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WO1997042150A1 - Compose de cyclopentadiene substitue par des groupes alkyles ramifies - Google Patents

Compose de cyclopentadiene substitue par des groupes alkyles ramifies Download PDF

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Publication number
WO1997042150A1
WO1997042150A1 PCT/NL1997/000212 NL9700212W WO9742150A1 WO 1997042150 A1 WO1997042150 A1 WO 1997042150A1 NL 9700212 W NL9700212 W NL 9700212W WO 9742150 A1 WO9742150 A1 WO 9742150A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl groups
cyclopentadiene
compound
compounds
cyclopentadiene compound
Prior art date
Application number
PCT/NL1997/000212
Other languages
English (en)
Inventor
Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
Richard Green
Matthijs Van Kessel
Original Assignee
Dsm N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU24090/97A priority Critical patent/AU2409097A/en
Publication of WO1997042150A1 publication Critical patent/WO1997042150A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
    • C07C13/15—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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

Definitions

  • the invention relates to a polysubstituted cyclopentadiene compound.
  • Cyclopentadiene compounds both substituted and unsubstituted, are used widely as a starting material for preparing ligands in metal complexes having catalytic activity.
  • cyclopentadiene will be abbreviated as Cp.
  • Cp cyclopentadienyl group
  • a drawback of many of the known substituted Cp compounds is that a metal complex in which known Cp compounds are present as a ligand is only moderately soluble in polar solvents, which hampers the preparation of metal complexes containing the substituted Cp compounds.
  • the object of the invention is to provide substituted Cp compounds whose metal complexes have improved solubility in polar solvents.
  • a further advantage of the Cp-compounds according to the invention is that during further substitution of these Cp-compounds less geminal substitution occurs. This is an advantage when one wants to include a further substituted Cp-compound in a metal complex.
  • the branched ' alkyl groups can be either identical or different.
  • Particularly suitable branched alkyl groups are, for example, 2-pentyl, 2-hexyl, 2- heptyl, 3-pentyl, 3-hexyl, 3-heptyl, 2-(3-methylbutyl) , 2-(3-methylpentyl) , 2-(4-methylpentyl ) , 3-(2- met-hylpentyl ) , 2-(3 , 3-dimethylbutyl ) , 2-(3- ethylpentyl) , 2-(3-methylhexyl) , 2-(4-methylhexyl) , 2- (5-methylhexyl) , 2-(3 , 3-dimethylpentyl ) , 2-(4,4- dimethylpentyl), 3-(4-methylhexyl ) , 3-(5-methylhexyl ) , 3-(2,4-dimethylp
  • the Cp compound may also contain further substituents.
  • alkyl groups both linear and branched, and cyclic, alkenyl and aralkyl groups. It is also possible for these to contain, apart from carbon and hydrogen, one or more hetero atoms from the groups 14-17 of the Periodic System of the Elements, for example 0, N, Si or F, a hetero atom not being bound directly to the Cp.
  • suitable groups are methyl, ethyl, (iso)propyl, sec-butyl, cyclohexyl, benzyl.
  • Substituted 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 here refers to Cp itself and Cp already substituted in 1 to 3 positions, with the option of two substituents forming a closed ring.
  • a virtually equivalent quantity with respect to the Cp-compound of the halogenated substituting 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 - 4 -
  • 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.
  • 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, for example by first mixing, the solution of the base with the other components of the reaction mixture and after some time separating the aqueous phase from the reaction mixture and replacing it by a fresh quantity of the solution of the base.
  • the temperature at which the reaction takes place can vary between wide limits, for example from -20 to 120°C, preferably between 10 and 50°C.
  • Initiating the reaction at room temperature is suitable, as a rule, whereupon the temperature of the reaction mixture may rise as a result of the heat liberated in the course of the reaction occurring.
  • 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 the Cp compound.
  • the organic phase contains the Cp compound and the substituting 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-butyl ⁇ ammonium iodide
  • cetyltrimethylammonium bromide or cetyltrimethylammonium chloride benzyltributyl-, tetra-n-pentyl-, tetra-n-hexyl- and trioctylpropylammonium chlorides and their brom
  • Usable phosphonium salts include, for example, tributylhexadecylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium iodide and tetrabutyl- phosphonium chloride.
  • Crown ethers and cryptands can also be used as a phase transfer catalyst, for example 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 4,7,13,16,21-pentaoxa-l,10- diazabicyclof8.8.5]tricosane (Kryptofix 221),
  • Quaternary ammonium salts, phosphonium salts, phosphoric acid triamides, crown ethers, polyethers and cryptands can also be used on supports such as, for example, on a crosslinked poly- styrene or another polymer.
  • the phase transfer 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 obtained from the organic phase by fractional distillation. This method can be used to obtain Cp compounds bi-, tri-, tetra- and pentasubstituted by the desired branched alkyl.
  • the substituted Cp compounds according to the invention are particularly suitable as a ligand in a metal complex, and the invention therefore also relates to the use of a cyclopentadiene compound substituted by at least two branched alkyl groups, for preparing a metal complex in a polar solvent.
  • These metal complexes have better thermal stability than complexes containing Cp ligands which are not substituted by branched groups.
  • Metal complexes which are catalytically active if one of their ligands is a compound according to the invention are complexes of metals from groups 4- 10 of the Periodic System of the Elements and rare earths.
  • complexes of metals from groups 4 and 5 are preferably used as a catalyst component for polymerizing olefins, complexes of metals from groups 6 and 7 in addition also for metathesis and ring-opening metathesis polymerizations, and complexes of metals from groups 8-10 for olefin copolymerizations with polar comonomers, hydrogenations and carbonylations.
  • For the Periodic System see the new IUPAC notation to be found on the insdie of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990.
  • metal complexes in which the metal is chosen from the group consisting of Ti, Zr, Hf, V and Cr.
  • olefins here and hereinafter refers to ⁇ -olefins, diolefins and other ethylenically unsaturated monomers. Where the term 'polymerization of olefins' is used, this hereinafter refers both to the polymerization of a single type of olefinic monomer and to the copolymerization of two or more olefins.
  • 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.
  • Particularly suitable for this purpose are the complexes of transition metals, not in their highest valence state, in which just one of the cyclopentadienyl compounds according to the invention is present as a ligand, and in which the metal during the polymerization is cationic.
  • 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 trialkylaluminium, alkylaluminium halides, 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 remaining 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 likewise deserve consideration. Equally, the monomer to be employed in the polymerization can be used as a dispersing agent or solvent. The invention will be explained with reference to the following examples, but is not limited thereto.
  • 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 ⁇ -NMR.

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

Abstract

Composé de cyclopentadiène polysubstitué dont au moins deux substituants sont des groupes alkyles C5-7 ramifiés, et leur utilisation dans la préparation d'un complexe métallique dans un solvant polaire. Le complexe métallique dans lequel est présent à titre de ligand au moins un composé de cyclopentadiène substitué, dont au moins deux substituants sont des groupes alkyles ramifiés, est utilisable comme constituant catalytique dans la polymérisation des alpha-oléfines.
PCT/NL1997/000212 1996-05-03 1997-04-23 Compose de cyclopentadiene substitue par des groupes alkyles ramifies WO1997042150A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24090/97A AU2409097A (en) 1996-05-03 1997-04-23 Cyclopentadiene compound substituted by branched alkyl groups

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1003006A NL1003006C2 (nl) 1996-05-03 1996-05-03 Met vertakte alkylgroepen gesubstitueerde cyclopentadieenverbinding.
NL1003006 1996-05-03

Publications (1)

Publication Number Publication Date
WO1997042150A1 true WO1997042150A1 (fr) 1997-11-13

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AU (1) AU2409097A (fr)
NL (1) NL1003006C2 (fr)
WO (1) WO1997042150A1 (fr)

Cited By (1)

* 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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849566A (en) * 1987-10-22 1989-07-18 Pennzoil Products Company Lubricants comprising novel cyclopentanes, cyclopentadienes, cyclopentenes, and mixtures thereof and methods of manufacture
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
WO1995000562A1 (fr) * 1993-06-24 1995-01-05 Exxon Chemical Patents Inc. Procede de production de poly-alpha-olefines amorphes au moyen d'un catalyseur a metal de transition de monocyclopentadienyle
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849566A (en) * 1987-10-22 1989-07-18 Pennzoil Products Company Lubricants comprising novel cyclopentanes, cyclopentadienes, cyclopentenes, and mixtures thereof and methods of manufacture
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
WO1995000562A1 (fr) * 1993-06-24 1995-01-05 Exxon Chemical Patents Inc. Procede de production de poly-alpha-olefines amorphes au moyen d'un catalyseur a metal de transition de monocyclopentadienyle
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

Cited By (1)

* 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

Also Published As

Publication number Publication date
AU2409097A (en) 1997-11-26
NL1003006C2 (nl) 1997-11-06

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