WO1997042149A1 - Compose de cyclopentadiene substitue par des groupes tertiaires - Google Patents

Compose de cyclopentadiene substitue par des groupes tertiaires Download PDF

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WO1997042149A1
WO1997042149A1 PCT/NL1997/000207 NL9700207W WO9742149A1 WO 1997042149 A1 WO1997042149 A1 WO 1997042149A1 NL 9700207 W NL9700207 W NL 9700207W WO 9742149 A1 WO9742149 A1 WO 9742149A1
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group
compound
substituted
cyclopentadiene compound
groups
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PCT/NL1997/000207
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English (en)
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Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
Henricus Johannes Arts
Ramon Hubertus Anna Maria Meijers
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Dsm N.V.
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Priority to AU25786/97A priority Critical patent/AU2578697A/en
Publication of WO1997042149A1 publication Critical patent/WO1997042149A1/fr

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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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
    • C07C13/15—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene ring
    • 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
    • C07C211/25—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings other than six-membered aromatic rings
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • 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

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. In J. of Organomet. Chem., 479 (1994), 1-29 an overview is provided of the influence of the substituents on cyclopentadiene as a ligand in metal complexes.
  • cyclopentadiene will be abbreviated as Cp.
  • Cp cyclopentadienyl group
  • a drawback of the known substituted Cp compounds is that, while they do impart a certain stability to the metal complex when they are used as ligand in a metal complex, at higher temperatures the stability of these complexes decreases faster than is desirable.
  • the object of the invention is to provide substituted Cp compounds which, when applied as ligand in a metal complex, give the metal complex a better resistance to higher temperatures than do the known Cp compounds. This object is achieved, according to the invention, in that the Cp compound is at least bisubstituted and at least one of the substituents is a tertiary alkyl group.
  • a tertiary group as substituent is here understood to mean a group in which a tertiary carbon atom is present which is bound directly to the Cp.
  • tertiary alkyl groups may be present as substituents. These may be either the same or different.
  • suitable tertiary substituents are 1, 1-dimethylpropyl , 1 , 1-dimethylbutyl , 1,1- dimethylpentyl , 1 , 1-dimethylhexyl , 1-methyl-l- ethylpropyl, 1-methyl-l-ethylbutyl , 1-methyl-l- ethylpentyl, 1-methyl-l-ethylhexyl , 1 , 1-diethylpropyl , 1 , 1-diethylbutyl , 1 , 1-diethylpentyl , 1 , 1-diethylhexyl.
  • two or three tertiary alkyl groups are substituted on the Cp compound according to the invention.
  • Metal complexes with the thus substituted Cp compound as ligand prove to exhibit a higher activity in the polymerization of ⁇ -olefines than in case the Cp compound is monosubstituted with a tertiary alkyl group.
  • at least one other group is substituted at another position of the Cp.
  • These groups may be chosen from, for example alkyl groups, linear as well as branched and cyclic ones, alkenyl and aralkyl groups.
  • one or more hetero atoms from groups 14-17 of the Periodic System may be present, for example O, N, Si or F, in which a hetero atom is not bound directly to the Cp.
  • suitable other groups are methyl, ethyl, (iso)propyl, secondary butyl, secondary pentyl, secondary hexyl and secondary octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl.
  • 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.
  • olefins here and hereinafter refers to ⁇ -olefins, diolefins and other ethylenically unsaturated monomers. Where the term 'polymerization of olefins' is used, this hereinafter refers both to the polymerization of a single type of olefinic monomer and to the copolymerization of two or more olefins.
  • 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 refers to Cp itself and Cp already substituted at at least one position, with the option of two substituents forming a closed ring.
  • An equivalent quantity is understood to be a quantity in moles which corresponds to the desired substitution multiplicity, for example 2 moles per mole of Cp compound, if disubstitution with the substituent in question is intended.
  • the substituents are preferably used in the process 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 5-60 moles, preferably 6-30 moles, per mole of Cp compound. It was found that the reaction time can be considerably shortened if the solution of the base is refreshed, for example by first mixing, the solution with the other components of the reaction mixture and after some time separating the aqueous phase and replacing it by a fresh quantity of the solution of the base.
  • the substitution takes place at atmospheric or elevated pressure, for example up to 100 MPa, the latter especially when volatile components are present.
  • the temperature at which the reaction takes place can vary between wide limits, for example from -20 to 120°C, preferably between 10 and 50°C. Initiating the reaction at room temperature is suitable, as a rule, whereupon the temperature of the reaction mixture may rise as a result of the heat liberated in the course of the reaction occurring.
  • phase transfer catalyst which is able to transfer OH-ions from the aqueous phase to the organic phase the OH-ions reacting in the organic phase with a H-atom which can be split off from the Cp compound.
  • the organic phase contains the Cp compound and the substituting compound.
  • phase transfer catalysts use can be made of quaternary ammonium, phosphonium, arsonium, antimony, bismuthonium, and tertiary sulphonium salts.
  • ammonium and phosphonium salts are used, for example tricapryl- methylammonium chloride, commercially available under the name Aliquat 336 (Fluka AG, Switzerland; General Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA).
  • benzyl-triethylammonium chloride TEBA
  • benzyltriethyl-ammonium bromide TEBA-Br
  • tetra-n-butylammonium chloride tetra-n-butylammonium bromide, tetra-n-butyl- ammonium iodide
  • cetyltrimethylammonium bromide or cetyltrimethyl ⁇ ammonium chloride benzyltributyl-, tetra-n-pentyl-, tetra-n-hexyl- and trioctylpropylammonium chlorides
  • Usable phosphonium salts are, for example, tributylhexa- decylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyl ⁇ triphenylphosphonium iodide and tetrabutylphosphonium chloride.
  • Crown ethers and cryptands can also be used as a phase transfer catalyst, for example 15-crown-5, 18-crown-6, dibenzo-18-crown-6 , dicyclohexano-18-crown- 6 , 4 , 7 , 13 , 16,21-pentaoxa-l,10-diazabicyclo-[ 8.8.5]- tricosane (Kryptofix 221), 4 , 7, 13 , 18-tetraoxa-l, 10- diazabicyclo[8.5.5]eicosane (Kryptofix 211) and
  • Polyethers such as ethers of ethylene glycols can also be used as a phase transfer catalyst. Quaternary ammonium salts, phosphonium salts, phosphoric acid triamides, crown ethers, polyethers and cryptands can also be used on supports such as, for example, on a crosslinked polystyrene or another polymer.
  • the phase transfer catalysts are used in an amount of 0.01 - 2, preferably 0.05 - 1, equivalents on the basis of the amount of Cp compound. In the implementation of the process the components can be added to the reactor in various sequences.
  • the aqueous phase and the organic phase which contains the Cp compound are separated.
  • the Cp compound is recovered from the organic phase by fractional distillation.
  • the substituted Cp compounds according to the invention are particularly suitable for incorporation as a ligand in a metal complex, and then bring about the favourable effect [set out] in the preceding that the complex is better resistant to higher temperatures than are complexes containing the known Cp ligands.
  • the invention therefore also relates to a metal complex in which at least one cyclopentadiene compound substituted with at least one tertiary alkyl group is present as ligand.
  • a bi- or polysubstituted Cp compound in which at least one of the substituents is a tertiary alkyl group yields a complex which, when used as a catalyst component in the polymerization of ⁇ -olefins, yields a catalyst that has a higher activity than can be obtained with known Cp compounds if at least one other substituent on the Cp compound has the form -RDR' n , where R is a linking group between the Cp and the DR' n group, D is a hetero atom chosen from group 15 or 16 of the Periodic System of the Elements or an aryl group, R' is a substituent and n the number of R' groups bound to D.
  • the Cp compounds according to the invention are found to be capable of stabilizing highly reactive intermediates such as organometal hydrides, organometal boron hydrides, organometal alkyls and organometal cations.
  • they are found to be suitable as stable and volatile precursors for use in Metal Chemical Vapour Deposition.
  • the invention therefore also relates to Cp compounds thus further substituted.
  • the length of the shortest link between the Cp and D is critical to the extent that, if the Cp compound is used as ligand in a metal complex, it is decisive for the accessibility of the metal by the DR'êt group in order thus to achieve the desired intramolecular coordination.
  • An unduly short length of the R group (or bridge) may cause the DR' n group to be unable to coordinate well as a result of ring tension.
  • the length of R is at least one atom.
  • the R' groups may each separately be a hydrocarbon radical containing 1 - 20 carbon atoms (such as alkyl, aryl, arylalkyl and the like).
  • R' may also be a substituent which contains one or more hetero atoms from groups 14 - 16 of the Periodic System of the Elements in addition to or instead of carbon and/or hydrogen.
  • a substituent may be a group containing N, 0 and/or Si.
  • R' must not be a cyclopentadienyl group or a group derived therefrom.
  • the R group may be a hydrocarbon group containing 1 - 20 carbon atoms (such as alkylidene, arylidene, arylalkylidene and the like). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, optionally having a substituted side chain.
  • the R group has the following structure:
  • R 2 groups may each be H or a group as defined for R'.
  • the main chain of the R group may thus contain silicon or germanium besides carbon.
  • R groups are: dialkylsilylene, dialkyl- germylene, tetra-alkyldisilylene or dialkylsilaethylene (-(CH 2 ) (SiR 2 2 )-) .
  • the alkyl groups (R 2 ) in such a group preferably have 1 - 4 C atoms and are, more preferably, 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 substituent (s) R' bound to D.
  • the hetero atom D is chosen from the group comprising nitrogen (N) , oxygen (O) , phosphorus (P) or sulphur (S); more preferably, the hetero atom is nitrogen (N).
  • 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.
  • a substituted Cp compound is deprotonated by reaction with a base, sodium or potassium.
  • organolithium compounds R 3 Li
  • organomagnesium compounds R 3 MgX
  • R 3 is an alkyl, aryl or aralkyl group
  • X is a halide, for example n-butyllithium or isopropylmagnesium 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.
  • Said reaction can be carried out in a polar dispersant, for example an ether.
  • a polar dispersant for example an ether.
  • suitable ethers are tetrahydrofuran (THF) or dibutyl ether.
  • Apolar solvents, such as, for example, toluene can also be used.
  • the cyclopentadienyl anion formed reacts with a compound of the formula (R' n D-R-Y) or (X- R-Sul ) , where D, R, R' and n are as defined previously.
  • Y is a halogen atom (X) or a sulphonyl group (Sul).
  • the halogen atom X may be 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.
  • sulphonyl groups are: phenylmethanesulphonyl, benzenesulphonyl, 1-butane- sulphonyl, 2,5-dichlorobenzenesulphonyl, 5-dimethyl- amino-1-naphthalenesulphonyl, pentafluorobenzene- sulphonyl, p-toluenesulphonyl, trichloromethane- sulphonyl, trifluoromethanesulphonyl, 2,4,6-triiso- propylbenzenesulphonyl, 2,4,6-trimethylbenzene- sulphonyl, 2-mesitylenesulphonyl, methanesulphonyl, 4-methoxybenzenesulphonyl, 1-naphthalenesulphonyl, 2-naphthalenesulphonyl, ethanesulphonyl, 4-fluoro- benzene-ulphonyl
  • the compound according to the formula (R' n D-R-Y) is formed in situ by reaction of an aminoalcohol compound (R' 2 NR-OH) with a base (such as described above), potassium or sodium, followed by a reaction with 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 reactions are carried out is between -60 and 80°C.
  • Reactions with X-R-Sul and with R' n D-R-Y in which Y is Br or I are usually carried out at a temperature between -20 and 20°C.
  • Reactions with DR' n -R-Y in which Y is Cl are usually carried out at a higher temperature (10 to 80°C).
  • the upper limit for the temperature at which the reactions are carried out is determined in part by the boiling point of the compound DR' n -R-Y and that of the solvent used.
  • Metal complexes in which at least a cyclo ⁇ pentadiene compound as defined above is present are found to have an improved stability compared with such complexes in which other Cp compounds are present as ligand, in particular when the metal in the complex is not in its highest valency state.
  • such complexes require less cocatalyst, as described above, the invention therefore relates also to said metal complexes and their use as catalyst component for the polymerization of olefins.
  • Metal complexes that are catalytically active if one of their ligands is a compound according to the invention, are the same as specified in the aforegoing.
  • the polymerization of ⁇ -olefins for example ethylene, propylene, 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 ligand.
  • Suitable in particular for this purpose are the complexes of transition metals, which are not in their highest valency state, in which just one of the cyclopentadienyl compounds according to the invention is present as 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. Examples are trialkylaluminium, alkyl- aluminium halides, alkylalumino-oxanes (such as methylaluminoxanes) , tris(pentafluoro-phenyl) borate, dimethylanilinium tetra(penta-fluorophenyl) borate or mixtures thereof.
  • 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 I Preparation of di(1,l-dimethyl-propyl)cyclopentadiene
  • 20 g of Aliquat 336 (49 mmol) and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added.
  • the reaction mixture was stirred turbulently for a few minutes.
  • 226.6 g of 2-bromo-2-methylbutane (1.05 mol) was added in one operation, cooling with water taking place at the same time.
  • Comparable tosylates can be prepared in an analogous way.
  • a tosylate is always coupled to alkylated Cp compounds. During this coupling, no geminal coupling takes place.
  • Exampl e IV a Preparation of (dimethylaminoethyi )di (1, 1- dimethylpropyl )cvclopentadiene
  • the copolymerizations of ethylene with octene were carried out in the following way. 600 mL of an alkane mixture (pentamethyl- heptane or special boiling point solvent) was intro ⁇ quizzed into a 1.5 L stainless steel reactor under dry N2 as reaction medium. Subsequently, the desired amount of dry octene was introduced into the reactor. The reactor was then heated to the desired temperature under a desired ethylene pressure while stirring was applied.
  • an alkane mixture penentamethyl- heptane or special boiling point solvent
  • the reaction mixture with methanol was washed with water and HCI so as to remove catalyst residues. Subsequently, the mixture was neutralized with NaHC0 3 . Then an antioxidant (Irganox 1076, TM) was added to the organic fraction to stabilize the polymer. The polymer was dried under a vacuum at 70°C during 24 hours.

Abstract

Composé de cyclopentadiène substitué dans lequel le composé de cyclopentadiène est au moins disubstitué et dans lequel au moins un substituant est un groupe alkyle tertiaire.
PCT/NL1997/000207 1996-05-03 1997-04-22 Compose de cyclopentadiene substitue par des groupes tertiaires WO1997042149A1 (fr)

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NL1003014A NL1003014C2 (nl) 1996-05-03 1996-05-03 Met tertiaire groepen gesubstitueerde cyclopentadieenverbinding.
NL1003014 1996-05-03

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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

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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
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
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GB869058A (en) * 1957-08-12 1961-05-25 Ici Ltd Tertiary alkyl ferrocenes
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
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
JPH05112611A (ja) * 1991-10-21 1993-05-07 Chisso Corp ポリオレフインの製造方法
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

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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

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