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WO1999058539A1 - Composes organometalliques, ligands et polymerisation d'olefines - Google Patents

Composes organometalliques, ligands et polymerisation d'olefines Download PDF

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Publication number
WO1999058539A1
WO1999058539A1 PCT/EP1999/003247 EP9903247W WO9958539A1 WO 1999058539 A1 WO1999058539 A1 WO 1999058539A1 EP 9903247 W EP9903247 W EP 9903247W WO 9958539 A1 WO9958539 A1 WO 9958539A1
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Prior art keywords
formula
compound
substituents
metallocene
group
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PCT/EP1999/003247
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English (en)
Inventor
Michael J. Elder
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Basell Technology Co BV
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Montell Technology Co BV
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Priority to CA002294608A priority Critical patent/CA2294608A1/fr
Priority to KR1020007000162A priority patent/KR20010021604A/ko
Priority to EP99924944A priority patent/EP0994886A1/fr
Priority to JP55623599A priority patent/JP2002513428A/ja
Priority to AU41419/99A priority patent/AU4141999A/en
Publication of WO1999058539A1 publication Critical patent/WO1999058539A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/30—Germanium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F110/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—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 non-bridged

Definitions

  • the present invention relates to a new class of metallocene compounds, to a catalyst for the
  • the invention also relates to the corresponding ligands useful as
  • Metallocene compounds with two cyclopendadienyl groups are known as catalyst components
  • European Patent 0 129 368 describes a catalyst system for the polymerization of
  • olefins comprising (a) a bis-cyclopentadienyl coordination complex with a transition metal and
  • European Patent Application EP 0 185 918 describes the use of
  • US Patent 5 489 659 relates to a class of silicon-containing metallocene compounds for the
  • EP 0 590 486 describes metallocene compounds containing a
  • polyolefins The only illustrative examples are bis(l-phospha-2,3,4,5-
  • metallocenes are useful for the polymerization of olefins.
  • a novel class of metallocene compounds having a particular cyclopentadienyl ligand system having a particular cyclopentadienyl ligand system
  • the present invention provides a metallocene compound of formula
  • R- is a structural bridge
  • Cp is a heterocyclic cyclopentadienyl group of formula (II):
  • substituents R 1 and R 2 are hydrogen atoms, C,-C 20 alkyl, C 3 -C 20
  • substituents R 1 and R 2 can contain silicon or germanium atoms
  • Z is NR 3 or O, R 3 being defined as substituents R 1 and R 2 ;
  • X and Y are selected from (CR 4 2 ) r , BR 4 2 , PR 4 , SiR 4 2 or GeR 4 2 ; and
  • substituents R 4 are hydrogen atoms, C,-C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20
  • R 4 can contain hetero atoms such as nitrogen, phosphor, oxygen, silicon or germanium atoms,
  • A is a group selected from substituted or unsubstituted cyclopentadienyls, which may carry one
  • M is a transition metal selected from those belonging to group 3, 4, 5 or 6 or to the lanthanides
  • the substituent L is a monoanionic ligand, selected from the group
  • substituents R 6 same or different, are linear or branched, saturated or unsaturated C,-C 20
  • alkyl C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, or C 7 -C 20 arylalkyl
  • radicals optionally containing silicon or germanium atoms
  • p is an integer from 0 to 3, p being equal to the oxidation state of the metal M minus two;
  • n is an integer ranging from 0 to 4.
  • r is an integer ranging from 1 to 4.
  • R, n, Cp, A have the meanings as reported above and q is 0 when n is 0 and is 1 when
  • n 1 to 4, particularly useful as intermediates in the preparation of the metallocene compounds
  • a further aspect of the present invention is a process for the preparation of ligands R réelle(Cp)(A) q
  • a still further aspect of the present invention is a process for the preparation of the metallocene
  • Another aspect of the present invention is a catalyst for the polymerization of olefins
  • formula (II) may be linked to an identical cyclopentadienyl group, to a cyclopentadienyl
  • cyclopentadienyls which may carry one or more aromatic or non-aromatic condensed cycles
  • the divalent group (QR 7 m ) n is selected from the group consisting of
  • CR 7 2 , SiR 7 2 , GeR 7 2 , NR 7 , PR 7 and (CR 7 2 ) 2 and the R 7 groups, equal or different, are linear or branched, saturated or unsaturated C,-C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl,
  • substituents R 7 can form a cycle comprising from 3 to 8 atoms. More preferably, said divalent
  • n is 1 or 2, being 1 when Q is N or P, and being 2 when Q is C, Si or Ge; n ranges from 0 to 6
  • the atoms Q can be the same or different, such as, for example, in the bridges
  • the transition metal is preferably titanium, zirconium and hafnium, more preferably it is
  • the substituents R 1 and R 2 are preferably hydrogen atoms.
  • the substituents L are preferably halogen atoms or R 6 groups, R 6 being defined as reported
  • cyclopentadienyl moieties of the metallocene compound of the invention are identical.
  • Non limitative examples of said metallocenes are:
  • azadisilolejzirconium dichloride or dimethyl isopropylidenebis ⁇ 2-(tert-butyl)-l,l,3,3,5-pentamethyl-l,2,3,3a-tetrahydrocyclopenta[c][l,2,5] azadisilole ⁇ zirconium dichloride or dimethyl;
  • Non limiting examples of said class are:
  • R is a structural bridge
  • Cp is a heterocyclic cyclopentadienyl group of formula (IV):
  • R, R 1 , R 2 , X, Y and Z, n and q have the meaning as reported,
  • A is a group selected
  • the two double bonds of the cyclopentadienyl ring of the ligands of formula (IV) can be in any
  • cyclopentadienyls which may carry one or more aromatic or non-aromatic condensed cycles
  • Non-limiting examples of this class of ligands according to the invention are:
  • a further interesting class of ligands according to the present invention corresponds to formula
  • Non limiting examples of said ligands are:
  • n is an integer from 1 to 4 and q is 1, i.e. the two groups Cp and A' are linked by a
  • A' is a group selected from substituted or unsubstituted cyclopentadienyls
  • Non-limiting examples of bases used to form the above compounds of formula (VI) are
  • organometallic lithium compounds Preferably, methyllithium or n-butyllithium is used.
  • Non-limiting examples of compounds able to form the anionic compounds of formula (VII) are
  • organometallic lithium compounds Preferably, methyllithium or n-butyllithium is used.
  • the synthesis of the above bridged ligands is preferably carried out by adding a solution of an
  • bridged ligand can be finally separated by conventional general known procedures.
  • apolar solvents suitable for the above process are pentane, hexane and benzene.
  • the temperature is preferably kept between -180°C and 80°C, and
  • a still further aspect of the present invention is a process for the preparation of the metallocene
  • the compound able to form said dianion is selected from the group consisting of hydroxides
  • organometallic lithium salts and preferably said anion is n-butyllithium.
  • Non-limiting examples of compounds of formula ML' p+2 are titanium tetrachloride, zirconium
  • cyclopentadienyl derivate can be prepared by first reacting the bridged ligands of formula (III),
  • titanium tetrachloride zirconium tetrachloride and hafnium tetrachloride.
  • bridged ligands are dissolved in an aprotic polar solvent and to the
  • anionic form is separated, dissolved in an aprotic polar solvent and thereafter
  • the temperature is preferably kept between -180°C and 80°C, and
  • formula (II) can be prepared by reacting the anions of the formula (VII) with a tetrahalide of
  • the metallocenes can be reacted with alkylmagnesium halides (Grignard reagents) or with
  • the temperature is preferably kept between -180°C and 80°C, and
  • heterocyclic metallocene compounds of the present invention can conveniently be used as
  • the alumoxane used as component (B) can be obtained by reacting water with an organo-
  • reaction the molar ratio of Al/water is comprised between 1 : 1 and 100: 1.
  • the molar ratio between aluminium and the metal of the metallocene is comprised between
  • alumoxanes used in the catalyst according to the invention are considered to be linear,
  • R 9 substituents same or different, are hydrogen atoms, C,-C 20 -alkyl, C 3 -C 20 -
  • germanium atoms or are a -O-Al(R 9 ) 2 group and, if appropriate, some R 9 substituents can be
  • n is 0 or an integer from 1 to 40 and the
  • R 9 substituents are defined as above, or alumoxanes of the formula:
  • n is an integer from 2 to 40 and the R 9
  • alumoxanes suitable for use according to the present invention are
  • MAO methylalumoxane
  • TIBAO isobutylalumoxane
  • both the heterocyclic metallocene compound of the formula (I) and the alumoxane can be
  • halogen atoms C,-C 20 -alkyl, C 3 -C 20 -cyclalkyl, C 6 -C 20 -aryl, C 7 -C 20 -alkylaryl or C 7 -C 20 -arylalkyl,
  • Non-limiting examples of aluminium compounds of the formula A1R 8 3 or A1 2 R 8 6 are: Al(Me) 3 ,
  • TMA trimethylaluminium
  • TIBAL triisobutylaluminium
  • TIOA tris(2,4,4-trimethyl-pentyl)aluminium
  • Non limitative examples of compounds able to form a metallocene alkyl cation are compounds
  • TJD a Broensted acid, able to give a proton and to react irreversibly
  • the anion D " comprises one or more boron atoms. More
  • the anion D " is an anion of the formula BAr' " ⁇ , wherein substituents Ar, the same or
  • aryl radicals such as phenyl, pentafluorophenyl,
  • the catalysts used in the process of the present invention can be also used on inert supports.
  • silica such as for example silica, alumina, styrene-divinylbenzene copolymers, polyethylene or
  • Catalysts of the present invention are useful in the homo- and copolymerization reaction of
  • a still further object of the present invention is a process for the polymerization of
  • olefins comprising the polymerization reaction of at least an olefinic monomer in the presence
  • the catalysts of the present invention can be used in the homo-polymerisation reaction of
  • olefins preferably of ethylene for the preparation of HDPE, or of a-olefins, such as propylene
  • heterocyclic metallocenes of the invention show
  • R 10 is an alkyl radical having from 1 to 10 carbon atoms, and cycloolefins.
  • these olefins are propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-
  • decene 1-dodecene, 1-tetradecene, 1-esadecene, 1-octadecene, 1-eicosene, allylcyclohexene,
  • the copolymers may also contain small proportions of units deriving from polyenes, in
  • isoprene 1,3-butadiene, 1,5-hexadiene and 1 ,6-heptadiene.
  • polienes are present in the copolymers preferably in amounts ranging from 1% to 20% by
  • the saturated elastomeric copolymers can contain ethylene units and ⁇ -olefins and/or non
  • the unsaturated elastomeric copolymers can be any unsaturated elastomeric copolymer.
  • the content of unsaturated units is preferably comprised between 0 and 5% by
  • Non limitative examples of suitable ⁇ -olefins comprise propylene, 1-butene and 4-methyl-l-
  • Suitable non conjugated diolefms able to cyclopolymerise comprise 1,5-hexadiene,
  • Non limitative examples of suitable polyenes are:
  • bicyclic diolefms such as 4,5,8,9-tetrahydroindene and 6 and 7-methyl-4,5,8,9-
  • alkenyl or alkyliden norbornenes such as 5-ethyliden-2-norbornene, 5-isopropyliden-
  • polycyclic diolefms such as dicyclopentadiene, tricyclo-[6.2.1.0 27 ]4,9-undecadiene
  • non-conjugated diolefms able to cyclopolymerise such as 1.5-hexadiene, 1 ,6-
  • conjugated dienes such as butadiene and isoprene.
  • Another object of the present invention is a process for the polymerisation of propylene carried
  • Monocychc and polycyclic olefin monomers can be either
  • aromatic such as toluene
  • aliphatic such as propane, hexane, heptane, isobutane
  • the polymerisation temperature is preferably ranging from about 0°C to about 250°C.
  • the elastomeric copolymers it is preferably comprised between 0°C and 200°C
  • the polymerization pressure is ranging from 0,5 to 100 bar, preferably from 2 to 50 bar, and
  • the molecular weight of the polymers can be also varied merely by varying the polymerization
  • weight regulators such as, for example, hydrogen.
  • the molecular weight distribution can be varied by using mixtures of different metallocenes, or
  • the polymerization yields depend on the purity of the metallocene component of the catalyst.
  • metallocenes are generally used
  • the components of the catalyst can be brought into contact before the polymerization.
  • contact concentrations are generally between 1 and 10 "8 mol/1 for the metallocene component
  • the pre-contact time is generally comprised between 1 minute and 24
  • Solvents were distilled from blue Na-benzophenone ketyl (Et 2 O), CaH 2 (CH 2 C1 2 ) or Al Bu 3
  • the melting point Tm (°C) and ⁇ H (J/g) of the polymers were measured by Differential
  • the density (g/ml) was determined by immersion of a sample of extruded copolymer in a
  • r is the relative reactivity of the alpha-comonomer versus ethylene and r 2 that of
  • Butylhthium (4.0 mmol of a 2.5 M sol. in hexanes) was added slowly to a solution of 1,1,3,3-
  • the catalyst system was prepared separately in 10 mL of hexane by
  • polymer was washed with acidic methanol, methanol, and dried in an oven at 60 °C under
  • the catalyst system was prepared separately in 10 mL

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Abstract

On décrit une classe de composés organométalliques représentés par la formule (I), dans laquelle Rn représente un pont structurel; Cp représente un groupe cyclopentadiényle hétérocyclique de formule (II) dans laquelle R1 et R2 représentent des groupes hydrogène ou hydrocarbure, M représente un métal de transition du groupe 3,4,5 ou 6 ou faisant partie des lanthanides ou des actinides du tableau périodique des éléments (nouvelle version UICPA). L représente un ligand monoanionique; Z représente NR3 ou O; X et Y sont sélectionnés parmi (CR42)n, BR42, PR4, SiR42 ou GeR42; et les substituants R4 sont des atomes d'hydrogène ou des radicaux hydrocarbure, à condition que X et Y ne puissent être tous les deux ensembles des atomes de carbone au même moment; A représente un groupe sélectionné entre des cyclopentanediényles substitués ou non substitués, qui peuvent supporter un ou plusieurs cycles condensés, des groupes =NR5, -O-, -S- et =PR5, R5 étant défini comme les substituants R1 et R2, et des groupes correspondant à la formule (II); p représente un entier compris entre 0 et 3. Ces composés organométalliques sont utiles en tant qu'éléments catalyseurs employés pour polymériser des oléfines.
PCT/EP1999/003247 1998-05-08 1999-05-07 Composes organometalliques, ligands et polymerisation d'olefines Ceased WO1999058539A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002294608A CA2294608A1 (fr) 1998-05-08 1999-05-07 Composes organometalliques, ligands et polymerisation d'olefines
KR1020007000162A KR20010021604A (ko) 1998-05-08 1999-05-07 메탈로센, 리간드 및 올레핀 중합 방법
EP99924944A EP0994886A1 (fr) 1998-05-08 1999-05-07 Composes organometalliques, ligands et polymerisation d'olefines
JP55623599A JP2002513428A (ja) 1998-05-08 1999-05-07 メタロセン、リガンド及びオレフィン重合
AU41419/99A AU4141999A (en) 1998-05-08 1999-05-07 Metallocenes, ligands and olefin polymerization

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98201501.8 1998-05-08
EP98201501 1998-05-08

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WO1999058539A1 true WO1999058539A1 (fr) 1999-11-18

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JP (1) JP2002513428A (fr)
KR (1) KR20010021604A (fr)
CN (1) CN1268951A (fr)
AU (1) AU4141999A (fr)
CA (1) CA2294608A1 (fr)
WO (1) WO1999058539A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6608224B2 (en) 2000-02-24 2003-08-19 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
US6703458B2 (en) 2000-12-22 2004-03-09 Basell Polyolefine Gmbh Catalyst components for the polymerization of olefins
KR100422940B1 (ko) * 2000-12-23 2004-03-12 주식회사 엘지화학 하프 메탈로센 촉매 및 이를 이용한 입체규칙성을 가진비닐 방향족 중합체의 제조방법
KR100497172B1 (ko) * 2002-11-11 2005-06-28 주식회사 엘지화학 양쪽 메탈로센 유도체 화합물을 리간드로 가진 다중핵반쪽 메탈로센 촉매 및 이를 이용한 스티렌 중합체의제조방법
US7022793B2 (en) 2001-11-27 2006-04-04 Basell Polyolefine Gmbh Process for the treatment of polymer compositions
US7122606B2 (en) 2003-07-04 2006-10-17 Basell Polyolefine Gmbh Olefin polymerization process
US7183332B2 (en) 2000-12-22 2007-02-27 Basell Poliolefine Italia S.P.A. Process for the preparation of porous polymers and polymers obtainable thereof
US7417006B2 (en) 2001-05-21 2008-08-26 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
US7482411B2 (en) 2003-04-17 2009-01-27 Basell Poliolefine Italia S.R.L. Gas-phase olefin polymerization process
US7531609B2 (en) 2004-11-09 2009-05-12 Basell Poyloefine Gmbh Process for the preparation of 1-butene/propylene copolymers
US7572859B2 (en) 2002-06-26 2009-08-11 Basell Polyolefine Italia S.R.L. Impact-resistant polyolefin compositions
US7799722B2 (en) 2004-03-12 2010-09-21 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefin
US7943716B2 (en) 2004-03-12 2011-05-17 Basell Polyolefine Gmbh Process for polymerizing 1-hexene or higher alpha-olefins
US7977444B2 (en) 2004-03-12 2011-07-12 Basell Polyolefine Gmbh Process for polymerizaing 1-hexene or higher alpha-olefins
US8084557B2 (en) 2007-12-18 2011-12-27 Basell Polyolefine Gmbh Gas-phase process for the polymerization of alpha-olefins
US8101695B2 (en) 2004-11-22 2012-01-24 Basell Polyolefine Gmbh Propylene based terpolymers
WO2019072695A1 (fr) 2017-10-11 2019-04-18 Basell Polyolefine Gmbh Système de catalyseur supporté

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6841501B2 (en) 2000-02-24 2005-01-11 Basell Poliolefine Italia S.P.A. Catalyst system for the polymerization of olefins
US6608224B2 (en) 2000-02-24 2003-08-19 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
US6878786B2 (en) 2000-02-24 2005-04-12 Basell Polyolefine Gmbh Process for the polymerization of olefins
US7183332B2 (en) 2000-12-22 2007-02-27 Basell Poliolefine Italia S.P.A. Process for the preparation of porous polymers and polymers obtainable thereof
US6703458B2 (en) 2000-12-22 2004-03-09 Basell Polyolefine Gmbh Catalyst components for the polymerization of olefins
KR100422940B1 (ko) * 2000-12-23 2004-03-12 주식회사 엘지화학 하프 메탈로센 촉매 및 이를 이용한 입체규칙성을 가진비닐 방향족 중합체의 제조방법
US7417006B2 (en) 2001-05-21 2008-08-26 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
US7022793B2 (en) 2001-11-27 2006-04-04 Basell Polyolefine Gmbh Process for the treatment of polymer compositions
US7572859B2 (en) 2002-06-26 2009-08-11 Basell Polyolefine Italia S.R.L. Impact-resistant polyolefin compositions
KR100497172B1 (ko) * 2002-11-11 2005-06-28 주식회사 엘지화학 양쪽 메탈로센 유도체 화합물을 리간드로 가진 다중핵반쪽 메탈로센 촉매 및 이를 이용한 스티렌 중합체의제조방법
US7482411B2 (en) 2003-04-17 2009-01-27 Basell Poliolefine Italia S.R.L. Gas-phase olefin polymerization process
US7122606B2 (en) 2003-07-04 2006-10-17 Basell Polyolefine Gmbh Olefin polymerization process
US7799722B2 (en) 2004-03-12 2010-09-21 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefin
US7943716B2 (en) 2004-03-12 2011-05-17 Basell Polyolefine Gmbh Process for polymerizing 1-hexene or higher alpha-olefins
US7977444B2 (en) 2004-03-12 2011-07-12 Basell Polyolefine Gmbh Process for polymerizaing 1-hexene or higher alpha-olefins
US7531609B2 (en) 2004-11-09 2009-05-12 Basell Poyloefine Gmbh Process for the preparation of 1-butene/propylene copolymers
US8101695B2 (en) 2004-11-22 2012-01-24 Basell Polyolefine Gmbh Propylene based terpolymers
US8084557B2 (en) 2007-12-18 2011-12-27 Basell Polyolefine Gmbh Gas-phase process for the polymerization of alpha-olefins
WO2019072695A1 (fr) 2017-10-11 2019-04-18 Basell Polyolefine Gmbh Système de catalyseur supporté

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KR20010021604A (ko) 2001-03-15
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AU4141999A (en) 1999-11-29
EP0994886A1 (fr) 2000-04-26
CA2294608A1 (fr) 1999-11-18

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