WO1997042160A1 - Compose de cyclopentadiene dans lequel deux ou trois heteroatomes sont presents dans les substituants - Google Patents

Compose de cyclopentadiene dans lequel deux ou trois heteroatomes sont presents dans les substituants Download PDF

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WO1997042160A1
WO1997042160A1 PCT/NL1997/000213 NL9700213W WO9742160A1 WO 1997042160 A1 WO1997042160 A1 WO 1997042160A1 NL 9700213 W NL9700213 W NL 9700213W WO 9742160 A1 WO9742160 A1 WO 9742160A1
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group
compound
substituents
cyclopentadiene compound
substituted
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PCT/NL1997/000213
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Gerardus Johannes Maria Gruter
Gerardus Henricus Josephus Van Doremaele
Johannes Antonius Maria Van Beek
Matthijs Van Kessel
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Dsm N.V.
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Priority to AU24091/97A priority Critical patent/AU2409197A/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
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/38—Lanthanides other than lanthanum
    • 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
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • 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

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 the great majority of cases, either unsubstituted cyclopentadiene or cyclopentadiene substituted with one to five methyl groups is used. Besides transition metals, lanthanides are also used as metals in these complexes.
  • cyclopentadiene will be abbreviated as Cp.
  • Cp cyclopentadienyl group
  • a drawback of the known substituted Cp compounds is that when used as a ligand on a lanthanide, they form a complex which exhibits only moderate activity as a catalyst component.
  • the object of the invention is to provide substituted Cp compounds which, when used as a ligand in a lanthanide complex, give catalyst components having a better catalytic activity than the known substituted Cp compounds, in particular for the polymerization of olefins.
  • olefins here and hereinafter 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 Cp 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 containing the Cp compounds according to the invention appear to be suitable as stable and volatile precursors for use in metal chemical vapour deposition.
  • 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 two or three hetero atoms can be identical or different. Further, they can be present together in one and the same Cp substituent, but the two or three hetero atoms can also be present in separate Cp substituents.
  • the Cp substituent in which one or more hetero atoms are present preferably 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 or an aryl group, R' is a substituent and n is the number of R' groups bonded to D.
  • 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 therefore has at least the length of one atom.
  • the R' groups The R' groups can each separately be a hydrocarbon radical with 1-20 carbon atoms (such as alkyl, aryl, aralkyl).
  • 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.
  • R' should not be a cyclopentadienyl or a cyclopentadienyl-based group.
  • 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 germylene, tetraalkyl 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 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' 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 compound of the form RDR' n can be substituted on an unsubstituted Cp, but also on a Cp already substituted on one or more places with another group.
  • Suitable other groups are for instance alkyl groups, both linear and branched ones, alkylene and aralkyl groups. It is also possible for these to contain, apart from carbon and hydrogen, one or more hetero atoms from groups 14-17 of the Periodic System, for example O, N, Si or F, a hetero atom not being bound directly to the Cp.
  • a substituted Cp compound can be substituted with a group in the form of -RDR' n , for example in accordance with the following synthesis route. During a first step of this route a substituted Cp compound is deprotonated by reaction with a base, sodium or potassium.
  • Possible bases to be used are, for example, 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, for example n-butyllithium or i-propylmagnesium chloride.
  • Potassium hydride, sodium hydride, inorganic bases, for example NaOH and KOH, and alcoholates of Li, K and Na can likewise be used as a base.
  • Mixtures of the abovementioned compounds can also be used.
  • This reaction can be carried out in a polar dispersing agent, for example an ether.
  • suitable ethers are tetrahydrofuran (THF) or dibutyl ether.
  • Nonpolar solvents such as, for example, toluene, can likewise be employed.
  • Y is a halogen atom (X) or a sulphonyl group (Sul).
  • Halogen atoms X to be mentioned are chlorine, bromine and iodine.
  • the halogen atom X is a chlorine atom or a bromine atom.
  • the sulphonyl group takes the form -0S0 2 R 6 , in which R 6 is a hydrocarbon radical containing 1-20 carbon atoms, for example alkyl, aryl, aralkyl. Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene, naphthalene. Instead of, or in addition to, carbon and/or hydrogen, 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.
  • sulphonyl groups are: phenylmethanesulphonyl , benzenesulphonyl , 1-butanesulphonyl , 2,5- dichlorobenzenesulphonyl , 5-dimethylamino-l- naphthalenesulphonyl, pentafluorobenzenesulphonyl , p- toluenesulphonyl , trichloromethanesulphonyl , trifluoromethanesulphonyl , 2,4,6- triisopropylbenzenesulphonyl, 2,4,6-trimethylbenzene- sulphonyl, 2-mesitylenesulphonyl, methanesulphonyl , 4- methoxybenzenesulphonyl, 1-naphthalenesulphonyl , 2- naphthalenesulphonyl , ethanesulphonyl , 4- fluorobenzen
  • D is a nitrogen atom and Y. is a sulphonyl group
  • 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 defined hereinabove), potassium or sodium, followed by a reaction with a sulphonyl halide (Sul-X).
  • the second reaction step can likewise be carried out in a polar dispersing agent such 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 as a rule carried out at a temperature between -20 and 20°C.
  • Reactions with R' n D-R-Y in which Y is Cl, are as a rule 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, inter alia, by the boiling point of the compound R' n D-R-Y and that of the solvent used.
  • 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.
  • the amount of geminal products formed is low if the synthesis is carried out starting from a substituted Cp compound having 1 substituent and increases as the substituted Cp compound contains more substituents.
  • no or virtually no geminal products are 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 with a pK a of 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 may be mentioned as an example of suitable weak Lewis bases.
  • geminal products have been formed during the process according to the invention, these products can be separated in a simple manner from the non- geminal products by converting the mixture of geminally and non-geminally substituted products into a salt, by reaction with potassium, sodium or a base, the salt then being washed with a dispersing agent in which the salt of the non-geminal products is insoluble or sparingly soluble.
  • Bases which can be used include the compounds as mentioned above.
  • Suitable dispersing agents are nonpolar dispersing agents such as alkanes. Examples of suitable alkanes are heptane and hexane.
  • the two hetero atoms can be present within one and the same -RDR' n group, in which case at least one R' is an RDR' group. Further, it is possible for the two hetero atoms te be present each separately in a group of the form -RDR' n ; these elements and groups can then be chosen independently of each other within the limits indicated in the foregoing for R, D and R'.
  • Cp compounds substituted with other groups can, for instance, be prepared by reacting a halide of the substituting compound in a mixture of Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst.
  • a virtually equivalent quantity of the halogenated substituting compound with respect to the Cp compound is 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.
  • Substituents that can be applied with the present process are the other substituents mentioned in the foregoing.
  • the substituents are preferably applied in the process in the form of their halides.
  • 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 portion 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 reaction.
  • 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.
  • benzyltriethylammonium chloride TEBA
  • benzyltriethylammonium bromide TEBA-Br
  • Triton B benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium hydrogen sulphate or tetra-n-butylammonium hydroxide and cetyltrimethylammonium bromide or cetyltrimethylammonium chloride, benzyltributyl-, tetra-n-pentyl-, tetra-n-hexyl-
  • Usable phosphonium salts include, for example, tributylhexadecylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium 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-1,10-diazabicyclo[8.8.5Jtricosane (Kryptofix 221), 4,7,13,18-tetraoxa-l,10- diazabicyclo[8.5.5Jeicosane (Kryptofix 211) and 4,7,13,16,21,24-hexaoxa-l,10-diazabicyclo[8.8.8]-hexa- cosane ("[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 polystyrene or another polymer.
  • the phase transfer catalyst is used in an amount of 0.01 - 2 equivalents, preferably 0.05 - 1 equivalent, 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 then recovered from the organic phase by fractional distillation.
  • Cp compounds di-, tri- and tetrasubstituted with the desired other groups can be obtained, on which subsequently the hetero-atom-containing group or groups can be substituted, in particular the group or groups of the form -RDR' n as described in the foregoing.
  • Lanthanide complexes comprising at least one cyclopentadiene compound as defined in the foregoing, appear to possess improved stability and activity in comparison with similar complexes comprising other Cp compounds as ligands.
  • the invention therefore also relates to such lanthanide complexes and their use as a catalyst component in the polymerization of olefins.
  • one or more Cp compounds according to the invention can be present as ligands? two of such ligands can be connected by a bridge.
  • corresponding complexes of other metals comprising Cp compounds according to the invention as ligands also appear to be suitable as catalyst components.
  • 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.
  • 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.
  • 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 which are not in their highest valency state, in which just one of the cyclopentadienyl 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.
  • trialkylaluminium alkylaluminium halides, alkylaluminooxanes (such as methylaluminoxanes) , tris(pentafluorophenyl) borate, dimethylanilinium tetra(pentafluorophenyl) 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 a. Preparation of bis(dimethylaminoethyl)triisopropyl- cvclopentadiene
  • reaction mixture containing l-(dimethylaminoethyl)-2,3,5-tri(2- propyl)cyclopentadienyltitanium(III)dichloride was slowly brought to room temperature, which was followed by another 18 hours' stirring. After cooling to -60°C,
  • Example II a Preparation of (N,N' ,N' -trimethyl-3,6-diazaheptyl)- tetramethylcyclopentadiene From 2-lithium-2-butene and
  • EtOC(0)CH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 the compound specified in the opening lines was prepared by the method described in DE-A-4303647, with a yield of 25% based on the amount of ester used as a starting material.
  • Example III a Preparation of l-(N-methvI-N-(dioxolylmethyl)ethyl)- 2,3,4,5-tetramethylcvclopentadienyltitanium(III)- dichloride [C 5 Me 4 (CH 2 ) 2 N(Me) (CH 2 C 3 H s 0 2 ) ) (Ti(III)Cl 2 ]
  • a stainless steel reactor of 1 litre was charged, under dry N 2 , with 400 mL of pentamethylheptane (PMH) and 30 ⁇ mol of triethylaluminium (TEA) or trioctylaluminium (TOA) as a scavenger.
  • the reactor was pressurized to 0.9 MPa with purified monomers and conditioned in such a way that the ratio propene:ethene in the gas above the PMH was 1:1.
  • the reactor contents were brought to the desired temperature while being stirred.
  • the metal complex (5 ⁇ mol) to be used as the catalyst component and the cocatalyst (30 ⁇ mol of BF 20 ) were premixed over a period of 1 minute and fed to the reactor by means of a pump.
  • the mixture was premixed in about 25 mL of PMH in a catalyst proportioning vessel and after-rinsing took place with about 75 mL of PMH, always under dry N 2 flow.
  • the monomer concentrations were kept as constant as possible by supplying the reactor with propene (125 litres [s.t.p. ]/hour) and ethene (125 litres [s.t.p. ]/hour) .
  • the reaction was monitored on the basis of the temperature trend and the progress of the monomer infeed.
  • the reaction mixture containing methanol was washed with water and HCl, in order to remove residues of catalyst. Then the mixture was neutralized with NaHC0 3 , after which the organic fraction was admixed with an antioxidant (Irganox 1076, registered trademark) in order to stabilize the polymer. The polymer was dried in vacuo for 24 hours at 70°C.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Composé de cyclopentadiène substitué dans lequel deux ou trois hétéroatomes choisis dans le groupe 15 ou 16 de la classification périodique des éléments sont présents dans les substituants, au moins un substituant étant de préférence sous la forme -RDR'n, où R représente un groupe de liaison entre le composé de 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. 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/NL1997/000213 1996-05-03 1997-04-23 Compose de cyclopentadiene dans lequel deux ou trois heteroatomes sont presents dans les substituants WO1997042160A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24091/97A AU2409197A (en) 1996-05-03 1997-04-23 Cyclopentadiene compound wherein two or three hetero atoms are present in the substituents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1003011 1996-05-03
NL1003011A NL1003011C2 (nl) 1996-05-03 1996-05-03 Met een heteroatoom bevattende groep gesubstitueerde cyclopentadieen- verbinding.

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WO1997042160A1 true WO1997042160A1 (fr) 1997-11-13

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WO (1) WO1997042160A1 (fr)

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EP0805142B1 (fr) * 1996-05-03 1999-03-24 Dsm N.V. Composé cyclopentadiène substitué par un groupe contenant un hétéroatome
EP1086957A1 (fr) * 1999-03-04 2001-03-28 Riken Composition de catalyseur

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Cited By (5)

* 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
EP1086957A1 (fr) * 1999-03-04 2001-03-28 Riken Composition de catalyseur
EP1086957A4 (fr) * 1999-03-04 2005-08-31 Riken Composition de catalyseur
US7196031B2 (en) 1999-03-04 2007-03-27 Riken Catalyst composition
EP2258730A3 (fr) * 1999-03-04 2011-03-09 Riken Composition de catalyseur

Also Published As

Publication number Publication date
AU2409197A (en) 1997-11-26
NL1003011C2 (nl) 1997-11-06

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