WO1997042165A1 - Fluorene substitue par un groupe comportant un heteroatome - Google Patents

Fluorene substitue par un groupe comportant un heteroatome Download PDF

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Publication number
WO1997042165A1
WO1997042165A1 PCT/NL1997/000214 NL9700214W WO9742165A1 WO 1997042165 A1 WO1997042165 A1 WO 1997042165A1 NL 9700214 W NL9700214 W NL 9700214W WO 9742165 A1 WO9742165 A1 WO 9742165A1
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group
fluorene
metal
substituted
compound
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PCT/NL1997/000214
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English (en)
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Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
Marc Herklots
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Dsm N.V.
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Priority to AU24092/97A priority Critical patent/AU2409297A/en
Publication of WO1997042165A1 publication Critical patent/WO1997042165A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/31—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the six-membered aromatic ring being part of a condensed ring system formed by at least three rings
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the invention relates to a substituted fluorene compound which comprises at least one substituent of the form -RDR' n , where R is a bonding group between the fluorene and the DR' n group, D is a hetero atom chosen from group 15 or 16 of the Periodic System of the Elements, R' is a substituent and n is the number of R' groups bonded to D.
  • R is a bonding group between the fluorene and the DR' n group
  • D is a hetero atom chosen from group 15 or 16 of the Periodic System of the Elements
  • R' is a substituent
  • n is the number of R' groups bonded to D.
  • fluorene will be abbreviated to 'Flu'. The same abbreviation will be used for a fiuorenyl group if it is clear, from the context, whether fluorene itself or its anion is meant.
  • Metal complexes comprising cyclopentadiene compounds as ligands are generally used as catalyst components for the polymerization of in particular ⁇ - olefins.
  • cyclopentadiene- based compounds such as fluorene can also be used as ligands.
  • fluorene compounds have only been used in so-called sandwich compounds. These are metal complexes in which two cyclopentadienyl derivatives are bound to the metal, at least one of which is a fluorene compound in this case. It is not known if and if so, in what other form and in what differently structured metal complexes suitable as a catalyst component, fluorene could be a suitable ligand.
  • Flu compounds according to the invention can stabilize highly reactive intermediates such as organometal hydrides, organometal boron hydrides, organometal alkyls and organometal cations.
  • the metal complexes appear to be suitable as stable and volatile precursors for use in metal chemical vapour deposition. 9-methyldimethylamine fluorene is known from
  • a substituted Flu compound is understood a fluorene substituted with at least one group of the form RDR' n .
  • other groups of the form R 2 as defined hereinafter may also be present on positions on the two 6-rings of the fluorene.
  • the RDR' n group is preferably present on the 9-position of the fluorene.
  • the Flu compound can also be a hetero fluorene compound.
  • a hetero fluorene group is understood to be a group that is derived from fluorene, but in which at least one of the carbon atoms thereof has been replaced by a hetero atom, the hetero atom being chosen from group 14, 15 or 16 of the Periodic System of the Elements. If more than one hetero atom is present, the hetero atoms can be identical or different. More preferably, the hetero atom has been chosen from group 15; still more preferably, the hetero atom is nitrogen.
  • the R 2 groups can each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl. Two adjacent hydrocarbon radicals may also be connected to each other in a ring system.
  • R 2 can also be a substituent which, in addition to or instead of carbon and/or hydrogen, comprises one or more hetero atoms from groups 14-17 of the Periodic System of the Elements. Thus a substituent can be a group comprising N, 0, F and/or Si.
  • R 2 should not be a cyclopentadienyl or a cyclopentadienyl-based group.
  • the R group constitutes the bridge between the Flu and the DR' n group.
  • the length of the shortest bridge between the Flu and D in the following referred to as "the main chain of R" is critical in that it determines the accessibility of the metal to the DR' n group, a factor which facilitates the desired intramolecular coordination. If the R group (or bridge) is too short, the DR' n group may not be able to coordinate properly owing to ring tension.
  • the R group is at least one atom long.
  • the R group can be a hydrocarbon group with 1-20 carbon atoms (such as alkylidene, arylidene, arylalkylidene, etc.). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, with or without a substituted side chain.
  • the R group preferably has the following structure:
  • R 3 groups are as defined for R 2 .
  • the main chain of the R group can also comprise silicon or germanium besides carbon.
  • R groups are: dialkyl silylene, dialkyl germylene, tetraalkyl disilylene or dialkyl silaethylene (-(CH 2 ) (SiR 3 2 ) ⁇ ) .
  • the alkyl groups (R 3 ) in such a group preferably have 1 to 4 carbon atoms and more preferably are a methyl or ethyl group.
  • the DR' n group comprises a hetero atom D chosen from group 15 or 16 of the Periodic System of the Elements and one or more substituents R' bound to D.
  • the hetero atom D is chosen from the group comprising nitrogen (N), oxygen (0), phosphorus (P) or sulphur (S); more prefer ⁇ ably, the hetero atom is nitrogen (N).
  • the R' groups can be identical or different and can be chosen from the same groups as defined for R 2 , with the exception of hydrogen.
  • the R' group is also preferably an alkyl, more preferably an n-alkyl group containing 1 - 20 C atoms.
  • the R' group is an n-alkyl containing 1 - 10 C atoms.
  • Another possibility is that two R' groups in the DR' n group are joined to each other to form a ring-type structure (so that the DR' n group may be a pyrrolidinyl group).
  • the DR' n group may bond coordinatively to a metal.
  • the optionally multiply substituted Flu compounds according to the invention When applied as a sole ligand in a metal complex in which the metal is not in its highest valency state, the optionally multiply substituted Flu compounds according to the invention appear to give compounds offering a good stability and a good catalytic effect.
  • the invention therefore also relates to this application.
  • the substituted Flu compounds also give good results when used singly or multiply as ligands on metals which actually are in their highest valency state. In that case as well, active catalysts are obtained, which in many cases give better results in a specific application than the known Flu-comprising ligands.
  • Metal complexes which are catalytically active if one of their ligands is a compound according to the invention are complexes of metals from groups 4- 10 of the Periodic System and rare earths.
  • complexes of metals from groups 4 and 5 are preferably used as a catalyst component for polymerizing olefins, complexes of metals from groups 6 and 7 in addition also for metathesis and ring-opening metathesis polymerizations, and complexes of metals from groups 8-10 for olefin copolymerizations with polar comonomers, hydrogenations and carbonylations.
  • Particularly suitable for the polymerization of olefins are such metal complexes in which the metal is chosen from the group consisting of Ti, Zr, Hf, V and Cr.
  • 'olefins' here and in the following refers to ⁇ -olefins, diolefins and other ethylenically unsaturated monomers. Where the term 'polymerization of olefins' is used, this refers both to the polymerization of a single type of olefinic monomer and to the copolymerization of two or more olefins.
  • the invention therefore also relates to metal complexes of said composition and their application as catalysts in particular for the polymerization of olefins, both linear and branched and cyclic ones and conjugated or non-conjugated dienes and mixtures thereof.
  • the group of the form RDR' n can be substituted on the 9-position of a Flu compound which may already have been substituted on one or more positions of the six-rings.
  • Processes for the substitution of Flu with groups other than RDR' n groups are known for instance from Bull. Chem. Soc. of Japan, 59, 97-103 (1986) and Liebigs Ann. Chem. 1976, 74-88.
  • the RDR' n group can be incorporated for instance by means of the following synthesis route, provided that the 9-position of the fluorene has not been substituted.
  • a substituted Flu compound is deprotonated by reaction with a base, sodium or potassium.
  • a base can be applied for instance organolithium compounds (R 3 Li) or organomagnesium compounds (R 3 MgX), where R 3 is an alkyl, aryl, or aralkyl group and X is a halide, such as for instance • n-butyl lithium or i-propylmagnesium chloride.
  • Potassium hydride, sodium hydride, inorganic bases, such as NaOH and KOH, and alcoholates of Li, K and Na can also be used as base.
  • a polar dispersing agent such as for instance an ether.
  • ethers are tetrahydrofuran (THF) and dibutyl ether.
  • Nonpolar solvents such as for instance toluene, can also be used.
  • the fiuorenyl anion obtained is reacted with a compound of the formula (R' n D-R-Y) or (X-R-Sul), where D, R, R' and n are as defined in the foregoing.
  • Y is a halogen atom (X) or a sulphonyl group (Sul).
  • the halogen atom X may be for instance chlorine, bromine and iodine.
  • the halogen atom X preferably is a chlorine or bromine atom.
  • the sulphonyl group has the form -OS0 2 R 6 , wherein R 6 is a hydrocarbon radical containing 1 - 20 carbon atoms, such as alkyl, aryl, aralkyl. Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene and naphthalene. R 6 may also contain one or more hetero atoms from groups 14 - 17 of the Periodic System of the Elements, such as N, 0, Si or F, in addition to or instead of carbon and/or hydrogen. Examples of sulphonyl groups are: phenylmethanesulphonyl, benzenesulphonyl, 1-butanesulphonyl, 2,5-dichlorobenzenesulphonyl,
  • the sulphonyl group is p- toluenesulphonyl or trifluoromethanesulphonyl.
  • the compound according to the formula (R' n D-R-Y) is formed in situ by reacting an aminoalcohol compound (R' 2 NR-OH) consecutively with a base (such as described above), potassium or sodium and a sulphonyl halide (Sul-X).
  • the second reaction step can also be carried out in a polar solvent as described for the first step.
  • the temperature at which the reaction is carried out is -60 to 80°C.
  • the synthesis of metal complexes with the above-described specific Flu compounds as a ligand can take place according to the processes known per se for this purpose.
  • the use of these Flu compounds does not require any adaptations of said known processes.
  • the substituted Flu compound is converted into an anion with the aid of for instance a lithium alkyl or a Grignard compound and subsequently the anion is reacted with a metal halide.
  • the Li-Flu compound or the corresponding Flu compound obtained with the aid of the Grignard compound can also be converted into a Si- or Sn-Flu compound, which is subsequently reacted with the metal halide.
  • the polymerization of ⁇ -olefins for example ethene, propene, butene, hexene, octene and mixtures thereof and combinations with dienes, can be carried out in the presence of the metal complexes with the fiuorenyl compounds according to the invention as ligand.
  • Suitable in particular for this purpose are complexes of transition metals which are not in their highest valency state, in which just one of the fiuorenyl compounds according to the invention is present as a ligand and in which the metal is cationic during the polymerization.
  • Said polymerizations can be carried out in the manner known for the purpose and the use of the metal complexes as catalyst component does not make any essential adaptation of these processes necessary.
  • the known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization.
  • the cocatalyst usually applied is an organometal compound, the metal being chosen from Groups 1, 2, 12 or 13 of the Periodic System of the Elements.
  • the polymerizations are carried out at temperatures between -50°C and +350°C, more particularly between 25 and 250°C.
  • the pressures used are generally between atmospheric pressure and 250 MPa, for bulk polymerizations more particularly between 50 and 250 MPa, and for the other polymerization processes between 0.5 and 25 MPa.
  • dispersants and solvents use may be made of, for example, hydrocarbons, such as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons, are also suitable.
  • the monomer applied in the polymerization can also be used as dispersant or solvent.
  • Example II a Preparation of (dimethylaminoethyl)fluorene 30 mL of a 1.6M solution of n-butyl lithium in hexane was added dropwise to a cooled (0°C) solution of fluorene (8 g; 48.1 mmol) in dry tetrahydrofuran (125 ml) in a 250 ml three-neck round-bottom flask provided with a magnetic stirrer and a dropping funnel. After stirring for 24 hours at room temperature, a solution in THF/hexane of 2-dimethylaminoethyl tosylate (48 mmol) prepared in situ was added.
  • the reaction mixture with methanol was washed with water and HCl in order to remove the catalyst residues. Then the mixture was neutralized with NaHC0 3 . Next, an antioxidant (Irganox 1076, TM) was added to the organic fraction for the purpose of stabilization of the polymer. The polymer was dried under vacuum at 70°C for 24 hours.
  • the catalyst obtained in example II was used at two different temperatures in polymerization experiments III and IV.
  • the catalyst obtained in example A was used at the same two temperatures in polymerization experiments B and C.
  • the actual conditions are stated in Table I.
  • MAO methyialuminoxane from Witco

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Composé de fluorène substitué comportant au moins un substituant sous la forme de -RDR'n, où R représente un groupe de liaison entre le fluorène et le groupe DR'n, D représente un hétéroatome choisi dans le groupe 15 ou 16 de la classification périodique des éléments, R' représente un substituant et n représente le nombre de groupes R' liés à D, et son utilisation comme ligand dans un complexe métallique. Les complexes métalliques dans lesquels est présent à titre de ligand au moins un de ces composés de cyclopentadiène sont utilisables comme catalyseurs dans la polymérisation des alpha-oléfines.
PCT/NL1997/000214 1996-05-03 1997-04-23 Fluorene substitue par un groupe comportant un heteroatome WO1997042165A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24092/97A AU2409297A (en) 1996-05-03 1997-04-23 Fluorene substituted with a group comprising a hetero atom

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NL1003017 1996-05-03
NL1003017A NL1003017C2 (nl) 1996-05-03 1996-05-03 Met een heteroatoom-bevattende groep gesubstitueerd fluoreen.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
EP0728769A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0728770A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Procédé de préparation de composants solides de catalyseur pour la polymérisation d'oléfines
EP0728724A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta

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DE4431643C2 (de) * 1994-07-22 2002-08-08 Borealis Polymere Holding Ag Verfahren zur Herstellung von Silizium-verbrückten unsymmetrischen Cyclopentadienyl-, Indenyl- und Fluorenyl-Ligandsystemen
ES2161919T3 (es) * 1994-11-22 2001-12-16 Atofina Res Metalocenos puenteados para uso en sistemas cataliticos para la polimerizacion de olefinas.

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Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
EP0728769A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0728770A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Procédé de préparation de composants solides de catalyseur pour la polymérisation d'oléfines
EP0728724A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta

Non-Patent Citations (1)

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Title
K.W. BENTLEY ET AL.: "Flavothebaone. Part V. Anomalous Beckmann Transformations.", JOURNAL OF ORGANIC CHEMISTRY, vol. 22, 1957, EASTON US, pages 424 - 429, XP002036556 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization

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