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WO1999015537A1 - Compose de metal de transition - Google Patents

Compose de metal de transition Download PDF

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Publication number
WO1999015537A1
WO1999015537A1 PCT/EP1998/005688 EP9805688W WO9915537A1 WO 1999015537 A1 WO1999015537 A1 WO 1999015537A1 EP 9805688 W EP9805688 W EP 9805688W WO 9915537 A1 WO9915537 A1 WO 9915537A1
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WO
WIPO (PCT)
Prior art keywords
unsubstituted
cyclopentadienyl
substituted
tert
vinylidene
Prior art date
Application number
PCT/EP1998/005688
Other languages
German (de)
English (en)
Inventor
Markus GÖRES
Cornelia Fritze
Gerhard Erker
Lothar Duda
Original Assignee
Targor Gmbh
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 Targor Gmbh filed Critical Targor Gmbh
Publication of WO1999015537A1 publication Critical patent/WO1999015537A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates to a transition metal compound and a process for its preparation and its use as a catalyst component in the production of polyolefins.
  • Lewis acidity can convert the neutral transition metal compound into a cation and stabilize it, known (EP-A 129 368, EP-A 351 392, EP-A 416 815).
  • Metallocenes are of great interest not only with regard to the polymerization or oligomerization of oiefins. They can also be used as hydrogenation, epoxidation, isomerization and C-C coupling catalysts (Chem. Rev. 1992, 92, 965-994).
  • Aluminoxanes are obtained from atactic polymers which are of little technical importance due to their unbalanced and inadequate product properties. In addition, certain olefin copolymers are not available.
  • the polymerization properties of a metallocene compound can be controlled by the ligand system.
  • Derivatives of zirconocene dichloride, in which the two substituted cyclopentadienyl groups are linked via a methyl, ethyl or dimethylsilyl bridge, can be used as catalysts for the isospecific polymerization of oiefins due to their conformative rigidity (EP-A 316 155).
  • a large number of complex examples of monocyclopentadienyl compounds are described in EP0416815, EP0514828, US 5026798, US 5057475, US 5096867, EP 0418044, WO 9212162.
  • the task was to provide new transition metal compounds.
  • the present invention thus relates to transition metal compounds of the formula (I)
  • M is a metal from group 3, 4, 5 or 6 of the periodic table of the elements and lanthanides or actinides, preferably titanium, zirconium or hafnium
  • R is a C 1 -C 40 carbon-containing group, such as C 1 -C 10 alkyl , for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, cyclopentyl, cyclohexyl, benzyl, C 6 -C 10 aryl, which on its part can be substituted, for example phenyl, tolyl ,
  • L is a cyclopentadienyl system which can carry C 1 -C 20 substituents, such as C 1 -C 20 hydrocarbon radicals (for example C 1 -C 20 alkyl or C 6 -C 20 aryl), which in turn are together can be linked to form a mono- or polycyclic ring system, for example cyclopentadienyl, methylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, trimethylsilylcyclopentadienyl, trimethylcyclopentadienyl, Tetramethylcyclopentadienyl, methyl tert-butylcyclopentadienyl, phenylcyclopentadienyl, unsubstituted or C 1 -C 20 substituted indenyl such as indenyl, 2-methylindenyl, 2-methyl-4-phenyl-indenyl, acen
  • x is 0 or 1, where x is 1 a spirosystem
  • a 1 and A 2 are the same or different and mean x for 1 is an oxygen atom, a sulfur atom, an NR 1 or PR 1 group, where R 1 is defined as R, or A 1 and A 2 is a cyclopentadienyl
  • CC 40 -carbon-containing group in particular methyl, ethyl, Isopropyl, butyl, cyclohexyl, phenyl, benzyl, substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, halogen, triflate, OR ⁇ SR ⁇ NR 1 2 , PR 1 2 , where R is defined as R.
  • Preferred transition metal compounds of the formula (I) are those in which
  • M is titanium, zirconium or hafnium
  • R is a C, -C 10 alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclohexyl, a C 6 -C 10 aryl group which may be substituted, for example Phenyl, naphthyl, tolyl, tert-butylphenyl, xylyl, mesityl, anisyl, trifluoromethylphenyl, halophenyl, dimethylaminophenyl, a C 7 -C 15 -
  • Alkylaryl group such as benzyl, a C 3 -C 30 -alkylsilyl group such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, cyclohexyldimethylsilyl
  • L is a cyclopentadienyl system which can carry further C, -C 20 substituents, which in turn can be linked together to form a mono- or polycyclic ring system, for example cyclopentadienyl, methylcyclopentadienyl, tert.-
  • a and A 2 are the same or different and for x is 1 is an oxygen atom, a sulfur atom, an NR 1 or PR 1 group, where R 1 is a C r C 40 carbon-containing group, or CC 20 - substituted or unsubstituted Are cyclopentadienyl, C r C 20 -substituted or unsubstituted indenyl, C ⁇ C ⁇ -substituted or unsubstituted fluorenyl, and for x is 0 a C 1 -C 40 carbon-containing group, in particular methyl, ethyl, isopropyl, butyl, cyclohexyl, phenyl , Benzyl, C r C 20 -substituted or unsubstituted cyclopentadienyl, C 1 -C 20 -substituted or unsubstituted indenyl, CC 20 - substituted or unsubstit
  • N-tri methyls lylamido-vinylidene-cyclopentadienyl-zirconium dichloride N-tri-methyls lylamido-vinylidene-cyclopentadienyl-titanium dichloride
  • N-tri-methyls lylamido-vinylidene-cyclamidentyl N-tr methyls lylamido-vinylidene-cyclopentadienyl-hafnium-bis (diethylamide) N-tr methyls lylamido-vinylidene-cyclopentadienyl-dimethyl-zirconium
  • N-Trimethylsilylamido-vinylidene-cyclopentadienyl (oxo-vinylidene-indenyl) -zirconium
  • N-Trimethylsilylamido-vinylidene (dioxo-vinylidene) zirconium
  • N-Trimethylsilylamido-vinylidene-cyclopentadienyl (thio-vinylidene-cyclopentadienyl) - zirconium
  • transition metal compounds of the formula (I) according to the invention can be prepared, for example, by a process which is illustrated by the following synthesis scheme.
  • the compounds of the formula (II) can be prepared by methods known from the literature (Chem. Lett. 1990, 1683; Tetrahedron Lett. 1990, 31, 545; Chem. Ber. 1964, 768, 539).
  • M 1 is an alkali metal and X is a C 1 -C 10 hydrocarbon radical which may contain one or more heteroatoms such as O, S, N or Si.
  • radicals R 2 are, independently of one another, the same or different and mean
  • Halogen a -C-C4o-carbon-containing group such as (C-
  • Phenyl or naphthyl group Phenyl or naphthyl group, (C2-C24) heteroaryl such as pyridyl, furyl, thienyl, pyri- midinyl, quinolyl, (C ⁇
  • C 3 -C 20 alkylsilyl- such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, C 6 -C 30 arylsilyl- such as triphenylsilyl, or C 6 -C 30 alkylarylsilyl- such as dimethylphenylsilyl, diphenylphenylmethylsilyl .
  • -Butylsilyl, and the radicals R 2 can each form a mono- or polycyclic C 3 -C 30 ring system with the atoms of the cyclopentadienyl ring connecting them, so that, for example, an indenyl, fluorenyl, benzindenyl or acenaphthindenyl system results, n is an integer greater than 0 and less than 4.
  • the compounds of formula (II) are reacted in the presence of a base such as, for example, triethylamine, diisopropylethylamine, NN-dimethylaniline, potassium carbonate, potassium tert-butoxide, DBU, DBN, with compounds of the RY type to give compounds of the formula (III), where R as defined in formula I and Y is halogen, alkyl sulfonate or aryl sulfonate such as triflate, mesylate, tosylate, benzene sulfonate, carboxylate such as acetate, formate, trifluoroacetate or diazonium.
  • a base such as, for example, triethylamine, diisopropylethylamine, NN-dimethylaniline, potassium carbonate, potassium tert-butoxide, DBU, DBN
  • compounds of the RY type to give compounds of the formula (III), where R as defined in formula I and
  • M is a transition metal from group 3, 4, 5, 6 of the periodic table of the elements and lanthanides or actinides, preferably titanium, zirconium or hafnium, Z means halogen, NR 2 , PR 2 , OR, SR, where R is as defined in formula I. is, 1, 3-
  • Dicarbonylate such as 1,3-acatylacetonate, halogenated 1,3-dicarbonylate such as hexafluoro-1,3-acetylacetonate, carboxylate, halogenated carboxylate such as trifluoroacetate, halogenated or unhalogenated alkyl or aryl sulfonate such as mesylate, triflate, tosylate, preferably halogen, OR, NR 2 , k is an integer greater than 0 and less than or equal to 6, and R, L, A L A 2 and X are defined as above.
  • Suitable solvents in which the reactions described are carried out are aliphatic or aromatic hydrocarbons, which may be halogenated, such as but not exclusively pentane, hexane, cyclohexane, methylene chloride, dichloroethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethers such as diethyl ether , Dibutyl ether, tetrahydrofuran, anisole, dioxane, 1, 2-
  • the transition metal compounds according to the invention are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands, the transition metal compounds can be obtained as a mixture of isomers.
  • the transition metal compounds are preferably used isomerically pure, but can also be used as a mixture of isomers.
  • the present invention further relates to a process for the preparation of a polyolefin by polymerizing one or more olefins in the presence of a catalyst system comprising at least one transition metal compound according to the invention and at least one cocatalyst.
  • a catalyst system comprising at least one transition metal compound according to the invention and at least one cocatalyst.
  • the term polymerization is understood to mean homopolymerization as well as copolymerization.
  • R a and R b are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 20 C atoms, in particular 1 to 10 carbon atoms, or R a and R b together with the atoms connecting them form one or more rings.
  • Examples of such olefins are 1-olefins having 1 to 20 carbon atoms, such as ethylene,
  • the polymerization is preferably carried out at a temperature of from -78 to 250.degree. C., particularly preferably from 50 to 200.degree.
  • the pressure is preferably 0.5 to
  • 2000 bar particularly preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • a preferred embodiment is gas phase polymerization and suspension polymerization.
  • the catalyst used in the process according to the invention preferably contains a transition metal compound. Mixtures of two or more transition metal compounds can also be used, e.g. for the production of polyolefins with a broad or multimodal molar mass distribution.
  • any compound is suitable as a cocatalyst in the process according to the invention which, owing to its Lewis acidity, can convert the neutral transition metal compound into a cation and stabilize it (“labile coordination”).
  • the cocatalyst or the anion formed from it should not undergo any further reactions with the cation formed (EP 427 697).
  • An aluminum compound and / or a boron compound is preferably used as the cocatalyst.
  • the boron compound preferably has the formula R 12 X NH 4 . X BR 13 4 , R 12 X PH 4 . X BR 13 4 ,
  • R 12 3 CBR 13 4 or BR 3 3 wherein x is a number from 1 to 4, preferably 3, the radicals R 12 are identical or different, preferably identical, and C r C 10 alkyl or C 6 -C 18 Aryl, or two radicals R 12 together with the atoms connecting them form a ring, and the radicals R 13 are the same or different, preferably the same, and are C 6 -C 18 aryl which is substituted by alkyl, haloalkyl or fluorine can be.
  • R 12 stands for ethyl, propyl, butyl or phenyl and R 13 stands for phenyl, pen- tafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).
  • An aluminum compound such as aluminoxane and / or an aluminum alkyl is preferably used as the cocatalyst.
  • An aluminoxane in particular of the formula Xa for the linear type and / or of the formula Xb for the cyclic type, is particularly preferably used as cocatalyst,
  • the radicals R 14 are the same or different and are hydrogen or a C Cgo hydrocarbon group such as a C r C 18 alkyl group, a C 6 -C 18 aryl group or benzyl and p is an integer from 2 to 50, preferably 10 to 35 means.
  • the R 14 radicals are preferably the same and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
  • R 14 radicals are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in a number fraction of from 0.01 to 40% (of the R 14 radicals).
  • the processes for producing the aluminoxanes are known.
  • the exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings combine to form larger two-dimensional or three-dimensional structures.
  • the preactivation of the transition metal compound is preferably carried out in solution.
  • the transition metal compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
  • An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon. Toluol is preferably used.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total amount of solution.
  • the transition metal compound can be used in the same concentration, but it is preferably used in an amount of 10 "4 to 1 mol per mol of aluminoxane.
  • the preactivation time is 5 minutes to 60 hours, preferably 5 to
  • the transition metal compound is preferably used in a concentration, based on the transition metal, of 10 "3 to 10 " 8 , preferably 10 "4 to 10 " 7 mol of transition metal per dm 3 solvent or per dm 3 reactor volume.
  • the aluminum minoxan is preferably used in a concentration of 10 "6 to 10 " 1 mol, preferably 10 5 to 10 "2 mol per dm 3 solvent or per dm 3 reactor volume.
  • the other cocatalysts mentioned are used in approximately equimolar amounts to the transition metal compound In principle, however, higher concentrations are also possible.
  • the aluminoxane can be prepared in various ways by known methods.
  • One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
  • an inert solvent such as toluene
  • two different aluminum trialkyls are reacted with water, for example in accordance with the desired composition.
  • cleaning with an aluminum compound, preferably an aluminum alkyl, such as trimethyl aluminum or triethyl aluminum is advantageous. This cleaning can take place both in the polymerization system itself, or the olefin is brought into contact with the aluminum compound before being added to the polymerization system and then separated off again.
  • Hydrogen can be added in the process according to the invention as a molecular weight regulator and / or to increase the catalyst activity.
  • low molecular weight polyolefins such as waxes can be obtained.
  • the transition metal compound is preferably reacted with the cocatalyst outside the polymerization reactor in a separate step using a suitable solvent. Carrying can be carried out.
  • a prepolymerization can be carried out using the transition metal compound.
  • the (or one of the) olefin (s) used in the polymerization is preferably used.
  • the catalyst used in the process according to the invention can be supported.
  • the support allows, for example, the grain morphology of the polyolefin produced to be controlled.
  • the transition metal compound can be reacted first with the support and then with the cocatalyst.
  • the cocatalyst can also first be supported and then reacted with the transition metal compound. It is also possible to slow the reaction product of transition metal compound and cocatalyst.
  • Suitable carrier materials are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic carrier materials such as magnesium chloride.
  • a suitable carrier material is also a polyolefin powder in finely divided form.
  • the preparation of a supported cocatalyst can, for example, as in
  • EP 567 952 can be performed.
  • the cocatalyst e.g. Aluminoxane
  • a carrier such as silica gels, aluminum oxides, solid aluminoxane, other inorganic carrier materials or a polyolefin powder in finely divided form and then reacted with the transition metal compound.
  • Oxides which have been generated by flame-pyrolytic combustion of element halides in a detonating gas flame or which can be prepared as silica gels in certain particle size distributions and particle shapes can be used as inorganic carriers.
  • the preparation of a supported cocatalyst can, for example, as described in EP 578 838, in the following manner in a stainless steel reactor in explosion-proof design with a pumping system of the pressure stage 60 bar, with inert gas supply, temperature control by jacket cooling and a second cooling circuit via a heat exchanger on the pump system.
  • the pumping system sucks the contents of the reactor through a connection in the bottom of the reactor with a pump and presses it into a mixer and back through a riser via a heat exchanger into the reactor.
  • the mixer is designed so that there is a narrow pipe cross-section in the inlet, where an increased flow velocity occurs, and in its turbulence zone, a thin feed line is guided axially and counter to the direction of flow, through which - clocked - a defined amount of water below 40 bar Argon can be fed.
  • the reaction is controlled by a sampler on the pump circuit. In principle, other reactors are also suitable.
  • transition metal compound according to the invention is then applied to the supported cocatalyst by stirring the dissolved transition metal compound with the supported cocatalyst.
  • the solvent is removed and replaced by a hydrocarbon in which both the cocatalyst and the transition metal compound are insoluble.
  • the reaction to the supported catalyst system takes place at a temperature of -20 to +120 C, preferably 0 to 100 C, particularly preferably at 15 to 40 C.
  • the transition metal compound is reacted with the supported cocatalyst in such a way that the cocatalyst as a suspension with 1 to 40 wt .-%, preferably with 5 to 20 wt .-% in an aliphatic, inert suspending agent such as n-decane, hexane, heptane, Diesel oil is combined with a solution of the transition metal compound in an inert solvent such as toluene, hexane, heptane, dichloromethane or with the finely ground solid of the transition metal compound.
  • a solution of the transition metal compound can also be reacted with the solid of the cocatalyst.
  • the reaction is carried out by intensive mixing, for example by stirring at a molar Al / M ratio of 100/1 to 10000/1, preferably from 100/1 to 3000/1 and a reaction time of 5 to 120 minutes, preferably 10 to 60 minutes, particularly preferably 10 to 30 minutes under inert conditions.
  • a reaction time for example by stirring at a molar Al / M ratio of 100/1 to 10000/1, preferably from 100/1 to 3000/1 and a reaction time of 5 to 120 minutes, preferably 10 to 60 minutes, particularly preferably 10 to 30 minutes under inert conditions.
  • the supernatant solution is separated off, for example by filtration or decanting.
  • the remaining solid is washed 1 to 5 times with an inert suspending agent such as toluene, n-decane, hexane, diesel oil, dichloromethane to remove soluble constituents in the catalyst formed, in particular to remove unreacted and thus soluble transition metal compound.
  • an inert suspending agent such as toluene, n-decane, hexane, diesel oil, dichloromethane to remove soluble constituents in the catalyst formed, in particular to remove unreacted and thus soluble transition metal compound.
  • the supported catalyst system produced in this way can be dried in vacuo as a powder or with solvent, resuspended and metered into the polymerization system as a suspension in one of the aforementioned inert suspending agents.
  • an inert solvent customary for the Ziegler low-pressure process is used.
  • an aliphatic or cycloaliphatic hydrocarbon such as propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane.
  • a gasoline or hydrogenated diesel oil fraction can also be used.
  • Toluene can also be used.
  • Polymerization is preferably carried out in the liquid monomer.
  • the supported catalyst system consisting of a transition metal compound according to the invention and a supported
  • another aluminum alkyl compound such as trimethylaluminum, triethylaluminium, triisobutylaluminum,
  • the monomers are added in gaseous or liquid form.
  • the duration of the polymerization is arbitrary, since the catalyst system to be used in the process according to the invention shows only a slight time-dependent drop in the polymerization activity.

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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

L'invention concerne un composé de métal de transition de formule (I), dans laquelle M, L, R, x, A<1> et A<2> ont la signification mentionnée dans la description.
PCT/EP1998/005688 1997-09-23 1998-09-08 Compose de metal de transition WO1999015537A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997141846 DE19741846A1 (de) 1997-09-23 1997-09-23 Übergangsmetallverbindung
DE19741846.5 1997-09-23

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WO1999015537A1 true WO1999015537A1 (fr) 1999-04-01

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
EP0816371A1 (fr) * 1996-06-28 1998-01-07 PCD-Polymere Gesellschaft m.b.H. Procédé de préparation stéréosélective de métallocènes chiraux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
EP0816371A1 (fr) * 1996-06-28 1998-01-07 PCD-Polymere Gesellschaft m.b.H. Procédé de préparation stéréosélective de métallocènes chiraux

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 129, Columbus, Ohio, US; abstract no. 189716, DUDA, LOTHAR ET AL: "Formation of a constrained-geometry Ziegler catalyst system containing a C1 instead of the usual Si1 connection between the cyclopentadienyl and amido ligand components" XP002088915 *
EUR. J. INORG. CHEM. (1998), (8), 1153-1162 CODEN: EJICFO;ISSN: 1434-1948, 1998 *

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