WO1997042161A1 - Compose de cyclopentadiene substitue par des groupes lineaires - Google Patents

Compose de cyclopentadiene substitue par des groupes lineaires Download PDF

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WO1997042161A1
WO1997042161A1 PCT/NL1997/000232 NL9700232W WO9742161A1 WO 1997042161 A1 WO1997042161 A1 WO 1997042161A1 NL 9700232 W NL9700232 W NL 9700232W WO 9742161 A1 WO9742161 A1 WO 9742161A1
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group
cyclopentadiene
groups
compound
substituted
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PCT/NL1997/000232
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English (en)
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Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
Richard Green
Edwin Gerard Ijpeij
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Dsm N.V.
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Priority to EP97919752A priority Critical patent/EP0900194A1/fr
Priority to JP53978497A priority patent/JP2001510443A/ja
Priority to AU24109/97A priority patent/AU2410997A/en
Publication of WO1997042161A1 publication Critical patent/WO1997042161A1/fr
Priority to US09/184,066 priority patent/US6117811A/en

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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • 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
    • 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 polysubstituted cyclopentadiene compound.
  • Cyclopentadiene compounds are generally used as a ligand in metal complexes which are active as catalyst components, in particular for the polyme ization of olefins. Depending on the metal, its valency state amd the ligands used, these complexes appear to be of varying suitability for specific applications.
  • cyclopentadiene compounds are unsubstituted cyclopentadiene or cyclopentadiene substituted with one to five methyl groups.
  • the metal is for instance Ti(III), Hf(III), Zr(III) or V(IV)
  • these appear to give catalyst components of a low to very low activity, in particular for olefin polymerization.
  • Ti is exemplary of the metals that are suitable as metal in the commonly used cyclopentadienyl-substituted metal complexes.
  • cyclopentadiene will be abbreviated as Cp.
  • Cp cyclopentadienyl group
  • 'olefins' here and in the following refers to -olefins, diolefins and other 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 copolymer- ization of two or more olefins.
  • the aim of the invention now is to provide Cp compounds which, when used as a ligand in a metal complex in which the metal is not in the highest valency state, give catalyst components with a higher activity than those with the usual Cp-containing ligands.
  • At least one substituent is of the form -RDR' n , where R is a bonding 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, R' is a substituent and n is the number of R' groups bonded to D, and in that at least one further substituent is a linear alkyl group comprising at least 2 carbon atoms.
  • Cp compounds thus substituted when used as a ligand in the above-described metal complexes, they give catalyst components that have a higher activity in the polymerization of olefins, in particular in ethylene polymerization, than the known Cp compounds.
  • the compound preferably contains at least two linear alkyl groups with at least two carbon atoms as substituents, because this gives a further increase in activity compared with the Cp compound that is monosubstituted with a linear alkyl group.
  • the Cp compounds according to the invention can stabilize highly reactive intermediates such as organometal hydrides, organometal boron hydrides, organometal alkyls and organometal kations.
  • the metal complexes containing Cp compounds according to the invention appear to be suitable as stable and volatile precursors for use in metal chemical vapour deposition.
  • Cp compounds according to the invention can also be used as ligands to metals which are in their highest valency state and yield special advantages then in specific cases.
  • the linear alkyl groups comprising at least two carbon atoms may be identical or different from each other.
  • the substituted Cp compound preferably contains 2, 3 or 4 linear alkyl groups as substituents, because with the number of these substituents the activity of the catalyst made from it appears to increase.
  • the linear alkyl groups do not contain a hetero atom from group 16 of the Periodic System of the Elements.
  • Groups that are suitable as linear substituents are for instance methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, docosyl, dodecyl, di-, tri- and tetravinyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-chloroethyl, 3-chloropropyl, 5- chloropentyl and 4-butenyl. Cp compounds that are tetrasubstituted with ethyl- and/or propyl groups are preferred.
  • substituents can also be present, for instance branched and cyclic alkyl groups, alkenyl and aralkyl groups.
  • substituents can also be present, for instance branched and cyclic alkyl groups, alkenyl 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 groups are iso-propyl, sec-butyl, -pentyl, -hexyl and -octyl, tert-butyl and higher homologues, cyclohexyl, benzyl, phenyl, paratolyl and trimethylsilyl.
  • 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 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 to be further 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.
  • a virtually equivalent quantity with respect to the Cp compound of the halogenated substituting compounds can be used.
  • 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 number of substituents to be applied in this way is 1-4 for the Cp compounds according to the invention, apart from any other substituents to be substituted in remaining free positions, as defined in the foregoing.
  • 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, preferably 6-30, mol per mole of Cp compound. It has appeared that a substantial reduction of the reaction time can be achieved if the solution of the base is refreshed during the reaction, for instance by first mixing the solution of the base with the other components of the reaction mixture and after some time isolating the aqueous phase and replacing it by a fresh quantity of solution of the base.
  • 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.
  • the substitution takes place in the presence of a 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.
  • phase transfer catalysts to be used are quaternary ammonium, phosphonium, arsonium, stibonium, bismuthonium, and tertiary sulphonium salts. More preferably, ammonium and phosphonium salts are used, for example tricaprylmethylammonium chloride, commercially available under the name Aliquat 336 (Fluka AG, Switzerland; General Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA).
  • benzyltriethylarruTtonium chloride TEBA
  • benzyltriethylammonium bromide TEBA-Br
  • Triton B benzyltrimethylammonium chloride, benzyltrimethylammonium bromide or benzyltrimethyl- ammonium hydroxide
  • tetra-n-butylammonium chloride tetra-n-butylammonium bromide, tetra-n-butyl ⁇ ammonium iodide
  • cetyltrimethylammonium bromide or cetyltrimethylammonium chloride benzyltributyl-, tetra-n-pentyl-, tetra-n-hexyl- and trioctylpropylammonium chlorides
  • Usable phosphonium salts include, for example, tributylhexadecylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium iodide and tetrabutyl- phosphonium 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 ,7,13,16,21,24-hexaoxa-l,10- diazabicyclo[8.8.8]-hexacosane ("[2.2.2]”) and its benzo derivative Kryptofix 222 B.
  • 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 poly- styrene or another polymer.
  • the phase transfer catalyst is used in an amount of 0.01 - 2, preferably 0.05 - 1 equivalents on the basis of the amount of Cp-compound.
  • 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.
  • a group of the form -RDR' n can subsequently be substituted on the Cp compound thus substituted.
  • the R group constitutes the bond between the Cp and the DR' n group.
  • the length of the shortest bond between the Cp and D is critical in that, if the Cp compound is used as a ligand in a metal complex, 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.
  • R is at least one atom long.
  • the R' groups 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, O and/or Si.
  • 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 2 groups can each be H or a group as defined for R'.
  • the main chain of the R group can also comprise silicon or germanium besides carbon.
  • R groups are: dialkyl silylene, dialkyl ger ylene, tetra-alkyl disilylene or dialkyl silaethylene (-(CH 2 ) (SiR 2 2 ) ⁇ ) .
  • the alkyl groups (R 2 ) 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 heteroatom 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 preferably, the hetero atom is nitrogen (N) or phosphorus (P).
  • 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.
  • 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 cyclopentadienyl anion obtained 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 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 ⁇ 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-butanesulphonyl, 2,5-dichlorobenzenesulphonyl, 5-dimethylamino-l-naphthalenesulphonyl, pentafluoro- benzenesulphonyl, p-toluenesulphonyl, trichloromethane- sulphonyl, trifluoromethanesulphonyl, 2,4,6- triisopropylbenzenesulphon 1, 2,4,6- t imethylbenzenesulphonyl, 2-mesitylenesulphonyl, methanesulphonyl, 4-methoxybenzenesulphonyl, 1- naphthalenesulphonyl, 2-naphthalenesulphonyl, ethane- sulphonyl, 4-fluorobenzenesulphonyl and
  • the compound according to the formula (R' n D-R-Y) is formed in situ by reacting an aminoalcohol compound (R' 2 NR-0H) 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.
  • 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 R' n D-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 R' n D-R-Y and that of the solvent used.
  • geminal products may in part be formed.
  • a geminal substitution is a substitution in which the number of substituents increases by 1, but in which the number of substituted carbon atoms does not increase.
  • Geminally substituted Cp compounds are not suitable for use as a ligand and are not considered to be within the scope of the invention.
  • the amount of geminal products formed is low if the synthesis is carried out starting from a substituted Cp compound containing 1 substituent and increases as the substituted Cp compound contains more substituents. If sterically large substituents are present on the substituted Cp compound, geminal products are not, or are scarcely, formed. Examples of sterically large substituents are secondary or tertiary alkyl substituents.
  • the amount of geminal product formed is also low if the second step of the reaction is carried out under the influence of a Lewis base whose conjugated acid has a dissociation constant for which pK a is less than or equal to -2.5.
  • the pK a values are based on D. D. Perrin: Dissociation Constants of Organic Bases in Aqueous Solution, International Union of Pure and Applied Chemistry, Butterworths, London 1965. The values have been determined in aqueous H 2 S0 4 solution. Ethers can be mentioned as examples of suitable weak Lewis bases.
  • geminal products have formed during the process according to the invention, said products can easily be separated from the nongeminal products by converting the mixture of geminally and nongeminally substituted products into a salt by reaction with potassium, sodium or a base, after which the salt is washed with a dispersant in which the salt of the nongeminal products is insoluble or sparingly soluble.
  • the compounds mentioned above may be used as base.
  • Suitable dispersants are nonpolar dispersants, such as alkanes.
  • suitable alkanes are: heptane and hexane.
  • 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 polyme izations, 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.
  • the invention therefore also relates to metal complexes in which at least one of the ligands is a substituted Cp compound according to the invention and in which the metal is in a valency state lower than the highest, and to the use of such metal complexes as catalyst for the polymerization of olefins.
  • 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 Cp 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 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.
  • 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.
  • Metal complexes were characterized using a Kratos MS80 mass spectrometer or a Finnigan Mat 4610 mass spectrometer.
  • Example I a. Preparation of tetra(ethyl)cyclopentadiene
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 1050 g of clear 50% strength NaOH (13.1 mol), followed by cooling to 10°C.
  • 32 g of Aliquat 336 (79 mmol) and 51 g (0.77 mol) of freshly cracked cyclopentadiene were added.
  • the reaction mixture was stirred turbulently for a few minutes.
  • 344 g of ethyl bromide (3.19 mol) were added gradually in one hour's time, cooling with water taking place at the same time. After 1 hour's stirring at room temperature the reaction mixture was heated to 35°C, followed by a further 6 hours' stirring.
  • a double-walled reactor having a volume of 1.5 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 900 g of clear 50% strength NaOH (11.3 mol), followed by cooling to 10°C.
  • 30 g of Aliquat 336 (74 mmol) and 48 g (0.72 mol) of freshly cracked cyclopentadiene were added.
  • the reaction mixture was stirred turbulently for a few minutes.
  • 577 g of octyl bromide (2.99 mol) were added in one hour 's time, cooling with water taking place at the same time. After 1 hour's stirring at room temperature the reaction mixture was heated to 35°C, followed by a further 6 hours' stirring.
  • a double-walled reactor having a capacity of 1 1 and provided with a baffle, condenser, top stirrer, thermometer and dropping funnel was filled with 1000 g (12.5 mol) of clear 50% NaOH, after which the mixture was cooled to 10°C. Then 30 g (74 mmol) of Aliquat 336 and 50 g (0.75 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 373 g (3.03 mol) of propyl bromide were added in one hour. During this process, the mixture was cooled with water. After stirring for 1 hour at room temperature, the reaction mixture was heated to 35°C, after which stirring was carried out again for 6 hours.
  • the geminal isomers were isolated from the nongeminal isomers by converting the nongeminal isomers into their sparingly soluble potassium salt and then washing this salt with a solvent in which it does not or only sparingly dissolve.
  • c Synthesis of l-(dimethylaminoethyl ) -2 ,3,4,5-tetra-n- propylcyclopentadienyltitaniumdlDdichloride and fl- (dimethylaminoethyl)-2,3,4,5-tetra-n-propyl- cvclopentadienyl1dimethyltitanium(III) rC 5 (n-Pr) (CH 2 ) ? NMe 7 TifIII)Cl 7 l and rc 5 (n- Pr ) 4 1CH,) ? NMe 7 Ti(III)Me 7 1
  • a 1-litre stainless steel reactor was filled with 400 ml of pentamethyl heptane (PMH) and 30 ⁇ mol of triethyl aluminium (TEA) or trioctyl aluminium (TOA) as scavenger.
  • the reactor was pressurized to 0.9 MPa with purified monomers and so conditioned that the propene : ethene ratio in the gas above the PMH was 1 : 1.
  • the reactor contents were brought to the required temperature with stirring.
  • the metal complex (5 ⁇ mol) to be used as catalyst component and the cocatalyst (30 ⁇ mol BF 20 ) were pre-mixed for 1 minute and supplied to the reactor with the aid of a pump.
  • the mixture was pre-mixed in about 25 ml of PMH in a catalyst dispensing vessel and purged with about 75 ml of PMH, all under a dry nitrogen flow.
  • the monomer concentrations were kept constant as much as possible by supplying propene (125 N-litres/h) and ethene (125 N-litres/h) to the reactor. The reaction was followed by monitoring the course of the temperature and the monomer supply.

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Abstract

Composé de cyclopentadiène polysubstitué dans lequel au moins un substituant est sous la forme -RDR'n, où R représente un groupe de liaison entre le cyclopentadiène 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 dans lequel au moins un autre substituant est un groupe alkyle linéaire comportant au moins deux atomes de carbone. 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/NL1997/000232 1996-05-03 1997-04-28 Compose de cyclopentadiene substitue par des groupes lineaires WO1997042161A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP97919752A EP0900194A1 (fr) 1996-05-03 1997-04-28 Compose de cyclopentadiene substitue par des groupes lineaires
JP53978497A JP2001510443A (ja) 1996-05-03 1997-04-28 直鎖基で置換されたシクロペンタジエン化合物
AU24109/97A AU2410997A (en) 1996-05-03 1997-04-28 Cyclopentadiene compound substituted with linear groups
US09/184,066 US6117811A (en) 1996-05-03 1998-11-02 Cyclopentadiene compound substituted with linear groups

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1003005 1996-05-03
NL1003005A NL1003005C2 (nl) 1996-05-03 1996-05-03 Met lineaire groepen gesubstitueerde cyclopentadieenverbinding.

Related Child Applications (1)

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US09/184,066 Continuation US6117811A (en) 1996-05-03 1998-11-02 Cyclopentadiene compound substituted with linear groups

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WO1997042161A1 true WO1997042161A1 (fr) 1997-11-13

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JP (1) JP2001510443A (fr)
AU (1) AU2410997A (fr)
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WO (1) WO1997042161A1 (fr)

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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201522437D0 (en) * 2015-12-18 2016-02-03 Univ Leeds Tethered ligands

Citations (2)

* Cited by examiner, † Cited by third party
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
DE4303647A1 (de) * 1993-02-09 1994-08-11 Basf Ag Cyclopentadiene mit funktionalisierter Kohlenwasserstoff-Seitenkette

Patent Citations (2)

* Cited by examiner, † Cited by third party
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
DE4303647A1 (de) * 1993-02-09 1994-08-11 Basf Ag Cyclopentadiene mit funktionalisierter Kohlenwasserstoff-Seitenkette

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

Also Published As

Publication number Publication date
AU2410997A (en) 1997-11-26
NL1003005C2 (nl) 1997-11-06
JP2001510443A (ja) 2001-07-31
EP0900194A1 (fr) 1999-03-10

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