WO1997042198A1 - Cyclopentadiene polysubstitue - Google Patents

Cyclopentadiene polysubstitue Download PDF

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Publication number
WO1997042198A1
WO1997042198A1 PCT/NL1997/000226 NL9700226W WO9742198A1 WO 1997042198 A1 WO1997042198 A1 WO 1997042198A1 NL 9700226 W NL9700226 W NL 9700226W WO 9742198 A1 WO9742198 A1 WO 9742198A1
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WIPO (PCT)
Prior art keywords
metal
substituents
compounds
compound
group
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PCT/NL1997/000226
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English (en)
Inventor
Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
Matthijs Van Kessel
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Dsm N.V.
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Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU24103/97A priority Critical patent/AU2410397A/en
Publication of WO1997042198A1 publication Critical patent/WO1997042198A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/30—Germanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the invention relates to a polysubstituted cyclopentadiene compound.
  • Cyclopentadiene compounds are generally used as ligands in metal complexes.
  • Cyclopentadiene compounds are generally used as ligands in metal complexes which are active as catalyst components, in particular for the polyme ization of olefins. Depending on the metal, its valency state and 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(lli) or V(IV)
  • these appear to give catalyst components of a low to very low activity, in particular for olefin polymerization.
  • E is an atom chosen from group 14 of the Periodic System of the Elements
  • D is a hetero atom chosen from group 15 or 16 of the Periodic System of the Elements
  • R and R' are substituents
  • cyclopentadiene will be abbreviated as Cp.
  • Cp cyclopentadienyl group
  • '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.
  • Groups that are suitable as linear substituents are for instance ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-pentadecyl, n-hexadecyl, n- octadecyl, n-icosyl, n-docosyl, di-, tri- and tetravinyl, 2-2-chloro-l,1,1-trifluoroethyl, 2- chloroethyl, 3-chloropropyl, 5-chloropentyl and 4- butenyl.
  • 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. Cp compounds that are tetrasubstituted with ethyl and/or propyl groups are preferred.
  • linear alkyl groups do not contain a hetero atom.
  • substituents having the form -(ER 2 ) p D(R') n H, whose presence is required within the scope of the invention, other substituents can also be present.
  • the polysubstituted Cp compound according to the invention comprises at least two linear alkyl groups, neither of which contains a hetero atom, as substituents, H not being considered to be a substituent.
  • the polysubstituted Cp compound can also comprise other substituents which optionally do contain a hetero atom.
  • Further substituents that can also be present are for instance alkyl groups branched and cyclic ones, aryl and aralkyl groups.
  • one or more hetero atoms from groups 14-17 of the Periodic System of the Elements can also be present, for example 0, N, Si or F.
  • Suitable groups are (iso)propyl, sec-butyl, -pentyl , -hexyl and -octyl , (tert-)butyl and higher homologues, cyclohexyl, benzyl, phenyl, paratolyl.
  • Substituted Cp compounds can, for instance, be prepared by reacting a halide of the substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst.
  • Cp compounds are understood here Cp as such and Cp which is already substituted in one to three positions, with the possibility of two substituents forming a closed ring.
  • the process according to the invention 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 compound 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.
  • Hydroxides of an alkali metal, for example K or Na are highly suitable as a base.
  • the base is present in an amount of 5-30, preferably 7-15, mol per mole of Cp compound. These quantities are much lower than 40 mol per mole of Cp compound, the quantity that is usually applied according to the state of the art.
  • 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 or as a result of external heating.
  • 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.
  • the phase transfer catalyst is used in an amount of 0.01 - 2 eguivalents on the basis of the amount of Cp.
  • the various components can be supplied to the reactor in various sequences in the implementation of the process.
  • the aqueous phase and the organic phase containing the Cp compound are separated.
  • the Cp compound is recovered from the organic phase by fractionated distillation.
  • E is chosen from group 14 of the Periodic System of the Elements and so can be C, Si, Ge and Sn. By preference, E is Si or Ge.
  • D is chosen from group 15 or 16 of the Periodic System of the Elements. If D is chosen from group 15, the coordination number of the element is 3, while if D is chosen from group 16, the coordination number of the element is 2.
  • D is N, 0, P or S.
  • D is N.
  • R and R' are substituents and can each separately be a hydrocarbon radical with 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl.
  • R' can also be a substituent which, in addition to or instead of carbon and/or hydrogen, comprises one or more hetero atoms from groups 14-16 of the Periodic System of the Elements.
  • a substituent can be a group comprising N, 0 and/or Si.
  • n represents the number of substituents bonded to D and is 1 if D is chosen from the group 15 elements and is 0 if D is chosen from the group 16 elements.
  • a Cp compound comprising a substituent of the form -(ER 2 ) p D( ') n H can be synthesized starting from a Cp compound substituted with at least two linear alkyl substituents having at least two carbon atoms.
  • This substituted Cp compound is deprotonated to the anion by means of 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.
  • Metal complexes which are catalytically active if one of their ligands is a compound according to the invention are complexes of metals from groups 4- 10 of the Periodic System of the Elements and rare earths.
  • complexes of metals from groups 4 and 5 are preferably used as a catalyst component for polymerizing olefins, complexes of metals from groups 6 and 7 in addition also for metathesis and ring-opening metathesis polymerizations, and complexes of metals from groups 8-10 for olefin copolymerizations with polar comonomers, hydrogenations and carbon lations.
  • 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 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.
  • Dimethoxymethane was distilled from potassium-sodium alloy, benzophenone being used as indicator.
  • the reactions were monitored by means of gas chromatography (GC type: Hewlett Packard 5890 Series II, equipped with autosampler type HP6890 Series Injector, integrator type HP3396A and HP Crosslinked Methyl Silicon Gum (25 m x 0.32 mm x 1.05 ⁇ m) column with one of the following temperature programmes: 50°C (5 min.) rate: 7.5°C/min. 250°C (29 minutes) or 150°C (5 min.) rate: 7.5°C/min. 250°C (29 minutes).
  • Example I the preparation of van (N-t- butylamino (dimethyl) (2.3,4,5- tetraethylcvclopentadienyl)silane titanium dichloride
  • Example IA the preparation of tetrafethyl)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 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.
  • Example IB the preparation of (N-t- butylamino) (dimethyl) (2,3,4,5- tetraethylcyclopentadienyl)silane
  • Example IC the preparation of van (N-t- butylamino) (dimethyl) (2,3,4,5- tetraethylcvclopentadienyl)silane titanium dichloride
  • Example II the preparation of van (N-t- butylamino) (dimethyl) (2,3,4,5- tetrapropylcvclopentadienyl) ⁇ ermane titanium dichloride
  • Example IIA the preparation of tetra(propyl)cvclopentadiene
  • a double-walled reactor having a volume of 1 L, provided with baffles, condenser, top stirrer, thermometer and dropping funnel was charged with 1000 g of clear 50% strength NaOH (12.5 mol), followed by cooling to 10°C. Then 30 g of Aliguat 336 (74 mmol) and 50 g (0.75 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 373 g of propyl bromide (3.03 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.
  • Example IIB the preparation of van (N-t- butylamino) (dimethylH2,3.4,5- tetrapropylcvclopentadienyl)germane
  • Example IIC the preparation of van (N-t- butylamino) (dimethyl) (2,3,4,5- tetrapropylcvclopentadienvD ⁇ ermane titanium dichloride
  • an antioxidant (Irganox 1076 ® ) was added to the organic fraction for the purpose of stabilization of the polymer.
  • the polymer was dried under vacuum at 70°C for 24 hours.

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

Abstract

Composé de cyclopentadiène polysubstitué comportant au moins un substituant ayant la forme (ER2)pD(R')nH, où E représente un atome choisi dans le groupe 14 de la classification périodique des éléments, D représente un hétéroatome choisi dans le groupe 15 ou 16 de la classification périodique des éléments, R et R' représentent des substituants, n représente le nombre de groupes R' liés à D, et p vaut 1 à 4, caractérisé en ce qu'au moins deux autres substituants sont des groupes alkyles linéaires à au moins deux atomes de carbone.
PCT/NL1997/000226 1996-05-03 1997-04-25 Cyclopentadiene polysubstitue WO1997042198A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24103/97A AU2410397A (en) 1996-05-03 1997-04-25 Polysubstituted cyclopentadiene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1003019A NL1003019C2 (nl) 1996-05-03 1996-05-03 Meervoudig gesubstitueerd cyclopentadieen.
NL1003019 1996-05-03

Publications (1)

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WO1997042198A1 true WO1997042198A1 (fr) 1997-11-13

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Cited By (4)

* 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
WO2000040622A1 (fr) * 1998-12-30 2000-07-13 Univation Technologies, Llc Metallocenes pontes par du germanium permettant d'obtenir des polymeres dotes d'une resistance accrue a la fusion
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization
US7446073B2 (en) 1998-12-30 2008-11-04 Exxonmobil Chemical Patents Inc. Catalyst compounds, catalyst systems thereof and their use in a polymerization process

Citations (3)

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

Patent Citations (3)

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

Cited By (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
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization
WO2000040622A1 (fr) * 1998-12-30 2000-07-13 Univation Technologies, Llc Metallocenes pontes par du germanium permettant d'obtenir des polymeres dotes d'une resistance accrue a la fusion
AU754627B2 (en) * 1998-12-30 2002-11-21 Univation Technologies Llc Germanium bridged metallocenes producing polymers with increased melt strength
US7446073B2 (en) 1998-12-30 2008-11-04 Exxonmobil Chemical Patents Inc. Catalyst compounds, catalyst systems thereof and their use in a polymerization process

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NL1003019C2 (nl) 1997-11-06
AU2410397A (en) 1997-11-26

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