EP0931099A1 - Procede de preparation de polymerisats d'olefine a point de fusion tres eleve - Google Patents

Procede de preparation de polymerisats d'olefine a point de fusion tres eleve

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Withdrawn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)
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 DE19757563A external-priority patent/DE19757563A1/de
Priority claimed from DE1997157262 external-priority patent/DE19757262A1/de
Application filed by Targor GmbH, Basell Polyolefine GmbH filed Critical Targor GmbH
Publication of EP0931099A1 publication Critical patent/EP0931099A1/fr
Withdrawn legal-status Critical Current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.

Landscapes

  • 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)

Abstract

L'invention concerne un procédé de préparation de polyoléfines par polymérisation d'oléfines à des pressions comprises entre 0,5 et 3000 bar et à des températures de l'ordre de -60 à 300 °C, en présence d'un catalyseur métallocène sur support, le catalyseur sur support utilisé contenant comme constituants: A) un complexe métallocène, B) un composé générateur d'ions métallocène, sélectionné dans le groupe comprenant des acides de Lewis et des composés ioniques avec des anions non coordonnants.
EP98920472A 1997-03-07 1998-03-05 Procede de preparation de polymerisats d'olefine a point de fusion tres eleve Withdrawn EP0931099A1 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE19709402 1997-03-07
DE19709402 1997-03-07
DE19713546 1997-04-02
DE19713546A DE19713546A1 (de) 1997-04-02 1997-04-02 Verfahren zur Herstellung substituierter Indanone
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
DE1997157262 DE19757262A1 (de) 1997-12-23 1997-12-23 Verfahren zur Herstellung von Olefinpolymerisaten mit erhöhtem Schmelzpunkt
DE19757563 1997-12-23
PCT/EP1998/001231 WO1998040419A1 (fr) 1997-03-07 1998-03-05 Procede de preparation de polymerisats d'olefine a point de fusion tres eleve

Publications (1)

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

Family

ID=27438564

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98920472A Withdrawn EP0931099A1 (fr) 1997-03-07 1998-03-05 Procede de preparation de polymerisats d'olefine a point de fusion tres eleve

Country Status (5)

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

Families Citing this family (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19962910A1 (de) 1999-12-23 2001-07-05 Targor Gmbh Chemische Verbindung, Verfahren zu deren Herstellung und deren Verwendung in Katalysatorsystemen zur Herstellung von Polyolefinen
DE10028432A1 (de) 2000-06-13 2001-12-20 Basell Polyolefine Gmbh Auf calciniertes Hydrotalcit geträgerter Katalysatorfeststoff zur Olefinpolymerisation
US6414095B1 (en) 2000-06-30 2002-07-02 Exxon Mobil Chemical Patents Inc. Metallocene compositions
US6380124B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380331B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US7122498B2 (en) 2000-06-30 2006-10-17 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
EP1313746B1 (fr) * 2000-06-30 2005-07-27 ExxonMobil Chemical Patents Inc. Metallocenes comprenant un systeme de ligands 4-phenyl-indenyl pontes utiles dans la polymerisation d'olefines
US6376413B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376409B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380123B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6870016B1 (en) 2000-06-30 2005-03-22 Exxonmobil Chemical Patents Inc. Polymerization process and polymer composition
US6380121B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376410B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380330B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376412B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380122B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376407B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376627B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376408B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380120B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380334B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6399723B1 (en) 2000-06-30 2002-06-04 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376411B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
EP1397371B1 (fr) 2001-06-22 2006-03-22 Basell Polyolefine GmbH Metallocenes, leur utilisation dans des systemes catalytiques pour la production de polymeres olefiniques
EP1421090B1 (fr) 2001-06-29 2014-03-26 ExxonMobil Chemical Patents Inc. Metallocènes et compositions catalytiques dérivées de ceux-ci
DE10145453A1 (de) 2001-09-14 2003-06-05 Basell Polyolefine Gmbh Monocyclopentadienylkomplexe mit einem kondensierten Heterocyclus
BR0212317A (pt) 2001-09-14 2004-09-21 Basell Polyolefine Gmbh Processo para a polimerização de olefinas na presença de um sistema de catalisador, uso do mesmo, e, polìmero
DE10158656A1 (de) 2001-11-30 2003-06-26 Basell Polyolefine Gmbh Organoübergangsmetallverbindung, Biscyclopentadienylligandsystem, Katalysatorsystem und Verfahren zur Herstellung von Polyolefinen
US7157591B2 (en) 2001-12-10 2007-01-02 Exxonmobie Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
ATE364047T1 (de) 2002-08-22 2007-06-15 Basell Polyolefine Gmbh Monocyclopentadienylkomplexe
JP2006512410A (ja) 2002-12-06 2006-04-13 バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング 有機金属遷移金属化合物、ビスシクロペンタジエニル配位子を有する化合物、触媒組成物、及びこれらを用いたポリオレフィンの製造法
EP1572360B1 (fr) 2002-12-20 2008-06-25 Basell Polyolefine GmbH Complexes de monocyclopentadienyle
RU2349606C2 (ru) 2002-12-20 2009-03-20 Базелль Полиолефине Гмбх СОПОЛИМЕРЫ ЭТИЛЕНА С α-ОЛЕФИНАМИ
DE602004006965T2 (de) 2003-02-07 2008-02-21 Basell Polyolefine Gmbh Polymerisationskatalysatoren, organische übergangsmetallverbindungen, verfahren zur herstellung von polyolefinen
EP1608690B1 (fr) 2003-04-03 2007-06-13 Basell Polyolefine GmbH Preparation de polyolefines de haut poids moleculaire en presence d'un compose de metal de transition organique dans un reacteur a lit fluidise en phase gazeuse
JP2006528951A (ja) 2003-05-21 2006-12-28 バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング 三座の窒素含有リガンドを有する遷移金属錯体
JP2007506820A (ja) 2003-09-25 2007-03-22 バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング 重合触媒、ポリオレフィンの製造方法、有機遷移金属化合物及びリガンド
DE10352139A1 (de) 2003-11-04 2005-06-09 Basell Polyolefine Gmbh Organoübergangsmetallverbindung, Biscyclopentadienylligandsystem und Verfahren zur Herstellung von Polyolefinen
DE10358082A1 (de) 2003-12-10 2005-07-14 Basell Polyolefine Gmbh Organübergangsmetallverbindung, Bscyclopentadienyligandsystem, Katalysatorsystem und Hertellung von Polyolefinen
ES2321947T3 (es) 2003-12-16 2009-06-15 Basell Polyolefine Gmbh Complejos de monociclopentadienilo.
WO2005058983A2 (fr) 2003-12-19 2005-06-30 Basell Polyolefine Gmbh Complexes de monocyclopentadienyle
DE102004020524A1 (de) 2004-04-26 2005-11-10 Basell Polyolefine Gmbh Polyethylen und Katalysatorzusammensetzung zu dessen Herstellung
DE102004027332A1 (de) 2004-06-04 2005-12-22 Basell Polyolefine Gmbh Übergangsmetallverbindung, Ligandsystem, Katalysatorsystem und Verfahren zur Herstellung von Polyolefinen
DE102004032581A1 (de) 2004-07-05 2006-02-09 Basell Polyolefine Gmbh Polymerisationskatalysatoren, Hauptgruppenkoordinationsverbindungen, Verfahren zur Herstellung von Polyolefinen und Polyolefine
DE102004039877A1 (de) 2004-08-17 2006-02-23 Basell Polyolefine Gmbh Silylhalogenidsubstituierte Cyclopentadienylkomplexe der Gruppe 6
DE102005014395A1 (de) 2005-03-24 2006-09-28 Basell Polyolefine Gmbh Monocyclopentadienylkomplexe
DE102005019393A1 (de) 2005-04-25 2006-10-26 Basell Polyolefine Gmbh Polyethylenformmassen für Spritzgussanwendungen
DE102005035477A1 (de) 2005-07-26 2007-02-01 Basell Polyolefine Gmbh Verfahren zur Steuerung der relativen Aktivität der unterschiedlichen aktiven Zentren von Hybridkatalysatoren
DE102005057559A1 (de) 2005-11-30 2007-05-31 Basell Polyolefine Gmbh Übergangsmetallverbindung, Ligandsystem, Katalysatorsystem und Verfahren zur Herstellung von Polyolefinen
DE102007017903A1 (de) 2007-04-13 2008-10-16 Basell Polyolefine Gmbh Polyethylen und Katalysatorzusammensetzung und Verfahren zu dessen Herstellung
EP2220101B1 (fr) 2007-12-18 2018-09-19 Basell Polyolefine GmbH Composés de métaux de transition
BRPI0821085A2 (pt) 2007-12-19 2015-06-16 Basell Polyolefine Gmbh Terpolímeros de etileno
US7999043B2 (en) 2007-12-24 2011-08-16 Basell Polyolefine Gmbh Multistage process for the polymerization of olefins
MX2010009009A (es) 2008-02-18 2010-12-15 Basell Polyolefine Gmbh Composicion polimerica adhesiva.
JP2012503687A (ja) 2008-09-25 2012-02-09 バーゼル・ポリオレフィン・ゲーエムベーハー 耐衝撃性ｌｌｄｐｅ組成物及びそれから製造されるフィルム
RU2509782C2 (ru) 2008-09-25 2014-03-20 Базелль Полиолефине Гмбх Ударопрочная композиция лпэнп и полученные из нее пленки
EP2356155B1 (fr) 2008-12-01 2013-01-23 Basell Polyolefine GmbH Procédé de polymérisation d éthylène et polymères d éthylène présentant une distribution large du poids moléculaire et une ramification des chaînes longues
WO2010069527A1 (fr) 2008-12-17 2010-06-24 Basell Polyolefine Gmbh Système catalyseur pour la polymérisation d'oléfines, sa production et son utilisation
EP2480707B1 (fr) 2009-09-21 2014-03-05 Basell Poliolefine Italia S.r.l. Filament polymère
EP2501756B1 (fr) 2009-11-17 2017-01-25 Basell Poliolefine Italia S.r.l. Compositions de polyoléfine souple présentant une aptitude à la transformation améliorée
CN106947166A (zh) 2009-11-24 2017-07-14 巴塞尔聚烯烃意大利有限责任公司 具有改善密封能力的聚烯烃组合物
US8999875B2 (en) 2010-05-28 2015-04-07 Basell Polyolefine Gmbh Process for preparing a supported catalyst system for olefin polymerization, the catalyst system and its use
WO2012049132A1 (fr) 2010-10-15 2012-04-19 Basell Poliolefine Italia S.R.L. Filament polymère
US20130274427A1 (en) 2010-12-22 2013-10-17 BASELL POLOYOLEFINE GmbH Process for controlling the relative activity of active centers of catalyst systems comprising at least one late transition metal catalyst component and at least one ziegler catalyst component
EP2607391A1 (fr) 2011-12-21 2013-06-26 Basell Polyolefine GmbH Procédé de contrôle de la composition de polymère d'un copolymère d'éthylène obtenu par un système de catalyseur comportant un composant de catalyseur métallique d'un métal de transition et composant de catalyseur Ziegler
KR101890545B1 (ko) 2015-05-26 2018-08-21 바셀 폴리올레핀 이탈리아 에스.알.엘 클로져용 폴리올레핀 개스킷
WO2021233875A1 (fr) 2020-05-22 2021-11-25 Basell Poliolefine Italia S.R.L. Composition de polyoléfines souples et à charge élevée
EP4263637A1 (fr) 2020-12-15 2023-10-25 Basell Poliolefine Italia S.r.l. Composition de polyoléfine à transparence élevée
EP4444945A1 (fr) 2021-12-10 2024-10-16 Basell Poliolefine Italia S.r.l. Filament de polyoléfine
EP4444944A1 (fr) 2021-12-10 2024-10-16 Basell Poliolefine Italia S.r.l. Filament de polyoléfine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0704461A2 (fr) * 1994-09-30 1996-04-03 Mitsui Petrochemical Industries, Ltd. Catalyseur pour la polymérisation d'oléfine et procédé pour la polymérisation d'oléfine
WO1996041808A1 (fr) * 1995-06-08 1996-12-27 Showa Denko K.K. Composes ioniques et catalyseurs destines a polymeriser les olefines au moyen de ces composes

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69033368T3 (de) * 1990-01-02 2008-07-03 Exxon Chemical Patents, Inc. Ionische Metallocenkatalysatoren auf Träger für Olefinpolymerisation
JP2882241B2 (ja) * 1993-06-07 1999-04-12 東ソー株式会社 オレフィン重合用触媒およびオレフィンの重合方法
US5498582A (en) * 1993-12-06 1996-03-12 Mobil Oil Corporation Supported metallocene catalysts for the production of polyolefins
US5939347A (en) * 1995-01-25 1999-08-17 W.R. Grace & Co. -Conn. Supported catalytic activator
DE69611554T2 (de) * 1995-02-20 2001-07-05 Tosoh Corp., Shinnanyo Katalysator für die Polymerisation von Olefinen und Verfahren zur Herstellung von Olefinpolymerisaten
DE19606167A1 (de) * 1996-02-20 1997-08-21 Basf Ag Geträgerte Katalysatorsysteme

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0704461A2 (fr) * 1994-09-30 1996-04-03 Mitsui Petrochemical Industries, Ltd. Catalyseur pour la polymérisation d'oléfine et procédé pour la polymérisation d'oléfine
WO1996041808A1 (fr) * 1995-06-08 1996-12-27 Showa Denko K.K. Composes ioniques et catalyseurs destines a polymeriser les olefines au moyen de ces composes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9840419A1 *

Also Published As

Publication number Publication date
WO1998040419A1 (fr) 1998-09-17
NO991113D0 (no) 1999-03-08
NO991113L (no) 1999-05-07
AU7332398A (en) 1998-09-29
CA2262493A1 (fr) 1998-09-17

Similar Documents

Publication Publication Date Title
WO1998040419A1 (fr) Procede de preparation de polymerisats d'olefine a point de fusion tres eleve
EP0859800B1 (fr) Systeme de catalyseur supporte, son procede de production et son utilisation dans la polymerisation d'olefines
EP1054911B1 (fr) Systeme catalyseur, son procede de production et son utilisation pour la polymerisation d'olefines
EP0942938B1 (fr) Systeme de catalyseur sur support, procede permettant de le produire et son utilisation pour la polymerisation d'olefines
EP1396495B1 (fr) Métallocènes comprenant un unique halogénure lié au métal
WO2000044799A1 (fr) Compose organometallique, systeme catalyseur contenant ledit compose organometallique et son utilisation
EP1042371A1 (fr) Systeme de catalyseur supporte pour la polymerisation d'olefines
EP0687682B1 (fr) Composés de metaux de transition
EP1082353B1 (fr) Systeme de catalyseur et son utilisation pour la polymerisation de propylene
EP1000073B1 (fr) Procede de fabrication de metallocenes
EP1003757B1 (fr) Procede de fabrication de metallocenes
EP0811640A1 (fr) Système catalytique sur support, procédé pour sa préparation et son utilisation pour la polymérisation d'oléfines
EP1054914B1 (fr) Compose zwitterionique neutre d'un metal de transition
DE19922020A1 (de) Übergangsmetallverbindung, Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE102004035308A1 (de) Verfahren zur Herstellung von ultrahochmolekularen Polymeren unter Verwendung von unverbrückten Metallocen-Katalysatoren
EP0780402B1 (fr) Système de catalyseur à support, procédé pour sa préparation et son utilisation dans la polymérisation des oléfines
WO2000020466A1 (fr) Systeme catalyseur
DE19823172A1 (de) Katalysatorsystem und seine Verwendung zur Polymerisation von Propylen
WO2001014429A1 (fr) Systemes de catalyseurs passives et procede de fabrication de polyalcenes-1 presentant un repartition bimodale ou multimodale de la masse molaire
DE19757262A1 (de) Verfahren zur Herstellung von Olefinpolymerisaten mit erhöhtem Schmelzpunkt
DE19713549A1 (de) Geträgertes Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE19713550A1 (de) Geträgertes Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE19900585A1 (de) Verfahren zur Aufreinigung von Metallocenen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990521

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FI FR GB IT NL

17Q First examination report despatched

Effective date: 20000419

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASELL POLYOLEFINE GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASELL POLYOLEFINE GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASELL POLYOLEFINE GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASELL POLYOLEFINE GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20060607