WO1997042199A1 - Cyclopentadiene polysubstitue - Google Patents

Cyclopentadiene polysubstitue Download PDF

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Publication number
WO1997042199A1
WO1997042199A1 PCT/NL1997/000227 NL9700227W WO9742199A1 WO 1997042199 A1 WO1997042199 A1 WO 1997042199A1 NL 9700227 W NL9700227 W NL 9700227W WO 9742199 A1 WO9742199 A1 WO 9742199A1
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Prior art keywords
group
substituent
cyclopentadiene
compound
substituents
Prior art date
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PCT/NL1997/000227
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English (en)
Inventor
Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
Ramon Hubertus Anna Maria Meijers
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Dsm N.V.
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Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU24104/97A priority Critical patent/AU2410497A/en
Publication of WO1997042199A1 publication Critical patent/WO1997042199A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C07F7/22—Tin compounds
    • C07F7/2284—Compounds with one or more Sn-N linkages
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a substituted cyclopentadiene compound.
  • Cyclopentadiene compounds both substituted and unsubstituted, are used widely as a starting material for preparing ligands in metal complexes having catalytic activity. In by far the majority of the cases either unsubstituted cyclopentadiene or cyclopentadiene substituted with one to five methyl groups is used. As metals in these complexes use is made in particular of transition metals and lanthanides.
  • cyclopentadiene compounds with a substituent of the form -(ER 2 ) p D(R ' ) n H, where E is an atom chosen from group 14 of the Periodic System of the
  • D is a hetero atom chosen from group 15 or 16 of the Periodic System of the Elements
  • R and R' are substituents
  • cyclopentadiene will be abbreviated as Cp.
  • Cp cyclopentadienyl group
  • At least one other substituent is a branched alkyl group with at least 3 carbon atoms, 1 t- butyl group being excluded as sole other substituent.
  • the presence of at least one branched alkyl group instead of hydrogen or methyl groups in a metal complex appears to result in a better resistance against elevated temperatures than if other Cp compounds are used as ligands.
  • Highly suitable branched alkyl groups are secondary alkyl groups, tertiary alkyl groups and cyclic alkyl groups.
  • 1 to 4 branched alkyl groups are substituted on the Cp compound according to the invention.
  • the branched alkyl groups can be either identical or different.
  • Particularly suitable branched alkyl groups are, for example, 2-pentyl, 2-hexyl, 2- heptyl, 3-pentyl , 3-hexyl, 3-heptyl, 2-(3-methylbutyl ) , 2-(3-methylpentyl) , 2-(4-methylpentyl) , 3-(2- methylpentyl) , 2-(3 ,3-dimethylbutyl) , 2-(3- ethylpentyl) , 2-(3-methylhexyl) , 2-(4-methylhexyl) , 2- (5-methylhexyl) , 2-(3 , 3-dimethylpentyl ) , 2-(4, 4- dimethylpentyl) , 3-(4-methylhexyl) , 3-(5-methylhexyl) , 3-(2 , 4-dimethylpentyl) , 3-(2-methylhexyl ) , 3-(4,4
  • branched alkyl groups are present as substituents; these can be identical or different.
  • substituents can be present on the remaining positions of the Cp.
  • substituent groups can be chosen for instance from alkyl groups, linear as well as cyclic ones, aryl and aralkyl groups.
  • one or more hetero atoms from groups 14-17 of the Periodic System of the Elements can also be present, for example 0, N, Si or F.
  • Suitable further groups are methyl, ethyl, n-butyl , n-pentyl , n-hexyl and n-octyl, benzyl, phenyl and tolyl.
  • 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 of the Elements 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 .
  • Substituted Cp compounds can, for instance, be prepared by reacting a halide of the substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst.
  • Cp compounds are understood here Cp as such and Cp which is already substituted in at least one position, with the possibility of two substituents forming a closed ring. The process described in the following thus enables unsubstituted compounds to be converted to mono- or polysubstituted ones, but also already mono- or polysubstituted Cp-based compounds to be substituted further, which can be followed by ring closure.
  • the reaction can be carried out with a virtually equivalent quantity with respect to the Cp compound of the halogenated substituting compound.
  • An equivalent quantity is understood as a quantity in moles which corresponds to the desired substitution multiplicity, for example 2 mol per mole of Cp compound if disubstitution with the substituent in question is intended.
  • the substituents are preferably used in the method in the form of their halides and more preferably in the form of their bromides. If bromides are used a smaller quantity of phase transfer catalyst is found to be sufficient, and a higher yield of the compound aimed for is found to be achieved.
  • the substitution takes place in a mixture of the Cp compound and an aqueous solution of a base.
  • concentration of the base in the solution is in the range between 20 and 80 wt.%.
  • Hydroxides of an alkali metal, for example K or Na are highly suitable as a base.
  • the base is present in an amount of 5-30 mol per mole of Cp compound, preferably 7-15 mol per mol.
  • the substitution takes place at atmospheric or elevated pressure, for instance up to 100 MPa, which higher level is applied in particular if volatile components are present.
  • the temperature at which the reaction takes place may vary within wide limits, for instance from -20 to 120°C, preferably between 10 and 50°C. Starting up the reaction at room temperature is usually suitable after which the temperature of the reaction mixture can rise due to the heat released in the reactions or as a result of external heating.
  • phase transfer catalyst which is able to transfer OH-ions from the aqueous phase to the organic phase containing Cp compound and halide, the OH-ions reacting in the organic phase with a H-atom which can be split off from the Cp compound.
  • the phase transfer catalysts are used in an amount of 0.01 - 2 equivalents on the basis of the amount of Cp.
  • the various components can be supplied to the reactor in various sequences in the implementation of the process.
  • the aqueous phase and the organic phase containing the Cp compound are separated.
  • the Cp compound is recovered from the organic phase by fractionated distillation. Depending on the size and the associated steric hindrance of the compounds to be substituted it is possible to obtain trisubstituted to hexasubstituted Cp compounds.
  • E is chosen from group 14 of the Periodic System of the Elements and so can be C, Si, Ge and Sn. By preference, E is Si or Ge.
  • D is chosen from group 15 or 16 of the Periodic System of the Elements. If D is chosen from group 15, the coordination number of the element is 3, while if D is chosen from group 16, the coordination number of the element is 2.
  • D is N, 0, P or S.
  • D is a nitrogen atom.
  • R and R' are substituents and can each separately be 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.
  • R' can also be a substituent which, in addition to or instead of carbon and/or hydrogen, comprises one or more hetero atoms from groups 14-16 of the Periodic System of the Elements.
  • a substituent can be a group comprising N, 0 and/or Si.
  • n represents the number of substituents bonded to D and is 1 if D is chosen from the group 15 elements and is 0 if D is chosen from the group 16 elements.
  • a Cp compound comprising a substituent of the form -(ER 2 ) p D(R ' ) n H can be synthesized starting from a Cp compound substituted with at least one branched alkyl group having at least three carbon atoms. This substituted Cp compound is deprotonated to the anion by means of a base, sodium or potassium.
  • R 3 Li organolithium compounds
  • R 3 MgX organomagnesium compounds
  • R 3 is an alkyl, aryl, or aralkyl group
  • 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. Mixtures of the above- mentioned compounds can also be used.
  • Metal complexes comprising at least one cyclopentadiene compound as defined in the foregoing, appear to possess improved stability in comparison with complexes comprising Cp compounds as ligands as described in EP-A-0.420.236.
  • the invention therefore also relates to said metal complexes and their use as a catalyst component in the polymerization of olefins.
  • the synthesis of metal complexes with the above-described specific Cp compounds as a ligand can take place according to the methods known per se for this purpose. The use of these Cp compounds does not require any adaptations of said known methods.
  • 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 cyclopentadienyl compounds according to the invention as a ligand.
  • Suitable in particular for this purpose are complexes of transition metals in which just one of the cyclopentadienyl compounds according to the invention is present as a ligand.
  • 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.
  • alkylaluminooxanes such as methylaluminoxanes
  • 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.
  • Dimethoxymethane was distilled from potassium-sodium alloy, benzophenone being used as indicator.
  • the reactions were monitored by means of gas chromatography (GC type: Hewlett Packard 5890 Series II, equipped with autosampler type HP6890 Series Injector, integrator type HP3396A and HP Crosslinked Methyl Silicon Gum (25 m x 0.32 mm x 1.05 ⁇ m ) column with one of the following temperature programmes: 50°C (5 min.) rate: 7.5°C/min. 250°C (29 minutes) or 150°C (5 min.) rate: 7.5°C/min. 250°C (29 minutes).
  • Complexes were characterized using mass spectrometer Kratos MS80 or Finnigan Mat 4610.
  • Example I the preparation of van (N-t- butylamino) (dimethyl ) (2 ,3,5-tri-2- butylcvclopentadienyl)silane titanium dichloride
  • Example Ia Preparation of tri (2-butyl )cyclopentadiene
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 400 g (5.0 mol) of clear 50% NaOH .
  • 9.6 g (24 mmol) of Aliquat 336 and 15.2 g (0.23 mol) of freshly cracked cyclopentadiene were added.
  • the reaction mixture was vigorously stirred for several minutes.
  • 99.8 g (0.73 mol) of 2-butyl bromide were added in half an hour. During this process, the mixture was cooled with water.
  • Example IB the preparation of (N-t- butylamino) (dimethyl ) (2 , 3 , 5-tri-2- butylcyclopentadienyl )silane
  • Example IC the preparation of van (N-t- butylamino) (dimethyl ) (2 , 3 , 5-tri-2- butylcyclopentadienyl )silane titanium dichloride
  • This reaction mixture was cooled to -78°C (dry-ice bath; at this low temperature a small amount of white precipitate formed) and through a bend or connector it was added to a blue slurry of 3.71 g of titanium trichloride (complexed with 3 equivalents of THF: "TiCl 3 .3THF"; 10 mmol) which also had been cooled to -78°C.
  • the reaction mixture assumed a dark colour, which became even much darker (purple/brown/black) when the dry-ice bath had been removed and the reaction mixture had been allowed to warm up to room temperature. After some 14 hours' stirring, 1.45 g of silver chloride (AgCl) was added (10.1 mmol).
  • the reaction mixture was stirred for 15 hours at room temperature, during which time the colour of the mixture turned to red, while a silver precipitate clearly formed.
  • the reaction mixture was filtered through a cross-over filter and the residue was evaporated to dryness. Then 50 ml of hexane was added to the residue and the mixture obtained was filtered. The precipitate on the filter was washed with 20 ml of hexane and the hexane fractions collected were boiled down until a light turbidity formed (about 35 ml). This turbid mixture was warmed up very mildly (35°C) and stored in a refrigerator at -20°C. After 17 hours crystals had formed.
  • Example II the preparation of van (N-t- butylamino) (dimethyl ) (2 , 3 , 5-tri-2- pentylcyclopentadienyl)silane titanium dichloride
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 900 g (11.25 mol) of clear 50% NaOH. Then 31 g (77 mmol) of Aliquat 336 and 26.8 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 155 g (1.03 mol) of 2-pentyl bromide were added in one hour. During this process, the mixture was cooled with water. After stirring for 3 hours at room temperature, the reaction mixture was heated to 70°C, after which stirring was carried out again for 2 hours. Stirring was stopped and phase separation was awaited.
  • the characterization was carried out with the aid of GC, GC-MS, 13 C- and ⁇ -NMR.
  • Example IIB the preparation of van (N-t- butylamino) (dimethyl) ( 2 ,3,5-tri-2- pentylcyclopentadienyl)silane
  • Example IIC the preparation of (N-t- butylamino) (dimethyl ) (2,3,5-tri-2- pentylcyclopentadienyl )silane titanium dichloride
  • an antioxidant (Irganox 1076®) 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 following conditions were varied: metal complex - temperature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Composé de cyclopentadiène polysubstitué comportant au moins un substituant ayant la forme (ER2)pD(R')nH, où E représente un atome choisi dans le groupe 14 de la classification périodique des éléments, D représente un hétéroatome choisi dans le groupe 15 ou 16 de la classification périodique des éléments, R et R' représentent des substituants, n représente le nombre de groupes R' liés à D, et p vaut 1 à 4, caractérisé en ce qu'au moins un autre substituant est un groupe alkyle ramifié à au moins trois atomes de carbone, un groupe t-butyle ne pouvant être le seul autre substituant.
PCT/NL1997/000227 1996-05-03 1997-04-25 Cyclopentadiene polysubstitue WO1997042199A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24104/97A AU2410497A (en) 1996-05-03 1997-04-25 Polysubstituted cyclopentadiene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1003021 1996-05-03
NL1003021A NL1003021C2 (nl) 1996-05-03 1996-05-03 Meervoudig gesubstitueerd cyclopentadieen.

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WO1997042199A1 true WO1997042199A1 (fr) 1997-11-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0805142B1 (fr) * 1996-05-03 1999-03-24 Dsm N.V. Composé cyclopentadiène substitué par un groupe contenant un hétéroatome
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420436A1 (fr) * 1989-09-13 1991-04-03 Exxon Chemical Patents Inc. Catalyseurs pour la polymérisation d'oléfines
US5096867A (en) * 1990-06-04 1992-03-17 Exxon Chemical Patents Inc. Monocyclopentadienyl transition metal olefin polymerization catalysts
EP0520732A1 (fr) * 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420436A1 (fr) * 1989-09-13 1991-04-03 Exxon Chemical Patents Inc. Catalyseurs pour la polymérisation d'oléfines
US5096867A (en) * 1990-06-04 1992-03-17 Exxon Chemical Patents Inc. Monocyclopentadienyl transition metal olefin polymerization catalysts
EP0520732A1 (fr) * 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0805142B1 (fr) * 1996-05-03 1999-03-24 Dsm N.V. Composé cyclopentadiène substitué par un groupe contenant un hétéroatome
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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AU2410497A (en) 1997-11-26
NL1003021C2 (nl) 1997-11-06

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