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EP0931099A1 - Verfahren zur herstellung von olefinpolymerisaten mit erhöhtem schmelzpunkt - Google Patents

Verfahren zur herstellung von olefinpolymerisaten mit erhöhtem schmelzpunkt

Info

Publication number
EP0931099A1
EP0931099A1 EP98920472A EP98920472A EP0931099A1 EP 0931099 A1 EP0931099 A1 EP 0931099A1 EP 98920472 A EP98920472 A EP 98920472A EP 98920472 A EP98920472 A EP 98920472A EP 0931099 A1 EP0931099 A1 EP 0931099A1
Authority
EP
European Patent Office
Prior art keywords
group
methyl
indenyl
cιo
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98920472A
Other languages
German (de)
English (en)
French (fr)
Inventor
Carsten Bingel
Markus Goeres
Volker Fraaije
Andreas Winter
Wolfgang Bidell
Heike Gregorius
Roland Hingmann
David Fischer
Carsten SÜLING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Targor GmbH
Basell Polyolefine GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19713546A external-priority patent/DE19713546A1/de
Priority claimed from DE1997157262 external-priority patent/DE19757262A1/de
Priority claimed from DE19757563A external-priority patent/DE19757563A1/de
Application filed by Targor GmbH, Basell Polyolefine GmbH filed Critical Targor GmbH
Publication of EP0931099A1 publication Critical patent/EP0931099A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP98920472A 1997-03-07 1998-03-05 Verfahren zur herstellung von olefinpolymerisaten mit erhöhtem schmelzpunkt Withdrawn EP0931099A1 (de)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE19709402 1997-03-07
DE19709402 1997-03-07
DE19713546A DE19713546A1 (de) 1997-04-02 1997-04-02 Verfahren zur Herstellung substituierter Indanone
DE19713546 1997-04-02
DE1997157262 DE19757262A1 (de) 1997-12-23 1997-12-23 Verfahren zur Herstellung von Olefinpolymerisaten mit erhöhtem Schmelzpunkt
DE19757262 1997-12-23
DE19757563A DE19757563A1 (de) 1997-03-07 1997-12-23 Geträgertes Katalysatorsystem, Verfahren zur Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE19757563 1997-12-23
PCT/EP1998/001231 WO1998040419A1 (de) 1997-03-07 1998-03-05 Verfahren zur herstellung von olefinpolymerisaten mit erhöhtem schmelzpunkt

Publications (1)

Publication Number Publication Date
EP0931099A1 true EP0931099A1 (de) 1999-07-28

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EP98920472A Withdrawn EP0931099A1 (de) 1997-03-07 1998-03-05 Verfahren zur herstellung von olefinpolymerisaten mit erhöhtem schmelzpunkt

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Country Link
EP (1) EP0931099A1 (no)
AU (1) AU7332398A (no)
CA (1) CA2262493A1 (no)
NO (1) NO991113L (no)
WO (1) WO1998040419A1 (no)

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DE10028432A1 (de) 2000-06-13 2001-12-20 Basell Polyolefine Gmbh Auf calciniertes Hydrotalcit geträgerter Katalysatorfeststoff zur Olefinpolymerisation
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