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WO1997042162A1 - Compose de cyclopentadiene substitue avec des groupes alkyle ramifies - Google Patents

Compose de cyclopentadiene substitue avec des groupes alkyle ramifies Download PDF

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Publication number
WO1997042162A1
WO1997042162A1 PCT/NL1997/000233 NL9700233W WO9742162A1 WO 1997042162 A1 WO1997042162 A1 WO 1997042162A1 NL 9700233 W NL9700233 W NL 9700233W WO 9742162 A1 WO9742162 A1 WO 9742162A1
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Prior art keywords
cyclopentadiene
dimethylaminoethyl
mmol
iii
added
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PCT/NL1997/000233
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English (en)
Inventor
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 JP09539785A priority Critical patent/JP2000510117A/ja
Priority to AU24110/97A priority patent/AU2411097A/en
Priority to EP97919753A priority patent/EP0900195A1/fr
Publication of WO1997042162A1 publication Critical patent/WO1997042162A1/fr
Priority to US09/184,065 priority patent/US6124488A/en

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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
    • 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
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    • 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
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5018—Cycloaliphatic phosphines
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
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    • 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
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    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the invention relates to a polysubstituted cyclopentadiene compound.
  • Cyclopentadiene compounds are generally used as ligands in metal complexes which are active as catalyst components, in particular for the polymerization of olefins.
  • Polyolefin polymerizations are often copolymerizations of ⁇ -olefins, for example ethene or propene with one or more other olefins and/or other vinyl monomers, including vinyl-aromatic monomers.
  • the cyclopentadiene compounds most often used are unsubstituted cyclopentadiene or cyclopentadiene substituted with one to five methyl groups.
  • olefins here and hereinafter refers to ⁇ -olefins, diolefins and other unsaturated monomers. If 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.
  • the object of the invention 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, provide catalysts which can be used to produce copolymers having a more favourable combination of molecular weight and comonomer incorporation.
  • At least one substituent being of the form -RDR' n , in which R is a bonding group between the Cp and the DR' n group, D is a hetero atom selected 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 by at least one further substituent being a branched alkyl group.
  • Cp compounds substituted in this manner when used as a ligand in the above- described metal complexes, are found to provide catalyst components, producing copolymers having a higher incorporation of comonomers in the case of ethene copolymerization, with the same molecular weight, than the known compounds, when used as catalyst component for the polymerisation of olefins.
  • the compound contains at least two branched alkyl groups as a substituent, because this affords a further improvement in the ratio between molecular weight and comonomer incorporation.
  • Corresponding complexes in which the Cp compound is not substituted in the manner described prove unstable or, if they have been stabilized in some other way, are found to provide less active catalysts than the complexes containing substituted Cp compounds according to the invention, in particular in the case of the polymerization of ⁇ -olefins.
  • the Cp compounds according to the invention are found to be able to stabilize highly reactive intermediates such as organometal hydrides, organometal borohydrides, organometal alkyls and organometal cations. Furthermore the metal complexes containing Cp compounds according to the invention prove suitable as stable and volatile precursors for the use in metal chemical vapour deposition.
  • the branched alkyl groups can be either identical or different.
  • the substituted Cp compound contains 1-4 branched alkyl groups as a substituent.
  • the activity of a metal complex in which the Cp compounds thus substituted are present as a ligand is found to increase when used as a catalyst component for the polymerization of ⁇ -olefins.
  • the branched alkyl groups do not contain any hetero atoms from group 16 of the Periodic System of the Elements.
  • Particularly suitable branched alkyl groups are, for example, 2-propyl, 2- butyl, 2-pentyl, 2-hexyl, 2-heptyl, 2-octyl, 2-nonyl, 2-decyl, 3-pentyl, 3-hexyl, 3-heptyl, 3-octyl, 3-nonyl, 3-decyl, 3-undecyl, 3-dodecyl, 2-(3-methylbutyl) , 2-(3- methylpentyl) , 2-(4-methylpentyl) , 3-(2-methylpentyl) , 2-(3,3-dimethylbutyl) , 2-(3-ethylpentyl) , 2-(3- methylhexyl) , 2-(4-methylhexyl) , 2-(5-methylhexyl) , 2- (3,3-dimethylpentyl) , 2-(4,4-dimethylpentyl
  • Cp compounds disubstituted or trisubstituted with branched alkyl groups are preferred.
  • further substituents may also be present, for example linear alkyl groups, alkenyl 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 of the Elements, for example 0, N, Si or F.
  • Cp compounds 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.
  • Cp compounds refers to Cp itself and
  • the substituents are preferably used in the method in the form of their halides and more preferably in the form of their bromides. If bromides are used a smaller quantity of phase transfer catalyst is found to be sufficient, and a higher yield of the compound aimed for is found to be achieved.
  • this method it is also possible, without intermediate isolation or purification, to obtain Cp compounds which are substituted with specific combinations of substituents.
  • disubstitution with the aid of a certain halide of a substituting compound can first be carried out and in the same reaction mixture a third substitution can be carried out with a different substituent, by adding a second, different halide of a substituting compound to the mixture after a certain time. This can be repeated, so that it is also possible to prepare Cp derivatives having three or more different substituents.
  • 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 mol, preferably 6-30 mol, per mole of Cp compound. It was found that the reaction time can be considerably shortened if the solution of the base is refreshed during the reaction is, 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, particularly 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 reactions which occur.
  • 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 an H-atom which can be split off from the Cp compound.
  • Possible phase transfer catalysts to be used are quaternary ammonium, phosphonium, arsonium, stibonium, bismuthonium, and tertiary sulphonium salts.
  • 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).
  • benzyltriethylammonium chloride TEBA
  • benzyltriethylammonium bromide TEBA-Br
  • tetra-n- butylammonium chloride tetra-n-butylammonium bromide
  • tetra-n-butylammonium iodide tetra-n-butylammonium hydrogen sulphate or tetra-n-butylammonium hydroxide
  • cetyltrimethylammonium bromide or cetyltrimethylammonium chloride benzyltributyl-, tetra-n-pentyl-, tetra-n-hexyl- and trioctylpropylammonium chlorides and their bromides
  • 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, dibenzol8-crown-6 , dicyclohexano-18-crown-6 ,
  • 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.
  • 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 obtained from the organic phase by fractional distillation.
  • the Cp compound thus substituted then undergoes substitution with a group of the form -RDR' n .
  • the R group forms the link between the Cp and the DR' n group.
  • the length of the shortest link between the Cp and D is critical insofar as it is determining, when the Cp compound is used as a ligand in a metal complex, for the accessibility of the metal by the DR' n group in order thus to achieve the desired intramolecular coordination. Too small a length of the R group (or bridge) may mean that owing to ring tension the DR' n group cannot coordinate effectively. R therefore has a length of at least one atom.
  • the R' groups may each, separately, be a hydrocarbon radical containing 1-20 carbon atoms (such as alkyl, aryl, aralkyl and the like). 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 contains one or more hetero atoms from group 14-16 of the Periodic System of the Elements.
  • a substituent can be an N-, 0- and/or Si-containing group.
  • the R group can 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, with or without a substituted side chain.
  • the R group 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 may consequently, in addition to carbon, also contain silicon or germanium.
  • R groups are: dialkylsilylene, dialkylgermylene, tetraalkyldisilylene or dialkylsilaethylene (-(CH 2 ) (SiR 2 2 )-) .
  • the alkyl groups (R 2 ) in such a group preferably contain 1-4 C atoms and are, more preferably, a methyl or ethyl group.
  • the DR' n group consists of a hetero atom D, selected 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 selected from the group consisting of nitrogen (N) , oxygen (O), phosphorus (P) or sulphur (S); more preferably, the hetero atom is nitrogen (N) or phosphorus (P).
  • the R' group is an alkyl, more preferably an n-alkyl group containing 1-20 C atoms. More preferably, the R' group is an n-alkyl containing 1-10 C atoms.
  • Another possibility is for two R' groups in the DR' n group to be joined together to give a ring- shaped structure (so that the DR' n group may be a pyrrolidinyl group).
  • the DR' n group can bind coordinatively to a metal.
  • the Cp compound substituted as described above can then 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.
  • suitable ethers such as, for example, toluene, can likewise be employed.
  • the cyclopentadienyl anion formed reacts with a compound according to the formula (R' n D-R-Y) or (X-R-Sul), in which D, R, R' and n are as defined hereinabove.
  • 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 bromine atom.
  • the sulphonyl group takes the form -OS0 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.
  • 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-fluorobenzene ⁇ sulphonyl and 1-hex
  • 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' providingD-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.
  • Geminally substituted Cp compounds are not suitable for use as a ligand and are not considered to be within the scope of the invention.
  • 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 geminal and non-geminal 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 spar ⁇ ingly 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.
  • 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 lanthanides.
  • 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 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, preferably, the metal is in a valency state below the highest valency state, and to the use of such metal complexes as a catalyst component for copolymerizing ⁇ -olefins with other ⁇ -olefins and in general vinyl monomers and in particular vinylaromatic monomers.
  • Vinyl-aromatic monomers which are incorporated effectively by means of these catalysts include styrene, chlorostyrene, n-butylstyrene, p- vinyltoluene and in particular styrene.
  • the synthesis of metal complexes containing the above-described specific Cp compounds as a ligand may take place according to the methods known per se for this purpose. The use of these Cp compounds does not require any adaptations of said known methods.
  • the polymerization of ⁇ -olefins for example ethene, propene, butene, hexene, octene and mixtures thereof and combinations with dienes can be carried out in the presence of the metal complexes containing the cyclopentadienyl compounds according to the invention as a ligand.
  • the metal complexes containing the cyclopentadienyl compounds according to the invention as a ligand.
  • the complexes of transition metals 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.
  • polymerizations can be carried out in the manner known for this purpose, and the use of the metal complexes as a catalyst component does not require any significant adaptation of these methods.
  • the known polymerizations are carried out in suspension, solution, emulsion, gas phase or as a bulk polymerization. It is customary to use, as a cocatalyst, an organometallic compound, the metal being selected from group 1, 2, 12 or 13 of the Periodic System of the Elements. Examples to be mentioned include alkylaluminoxanes (such as methylaluminoxanes) , tris(pentafluorophenyl) borane, dimethylanilinium tetra(pentafluorophenyl) borate or mixtures thereof.
  • alkylaluminoxanes such as methylaluminoxanes
  • tris(pentafluorophenyl) borane dimethylanilinium tetra(pentafluorophenyl) borate or mixtures thereof.
  • the polymerizations are carried out at temperatures between -50°C and +350°C, more in particular between 25 and 250°C. Pressures used are generally between atmospheric pressure and 250 MPa, for bulk polymerizations more in particular between 50 and 250 MPa, for the other polymerization processes between 0.5 and 25 MPa.
  • Dispersing agents and solvents to be used include, for example, hydrocarbons such as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons are also suitable.
  • the monomer to be employed in the polymerization can also be used as a dispersing agent or solvent.
  • the synthesis of the catalyst components was performed under dry Ar or N 2 .
  • GC Gas chromatography
  • GC-MS Combined gas chromatography/ mass spectrometry
  • a Fisons MD800 equipped with a quadrupole mass detector, autoinjector Fisons AS800 and CPSil ⁇ column (30 m x 0.25 mm x 1 ⁇ m, low bleed).
  • Kratos MS80 or alternatively a Finnigan Mat 4610 mass spectrometer.
  • GC was used to show that at that instant 92% of di(2- propyl)cyclopentadiene were present in the mixture of di- and tri(2-propyl)cyclopentadiene.
  • the product was distilled at 10 mbar and 70°C. After distillation, 25.35 g of di(2-propyl)cyclopentadiene were obtained. Characterization took place with the aid of GC, GC-MS, 13 C- and X H-NMR.
  • GC was used to show that approximately 30 minutes after the addition of all the 2-propyl bromide (monosubstituted) 2-propylcyclopentadiene had been formed.
  • the reaction mixture was then warmed to 50°C. After 2 hours, stirring was stopped and phase separation was awaited. The water layer was drawn off, and 180 g (2.25 mol) of fresh 50% strength NaOH were added. Stirring then continued for a further one hour at 50°C.
  • GC was used to show that at that instant between 90 and 95% of tri(2-propyl)cyclopentadiene were present in the mixture of di-, tri- and tetra(2- propyl)cyclopentadiene.
  • the product was distilled at 1.3 mbar and 77-78°C. After distillation, 31.9 g of tri(2-propyl)cyclopentadiene were obtained. Characterization took place with the aid of GC, GC-MS, 13 C- and ⁇ -NMR.
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% strength NaOH (7.5 mol), followed by cooling to 8°C. Then 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. Then 172 g of cyclohexyl bromide (1.05 mol) were added, cooling with water taking place at the same time. After 2 hours' stirring at room temperature the reaction mixture was warmed to 70°C, followed by a further 6 hours' stirring.
  • GC was used to show that at that instant 79% of di (cyclohexyl)cyclopentadiene were present.
  • the product was distilled at 0.04 mbar and 110-120°C. After distillation, 73.6 g of di(cyclohexyl)cyclopentadiene were obtained. Characterization took place with the aid of GC, GC-MS, 13 C- and X H-NMR.
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 430 g (5.4 mol) of clear 50% strength NaOH. Then 23 g of Aliquat 336 (57 mmol) and 27 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 150 g of 3-pentyl bromide (1.0 mol) were added over a period of 1 hour, cooling with water taking place at the same time. After 1 hour 's stirring at room temperature the reaction mixture was warmed to 70°C, followed by a further 3 hours' stirring. Stirring was stopped and phase separation was awaited.
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% strength NaOH (7.5 mol), followed by cooling to 8°C. Then 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. Then 256 g of cyclohexyl bromide (1.57 mol) were added, cooling with water taking place at the same time. After 1 hour's stirring at room temperature the reaction mixture was warmed to 70°C, followed by a further 2 hours' stirring.
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% strength NaOH (7.5 mol), followed by cooling to 10°C. Then 30 g of Aliquat 336 (74 mmol) and 48.2 g (0.73 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 200 g of 2-butyl bromide (1.46 mol) were added over a period of half an hour, cooling with water taking place at the same time. After 2 hours' stirring at room temperature the reaction mixture was warmed to 60°C, followed by a further 4 hours' stirring.
  • GC was used to show that at that instant more than 90% of di(2- butyl)cyclopentadiene were present in the mixture.
  • the product was distilled at 20 mbar and 80-90°C. After distillation, 90.8 g of di(2-butyl)cyclopentadiene were obtained. Characterization took place with the aid of GC, GC-MS, 13 C- and X H-NMR.
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 400 g of clear 50% strength NaOH (5 mol). Then 9.6 g of Aliquat 336 (24 mmol) and 15.2 g (0.23 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 99.8 g of 2-butyl bromide (0.73 mol) were added over a period of half an hour, cooling with water taking place at the same time. After half an hour's stirring at room temperature the reaction mixture was warmed to 70°C, followed by a further three hours' stirring. Stirring was stopped and phase separation was awaited.
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 900 g (11.25 mol) of clear 50% strength NaOH. Then 31 g of
  • GC was used to show that at that instant the mixture consisted of di- and tri(2- pentyl)cyclopentadiene (approximately 1 : 1).
  • the products were distilled at 2 mbar, 79-81°C and 0.5 mbar, 102°C, respectively.
  • 28 g of di- and 40 g of tri(2-pentylJcyclopentadiene were obtained. Characterization took place with the aid of GC , GC-MS, 13 C- and X H-NMR.
  • tosylates can be prepared.
  • a tosylate is in each case coupled with alkylated Cp compounds.
  • the required substitution reaction is also accompanied by geminal coupling.
  • the reaction is carried out in a manner identical to that for (dimethylaminoethyl)-di-(2- pentyl)cyclopentadiene, the tosylate of N,N-di-n- butylaminoethanol being prepared in situ.
  • the conversion was 88%.
  • the (di-n-butylaminoethyl)-di-(2- pentyl)cyclopentadiene was obtained after preparative column purification on silica gel using, successively, petroleum ether (40-60°C) and THF, followed by distillation under reduced pressure, the yield being 51%.
  • Example XVI a Preparation of (dimethylaminoethyl )di (2- propyl )cvclopentadiene The reaction was carried out in a manner identical to that for (dimethylaminoethyl)tri(2- propyl )cyclopentadiene. The conversion was 97%. The dimethylaminoethyldiisopropylcyclopentadiene was obtained by distillation, with a yield of 54%.
  • the reaction was carried out in a manner identical to that for (dimethylaminoethyl)tri(2- propyl)cyclopentadiene.
  • the conversion was 92%.
  • the product was obtained by distillation, with a yield of 64%.
  • the reaction was carried out in a manner identical to that for (dimethylaminoethyl)di(2- propyl)cyclopentadiene.
  • the conversion was 99%.
  • the (dimethylaminoethyl)di(3-pentyl)cyclopentadiene was obtained with a yield of 85% after preparative column purification on silica gel using, successively, petroleum ether (40-60°C) and THF.
  • the reaction was carried out in a manner identical to that for (dimethylaminoethyl)di(2- propyl )cyclopentadiene, the tosylate of N,N-di-n- butylaminoethanol being prepared in situ.
  • the conversion was 94%.
  • the non-geminal di-n- butylaminoethyldi(2-propyl)cyclopentadiene was obtained by distillation with a yield of 53%.
  • the reaction was carried out in a manner identical to that for (dimethylaminoethyl)tri(2- propyl)cyclopentadiene.
  • the conversion was 90%.
  • the non-geminal dimethylaminoethyldiisopropyl- cyclopentadiene was obtained by distillation, with a yield of 54%.
  • the (dimethylaminoethyl)-tri-(2- pentyl )cyclopentadiene was obtained with a yield of 57% after preparative column purification on silica gel using, successively, petroleum ether (40-60°C) and THF.
  • Example XXV Preparation of bis(dimethylaminoethyl)triisopropylcyclopentadiene
  • a solution of 62.5 mL of n- butyllithium (1.6M in n-hexane; 100 mmol) was added under a dry nitrogen atmosphere to a solution of 19.2 g (100 mmol) of triisopropylcyclopentadiene in 250 mL of THF at -60°C. After warming to room temperature (in approximately 1 hour) stirring continued for a further 2 hours.
  • the reaction was carried out in a manner identical to that for (dimethylaminoethyl)- dicyclohexylcyclopentadiene.
  • the conversion was 91%.
  • the product was obtained with a yield of 80% via preparative column purification on silica gel using, successively, petroleum ether (40-60°C) and THF as the eluent. b.
  • Example XXVII a Preparation of (di-n-butylaminoethyl)-tri-(2- pentyl)cyclopentadiene The reaction was carried out in a manner identical to that for (di-n-butylaminoethyl)-di-(3- pentyl)cyclopentadiene. The conversion was 88%. The (2- di-n-butylaminoethyl)-tri-(2-pentyl)cyclopentadiene was obtained with a yield of 51% after preparative column purification on silica gel using, successively, petroleum ether (40-60°C) and THF, followed by distillation under reduced pressure.
  • n-butyllithium (1.6M in hexane; 6.11 mmol) were added. After stirring for 18 hours at room temperature, the clear light-yellow solution was boiled down followed by washing once with 25 mL of petroleum ether. The solvent was then completely evaporated, leaving behind 1.58 g of a yellow oil containing lithium 1-(di-n-butylaminoethyl)-2,3,5- tri(2-pentyl)cyclopentadienyl.
  • organolithium compound was dissolved in 50 mL of tetrahydrofuran and added, at -78°C, to 9.23 g (24.9 mmol) of Ti(III)Cl 3 .3THF in 50 mL of tetrahydrofuran. After 18 hours' stirring at room temperature a dark-green solution had formed. After this solution had been completely boiled down, 1.52 g of a green oil remained, containing l-(di-n-butylaminoethyl)-2,3,5-tri(2- pentyl)cyclopentadienyltitanium(III) dichloride.
  • 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 approx. 25 ml of PMH in a catalyst-dispensing vessel and after-rinsing took place with approx. 75 ml of PMH, always under a dry N 2 flow.
  • the monomer concentrations were kept as constant as possible by means of the reactor being supplied 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. After 10 minutes' polymerization the monomer feed was stopped and the solution was drawn off under pressure and collected. The polymer was dried in vacuo for 16 hours at approximately 120°C.
  • the reaction mixture containing methanol was washed with water and HCI 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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Abstract

Cette invention se rapporte à un composé de cyclopentadiène polysubstitué, dans lequel au moins un substituant se présente sous la forme -RDR'n', où R représente un groupe de liaison, D représente un atome hétéro choisi dans le groupe 15 ou 16 du système 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 constitué par un groupe alkyle ramifié. Des complexes métalliques, dans lesquels au moins l'un de ces composés de cyclopentadiène est présent comme ligand, sont utiles comme catalyseurs pour la polymérisation des alpha-oléfines.
PCT/NL1997/000233 1996-05-03 1997-04-28 Compose de cyclopentadiene substitue avec des groupes alkyle ramifies WO1997042162A1 (fr)

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JP09539785A JP2000510117A (ja) 1996-05-03 1997-04-28 分枝アルキル基で置換されたシクロペンタジエン化合物
AU24110/97A AU2411097A (en) 1996-05-03 1997-04-28 Cyclopentadiene compound substituted with branched alkyl groups
EP97919753A EP0900195A1 (fr) 1996-05-03 1997-04-28 Compose de cyclopentadiene substitue avec des groupes alkyle ramifies
US09/184,065 US6124488A (en) 1996-05-03 1998-11-02 Cyclopentadiene compound substituted with branched alkyl groups

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NL1003007A NL1003007C2 (nl) 1996-05-03 1996-05-03 Met vertakte alkylgroepen gesubstitueerde cyclopentadieenverbinding.

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EP0854147A2 (fr) * 1997-01-21 1998-07-22 Basf Aktiengesellschaft Dérivés tripodaux du cyclopentadiène et leur utilisation
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
WO2002092610A1 (fr) * 2001-05-14 2002-11-21 Dow Global Technologies Inc. Complexes metalliques a substitution aryle en 3, et processus de polymerisation

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KR20230102179A (ko) 2021-12-30 2023-07-07 (주)디엔에프 인듐 화합물, 이의 제조방법, 인듐 함유 박막증착용 조성물 및 인듐 함유 박막의 제조방법

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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 (6)

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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
EP0854147A2 (fr) * 1997-01-21 1998-07-22 Basf Aktiengesellschaft Dérivés tripodaux du cyclopentadiène et leur utilisation
EP0854147A3 (fr) * 1997-01-21 1999-03-03 Basf Aktiengesellschaft Dérivés tripodaux du cyclopentadiène et leur utilisation
US6166234A (en) * 1997-01-21 2000-12-26 Basf Aktiengesellschaft Tripodal cyclopentadiene derivatives and their use
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization
WO2002092610A1 (fr) * 2001-05-14 2002-11-21 Dow Global Technologies Inc. Complexes metalliques a substitution aryle en 3, et processus de polymerisation

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