EP1497244A1 - Method for oligomerizing olefins - Google Patents

Method for oligomerizing olefins

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Publication number
EP1497244A1
EP1497244A1 EP03724987A EP03724987A EP1497244A1 EP 1497244 A1 EP1497244 A1 EP 1497244A1 EP 03724987 A EP03724987 A EP 03724987A EP 03724987 A EP03724987 A EP 03724987A EP 1497244 A1 EP1497244 A1 EP 1497244A1
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Prior art keywords
transition metal
complex
alkylalumoxane
olefin
oligomerization
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German (de)
French (fr)
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Shahram Mihan
Heiko Maas
Martina Prinz
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/24—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for oligomerizing olefins, in which an olefin is brought into contact with a catalyst system which comprises at least one transition metal complex with a multidentate complex ligand and an alkylalumoxane.
  • Olefin oligomers with up to 30 carbon atoms are of great economic importance as comonomers for plastics or as precursors for oxo alcohols, which in turn are part of surfactants and plasticizers for plastics.
  • Process for oligomerizing lower olefins, e.g. B. originate from steam crackers, is therefore of central importance in the manufacture of everyday products.
  • WO 00/58319 describes a process for the preparation of oligomers of olefins using an oligomerization catalyst which can be obtained from a chromium compound and a 1,3,5-triazacyclohexane and an activating additive, such as an alkylalumoxane.
  • EP-A-0 537 609 describes the oligomerization of ethene in the presence of a catalyst which comprises a chromium complex with a multidentate complex ligand and an alkylalumoxane.
  • the catalyst system is then discarded.
  • the alkylalumoxane is usually used in a large excess, based on the transition metal complex, in order to achieve sufficient activation.
  • the associated high consumption of alkylalumoxane is therefore a significant cost factor for such olefin oligomerization processes.
  • the object of the invention is to provide a process for oligomerizing olefins, in which an olefin is brought into contact with a catalyst system which comprises a transition metal complex and an alkylalumoxane, the process allowing optimum use of the alkylalumoxane.
  • this object is achieved by a process for the oligomerization of olefins, in which an olefin is brought into contact with a catalyst system which
  • b) comprises an alkylalumoxane in amounts such that the molar ratio of aluminum: transition metal is more than 10, at least part of the amount of the transition metal complex being added continuously or in portions in the course of the oligomerization.
  • Suitable alkylalumoxanes are known, for example, from DE-A-3 007 725, their structures being largely unexplained. These are products of the careful partial hydrolysis of aluminum alkyls. These products do not appear to be pure, but as mixtures of open-chain and cyclic structures of type Ia and Ib, which are probably in dynamic equilibrium with one another.
  • the groups R are the same or lg different and are independently C 1 -C 2 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl , tert-butyl, n-pentyl, i-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, i-amyl, n-hexyl, i-hexyl, sec-hexyl, n-heptyl, i-heptyl , n-octyl, n-nonyl, n-decyl and
  • n-dodecyl preferably Ci-C ß- alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, i-pentyl, sec-pentyl, neo- Pentyl, 1,2-dimethylpropyl, i-amyl, n-hexyl, i-hexyl.
  • Methylalumoxane is particularly preferred, m is an integer from 0 to 40, preferably 0 to 25 and
  • alkylalumoxanes fulfill their suitability for the purposes of the present invention regardless of their structural nature.
  • the transition metal complex can be any complex which, after activation, is capable of oligomerizing olefins. Suitable catalysts of this type are described in "Frontiers in metal-catalyzed Polymerization", Chem. Rev. April 2000, Vol. 100 No. 4, pp. 1167-1645. The transition measure
  • 40 tall in preferred complexes is selected from chromium, vanadium, tantalum and titanium.
  • Suitable transition metal complexes can be represented by the formula k LMeX, wherein Me is a transition metal, preference - 5 as Cr, V or Ti, L represents a multidentate Komplexli- ganden, X represents the same or different anions, and k represents 2 or 3.
  • the multidentate complex ligand preferably occupies three adjacent coordination sites of the octahedrally coordinated metal atom.
  • Nitrogen-containing multidentate complex ligands are preferred.
  • Cyclic polyamine ligands are particularly preferred, in particular those which comprise a 1,3,5-triazacyclohexane or a 1,4,7-triazacyclononane skeleton.
  • Suitable complex ligands with a 1,3,5-triazacyclohexane skeleton are described in WO 00/58319, to the disclosure of which reference is made.
  • 1,3,5-triazacyclohexanes are preferred, the nitrogen atoms of which are independently substituted by optionally substituted C 1 -C 2 -alkyl, C ß- cis-aryl or C -C 5 arylalkyl, for. B.
  • Suitable 1,4,7-triazacyclononanes can be substituted on the nitrogen atoms by substituents such as those listed above.
  • 1, 4, 7-trimethyl-l, 4, 7-triazacyclononane is commercially available.
  • Alternative polydentate complex ligands are cyclopentadienyl anion of the formula CsH (5 _ U) R u and their benzo-fused derivatives, wherein 6 alkyl, C 2 -C n is an integer from 0 to 5 and R is C ⁇ -C 6 alkenyl, C 6 -C ⁇ 0 aryl, C 7 -C ⁇ 4 aralkyl, R ⁇ R ⁇ PX or NX, wherein R 1 is C ⁇ -C6 alkyl, Cs-C ⁇ cycloalkyl or C ß -Cio- Aryl and X represents -C 6 alkylene.
  • N is preferably 1.
  • Suitable cyclopentadienyl ligands are, for. B.
  • R 2 is hydrogen, -CC 6 -alkyl or Ci-C ß -alkoxy and Y is N-methylimidazol-2-yl, R 1 2 PX- or R ⁇ NX-, wherein R 1 is Ci-C ⁇ -Alkyl, Cs-Cg-cycloalkyl or C 6 -C ⁇ o-alkyl and X is Ci-C ß -alkylene.
  • Suitable anions X are in particular halogen, such as fluorine, bromine, iodine and in particular chlorine; Tosylate, triflate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraphenylborate; Ci-Ci ⁇ -carboxylate, such as acetate, butyrate, neopentanoate, laurate, stearate or 2-ethylhexanoate.
  • halogen such as fluorine, bromine, iodine and in particular chlorine
  • Tosylate triflate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraphenylborate
  • Ci-Ci ⁇ -carboxylate such as acetate, butyrate, neopentanoate, laurate, stearate or 2-ethylhexanoate.
  • transition metal complexes can be obtained by methods known to those skilled in the art or analogously to these (cf., for example, W. A. Herrmann, A. Salzer: “Synthetic Methods of Organometallic and Inorganic Chemistry", Thieme Verlag, Stuttgart 1996). Suitable complexes are described in WO 00/58319 of EP-A-0 537 609, Rüther, T. et al., Organometallics 2001, 20, pp. 1247-1250; Döhring A. et al., Organo etallics 2001, 20, pp. 2234-2245 and Deckers P. J. W. et al., Angew. Chem. 2001, 113, No. 13, pp. 2584-2587.
  • the transition metal complex and the alkylalumoxane are used in such amounts that a molar ratio of aluminum: transition metal of more than 10, eg. B. 10 to 10,000, preferably 10 to 500.
  • at least part of the amount of the transition metal complex used is added continuously or in portions in the course of the oligomerization, ie after olefin, alkylalumoxane and a part of the complex have been brought into contact under conditions under which oligomerization of the olefin takes place.
  • the entire amount of alkylalumoxane and a partial amount of the complex are combined in situ immediately before use in the oligomerization reaction.
  • the olefin to be oligomerized can also be initially introduced and / or added continuously or in portions to the combined catalyst components become. Alternatively, you can submit the alumoxane and olefin and add the first portion of the transition metal complex.
  • the activity of the catalyst system becomes noticeably worse, e.g. B. after a time interval of at least 30 min or 1 hour, a further subset of the transition metal complex can be added to the polymerizing system.
  • This process can be repeated as often as long as the total amount of transition metal complex in the reaction system, i. H. the sum of the quantities added and added, and the amount of alkylalumoxane give a molar ratio aluminum: transition metal of more than 10.
  • a subset of the transition metal complex is introduced together with the alkylalumoxane and the molar ratio aluminum: transition metal is reduced to less than half of the initial value by adding at least a further subset of the transition metal complex in the course of the oligomerization.
  • the initial molar aluminum: transition metal ratio is expediently more than 100, preferably more than 200, in particular more than 300.
  • the transition metal complex can also be metered in continuously during the oligomerization, in order, for example, to have high catalyst activity over a longer period Period.
  • Suitable solvents are aprotic solvents, e.g. B. aliphatic saturated hydrocarbons, such as butane, pentane, 3-methylpentane, hexane, heptane, 2-methylhexane, octane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, decalin; halogenated hydrocarbons, such as dichloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, mesitylene, tetralin or the oligomeric reaction products which are liquid under the reaction conditions, such as 1-hexene itself.
  • solvents can be used either individually or as a mixture.
  • the process according to the invention is suitable for the oligomerization, in particular the selective trimerization, of ethene.
  • the process according to the invention is also suitable for oligomerization, in particular the selective trimerization of ⁇ -olefins with at least three, e.g. B. three to twelve carbon atoms, such as 1-propene, 1-butene, 1-hexene, 1-decene.
  • Particularly suitable as olefin is 1-butene, optionally in a mixture with its isomers, such as are present in raffinate II.
  • the process according to the invention is generally carried out with extensive exclusion of moisture. It is preferable to work under protective gas. All gases which are chemically inert under the reaction conditions, such as nitrogen or argon, can be used as protective gases.
  • the olefin to be converted can itself take on the function of the protective gas, provided that it has a sufficiently high vapor pressure under the reaction conditions.
  • the oligomerization is preferably carried out at a temperature in the range from 0 to 120 and in particular 25 to 110 ° C. It takes place at a pressure of ambient pressure up to 120 bar.
  • the catalyst system is generally deactivated.
  • Suitable deactivators are, for example, water, which may be acidified, or lower alcohols.
  • the products of the oligomerization are expediently cleaned by distillation. Unreacted raw material can be recovered and returned to the implementation.

Abstract

The invention relates to a method for oligomerizing olefins according to which an olefin is brought into contact with a catalyst system comprising: a) at least one transition metal complex having a multidentate complex ligand, and; b) an alkylalumoxane in quantities in which the molar ratio of aluminum to transition metal is greater than 10, whereby at least one portion of the quantity of the transition complex is added continuously or in portions over the course of oligomerization. The method enables the production of greater quantities of olefin oligomers with a given quantity of alkylalumoxane.

Description

Verfahren zur Oligomerisierung von OlefinenProcess for oligomerizing olefins
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Oligomerisierung von Olefinen, bei dem man ein Olefin mit einem Katalysatorsystem in Kontakt bringt, das wenigstens einen Übergangsmetallkomplex mit einem mehrzähnigen Komplexliganden und ein Al- kylalumoxan umfasst.The present invention relates to a process for oligomerizing olefins, in which an olefin is brought into contact with a catalyst system which comprises at least one transition metal complex with a multidentate complex ligand and an alkylalumoxane.
Olefin-Oligomere mit bis zu 30 Kohlenstoffato en haben große wirtschaftliche Bedeutung als Comonomere für Kunststoffe oder als Vorprodukte für Oxoalkohole, die ihrerseits Bestandteil von Ten- siden und Weichmachern für Kunststoffe sind. Verfahren zur Oligomerisierung niederer Olefine, die z. B. Steamcrackern entstammen, kommt somit eine zentrale Bedeutung in der Herstellung von Produkten des täglichen Bedarfs zu.Olefin oligomers with up to 30 carbon atoms are of great economic importance as comonomers for plastics or as precursors for oxo alcohols, which in turn are part of surfactants and plasticizers for plastics. Process for oligomerizing lower olefins, e.g. B. originate from steam crackers, is therefore of central importance in the manufacture of everyday products.
Die WO 00/58319 beschreibt ein Verfahren zur Herstellung von Oli- gomeren von Olefinen unter Verwendung eines Oligomerisierungska- talysators, der aus einer Chromverbindung und einem 1,3,5-Triaza- cyclohexan sowie einem aktivierenden Zusatzstoff, wie einem Alkylalumoxan, erhältlich ist.WO 00/58319 describes a process for the preparation of oligomers of olefins using an oligomerization catalyst which can be obtained from a chromium compound and a 1,3,5-triazacyclohexane and an activating additive, such as an alkylalumoxane.
Die EP-A-0 537 609 beschreibt die Oligomerisierung von Ethen in Gegenwart eines Katalysators, der einen Chromkomplex mit einem mehrzähnigen Komplexliganden und ein Alkylalumoxan umfasst.EP-A-0 537 609 describes the oligomerization of ethene in the presence of a catalyst which comprises a chromium complex with a multidentate complex ligand and an alkylalumoxane.
Obgleich der Mechanismus der Olefin-Oligomerisierung an Übergangsmetallkomplexen nicht völlig geklärt ist, wird davon ausgegangen, dass bei der so genannten "Aktivierung" des Übergangsmetallkomplexes mit dem Alkylalumoxan eine Liganden-Austauschreaktion zwischen einem abstrahierbaren Liganden des Komplexes und der Alkylgruppe des Alkylalumoxans stattfindet. Es bildet sich eine katalytisch aktive Spezies, die schrittweise Olefinmoleküle anlagert. In der Koordinationssphäre des Übergangsmetallkomplexes reagieren die Olefinmoleküle zu einem Oligomeren. Durch Freisetzung des Oligomeren wird die katalytisch aktive Spezies regene- riert. Selbst bei weitgehendem Ausschluss von Verunreinigungen kommt die katalytische Aktivität des Katalysatorsystems allerdings nach einiger Zeit zum Erliegen. In der Regel wird das Katalysatorsystem dann verworfen. Das Alkylalumoxan wird meist in einem großen Überschuss, bezogen auf den Übergangsmetallkomplex, eingesetzt, um eine ausreichende Aktivierung zu erzielen. Der damit verbundene hohe Verbrauch an Alkylalumoxan stellt daher einen erheblichen Kostenfaktor für derartige Olefin-Oligomerisierungsverfahren dar.Although the mechanism of olefin oligomerization on transition metal complexes is not completely clarified, it is assumed that the so-called "activation" of the transition metal complex with the alkylalumoxane results in a ligand exchange reaction between an abstractable ligand of the complex and the alkyl group of the alkylalumoxane. A catalytically active species is formed, which gradually attaches olefin molecules. In the coordination sphere of the transition metal complex, the olefin molecules react to form an oligomer. The catalytically active species is regenerated by the release of the oligomer. Even if impurities are largely excluded, the catalytic activity of the catalyst system comes to a standstill after some time. As a rule, the catalyst system is then discarded. The alkylalumoxane is usually used in a large excess, based on the transition metal complex, in order to achieve sufficient activation. The associated high consumption of alkylalumoxane is therefore a significant cost factor for such olefin oligomerization processes.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Oligomerisierung von Olefinen bereitzustellen, bei dem man ein Olefin mit einem Katalysatorsystem in Kontakt bringt, das einen Übergangsmetallkomplex und ein Alkylalumoxan umfasst, wobei das Verfahren eine optimale Ausnutzung des Alkylalumoxans gestattet.The object of the invention is to provide a process for oligomerizing olefins, in which an olefin is brought into contact with a catalyst system which comprises a transition metal complex and an alkylalumoxane, the process allowing optimum use of the alkylalumoxane.
Erfindungsgemäß wird diese Aufgabe gelöst durch ein Verfahren zur Oligomerisierung von Olefinen, bei dem man ein Olefin mit einem Katalysatorsystem in Kontakt bringt, dasAccording to the invention, this object is achieved by a process for the oligomerization of olefins, in which an olefin is brought into contact with a catalyst system which
a) wenigstens einen Übergangsmetallkomplex mit einem mehrzähnigen Komplexliganden unda) at least one transition metal complex with a multidentate complex ligand and
b) ein Alkylalumoxan in solchen Mengen umfasst, dass das molare Verhältnis von Aluminium:Ubergangsmetall mehr als 10 beträgt, wobei man zumindest einen Teil der Menge des Übergangsmetallkomplexes im Verlauf der Oligomerisierung kontinuierlich oder portionsweise hinzufügt.b) comprises an alkylalumoxane in amounts such that the molar ratio of aluminum: transition metal is more than 10, at least part of the amount of the transition metal complex being added continuously or in portions in the course of the oligomerization.
Geeignete Alkylalumoxane sind beispielsweise bekannt aus der DE-A-3 007 725, wobei ihre Strukturen weitgehend unaufgeklärt sind. Es handelt sich um Produkte der vorsichtigen partiellen Hydrolyse von Aluminiumalkylen. Diese Produkte liegen offenbar nicht rein vor, sondern als Gemische von offenkettigen und zyklischen Strukturen des Typs Ia und Ib, die miteinander vermutlich in dynamischem Gleichgewicht stehen. Suitable alkylalumoxanes are known, for example, from DE-A-3 007 725, their structures being largely unexplained. These are products of the careful partial hydrolysis of aluminum alkyls. These products do not appear to be pure, but as mixtures of open-chain and cyclic structures of type Ia and Ib, which are probably in dynamic equilibrium with one another.
1010
Ia IbIa Ib
In den Formeln Ia und Ib sind die Gruppen R gleich oder lg verschieden und stehen unabhängig voneinander für Cι-Cι2-Alkyl, wie Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, sec-Butyl, tert-Butyl, n-Pentyl, i-Pentyl, sec-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, i-Amyl, n-Hexyl, i-Hexyl, sec-Hexyl, n-Heptyl, i-Heptyl, n-Octyl, n-Nonyl, n-Decyl undIn the formulas Ia and Ib, the groups R are the same or lg different and are independently C 1 -C 2 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl , tert-butyl, n-pentyl, i-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, i-amyl, n-hexyl, i-hexyl, sec-hexyl, n-heptyl, i-heptyl , n-octyl, n-nonyl, n-decyl and
20 n-Dodecyl; bevorzugt Ci-Cß-Alkyl wie Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, sec-Butyl, tert-Butyl, n-Pentyl, i-Pentyl, sec-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, i-Amyl, n-Hexyl, i-Hexyl. Methylalumoxan ist besonders bevorzugt, m ist eine ganze Zahl von 0 bis 40, vorzugsweise 0 bis 25 und20 n-dodecyl; preferably Ci-C ß- alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, i-pentyl, sec-pentyl, neo- Pentyl, 1,2-dimethylpropyl, i-amyl, n-hexyl, i-hexyl. Methylalumoxane is particularly preferred, m is an integer from 0 to 40, preferably 0 to 25 and
25 insbesondere 0 bis 22.25 in particular 0 to 22.
In der Literatur werden auch käfigartige Strukturen für Alumoxane diskutiert (vgl. Organometallics 1996, 15, S. 2213-26; Makromol. Sy p. 1995, 97 S. 15-25).Cage-like structures for alumoxanes are also discussed in the literature (cf. Organometallics 1996, 15, pp. 2213-26; Makromol. Sy p. 1995, 97 pp. 15-25).
3030
Ihre Eignung für die Zwecke der vorliegenden Erfindung erfüllen die Alkylalumoxane unabhängig von ihrer strukturellen Beschaffenheit.The alkylalumoxanes fulfill their suitability for the purposes of the present invention regardless of their structural nature.
35 Bei dem Übergangsmetallkomplex kann es sich um einen beliebigen Komplex handeln, der - nach Aktivierung - zur Oligomerisierung von Olefinen fähig ist. Geeignete derartige Katalysatoren sind in "Frontiers in metal-catalyzed Polymerization", Chem. Rev. April 2000, Vol. 100 Nr. 4, S. 1167-1645 beschrieben. Das Ubergangsme¬ 35 The transition metal complex can be any complex which, after activation, is capable of oligomerizing olefins. Suitable catalysts of this type are described in "Frontiers in metal-catalyzed Polymerization", Chem. Rev. April 2000, Vol. 100 No. 4, pp. 1167-1645. The transition measure
40 tall in bevorzugten Komplexen ist unter Chrom, Vanadium, Tantal und Titan ausgewählt.40 tall in preferred complexes is selected from chromium, vanadium, tantalum and titanium.
Geeignete Übergangsmetallkomplexe können durch die Formel LMeXk dargestellt werden, worin Me für ein Ubergangsmetall, vorzugs- -5 weise Cr, V oder Ti, steht, L für einen mehrzähnigen Komplexli- ganden, X für gleiche oder verschiedene Anionen steht, und k für 2 oder 3 steht.Suitable transition metal complexes can be represented by the formula k LMeX, wherein Me is a transition metal, preference - 5 as Cr, V or Ti, L represents a multidentate Komplexli- ganden, X represents the same or different anions, and k represents 2 or 3.
Der mehrzähnige Komplexligand besetzt vorzugsweise drei benach- barte Koordinationsstellen des oktaedrisch koordinierten Metallatoms. Stickstoffhaltige mehrzähnige Komplexliganden sind bevorzugt. Besonders bevorzugt sind cyclische Polyaminliganden, insbesondere solche, die ein 1,3,5-Triazacyclohexan- oder ein 1,4, 7-Triazacyclononangerüst umfassen.The multidentate complex ligand preferably occupies three adjacent coordination sites of the octahedrally coordinated metal atom. Nitrogen-containing multidentate complex ligands are preferred. Cyclic polyamine ligands are particularly preferred, in particular those which comprise a 1,3,5-triazacyclohexane or a 1,4,7-triazacyclononane skeleton.
Geeignete Komplexliganden mit einem 1,3,5-Triazacyclohexangerüst sind in der WO 00/58319 beschrieben, auf deren Offenbarung verwiesen wird. Darunter sind solche 1,3,5-Triazacyclohexane bevorzugt, deren Stickstoffatome unabhängig voneinander durch gegebenenfalls substituiertes Cι-Cι2-Alkyl, Cß-Cis-Aryl oder C -Cι5-Arylalkyl substituiert sind, z. B. durch Methyl, Ethyl, N,N-dimethylaminoethyl, n-Propyl, n-Butyl, tert-Butyl, Hexyl, Octyl, Dodecyl, 1, 1-Dimethyldodecyl oder 1-Phenylethyl.Suitable complex ligands with a 1,3,5-triazacyclohexane skeleton are described in WO 00/58319, to the disclosure of which reference is made. Among these, 1,3,5-triazacyclohexanes are preferred, the nitrogen atoms of which are independently substituted by optionally substituted C 1 -C 2 -alkyl, C ß- cis-aryl or C -C 5 arylalkyl, for. B. by methyl, ethyl, N, N-dimethylaminoethyl, n-propyl, n-butyl, tert-butyl, hexyl, octyl, dodecyl, 1, 1-dimethyldodecyl or 1-phenylethyl.
Bevorzugte 1,3,5-Triazacyclohexane sindPreferred 1,3,5-triazacyclohexanes are
1,3, 5-Tri-tert-butyl-l, 3, 5-Triazacyσlohexan,1,3,5-tri-tert-butyl-l, 3,5-triazacyσlohexane,
1,3, 5-Triethyl-l , 3 , 5-Triazacyclohexan,1,3,5-triethyl-1,5,5-triazacyclohexane,
1,3,5-Tris[ ( 1-phenylethyl) ]-l,3,5-triazacyclohexan,1,3,5-tris [(1-phenylethyl)] -l, 3,5-triazacyclohexane,
1,3, 5-Tris- [ ( 1, 1-dimethyl )dodecyl] -1 , 3 , 5-triazacyclohexan und 1 , 3-Di-n-dodecyl-5-[2-(N,N-dimethylamino)ethyl ] -1, 3 , 5-triaza- cyclohexan sowie besonders bevorzugt1,3,5-tris [(1,1-dimethyl) dodecyl] -1,3,5-triazacyclohexane and 1,3-di-n-dodecyl-5- [2- (N, N-dimethylamino) ethyl ] -1, 3, 5-triazacyclohexane and particularly preferred
1,3, 5-Tri-n-octyl-l, 3 , 5-triazacyclohexan,1,3,5-tri-n-octyl-1,5,5-triazacyclohexane,
1,3, 5-Tri-n-dodecyl-l , 3 , 5-triazacyclohexan,1,3,5-tri-n-dodecyl-l, 3,5-triazacyclohexane,
1,3, 5-Tribenzyl-l, 3 , 5-triazacyclohexan, 1,3, 5-Tris- ( 2-ethylhexyl) -1 , 3 , 5-triazacyclohexan,1,3,5-tribenzyl-1,5,5-triazacyclohexane, 1,3,5-tris- (2-ethylhexyl) -1,3,5-triazacyclohexane,
1,3, 5-Tris (2-n-propylheptyl)-1 , 3, 5-triazacyclohexan.1,3,5-tris (2-n-propylheptyl) -1,3,5-triazacyclohexane.
Geeignete 1,4,7-Triazacyclononane können an den Stickstoffatomen durch Substituenten wie den vorstehend aufgeführten substituiert sein. 1, 4, 7-Trimethyl-l, 4 , 7-triazacyclononan ist käuflich.Suitable 1,4,7-triazacyclononanes can be substituted on the nitrogen atoms by substituents such as those listed above. 1, 4, 7-trimethyl-l, 4, 7-triazacyclononane is commercially available.
Alternative mehrzähnige Komplexliganden sind Cyclopentadienyl- anionen der Formel CsH(5_U)Ru und deren benzanellierten Derivate, worin n für eine ganze Zahl von 0 bis 5 und R für Cι-C6-Alkyl, C2-C6-Alkenyl, C6-Cι0-Aryl, C7-Cι4-Aralkyl, R^P-X- oder R-^N-X- steht, wobei R1 für Cι-C6-Alkyl, Cs-Cβ-Cycloalkyl oder Cß-Cio-Aryl und X für Cι-C6-Alkylen steht. Vorzugsweise steht n für 1. Geeignete Cyclopentadienylliganden sind z. B. 2-Di(Ci-Cβ-alkyl )phosphinoethylcyclopentadienyl, 3-Di(Cι-C6-alkyl)phosphinopropylcyclopentadienyl, 2-Di (Ci-Cδ-alkyl ) aminoethylcyclopentadienyl, t-Butylcyclopentadienyl oder 2-Phenylprop-2-ylcyclopentadienyl,Alternative polydentate complex ligands are cyclopentadienyl anion of the formula CsH (5 _ U) R u and their benzo-fused derivatives, wherein 6 alkyl, C 2 -C n is an integer from 0 to 5 and R is Cι-C 6 alkenyl, C 6 -Cι 0 aryl, C 7 -Cι 4 aralkyl, R ^ R ^ PX or NX, wherein R 1 is Cι-C6 alkyl, Cs-Cβ cycloalkyl or C ß -Cio- Aryl and X represents -C 6 alkylene. N is preferably 1. Suitable cyclopentadienyl ligands are, for. B. 2-di (Ci-Cβ-alkyl) phosphinoethylcyclopentadienyl, 3-di (Cι-C 6 -alkyl) phosphinopropylcyclopentadienyl, 2-di (Ci-C δ- alkyl) aminoethylcyclopentadienyl, t-butylcyclopentadienyl or 2-phenylprop-2-ylcyclopentadienyl,
Weitere alternative mehrzähnige Komplexliganden sind Bis(N-methylimidazol-2-yl) -Verbindungen der FormelOther alternative multidentate complex ligands are bis (N-methylimidazol-2-yl) compounds of the formula
worin R2 für Wasserstoff, Cι-C6-Alkyl oder Ci-Cß-Alkoxy steht und Y für N-Methylimidazol-2-yl, R1 2P-X- oder R^N-X- steht, wobei R1 für Ci-Cβ-Alkyl, Cs-Cg-Cycloalkyl oder C6-Cχo-Alkyl und X für Ci-Cß-Alkylen steht.wherein R 2 is hydrogen, -CC 6 -alkyl or Ci-C ß -alkoxy and Y is N-methylimidazol-2-yl, R 1 2 PX- or R ^ NX-, wherein R 1 is Ci-Cβ -Alkyl, Cs-Cg-cycloalkyl or C 6 -Cχo-alkyl and X is Ci-C ß -alkylene.
Geeignete Anionen X sind insbesondere Halogen, wie Fluor, Brom, Jod und insbesondere Chlor; Tosylat, Triflat, Tetrafluoroborat, Hexafluorophosphat, Hexafluoroantimonat, Tetraphenylborat; Ci-Ciβ- Carboxylat, wie Acetat, Butyrat, Neopentanoat, Laurat, Stearat oder 2-Ethylhexanoat.Suitable anions X are in particular halogen, such as fluorine, bromine, iodine and in particular chlorine; Tosylate, triflate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraphenylborate; Ci-Ciβ-carboxylate, such as acetate, butyrate, neopentanoate, laurate, stearate or 2-ethylhexanoate.
Die Übergangsmetallkomplexe sind nach dem Fachmann bekannten Methoden oder analog zu diesen erhältlich (vgl. etwa W. A. Herrmann, A. Salzer: "Synthetic Methods of Organometallic and Inorga- nic Chemistry", Thieme Verlag, Stuttgart 1996). Geeignete Komplexe sind in der WO 00/58319 der EP-A-0 537 609, Rüther, T. et al., Organometallics 2001, 20, S. 1247-1250; Döhring A. et al., Organo etallics 2001, 20, S. 2234-2245 und Deckers P. J. W. et al., Angew. Chem. 2001, 113, Nr. 13, S. 2584-2587 beschrieben.The transition metal complexes can be obtained by methods known to those skilled in the art or analogously to these (cf., for example, W. A. Herrmann, A. Salzer: "Synthetic Methods of Organometallic and Inorganic Chemistry", Thieme Verlag, Stuttgart 1996). Suitable complexes are described in WO 00/58319 of EP-A-0 537 609, Rüther, T. et al., Organometallics 2001, 20, pp. 1247-1250; Döhring A. et al., Organo etallics 2001, 20, pp. 2234-2245 and Deckers P. J. W. et al., Angew. Chem. 2001, 113, No. 13, pp. 2584-2587.
Der Übergangsmetallkomplex und das Alkylalumoxan werden in sol- chen Mengen eingesetzt, dass sich ein molares Verhältnis von Aluminium:Ubergangsmetall von mehr als 10, z. B. 10 bis 10000, vorzugsweise 10 bis 500 einstellt. Erfindungsgemäß wird wenigstens ein Teil der eingesetzten Menge des Übergangsmetallkomplexes kontinuierlich oder portionsweise im Verlauf der Oligomerisierung hinzugefügt, d. h. nachdem Olefin, Alkylalumoxan und eine Teilmenge des Komplexes unter Bedingungen in Kontakt gebracht wurden, unter denen eine Oligomerisierung des Olefins abläuft. In der Regel wird die gesamte Menge Alkylalumoxan und eine Teilmenge des Komplexes in situ unmittelbar vor dem Einsatz in der Oligomeri- sierungsreaktion kombiniert. Das zu oligomerisierende Olefin kann ebenfalls mit vorgelegt werden und/oder zu den vereinigten Katalysatorkomponenten kontinuierlich oder portionsweise hinzugefügt werden. Alternativ kann man das Alumoxan und das Olefin vorlegen und die erste Teilmenge des Übergangsmetallkomplexes hinzufügen.The transition metal complex and the alkylalumoxane are used in such amounts that a molar ratio of aluminum: transition metal of more than 10, eg. B. 10 to 10,000, preferably 10 to 500. According to the invention, at least part of the amount of the transition metal complex used is added continuously or in portions in the course of the oligomerization, ie after olefin, alkylalumoxane and a part of the complex have been brought into contact under conditions under which oligomerization of the olefin takes place. As a rule, the entire amount of alkylalumoxane and a partial amount of the complex are combined in situ immediately before use in the oligomerization reaction. The olefin to be oligomerized can also be initially introduced and / or added continuously or in portions to the combined catalyst components become. Alternatively, you can submit the alumoxane and olefin and add the first portion of the transition metal complex.
Im Verlauf der Oligomerisierung, zweckmäßigerweise wenn die Akti- vität des Katalysatorsystems merklich schlechter wird, z. B. nach einem Zeitintervall von wenigstens 30 min oder 1 Stunde, kann eine weitere Teilmenge des Übergangsmetallkomplexes zum polymeri- sierenden System hinzugefügt werden. Dieser Vorgang kann beliebig oft wiederholt werden, solange die insgesamt im ReaktionsSystem befindliche Menge Übergangsmetallkomplex, d. h. die Summe aus vorgelegten und hinzugefügten Teilmengen, und die Menge an Alkylalumoxan ein molares Verhältnis Aluminium:Ubergangsmetall von mehr als 10 ergeben.In the course of the oligomerization, expediently if the activity of the catalyst system becomes noticeably worse, e.g. B. after a time interval of at least 30 min or 1 hour, a further subset of the transition metal complex can be added to the polymerizing system. This process can be repeated as often as long as the total amount of transition metal complex in the reaction system, i. H. the sum of the quantities added and added, and the amount of alkylalumoxane give a molar ratio aluminum: transition metal of more than 10.
In einer bevorzugten Ausführungsform legt man eine Teilmenge des Übergangsmetallkomplexes zusammen mit dem Alkylalumoxan vor und erniedrigt das molare Verhältnis Aluminium:Ubergangsmetall durch Zugabe wenigstens einer weiteren Teilmenge des Übergangsmetallkomplexes im Verlauf der Oligomerisierung auf weniger als die Hälfte des anfänglichen Wertes . Das anfängliche molare Verhältnis Aluminium:Ubergangsmetall beträgt zweckmäßigerweise mehr als 100, vorzugsweise mehr als 200, insbesondere mehr als 300. Anstelle einer portionsweisen Zugabe des Chromkomplexes kann man den Übergangsmetallkomplex auch während der Oligomerisierung kontinuier- lieh zudosieren, um beispielsweise eine hohe Katalysatoraktivität über einen längeren Zeitraum zu erhalten.In a preferred embodiment, a subset of the transition metal complex is introduced together with the alkylalumoxane and the molar ratio aluminum: transition metal is reduced to less than half of the initial value by adding at least a further subset of the transition metal complex in the course of the oligomerization. The initial molar aluminum: transition metal ratio is expediently more than 100, preferably more than 200, in particular more than 300. Instead of adding the chromium complex in portions, the transition metal complex can also be metered in continuously during the oligomerization, in order, for example, to have high catalyst activity over a longer period Period.
Durch die erfindungsgemäße Verfahrensführung ist es möglich, bei einer gegebenen eingesetzten Menge an Alumoxan eine deutlich hö- here Ausbeute an Olefinoligomer zu erhalten.By carrying out the process according to the invention, it is possible to obtain a significantly higher yield of olefin oligomer for a given amount of alumoxane used.
Das erfindungsgemäße Verfahren erfolgt in der Regel in flüssiger Phase in einem Lösungsmittel. Geeignete Lösungsmittel sind dabei aprotische Lösungsmittel, z. B. aliphatische gesättigte Kohlen- Wasserstoffe, wie Butan, Pentan, 3-Methylpentan, Hexan, Heptan, 2-Methylhexan, Octan, Cyclohexan, Methylcyclohexan, 2,2,4-Trime- thylpentan, Decalin; halogenierte Kohlenwasserstoffe, wie Di- chlorethan; aromatische Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Ethylbenzol, Mesitylen, Tetralin oder die unter Reaktions- bedingungen flüssigen oligomeren Reaktionsprodukte, wie 1-Hexen selbst eingesetzt werden. Diese Lösungsmittel können entweder einzeln oder als Gemisch verwendet werden.The process according to the invention is generally carried out in the liquid phase in a solvent. Suitable solvents are aprotic solvents, e.g. B. aliphatic saturated hydrocarbons, such as butane, pentane, 3-methylpentane, hexane, heptane, 2-methylhexane, octane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, decalin; halogenated hydrocarbons, such as dichloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, mesitylene, tetralin or the oligomeric reaction products which are liquid under the reaction conditions, such as 1-hexene itself. These solvents can be used either individually or as a mixture.
Das erfindungsgemäße Verfahren eignet sich zur Oligomerisierung, insbesondere der selektiven Trimerisierung, von Ethen. Das erfindungsgemäße Verfahren eignet sich außerdem zur Oligomerisierung, insbesondere der selektiven Trimerisierung von α-Olefinen mit we- nigstens drei, z. B. drei bis zwölf Kohlenstoffatomen, wie 1-Pro- pen, 1-Buten, 1-Hexen, 1-Decen. Als Olefin eignet sich insbesondere 1-Buten, gegebenenfalls im Gemisch mit seinen Isomeren, wie sie etwa im Raffinat II vorliegen.The process according to the invention is suitable for the oligomerization, in particular the selective trimerization, of ethene. The process according to the invention is also suitable for oligomerization, in particular the selective trimerization of α-olefins with at least three, e.g. B. three to twelve carbon atoms, such as 1-propene, 1-butene, 1-hexene, 1-decene. Particularly suitable as olefin is 1-butene, optionally in a mixture with its isomers, such as are present in raffinate II.
Wegen der Hydrolyseneigung des Alkylalumoxans wird das erfindungsgemäße Verfahren in der Regel unter weitgehendem Feuchtig- keitsausschluss durchgeführt. Vorzugsweise arbeitet man unter Schutzgas . Als Schutzgase können alle unter Reaktionsbedingungen chemisch inerten Gase, wie Stickstoff oder Argon, verwendet werden. Daneben kann das umzusetzende Olefin selbst die Funktion des Schutzgases übernehmen, sofern es unter den Reaktionsbedingungen einen hinreichend hohen Dampfdruck hat.Because of the tendency of the alkylalumoxane to hydrolyze, the process according to the invention is generally carried out with extensive exclusion of moisture. It is preferable to work under protective gas. All gases which are chemically inert under the reaction conditions, such as nitrogen or argon, can be used as protective gases. In addition, the olefin to be converted can itself take on the function of the protective gas, provided that it has a sufficiently high vapor pressure under the reaction conditions.
Die Oligomerisierung wird vorzugsweise bei einer Temperatur im Bereich von 0 bis 120 und insbesondere 25 bis 110 °C durchgeführt. Sie erfolgt bei einem Druck von ümgebungsdruck bis 120 bar.The oligomerization is preferably carried out at a temperature in the range from 0 to 120 and in particular 25 to 110 ° C. It takes place at a pressure of ambient pressure up to 120 bar.
Nach beendeter Umsetzung wird das Katalysatorsystem in der Regel desaktiviert. Als Desaktivator eignet sich beispielsweise Wasser, das gegebenenfalls angesäuert ist, oder niedere Alkohole. Die Produkte der Oligomerisierung werden zweckmäßigerweise destilla- tiv gereinigt. Nicht umgesetztes Ausgangsmaterial kann zurückgewonnen und in die Umsetzung zurückgeführt werden.After the reaction has ended, the catalyst system is generally deactivated. Suitable deactivators are, for example, water, which may be acidified, or lower alcohols. The products of the oligomerization are expediently cleaned by distillation. Unreacted raw material can be recovered and returned to the implementation.
Die Erfindung wird durch die folgenden Beispiele näher veranschaulicht.The invention is illustrated in more detail by the following examples.
Beispielexample
In einem mit Kontaktthermometer, Rührer, Heizpilz und Gaseinleitungsrohr versehenen Ein-Liter-Vierhalskolben wurde unter einer Argonatmosphäre 42,1 μmol [ ( l,3,5-Tris-n-dodecyl-l,3,5-triazacy- clohexan)CrCl3] in 250 ml Toluol bei 40 °C vorgelegt. Die Lösung wurde mit Buten gesättigt. Dann setzte man 14,74 mmol Methylalu- moxan (MAO), entsprechend einem Molverhältnis Aluminium:Chrom von 350 (in Form einer 1,6 M Lösung in Toluol) zu. Durch die nach der Zugabe des MAO erhaltene hellgrün/gelbe Lösung wurde 1-Buten geleitet. Nach einer Stunde fügte man weitere 40,2 μmol Chromkom- plex hinzu, so dass das Molverhältnis Aluminium:Chrom nun 180 betrug. Nach einer weiteren Stunde wurden nochmals 40,5 μmol Chromkomplex hinzugefügt und das Molverhältnis Aluminium:Chrom betrug dann 120. Nach insgesamt 3 Stunden wurde die Reaktion durch Zugabe von 15 ml konzentrierter Salzsäure in 50 ml Methanol beendet und die Reaktionsmischung noch 15 Minuten nachgerührt. Danach wurden 250 ml Methanol zugegeben und weitere 15 Minuten gerührt. Das Produkt wurde dreimal mit Wasser gewaschen und über Natrium- sulfat getrocknet. Die Ausbeute an Dodecen wurde gaschromatogra- phisch aus der so erhaltenen Lösung bestimmt. Es wurden insgesamt 25,8 g Dodecen gebildet.In a one-liter four-necked flask equipped with a contact thermometer, stirrer, heating element and gas inlet tube, 42.1 μmol [(1,3,5-tris-n-dodecyl-1,3,5-triazacyclohexane) CrCl 3 was added under an argon atmosphere ] presented in 250 ml of toluene at 40 ° C. The solution was saturated with butene. Then 14.74 mmol of methylaluminoxane (MAO), corresponding to an aluminum: chromium molar ratio of 350 (in the form of a 1.6 M solution in toluene), were added. 1-Butene was passed through the light green / yellow solution obtained after the addition of the MAO. After an hour, a further 40.2 μmol chromium complex was added, so that the molar ratio aluminum: chromium was now 180. After a further hour, a further 40.5 μmol of chromium complex were added and the molar ratio of aluminum: chromium was then 120. After a total of 3 hours, the reaction was terminated by adding 15 ml of concentrated hydrochloric acid in 50 ml of methanol and the reaction mixture was stirred for a further 15 minutes. Then 250 ml of methanol were added and the mixture was stirred for a further 15 minutes. The product was washed three times with water and over sodium dried sulfate. The yield of dodecene was determined by gas chromatography from the solution thus obtained. A total of 25.8 g of dodecene was formed.
VergleichsbeispielComparative example
In einem mit Kontaktthermometer, Rührer, Heizpilz und Gaseinleitungsrohr versehenen Ein-Liter-Vierhalskolben wurden 40,9 μmol [ (l,3,5-Tris-n-dodecyl-l,3,5-triazacyclohexan)CrCl3] in 250 ml To- luol bei 40 °C vorgelegt. Die Lösung wurde mit Buten gesättigt. Danach setzte man 14,32 mmol MAO, entsprechend einem Molverhältnis Aluminium:Chrom von 350 (in Form einer 1,6 M Lösung in Toluol) zu. Durch die Lösung wurde 1-Buten geleitet. Nach einer Stunde nahm die Dodecen-Produktion deutlich ab. Die Aufarbeitung erfolgte wie im vorstehenden Beispiel beschrieben. Es wurden 10,2 g Dodecen erhalten. In a one-liter four-necked flask equipped with a contact thermometer, stirrer, heating element and gas inlet tube, 40.9 μmol [(1,3,5-tris-n-dodecyl-1,3,5-triazacyclohexane) CrCl 3 ] in 250 ml To - submitted toluene at 40 ° C. The solution was saturated with butene. Then 14.32 mmol of MAO, corresponding to an aluminum: chromium molar ratio of 350 (in the form of a 1.6 M solution in toluene), were added. 1-Butene was passed through the solution. After an hour, dodecene production decreased significantly. Working up was carried out as described in the example above. 10.2 g of dodecene were obtained.

Claims

Patentansprüche claims
1. Verfahren zur Oligomerisierung von Olefinen, bei dem man ein Olefin mit einem Katalysatorsystem in Kontakt bringt, das1. A process for oligomerizing olefins, in which an olefin is brought into contact with a catalyst system which
a) wenigstens einen Übergangsmetallkomplex mit einem mehrzähnigen Komplexliganden unda) at least one transition metal complex with a multidentate complex ligand and
b) ein Alkylalumoxan in solchen Mengen umfasst, dass das molare Verhältnis von Aluminium:Ubergangsmetall mehr als 10 beträgt,b) comprises an alkylalumoxane in amounts such that the molar ratio of aluminum: transition metal is more than 10,
dadurch gekennzeichnet, dass man zumindest einen Teil der Menge des Übergangsmetallkomplexes im Verlauf der Oligomerisierung kontinuierlich oder portionsweise hinzufügt.characterized in that at least part of the amount of the transition metal complex is added continuously or in portions in the course of the oligomerization.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man eine Teilmenge des Übergangsmetallkomplexes zusammen mit dem Alkylalumoxan vorlegt und durch Zugabe wenigstens einer weiteren Teilmenge des Übergangsmetallkomplexes das molare Verhältnis Aluminium:Ubergangsmetall auf weniger als die Hälfte des anfänglichen Wertes erniedrigt.2. The method according to claim 1, characterized in that a subset of the transition metal complex is submitted together with the alkylalumoxane and by adding at least a further subset of the transition metal complex the molar ratio aluminum: transition metal is reduced to less than half of the initial value.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass das anfängliche molare Verhältnis Aluminium:Übergangsmetall mehr als 100 beträgt.3. The method according to claim 2, characterized in that the initial molar aluminum: transition metal ratio is more than 100.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es sich bei dem Ubergangsmetall um Chrom handelt.4. The method according to any one of the preceding claims, characterized in that it is chromium in the transition metal.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es sich bei dem Komplexliganden um einen mehrzähnigen stickstoffhaltigen Komplexliganden handelt.5. The method according to any one of the preceding claims, characterized in that the complex ligand is a multidentate nitrogen-containing complex ligand.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der Komplexligand ein 1, 3,5-Triazacyclohexan- oder ein6. The method according to claim 5, characterized in that the complex ligand is a 1, 3,5-triazacyclohexane or
1,4, 7-Triazacyclononan-Gerüst umfasst .1,4, 7-triazacyclononane backbone.
Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Alkylalumoxan Methylalumoxan ist. Method according to one of the preceding claims, characterized in that the alkylalumoxane is methylalumoxane.
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US7214842B2 (en) 2007-05-08
JP4086159B2 (en) 2008-05-14
AU2003227586A1 (en) 2003-10-20
KR20040097307A (en) 2004-11-17
DE10215754A1 (en) 2003-10-30
CN1646453A (en) 2005-07-27

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