally obtained by the following process steps
a) Umsetzung eines anorganischen Trägermaterials, vorzugsweise poröses Siliciumdioxid wie vorher beschrieben, mit einem In- ertisierungsmittel, wie vorher beschrieben, vorzugsweise einem Aluminiumtri-Cι-Cιo-alkyl, wie Trimethylaluminium, Tri- ethylaluminium, Triisobutylaluminium,a) reaction of an inorganic support material, preferably porous silicon dioxide as described above, with an inerting agent, as described above, preferably an aluminum tri-Cι-Cιo-alkyl, such as trimethylaluminium, triethylaluminium, triisobutylaluminum,
b) Umsetzung des so erhaltenen Materials mit einem Metallocenkomplex A) - vorzugsweise einem der Formel I - in feiner Me- talldihalogenid-Form und einer metalloceniumionenbildenden Verbindung B) und anschließendeb) reaction of the material thus obtained with a metallocene complex A) - preferably one of the formula I - in fine metal dihalide form and a compound B) forming metallocenium ions and subsequent
c) Umsetzung mit einer Alkali-, Erdalkali- oder Hauptgruppe -III- organometallverbindung, vorzugsweise Aluminiumtri- Cι-Cιo-alkyl, wie Trimethylaluminium, Triethylaluminium oder Triisobutylaluminium.c) reaction with an alkali metal, alkaline earth metal or main group -III- organometallic compound, preferably aluminum tri- Cι-Cιo-alkyl, such as trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
Dieses Verfahren ist in DE-A 19 606 197, auf die hiermit ausdrücklich Bezug genommen wird, ausführlich beschrieben. Als Olefine werden solche der Formel Rm-CH=CH-Rn verwendet, worin 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. Beispiele für solche Olefine sind 1-Olefine mit 2 bis 40, vorzugsweise 2 bis 10 C-Atomen, wie Ethen, Propen, 1 -Buten, 1-Penten, 1-Hexen, 4 -Methyl -1-penten oder 1-Octen, Styrol, Diene wie 1, 3 -Butadien, 1, 4-Hexadien, Vinylnorbornen, Norbornadien, Ethylnorbornadien und cyclische Olefine wie Norbornen, Tetracy- clododecen oder Methylnorbornen. Bevorzugt werden in dem erfindungsgemäßen Verfahren Ethen oder Propen homopolymerisiert, oder Ethen mit einem oder mehreren 1-Olefinen mit 3 bis 20 C-Atomen, wie Propen, und/oder einem oder mehreren Dienen mit 4 bis 20 C-Atomen, wie 1, 4 -Butadien, Norbornadien oder Ethylnorbornadien, copolymerisiert. Beispiele solcher Copolymere sind Ethen/Propen- Copolymere oder Ethen/Propen/1, 4 -Hexadien-Terpolymere.This process is described in detail in DE-A 19 606 197, to which express reference is hereby made. The olefins used are those of the formula R m -CH = CH-R n , in which R m and R n are identical or different and are 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. 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, tetracyclododecene or methyl norbornene. Ethene or propene are preferably homopolymerized in the process according to the invention, or ethene with one or more 1-olefins with 3 to 20 C atoms, such as propene, and / or one or more dienes with 4 to 20 C atoms, such as 1, 4 -Butadiene, norbornadiene or ethylnorbornadiene, copolymerized. 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, durchgeführt. Der Druck beträgt 0,5 bis 3000 bar, bevorzugt 5 bis 64 bar.The polymerization is carried out at a temperature of -60 to 300 ° C, preferably 50 to 200 ° C. The pressure is 0.5 to 3000 bar, preferably 5 to 64 bar.
Die Polymerisation kann in Lösung, in Masse, in Suspension oder in der Gasphase, kontinuierlich oder diskontinuierlich, ein- oder mehrstufig durchgeführt werden.The polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
Die erfindungsgemäßen Polyolefine zeichnen sich unter anderem dadurch aus, daß sie eine hohe Kristallinintät, unter anderem ausgedrückt durch einen hohen DSC-Schmelzpunkt, und hohe Steifigkeit haben. Dieses Eigenschaftsprofil kann nach derzeitigem Kenntnisstand auf eine besondere MikroStruktur der Polymerketten zurückgeführt werden.The polyolefins according to the invention are distinguished, inter alia, by the fact that they have a high crystallinity, expressed, inter alia, by a high DSC melting point, and high rigidity. Based on current knowledge, this property profile can be traced back to a special microstructure of the polymer chains.
BeispieleExamples
Vergleichsbeispiel 1 (Aluminoxan-Katalysator)Comparative Example 1 (aluminoxane catalyst)
a) Herstellung des Trägermaterialsa) Production of the carrier material
1000 g Kieselgel (60 μm, Fa. Grace, 8 h bei 180°C im Vakuum1000 g of silica gel (60 μm, Grace), 8 h at 180 ° C in a vacuum
(1 mbar) ausgeheizt) wurden in 5 1 Toluol unter N -Atmosphäre suspendiert. Bei einer Temperatur von 18°C wurden 7,75 1 (6,83 kg) 1,53 molare Methylaluminoxan (MAO) lösung (in Toloul, Fa. Witco) über 120 Minuten zugegeben. Anscließend wurde 7 h bei Raumtempe- ratur nachgerührt, filtriert und der Filterkuchen zweimal je mit 2,5 1 Toluol gewaschen. Anschließend wurde im Vakuum getrocknet. b) Beladung mit Metallocenkomplex(1 mbar) baked out) were suspended in 5 l of toluene under an N atmosphere. At a temperature of 18 ° C., 7.75 l (6.83 kg) of 1.53 molar methylaluminoxane (MAO) solution (in Toloul, Witco) were added over 120 minutes. The mixture was then stirred for 7 h at room temperature, filtered and the filter cake was washed twice with 2.5 l of toluene each. It was then dried in vacuo. b) loading with metallocene complex
10 g des unter a) hergestellten MAO beladenen Kieselgels wurden in einem evakuierten Gefäß vorgelegt. Anschließend wurde unter Rühren eine Lösung von 58 mg (0,1 mmol) rac. -Dimethylsilylen- bis (2 -methylbenzindenyl) zirkondichlorid in 13,2 ml 1,53 molarer MAO-Lösung (Toloul) zugegeben. Nach dem Druckausgleich mit N2 wurde 30 Minuten beim Raumtemperatur durchmischt. Dann wurde, zunächst bei 20°C, die Hauptmenge Lösungsmittel im Vakuum ab- destilliert (bis kein Lösungsmittel mehr überging) . Anschließend wurde die Temperatur in 5°C Schritten auf 55°C erhöht und der Katalysator solange getrocknet, bis er als oranges, gut riesel- fähiges Pulver zurückblieb.10 g of the silica gel loaded under a) prepared were placed in an evacuated vessel. A solution of 58 mg (0.1 mmol) rac. -Dimethylsilylen- bis (2 -methylbenzindenyl) zirconium dichloride in 13.2 ml 1.53 molar MAO solution (Toloul) was added. After pressure equalization with N2, the mixture was mixed for 30 minutes at room temperature. The main amount of solvent was then distilled off in vacuo (initially at 20 ° C. until no more solvent passed over). The temperature was then increased in 5 ° C. steps to 55 ° C. and the catalyst was dried until it remained as an orange, free-flowing powder.
Vergleichsbeispiel 2 (Aluminoxan Katalysator)Comparative Example 2 (aluminoxane catalyst)
wie Vergleichsbeispiel 1, jedoch wurde als Metallocen rac- Dimethylsilandiylbis (2 -methyl-4 -phenyl -indenyl) zirkoniumdichlorid verwendet.as Comparative Example 1, but rac-dimethylsilanediylbis (2-methyl-4-phenyl -indenyl) zirconium dichloride was used as the metallocene.
Vergleichsbeispiel 3 (Aluminoxan- Katalysator)Comparative Example 3 (aluminoxane catalyst)
wie Vergleichsbeispiel 1, jedoch wurde als Metallocen rac- Dimethylsilandiylbis (2 -methyl-4- (1-naphtyl) indenyl) zirkonium- dichlorid verwendet.as comparative example 1, but rac-dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride was used as the metallocene.
Beispiel 1 (Borat-Katalysator)Example 1 (borate catalyst)
a) Herstellung des Trägermaterialsa) Production of the carrier material
500 g Kieselgel (60 μm, Fa. Grace, 8 h bei 180°C im Vakuum (1 mbar) ausgeheizt) wurden in 4 1 trockenem Heptan unter N -Atmosphäre suspendiert. Bei Raumtemperatur wurden 2 1 Triiso -butyl - aluminium (2 molar in Heptan) in 120 Minuten zugegeben, wobei sich die Suspension auf 40°C erwärmt. Anschließend wurde 2 h bei Raumtemperatur nachgerührt, filtriert und der Filterkuchen mit 2 1 Heptan gewaschen. Anschließend wurde im Vakuum getrocknet.500 g of silica gel (60 μm, Grace, heated for 8 hours at 180 ° C. in a vacuum (1 mbar)) were suspended in 4 liters of dry heptane under an N atmosphere. At room temperature, 2 liters of triiso-butyl aluminum (2 molar in heptane) were added in 120 minutes, the suspension heating to 40 ° C. The mixture was then stirred at room temperature for 2 h, filtered and the filter cake was washed with 2 l of heptane. It was then dried in vacuo.
b) Beladung mit Metallocenkomplexb) loading with metallocene complex
10 g des unter a) hergestellten desaktivierten Kieselgels wurden in einem vorher inertisierten Gefäß vorgelegt und in 40 ml trok- kenem Toloul suspendiert. Zu dieser Suspension wurden nacheinander 290 mg (0,5 1 mmol) Dimethylsilylenbis (2 -methylbenz - indenyl) zirkondichlorid, 488 mg (0,61 mmol) N,N-Dimethylanilini- um-tetrakis (pentaflourphenyl) borat und 2 ml Triisobutyl -aluminium (2 molar in Heptan) zugegeben. Die Suspension wurde auf 70°C er- wärmt und bei dieser Temperatur 1 h gerührt. Nach 4 h Nachrühren bei Raumtemperatur wurde das Lösungsmittel im Ölpumpenvakuum entfernt. Man erhielt ein frei fließendes, rot -braunes Pulver.10 g of the deactivated silica gel prepared under a) were placed in a previously inertized vessel and suspended in 40 ml of dry toloule. 290 mg (0.5 1 mmol) of dimethylsilylenebis (2-methylbenz - indenyl) zirconium dichloride, 488 mg (0.61 mmol) of N, N-dimethylanilinium-tetrakis (pentaflourphenyl) borate and 2 ml of triisobutyl - aluminum (2 molar in heptane) added. The suspension was at 70 ° C warms and stirred at this temperature for 1 h. After stirring for 4 h at room temperature, the solvent was removed in an oil pump vacuum. A free-flowing, red-brown powder was obtained.
Beispiel 2 (Borat-Katalysator)Example 2 (borate catalyst)
wie Beispiel 1, jedoch wurde als Metallocen rac-Dimethylsilandi- ylbis (2 -methyl -4 -phenyl- indenyl) zirkoniumdichlorid verwendet.as in Example 1, but the metallocene used was rac-dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride.
Beispiel 3 (Borat-Katalysator)Example 3 (borate catalyst)
wie Beispiel 1, jedoch wurde als Metallocen rac-Dimethylsilandi- ylbis (2 -methyl -4 (1-naphtyl) indenyl) zirkoniumdichlorid verwendet.as in Example 1, but the metallocene used was rac-dimethylsilanediylbis (2 -methyl -4 (1-naphthyl) indenyl) zirconium dichloride.
PropylenpolymerisationPropylene polymerization
Allgemeine PolymerisationsvorschrittGeneral pre-polymerization step
In einem mit Stickstoff gespülten 1- 1- Stahlautoklav wurden 0,6 1 flüssiges Propylen bei Raumtemperatur vorgelegt. Über eineIn a 1- 1 steel autoclave flushed with nitrogen, 0.6 l of liquid propylene were placed at room temperature. Over a
Schleuse wurden 4 mmol Tri -isobutyl -aluminium (2 molare Lösung in Heptan) zugegeben. Nach 5 min. Rühren wurde ebenfalls über die Schleuse der geträgerte Katalysator zugegeben und der Autoklav auf 60°C aufgeheizt. Die Polymerisation wurde bei 60°C über einen Zeitraum von 90 Minuten durchführt. Das Polymerisat fiel in Form eines gut rieselfähigen Grießes an. Lock 4 mmol of tri-isobutyl aluminum (2 molar solution in heptane) were added. After 5 min. The supported catalyst was likewise added via the lock and the autoclave was heated to 60.degree. The polymerization was carried out at 60 ° C for 90 minutes. The polymer was obtained in the form of a free-flowing semolina.
Die Schmelzpunkte der entsprechenden Polymeren sind der Tabelle zu entnehmen.The melting points of the corresponding polymers can be found in the table.
Figure imgf000019_0001
Figure imgf000019_0001
D VergleichsbeispielD comparative example
2) Beispiel 3) Mit MAO-Aktivierung, ohne Träger 4) Schmelztemperaturen, gemessen mit DSC nach ISO 3146. 5) US 5,455,366 6) EP-A 576 970 2) Example 3) With MAO activation, without carrier 4) Melting temperatures, measured with DSC according to ISO 3146. 5) US 5,455,366 6) EP-A 576 970

Claims

Patentansprüche claims
Verfahren zur Herstellung von Polyolefinen durch Polymerisation von Olefinen bei Drücken im Bereich von 0,5 bis 3000 bar und Temperaturen im Bereich von -60 bis 300°C in Gegenwart eines Metallocen-Trägerkatalysators, dadurch gekennzeichnet, daß man einen Metallocen-Trägerkatalysator, enthaltend als aktive BestandteileProcess for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C in the presence of a supported metallocene catalyst, characterized in that a supported supported metallocene catalyst is used as active ingredients
A) einen MetallocenkomplexA) a metallocene complex
B) eine metalloceniumionenbildende Verbindung, ausgewählt aus der Gruppe bestehend aus Lewissäuren und ionischen Verbindungen mit nicht-koordinierenden Anionen verwendet.B) a metallocenium ion-forming compound selected from the group consisting of Lewis acids and ionic compounds with non-coordinating anions.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Metallocenkomplex A) solche der allgemeinen Formel (I)2. The method according to claim 1, characterized in that as the metallocene complex A) those of the general formula (I)
Figure imgf000020_0001
Figure imgf000020_0001
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 Wasserstoff - atom, eine Ci-Cio -Alkylgruppe, eine Cι-Cιo-Alkoxygruppe, eine C6-CQ-Arylgruppe, eine C6 -Cio-Aryloxygruppe, eine C -Cιo-Alkenylgruppe, eine OH-Gruppe, eine NRi2 -Gruppe, wobei R12 eine Ci- bis C2 -Alkylgruppe oder C6- bis Cι4-Arylgruppe ist, oder ein Halogenatom bedeuten, R3 bis R8 und R3' bis R8' gleich oder verschieden sind und ein Wasserstoff atom eine Cι-C4o-Kohlenwasserstof f gruppe, die linear, cyclisch oder verzweigt sein kann, z.B. eine Cι-Cιo-Alkylgruppe, C -Cι0- Alkenylgruppe, C6 -C20 -Arylgruppe, eine C -C4o-Aryl alkylgruppe, eine C -C4o-Alkylarylgruppe oder eine Ca-C4o-Aryl alkenylgruppe, bedeuten, oder benachbarte Reste R4 bis R8 und/oder R4' bis R8' mit den sie verbindenden Atomen ein Ringsystem bilden, R9 R 1 and R 2 are the same or different and are a hydrogen atom, a Ci-Cio-alkyl group, a Cι-Cιo-alkoxy group, a C 6 -CQ-aryl group, a C 6 -Cio-aryloxy group, a C -Cιo- Alkenyl group, an OH group, an NR i2 group, where R 12 is a Ci to C 2 alkyl group or C 6 to C 4 aryl group, or a halogen atom, R 3 to R 8 and R 3 'to R 8 'are the same or different and one Hydrogen atom is a C 1 -C 4 -hydrocarbon group which can be linear, cyclic or branched, for example a C 1 -C 8 -alkyl group, C -C 0 -alkenyl group, C 6 -C 20 aryl group, a C -C 4 o-aryl alkyl group, a C -C 4 o-alkylaryl group or a Ca-C 4 o-aryl alkenyl group, or adjacent radicals R 4 to R 8 and / or R 4 'to R 8 ' with the atoms connecting them Form ring system, R 9
RIO Rιo RlO RIO RIORIO R ιo RlO RIO RIO
■0- M2 0- ■0- M2 C M2- ■ 0- M 2 0- ■ 0- M 2 CM 2 -
R11 , RU , Rll Rll RllR 11 , RU, Rll Rll Rll
RIO R10 RIO RIO RIORIO R 10 RIO RIO RIO
M2- M2 M2-M 2 - M 2 M 2 -
RU RU RU Rll RURU RU RU Rll RU
Figure imgf000021_0001
Figure imgf000021_0001
^BR °, AIR10, Ge , 0 , S , SO, S02, ^ BR °, AIR 10 , Ge, 0, S, SO, S0 2 ,
NNR10, CO, PRi° oder R(0)R10, N NR 10 , CO, PR i ° or R (0) R 10 ,
bedeutet, wobeimeans where
Rio und RU gleich oder verschieden sind und ein Wasserstoff - atom, ein Halogenatom oder eine C1-C40 -kohlenstoffhaltigeR i o and R U are the same or different and are a hydrogen atom, a halogen atom or a C 1 -C 40 carbon-containing atom
Gruppe ist wie eine Cι-C o-Alkyl- , eine Cι-Cιo-Fluoralkyl- , eine Cι-Cιo-Alkoxy- , eine C6-Ci4 -Aryl- , eine C6-Cιo-Fluoraryl- eine C6-Cιo-Aryloxy- , eine C -Cιo-Alkenyl- , eine C -C4o-Aralkyl- , eine C -C4o-Alkylaryl- oder eine Ca-Cιo-Aryl- alkenylgruppe oder Ri0 und Ru jeweils mit den sie verbinden- den Atomen einen oder mehrere Ringe bilden und x eine ganze Zahl von Null bis 18 ist,Group is like a C 1 -C 8 alkyl, a C 1 -C 4 fluoroalkyl, a C 1 -C 8 alkoxy, a C 6 -Ci 4 aryl, a C 6 -Cιo fluoroaryl, a C 6 - Cιo-aryloxy, a C -Cιo alkenyl, a C -C 4 o aralkyl, a C -C 4 o alkylaryl or a Ca -Cιo aryl alkenyl group or R i0 and R u each with the they connect- form one or more rings in the atoms and x is an integer from zero to 18,
M2 Silizium, Germanium oder Zinn ist, und die Ringe A und B gleich oder verschieden, gesättigt, ungesättigt oder teilweise gesättigt sind,M 2 is silicon, germanium or tin and the rings A and B are the same or different, saturated, unsaturated or partially saturated,
verwendet.used.
3. Verfahren nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß man als Metallocenkomplex A) _ solche verwendet, in welchen die Liganden Indenyl- oder Tetrahydroindenylderivate sind und wobei R3, R5, R3' und R5' nicht Wasserstoff bedeuten.3. Process according to claims 1 to 2, characterized in that those used as the metallocene complex A) _ in which the ligands are indenyl or tetrahydroindenyl derivatives and where R 3 , R 5 , R 3 'and R 5 ' are not hydrogen .
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man als Metallocenkomplex A) solche verwendet, in welchen die Liganden Indenyl- oder Tetrahydroindenylderivate sind und wobei R3, R3' nicht Wasserstoff und R5, R5' eine Cδ-Cio-Arylgruppe, C -Cχo-Arylalkylgruppe, C7- bis C4o-Alkyl- arylgruppe oder Cg-C^o-Alkenylarylgruppe bedeuten.4. Process according to claims 1 to 3, characterized in that those used as the metallocene complex A) in which the ligands are indenyl or tetrahydroindenyl derivatives and wherein R 3 , R 3 'is not hydrogen and R 5 , R 5 ' is a C. δ -Cio-aryl group, C -Cχo-arylalkyl group, C 7 - to C 4 o-alkyl aryl group or Cg-C ^ o-alkenylaryl group mean.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß man Propylen im wesentlichen isotaktisch homopoly- merisiert oder mit Comonomeren, ausgewählt aus der Gruppe be- stehend aus Ethylen und C4- bis Cχo-Alk-1-enen, copoly- merisiert.5. Process according to claims 1 to 4, characterized in that propylene is substantially isotactically homopolymerized or with comonomers selected from the group consisting of ethylene and C 4 - to Cχo-alk-1-enes, copoly- merized.
6. Polyolefine, erhältlich nach den Verfahrensmerkmalen, gemäß den Ansprüchen 1 bis 5.6. polyolefins, obtainable according to the process features, according to claims 1 to 5.
Verwendung der, gemäß den Verfahrensmerkmalen des Verfahrens nach den Ansprüchen 1 bis 5, erhältlichen Polymerisate von C - bis Cιo-Alk-1-enen zur Herstellung von Fasern, Folien und Formkörpern. Use of the polymers of C - to Cιo-alk-1-enes obtainable according to the process features of the process according to claims 1 to 5 for the production of fibers, films and moldings.
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Cited By (70)

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US6414095B1 (en) 2000-06-30 2002-07-02 Exxon Mobil Chemical Patents Inc. Metallocene compositions
WO2003002583A2 (en) 2001-06-29 2003-01-09 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
WO2003025028A1 (en) 2001-09-14 2003-03-27 Basell Polyolefine Gmbh Method for the polymerization of olefins
WO2004052945A1 (en) * 2002-12-06 2004-06-24 Basell Polyolefine Gmbh Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and process for preparing polyolefins
US6870016B1 (en) 2000-06-30 2005-03-22 Exxonmobil Chemical Patents Inc. Polymerization process and polymer composition
US6924248B2 (en) 2000-06-13 2005-08-02 Basell Polyolefine Gmbh Catalyst system for carrying out olefin polymerization comprising a calcined hydro-talcite serving as a supporting material
US7101940B2 (en) 1999-12-23 2006-09-05 Basell Polyolefine Gmbh Chemical compound, method for the production thereof and its use in catalyst systems for producing polyolefins
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US7122498B2 (en) 2000-06-30 2006-10-17 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
US7157591B2 (en) 2001-12-10 2007-01-02 Exxonmobie Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
US7202373B2 (en) 2002-08-22 2007-04-10 Basell Polyolefine Gmbh Monocyclopentadienyl complexes
US7241903B2 (en) 2001-06-22 2007-07-10 Basell Polyolefine Gmbh Metallocenes, use in catalyst system for producing olefin polymers
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US7452949B2 (en) 2003-12-10 2008-11-18 Basell Polyolefine Gmbh Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins
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US7507782B2 (en) 2003-05-21 2009-03-24 Basell Polyolefine Gmbh Transition-metal complexes with tridentate, nitrogen-containing ligands
US7507688B2 (en) 2002-12-20 2009-03-24 Basell Polyolefine Gmbh Monocyclopentadienyl complexes
US7534847B2 (en) 2002-12-20 2009-05-19 Basell Polyolefine Gmbh Copolymers of ethylene with α-olefins
US7544749B2 (en) 2003-02-07 2009-06-09 Basell Polyolefine Gmbh Polymerization catalysts, organic transition metal compounds, process for preparing polyolefins and polyolefins
US7544826B2 (en) 2003-12-16 2009-06-09 Basell Polyolefine Gmbh Monocyclopentadienyl complexes
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US8735498B2 (en) 2009-11-17 2014-05-27 Basell Poliolefine Italia S.R.L. Soft polyolefin compositions with improved processability
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991009882A1 (en) * 1990-01-02 1991-07-11 Exxon Chemical Patents Inc. Supported ionic metallocene catalysts for olefin polymerization
EP0628574A1 (en) * 1993-06-07 1994-12-14 Tosoh Corporation Olefin polymerization catalyst and olefin polymerization process
WO1995015815A1 (en) * 1993-12-06 1995-06-15 Mobil Oil Corporation Catalyst for use in olefin polymerization or copolymerization
WO1996023005A1 (en) * 1995-01-25 1996-08-01 W.R. Grace & Co.-Conn. A supported catalytic activator
EP0727443A1 (en) * 1995-02-20 1996-08-21 Tosoh Corporation Catalyst for olefin polymerization and process for producing olefin polymers
WO1997031038A1 (en) * 1996-02-20 1997-08-28 Basf Aktiengesellschaft Supported catalyst system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991009882A1 (en) * 1990-01-02 1991-07-11 Exxon Chemical Patents Inc. Supported ionic metallocene catalysts for olefin polymerization
EP0628574A1 (en) * 1993-06-07 1994-12-14 Tosoh Corporation Olefin polymerization catalyst and olefin polymerization process
WO1995015815A1 (en) * 1993-12-06 1995-06-15 Mobil Oil Corporation Catalyst for use in olefin polymerization or copolymerization
WO1996023005A1 (en) * 1995-01-25 1996-08-01 W.R. Grace & Co.-Conn. A supported catalytic activator
EP0727443A1 (en) * 1995-02-20 1996-08-21 Tosoh Corporation Catalyst for olefin polymerization and process for producing olefin polymers
WO1997031038A1 (en) * 1996-02-20 1997-08-28 Basf Aktiengesellschaft Supported catalyst system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HLATKY G G ET AL: "SUPPORTED IONIC METALLOCENE POLYMERIZATION CATALYSTS", MACROMOLECULES, vol. 29, no. 24, 18 November 1996 (1996-11-18), pages 8019/8020, XP000631135 *
KAZUO SOGA ET AL: "POLYMERIZATION OF OLEFINS WITH THE CATALYST SYSTEM (RCP)TICL3 (R = H, CH3)/SIO2-COMMON ALKYLALUMINIUM ACTIVATED WITH A SUITABLE LEWIS ACID", MAKROMOLEKULARE CHEMIE, MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 193, no. 7, 1 July 1992 (1992-07-01), pages 1687 - 1694, XP000282074 *

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