EP1487764A1 - Oligomerization of olefins comprising at least three carbon atoms - Google Patents

Oligomerization of olefins comprising at least three carbon atoms

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Publication number
EP1487764A1
EP1487764A1 EP03743871A EP03743871A EP1487764A1 EP 1487764 A1 EP1487764 A1 EP 1487764A1 EP 03743871 A EP03743871 A EP 03743871A EP 03743871 A EP03743871 A EP 03743871A EP 1487764 A1 EP1487764 A1 EP 1487764A1
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Prior art keywords
alkyl
tri
aluminum
carbon atoms
olefins
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German (de)
French (fr)
Inventor
Shahram Mihan
Heiko Maas
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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
    • C07C2/26—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
    • C07C2/02—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
    • 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
    • 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

Definitions

  • the present invention relates to a process for the oligomerization of ⁇ -olefins having at least three carbon atoms.
  • 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 activated additive.
  • the radicals on the nitrogen atoms of the triazacyclohexane should preferably be ⁇ -alkyl-substituted alkyl, for example 2-ethylhexyl or 2-n-propylheptyl.
  • Preferred olefins for oligomerization are those with 2 to 10 carbon atoms.
  • WO 00/58319 illustrate the oligomerization of ethene or 1-butene.
  • a catalyst is used in which the residues on the nitrogen atoms of the triazacyclohexane have a ⁇ -alkyl branch.
  • a boron compound and an aluminum alkyl can be used as the activating additive.
  • the invention is based on the object of specifying a process mentioned at the outset which leads to olefin oligomers in high yield and preferably to defined oligomers, in particular trimers, with high selectivity.
  • this object is achieved by a process for the oligomerization of ⁇ -olefins having at least three carbon atoms, in which the olefin is brought into contact with a catalyst system which is obtainable from
  • R 1 to R 3 independently represent C 4 -C 3 o-alkyl which has no ⁇ , ⁇ or ⁇ branching
  • R A stands for an organic group having 1 to 30 carbon atoms bonded via a silicon atom or a carbon atom
  • p represents 0 to 6, preferably 0 to 3 and
  • R 1 to R 3 independently represent C 4 -C 3 o-alkyl which has no ⁇ , ⁇ or ⁇ branching; however, they may have a branch at a position farther from the nitrogen atom to which they are attached.
  • R 1 to R 3 independently represent linear CC 30 alkyl, preferably linear C 4 -C 8 alkyl, such as n-butyl, n-hexyl, n-octyl or n-dodecyl.
  • R A is, for example, Ci-Cia-alkyl, preferably -C-Ci 2 alkyl such as methyl, ethyl, n-propyl, i-propyl, butyl, pentyl, hexyl;
  • C 5 -C 7 cycloalkyl such as cyclopentyl and cyclohexyl
  • C 6 -C 5 aryl such as phenyl, methylphenyl or naphthyl
  • C 7 -C 5 arylalkyl such as
  • Trialkylsilyl groups such as trimethylsilyl. If p for
  • radicals R A are preferably arranged symmetrically, ie each carbon atom in the triazacyclohexane ring carries a radical R A.
  • Preferred ligands of the formula I are 1,3,5-tri-n-dodecyl-1,3,5-triazacyclohexane, 1,3,5-tri-n-octyl-1,5,5-triazacyclohexane, l, 3,5-tri-n-hexyl-l, 3,5-triazacyclohexane and 1,3,5-trin-butyl-l, 3,5-triazacyclohexane.
  • ligands of the formula I in which p is 0 and the radicals R 1 to R 3 are the same can be prepared in a manner known per se, in particular by reacting primary amines with formaldehyde or paraformaldehyde.
  • ligands of the formula I which carry radicals R A on the carbon atoms of the triazacyclohexane ring are composed of primary amines and corresponding aldehydes and / or Ketones available.
  • suitable production processes reference is made to WO 00/58319 and the literature cited therein. The processes described can be used analogously to the preparation of the ligands of the formula I.
  • Chromium (II) and / or preferably chromium (II) compounds are suitable as the chromium source.
  • Suitable chromium (III) compounds are in particular those of the formula CrX 3 , in which X represents an abstractable counterion, in particular halogen, such as fluorine, bromine, iodine and in particular chlorine, tosylate, triflate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraphenyIbora; Ci-cis-carboxylate, such as acetate, butyrate, neopentanoate, laurate, stearate or 2-ethylhexanoate. CrCl 3 has proven particularly useful.
  • chromium source compounds of the formula CrXL 3 , in which X has the meaning given above and L stands for a neutral complex ligand, for.
  • B. ether complexes such as CrCl 3 (tetrahydrofuran) 3 , CrCl 3 (dioxane) 3 , ester complexes such as CrCl 3 (n-butyl acetate), CrCl 3 (ethyl acetate), alcohol complexes such as CrCl 3 (i-propanol) 3 , CrCl 3 (2-ethylhexanol) 3 , amine complexes such as CrCl 3 (pyridine) 3 , CrCl 3 (i-propylamine) 3 or nitrile complexes such as CrCl 3 (acetonitrile) 3 .
  • a chromium complex can be produced from the chromium source and the ligand of the formula I by methods known per se (cf. for example WA Herrmann, A. Salzer: “Synthetic Methods of Organometallic and Inorganic Chemistry", Vol. 1, Thieme-Verlag Stuttgart, 1996) are isolated and used in the process according to the invention.
  • the chromium source and the ligand of the formula I are brought into contact in situ in the reaction medium.
  • the ligand of the formula I is generally used in at least an equimolar amount, based on the chromium source (calculated as chromium atoms).
  • an activator is furthermore used which comprises at least one boron compound.
  • the boron compound is used in an amount such that the molar ratio B: Cr is at least 5, preferably 10 to 100.
  • Suitable boron compounds are for example those of the formula BZ 3 and / or Kat® BZ 4 ®, wherein Z is an electron-withdrawing radical, preferably a phenyl radical which carries ten optionally two to five fluoro atoms, trifluoromethyl and pentafluoroethyl selected Substituen- and Kat® for a cation, preferably a tertiary or quaternary ammonium cation or a triaryl carbonium ion.
  • Preferred Z radicals are pentafluorophenyl and ⁇ 3,5-bisperfluoromethylphenyl.
  • Suitable Kat® cations are e.g. B. tritylium, tri- (-C 8 alkyl) ammonium, tetra (-C 8 alkyl) ammonium, Di (-C 4 alkyl) anilinium, di (C 4 alkyl) benzylammonium and the like.
  • Preferred boron compounds include trispentafluorophenylborane, N, N-dimethylanilinium tetrakispentafluorophenylborate, tri-n-butylammonium tetrakispentafluorophenylborate,, N-dimethylanilinium tetrakis (3,5-bisperfluoromethyl) -phenyl n-butylammonium tetrakis (3, 5-bisperu luormethyl) phenylborate and tritylium tetrakispentafluorophenylborate are selected.
  • tritylium tetrakispentafluorophenylborate trispentafluorophenylborane and in particular dimethylanilinium tetrakis (pentafluorophenyl) borate are particularly preferred.
  • the activator generally contains a metal compound with at least one metal-carbon bond, which are collectively referred to as "metal alkyl compounds" for the purposes of the present application.
  • metal alkyl compounds are alkyl aluminum compounds, alkyl magnesium compounds, alkyl zinc compounds and / or alkyl lithium compounds. Of these, alkyl aluminum compounds are preferred.
  • R and R ' are independently methyl, ethyl or a straight-chain or branched C 3 - C 8 alkyl group and R 'can also stand for aryl, such as phenyl, and Hai stands for a halogen atom, such as fluorine, bromine, iodine or especially chlorine.
  • Representative compounds are trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum ethoxide, diethyl aluminum aluminum phenoxy and ethyl aluminum aluminum oxide.
  • the activator comprises an aluminum trialkyl, such as trimethyl aluminum, triethyl aluminum, trin-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum or tri-iso-butyl aluminum, and an alkyl aluminum, such as diethyl aluminum or diethyl aluminum bromide.
  • the molar ratio of trialkyl aluminum and alkyl aluminum halide is preferably 1 to 50: 1, in particular 3 to 20: 1.
  • the molar ratio of chromium source and metal alkyl compound, in particular alkyl aluminum compound, is usually 1: 1 to 1: 200, preferably 1: 5 to 1: 100.
  • Suitable solvents are aprotic solvents, e.g. B. aliphatic saturated coal Hydrogen 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 or tetralin.
  • aliphatic saturated coal Hydrogen such as butane, pentane, 3-methylpentane, hexane, heptane, 2-methylhexane, octane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, decalin
  • the process according to the invention is suitable for oligomerization, in particular selective tri erization, of ⁇ -olefins having at least 3 to preferably 10 carbon atoms, such as 1-propene, 1-butene, 1-hexene or 1-decene.
  • ⁇ -olefins having at least 3 to preferably 10 carbon atoms, such as 1-propene, 1-butene, 1-hexene or 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 the 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 usually 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 oligomerization products are expediently purified by distillation. Unreacted raw material can be recovered and returned to the implementation.
  • Example 4 In a 1 1 four-necked flask equipped with a contact thermometer, stirrer, heating element and gas inlet tube, the amount [(1,3,5-tri-n-dodecyl-l, 3,5-triazacyclohexane) CrCT 3 ] (Examples 1-3) or [(1,3,5-tris- (2-ethylhexyl) -1,3,5-triazacyclohexane) CrCl 3 ] (Example 4, corresponds to Example 21 of WO 00/58319) presented in 250 ml of toluene at 40 ° C.
  • DMAB Dimethylanilinium tetrakis (pentafluorophenyl) borate
  • TIBAL triisobutylaluminum
  • DEC diethylaluminum chloride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a method for the oligomerization of α-olefins comprising at least 3 carbon atoms. According to said method, the olefin is brought into contact with a catalyst system, which can be obtained from a chromium source, a 1,3,5-trialkyl-1,3,5-triazacyclohexane, in which the alkyl group does not comprise an α-, β-, or η-branch and from at least one activator comprising a boron compound, the molar ratio B:Cr being at least 5. The method permits the production of trimers of the α-olefins with a high yield and a high degree of selectivity.

Description

Oligomerisierung von Olefinen mit wenigstens drei KohlenstoffatomenOligomerization of olefins with at least three carbon atoms
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Oligomerisierung von α-Olefinen mit wenigstens drei Kohlenstoffatomen.The present invention relates to a process for the oligomerization of α-olefins having at least three carbon atoms.
Olefinoligomere mit bis zu 30 Kohlenstoffatomen 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 aktivierten Zusatzstoff erhältlich ist. Gemäß der WO 00/58319 soll es sich bei den Resten an den Stickstoffatomen des Triazacyclohexans vorzugsweise um ß-Alkyl-substi- tuiertes Alkyl, beispielsweise 2-Ethylhexyl oder 2-n-Propylheptyl handeln. Bevorzugte Olefine für die Oligomerisierung sind solche mit 2 bis 10 Kohlenstoffatomen. In den Ausführungsbeispielen der WO 00/58319 ist die Oligomerisierung von Ethen bzw. von 1-Buten veranschaulicht. In sämtlichen Beispielen, in denen 1-Buten eingesetzt wird, wird ein Katalysator verwendet, in dem die Reste an den Stickstoffatomen des Triazacyclohexans eine ß-Alkylverzweigung aufweisen. Gemäß der WO 00/58319 kann man als aktivierenden Zusatzstoff eine Borverbindung und ein Aluminiumalkyl verwenden.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 activated additive. According to WO 00/58319, the radicals on the nitrogen atoms of the triazacyclohexane should preferably be β-alkyl-substituted alkyl, for example 2-ethylhexyl or 2-n-propylheptyl. Preferred olefins for oligomerization are those with 2 to 10 carbon atoms. The exemplary embodiments of WO 00/58319 illustrate the oligomerization of ethene or 1-butene. In all examples in which 1-butene is used, a catalyst is used in which the residues on the nitrogen atoms of the triazacyclohexane have a β-alkyl branch. According to WO 00/58319, a boron compound and an aluminum alkyl can be used as the activating additive.
Der Erfindung liegt die Aufgabe zu Grunde, ein eingangs genanntes Verfahren anzugeben, das mit hoher Ausbeute zu Olefinoligomeren und vorzugsweise mit hoher Selektivität zu definierten Oligome- ren, insbesondere Trimeren, führt.The invention is based on the object of specifying a process mentioned at the outset which leads to olefin oligomers in high yield and preferably to defined oligomers, in particular trimers, with high selectivity.
Erfindungsgemäß wird diese Aufgabe gelöst durch ein Verfahren zur Oligomerisierung von α-Olefinen mit wenigstens drei Kohlenstoffatomen, bei dem man das Olefin mit einem Katalysatorsystem in Kontakt bringt, das erhältlich ist ausAccording to the invention, this object is achieved by a process for the oligomerization of α-olefins having at least three carbon atoms, in which the olefin is brought into contact with a catalyst system which is obtainable from
a) wenigstens einer Chromquelle,a) at least one chromium source,
b) wenigstens einem Liganden der Formel I b) at least one ligand of the formula I.
worin R1 bis R3 unabhängig für C4-C3o-Alkyl stehen, das keine α-, ß- oder γ-Verzweigung aufweist,where R 1 to R 3 independently represent C 4 -C 3 o-alkyl which has no α, β or γ branching,
RA für eine über ein Siliziumatom oder ein Kohlenstoffatom gebundene organische Gruppe mit 1 bis 30 Kohlenstoffatomen steht, undR A stands for an organic group having 1 to 30 carbon atoms bonded via a silicon atom or a carbon atom, and
p für 0 bis 6 steht, vorzugsweise 0 bis 3 undp represents 0 to 6, preferably 0 to 3 and
c) wenigstens einem eine Borverbindung umfassenden Aktivator, wobei das molare Verhältnis B:Cr mindestens 5 beträgt.c) at least one activator comprising a boron compound, the molar ratio B: Cr being at least 5.
Die Reste R1 bis R3 stehen unabhängig für C4-C3o-Alkyl, das keine α-, ß- oder γ-Verzweigung aufweist; sie können jedoch an einer vom Stickstoffatom, an das sie gebunden sind, weiter entfernten Position eine Verzweigung aufweisen. Vorzugsweise stehen R1 bis R3 unabhängig für lineares C-C30-Alkyl, vorzugsweise lineares C4-Cι8-Alkyl, wie n-Butyl, n-Hexyl, n-Octyl oder n-Dodecyl.The radicals R 1 to R 3 independently represent C 4 -C 3 o-alkyl which has no α, β or γ branching; however, they may have a branch at a position farther from the nitrogen atom to which they are attached. Preferably R 1 to R 3 independently represent linear CC 30 alkyl, preferably linear C 4 -C 8 alkyl, such as n-butyl, n-hexyl, n-octyl or n-dodecyl.
RA steht beispielsweise für Ci-Cia-Alkyl, vorzugsweise Cι-Ci2-Alkyl wie Methyl, Ethyl, n-Propyl, i-Propyl, Butyl, Pentyl, Hexyl;R A is, for example, Ci-Cia-alkyl, preferably -C-Ci 2 alkyl such as methyl, ethyl, n-propyl, i-propyl, butyl, pentyl, hexyl;
C5-C7-Cycloalkyl, wie Cyclopentyl und Cyclohexyl; C6-Cι5-Aryl, wie Phenyl, Methylphenyl oder Naphthyl; oder C7-Cι5-Arylalkyl, wieC 5 -C 7 cycloalkyl such as cyclopentyl and cyclohexyl; C 6 -C 5 aryl, such as phenyl, methylphenyl or naphthyl; or C 7 -C 5 arylalkyl, such as
Benzyl. Als über ein Siliziumatom gebundene Reste RA kommen z. B.Benzyl. As radicals R A bonded via a silicon atom, z. B.
Trialkylsilylgruppen, wie Trimethylsilyl, in Betracht. Wenn p fürTrialkylsilyl groups, such as trimethylsilyl. If p for
3 steht, sind die Reste RA vorzugsweise symmetrisch angeordnet, d. h. jedes Kohlenstoffatom im Triazacyclohexanring trägt einen Rest RA.3, the radicals R A are preferably arranged symmetrically, ie each carbon atom in the triazacyclohexane ring carries a radical R A.
Bevorzugte Liganden der Formel I sind 1,3,5-Tri-n-dode- cyl-1 , 3 , 5-triazacyclohexan, 1,3, 5-Tri-n-octyl-l, 3 , 5-triazacyclo- hexan, l,3,5-Tri-n-hexyl-l,3,5-triazacyclohexan und 1,3,5-Tri- n-butyl-l,3,5-triazacyclohexan.Preferred ligands of the formula I are 1,3,5-tri-n-dodecyl-1,3,5-triazacyclohexane, 1,3,5-tri-n-octyl-1,5,5-triazacyclohexane, l, 3,5-tri-n-hexyl-l, 3,5-triazacyclohexane and 1,3,5-trin-butyl-l, 3,5-triazacyclohexane.
Die Liganden der Formel I, in denen p für 0 steht und die Reste R1 bis R3 gleich sind, lassen sich in an sich bekannter Weise herstellen, insbesondere durch Umsetzung primärer Amine mit Formal- dehyd oder Paraformaldehyd. Entsprechend sind Liganden der Formel I, die an den Kohlenstoffatomen des Triazacyclohexanrings Reste RA tragen, aus primären Aminen und entsprechenden Aldehyden und/oder Ketonen erhältlich. Bezüglich geeigneter Herstellungsverfahren wird auf die WO 00/58319 und die darin zitierte Literatur verwiesen. Die beschriebenen Verfahren können analog zur Herstellung der Liganden der Formel I herangezogen werden.The ligands of the formula I in which p is 0 and the radicals R 1 to R 3 are the same can be prepared in a manner known per se, in particular by reacting primary amines with formaldehyde or paraformaldehyde. Correspondingly, ligands of the formula I which carry radicals R A on the carbon atoms of the triazacyclohexane ring are composed of primary amines and corresponding aldehydes and / or Ketones available. With regard to suitable production processes, reference is made to WO 00/58319 and the literature cited therein. The processes described can be used analogously to the preparation of the ligands of the formula I.
Als Chromquelle eignen sich Chrom(II)- und/oder vorzugsweise Chrom( II) -Verbindungen. Geeignete Chrom(III) -Verbindungen sind insbesondere solche der Formel CrX3, worin X für ein abstrahierbares Gegenion steht, insbesondere Halogen, wie Fluor, Brom, Iod und insbesondere Chlor, Tosylat, Triflat, Tetrafluoroborat, Hexa- fluorophosphat, Hexafluoroantimonat, TetraphenyIbora ; Ci-Cis-Car- boxylat, wie Acetat, Butyrat, Neopentanoat, Laurat, Stearat oder 2-Ethylhexanoat. CrCl3 hat sich besonders bewährt.Chromium (II) and / or preferably chromium (II) compounds are suitable as the chromium source. Suitable chromium (III) compounds are in particular those of the formula CrX 3 , in which X represents an abstractable counterion, in particular halogen, such as fluorine, bromine, iodine and in particular chlorine, tosylate, triflate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraphenyIbora; Ci-cis-carboxylate, such as acetate, butyrate, neopentanoate, laurate, stearate or 2-ethylhexanoate. CrCl 3 has proven particularly useful.
Als Chromquelle eignen sich auch Verbindungen der Formel CrXL3, worin X die oben angegebenen Bedeutung hat und L für einen neutralen Komplexliganden steht, z. B. Etherkomplexe wie CrCl3(Tetra- hydrofuran)3, CrCl3(Dioxan)3, Esterkomplexe wie CrCl3 (n-Butylace- tat), CrCl3(Ethylacetat) , Alkoholkomplexe wie CrCl3(i-Propanol)3, CrCl3(2-Ethylhexanol)3, Aminkomplexe wie CrCl3(Pyridin)3, CrCl3(i- Propylamin)3 oder Nitrilkomplexe wie CrCl3(Acetonitril)3.Also suitable as a chromium source are compounds of the formula CrXL 3 , in which X has the meaning given above and L stands for a neutral complex ligand, for. B. ether complexes such as CrCl 3 (tetrahydrofuran) 3 , CrCl 3 (dioxane) 3 , ester complexes such as CrCl 3 (n-butyl acetate), CrCl 3 (ethyl acetate), alcohol complexes such as CrCl 3 (i-propanol) 3 , CrCl 3 (2-ethylhexanol) 3 , amine complexes such as CrCl 3 (pyridine) 3 , CrCl 3 (i-propylamine) 3 or nitrile complexes such as CrCl 3 (acetonitrile) 3 .
Aus der Chromquelle und dem Liganden der Formel I kann nach an sich bekannten Methoden (vgl. etwa W. A. Herrmann, A. Salzer: "Synthetic Methods of Organometallic and Anorganic Chemistry", Vol. 1, Thieme-Verlag Stuttgart, 1996) ein Chromkomplex hergestellt werden, der isoliert und im erfindungsgemäßen Verfahren eingesetzt wird. Alternativ bringt man die Chromquelle und den Liganden der Formel I in situ im Reaktionsmedium in Kontakt. Der Ligand der Formel I wird in der Regel in wenigstens äquimolarer Menge, bezogen auf die Chromquelle (gerechnet als Chromatome), eingesetzt.A chromium complex can be produced from the chromium source and the ligand of the formula I by methods known per se (cf. for example WA Herrmann, A. Salzer: "Synthetic Methods of Organometallic and Inorganic Chemistry", Vol. 1, Thieme-Verlag Stuttgart, 1996) are isolated and used in the process according to the invention. Alternatively, the chromium source and the ligand of the formula I are brought into contact in situ in the reaction medium. The ligand of the formula I is generally used in at least an equimolar amount, based on the chromium source (calculated as chromium atoms).
Erfindungsgemäß wird weiterhin ein Aktivator verwendet, der we- nigstens eine Borverbindung umfasst. Die Borverbindung wird in einer Menge eingesetzt, dass das molare Verhältnis B:Cr mindestens 5, vorzugsweise 10 bis 100, beträgt. Geeignete Borverbindungen sind beispielsweise solche der Formel BZ3 und/oder Kat® BZ4®, worin Z für einen elektronenziehenden Rest, vorzugsweise einen Phenylrest, der gegebenenfalls zwei bis fünf unter Fluoratomen, Trifluormethyl und Pentafluorethyl ausgewählte Substituen- ten trägt, und Kat® für ein Kation, vorzugsweise ein tertiäres oder quaternäres Ammoniumkation oder ein Triarylcarboniu ion, steht. Bevorzugte Reste Z sind Pentafluorphenyl und~3,5-Bisper- fluormethyl-phenyl . Geeignete Kationen Kat® sind z. B. Tritylium, Tri- (Cι-C8-alkyl ) ammonium, Tetra- (Cι-C8-alkyl) ammonium, Di ( Cι-C4-alkyl ) anilinium, Di (Cι-C4-alkyl ) benzylammonium und dergleichen .According to the invention, an activator is furthermore used which comprises at least one boron compound. The boron compound is used in an amount such that the molar ratio B: Cr is at least 5, preferably 10 to 100. Suitable boron compounds are for example those of the formula BZ 3 and / or Kat® BZ 4 ®, wherein Z is an electron-withdrawing radical, preferably a phenyl radical which carries ten optionally two to five fluoro atoms, trifluoromethyl and pentafluoroethyl selected Substituen- and Kat® for a cation, preferably a tertiary or quaternary ammonium cation or a triaryl carbonium ion. Preferred Z radicals are pentafluorophenyl and ~ 3,5-bisperfluoromethylphenyl. Suitable Kat® cations are e.g. B. tritylium, tri- (-C 8 alkyl) ammonium, tetra (-C 8 alkyl) ammonium, Di (-C 4 alkyl) anilinium, di (C 4 alkyl) benzylammonium and the like.
Bevorzugte Borverbindungen sind unter Trispentaf luorphenylboran, N , N-Dimethylanilinium-tetrakispentaf luorpheny lborat , Tri-n-bu- tylammonium-tetrakispentaf luorpheny lborat , , N-Dimethylanilinium- tetrakis- ( 3 , 5-bisperf luormethyl ) -pheny lborat , Tri-n-butylammo- nium-tetrakis- ( 3 , 5-bisperf luormethyl ) -pheny lborat und Tritylium- tetrakispentaf luorpheny lborat ausgewählt . Davon sind Tritylium- tetrakispentaf luorpheny lborat , Trispentaf luorphenylboran und insbesondere Dimethylanilinium-tetrakis- (pentaf luorphenyl ) -borat besonders bevorzugt .Preferred boron compounds include trispentafluorophenylborane, N, N-dimethylanilinium tetrakispentafluorophenylborate, tri-n-butylammonium tetrakispentafluorophenylborate,, N-dimethylanilinium tetrakis (3,5-bisperfluoromethyl) -phenyl n-butylammonium tetrakis (3, 5-bisperu luormethyl) phenylborate and tritylium tetrakispentafluorophenylborate are selected. Of these, tritylium tetrakispentafluorophenylborate, trispentafluorophenylborane and in particular dimethylanilinium tetrakis (pentafluorophenyl) borate are particularly preferred.
Neben der Borverbindung enthält der Aktivator in der Regel eine Metallverbindung mit wenigstens einer Metall-Kohlenstof f -Bindung, die für die Zwecke der vorliegenden Anmeldung kollektiv als "Me- tallalkylverbindungen" bezeichnet werden . Repräsentative Me- tallalkylverbindungen sind Alkylalu iniumverbindungen, Alkyl- magnesiumverbindungen, Alkylzinkverbindungen und/oder Alkylli- thiumverbindungen. Davon sind Alkylaluminiumverbindungen bevorzugt . Sie können die Formeln AlR3 , AlR2Hal , AlRHal2 , AlR2OR' , Al- RHalOR' oder Al2R3Hal3 aufweisen, worin R und R' unabhängig für Methyl , Ethyl oder eine geradkettige oder verzweigte C3-C8-Alkyl- gruppe stehen und R' auch für Aryl , wie Phenyl , stehen kann und Hai für ein Halogenatom, wie Fluor, Brom, Iod oder insbesondere Chlor steht . Repräsentative Verbindungen sind Trimethylaluminium, Triethylaluminium, Tri-n-propylaluminium, Tri-iso-propylalumi- nium, Tri-n-butylaluminium, Triisobutylaluminium, Diethylalumi- niumchlorid, Diethylaluminiumbromid, Diethylaluminiumethoxid, Diethylaluminiumphenoxid und Ethylaluminiumethoxyf luorid.In addition to the boron compound, the activator generally contains a metal compound with at least one metal-carbon bond, which are collectively referred to as "metal alkyl compounds" for the purposes of the present application. Representative metal alkyl compounds are alkyl aluminum compounds, alkyl magnesium compounds, alkyl zinc compounds and / or alkyl lithium compounds. Of these, alkyl aluminum compounds are preferred. They can have the formulas AlR 3 , AlR 2 Hal, AlRHal 2 , AlR 2 OR ', Al-RHalOR' or Al 2 R 3 Hal 3 , where R and R 'are independently methyl, ethyl or a straight-chain or branched C 3 - C 8 alkyl group and R 'can also stand for aryl, such as phenyl, and Hai stands for a halogen atom, such as fluorine, bromine, iodine or especially chlorine. Representative compounds are trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum ethoxide, diethyl aluminum aluminum phenoxy and ethyl aluminum aluminum oxide.
In bevorzugten Aus führungs formen umfasst der Aktivator ein Alumi- niumtrialkyl , wie Trimethylaluminium, Triethylaluminium, Tri- n-propylaluminium, Tri-iso-propylaluminium, Tri-n-butylaluminium oder Tri-iso-butylaluminium, und ein AlkylaluminiumhiäTögeήid, wie Diethylaluminiumchlorid, Ethylaluminiumdichlorid oder Diethylaluminiumbromid . Das molare Verhältnis von Trialkylaluminium und Alkylaluminiumhalogenid beträgt vorzugsweise 1 bis 50 : 1 , insbesondere 3 bis 20 : 1 .In preferred embodiments, the activator comprises an aluminum trialkyl, such as trimethyl aluminum, triethyl aluminum, trin-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum or tri-iso-butyl aluminum, and an alkyl aluminum, such as diethyl aluminum or diethyl aluminum bromide. The molar ratio of trialkyl aluminum and alkyl aluminum halide is preferably 1 to 50: 1, in particular 3 to 20: 1.
Das molare Verhältnis von Chromquelle und Metallalkylverbindung, insbesondere Alkylaluminiumverbindung, beträgt üblicherweise 1:1 bis 1:200, vorzugsweise 1:5 bis 1:100.The molar ratio of chromium source and metal alkyl compound, in particular alkyl aluminum compound, is usually 1: 1 to 1: 200, preferably 1: 5 to 1: 100.
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, Dekalin; halogenierte Kohlenwasserstoffe, wie Dichlo- rethan; aromatische Kohlenwasserstoffe, wie Benzol, Toluol, Xy- lol, Ethylbenzol, Mesitylen oder Tetralin.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 coal Hydrogen 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 or tetralin.
Das erfindungsgemäße Verfahren eignet sich zur Oligomerisierung, insbesondere der selektiven Tri erisierung, von α-Olefinen mit wenigstens 3 bis vorzugsweise 10 Kohlenstoffatomen, wie 1-Propen, 1-Buten, 1-Hexen oder 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 oligomerization, in particular selective tri erization, of α-olefins having at least 3 to preferably 10 carbon atoms, such as 1-propene, 1-butene, 1-hexene or 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 der als Aktivatoren eingesetzten Me- tallalkylverbindungen wird das erfindungsgemäße Verfahren in der Regel unter weitgehendem Feuchtigkeitsausschluss 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 towards hydrolysis of the metal alkyl compounds used as activators, the process according to the invention is generally carried out with the 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 in der Regel bei einem Druck von Umgebungsdruck 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 usually 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 destillativ 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 oligomerization products are expediently purified 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.
BeispieleExamples
In einem mit Kontaktthermometer, Rührer, Heizpilz und Gaseinleitungsrohr versehenen 1 1-Vierhalskolben wurde unter Argon die in der nachstehenden Tabelle angegebenen Menge [ ( 1,3,5-Tri-n-dode- cyl-l,3,5-triazacyclohexan)CrCT3] (Beispiele 1 - 3) bzw. [ ( l,3,5-Tris-(2-ethylhexyl)-l,3,5-triazacyclohexan)CrCl3] (Beispiel 4, entspricht Beispiel 21 der WO 00/58319) in 250 ml Toluol bei 40 °C vorgelegt. Man gab die in der Tabelle angegebene Menge Dimethylanilinium-tetrakis- (pentafluorophenyl)-borat (DMAB) hinzu, erhitzte die Reaktionsmischung auf 70 °C, kühlte auf 40 °C ab und fügte die angegebenen Mengen Triisobutylaluminium (TIBAL) und Diethylaluminiumchlorid (DEAC) hinzu.In a 1 1 four-necked flask equipped with a contact thermometer, stirrer, heating element and gas inlet tube, the amount [(1,3,5-tri-n-dodecyl-l, 3,5-triazacyclohexane) CrCT 3 ] (Examples 1-3) or [(1,3,5-tris- (2-ethylhexyl) -1,3,5-triazacyclohexane) CrCl 3 ] (Example 4, corresponds to Example 21 of WO 00/58319) presented in 250 ml of toluene at 40 ° C. The amount given in the table was given Dimethylanilinium tetrakis (pentafluorophenyl) borate (DMAB), heated the reaction mixture to 70 ° C, cooled to 40 ° C and added the indicated amounts of triisobutylaluminum (TIBAL) and diethylaluminum chloride (DEAC).
Durch die erhaltene hellgrün/gelbe Lösung wurde 1-Buten geleitet. Die Temperatur wurde bei 40 °C gehalten. Nach einer Stunde 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. Nach Abfiltrieren wurde das Produkt dreimal mit Wasser gewaschen und über Natriumsulfat getrocknet. Die Ausbeute an Dodecen wurde gaschromatographisch aus der so erhaltenen Lösung bestimmt.1-Butene was passed through the light green / yellow solution obtained. The temperature was kept at 40 ° C. After one hour, 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. After filtering off, the product was washed three times with water and dried over sodium sulfate. The yield of dodecene was determined by gas chromatography from the solution thus obtained.
Tabelletable
* Molverhältnis B:Cr ** Molverhältnis Al:Cr *** Vergleichsbeispiele * Molar ratio B: Cr ** Molar ratio Al: Cr *** Comparative examples

Claims

Patentansprücheclaims
8. Verfahren zur Oligomerisierung von α-Olefinen mit wenigstens 5 drei Kohlenstoffatomen, bei dem man das Olefin mit einem Katalysatorsystem in Kontakt bringt, das erhältlich ist aus8. A process for the oligomerization of α-olefins having at least 5 three carbon atoms, in which the olefin is brought into contact with a catalyst system which is obtainable from
a) wenigstens einer Chromquelle,a) at least one chromium source,
10 b) wenigstens einem Liganden der Formel I10 b) at least one ligand of the formula I.
worin R1 bis R3 unabhängig für C4-C3o-Alkyl stehen, das 20 keine α-, ß- oder γ-Verzweigung aufweist,where R 1 to R 3 independently represent C 4 -C 3 o-alkyl which 20 has no α, β or γ branching,
RA für eine über ein Siliziumatom oder ein Kohlenstoffatom gebundene organische Gruppe mit 1 bis 30 Kohlenstoffatomen steht, undR A stands for an organic group having 1 to 30 carbon atoms bonded via a silicon atom or a carbon atom, and
25 p für 0 bis 6 steht, und25 p represents 0 to 6, and
c) wenigstens einem eine Borverbindung umfassenden Aktivator, wobei das molare Verhältnis B:Cr mindestens 5 be- 30 trägt.c) at least one activator comprising a boron compound, the molar ratio B: Cr being at least 5.
9. Verfahren nach Anspruch 1, wobei der Aktivator zusätzlich eine Alkylaluminiumverbindung umfasst.9. The method of claim 1, wherein the activator additionally comprises an alkyl aluminum compound.
35 10. Verfahren nach Anspruch 2, wobei der Aktivator ein Aluminium- trialkyl und ein Alkylaluminiumhalogenid umfasst.35 10. The method of claim 2, wherein the activator comprises an aluminum trialkyl and an alkyl aluminum halide.
11. Verfahren nach einem der vorhergehenden Ansprüche, wobei man als Ligand l,3,5-Tri-n-dodecyl-l,3,5-triazacyclohexan verwen-11. The method according to any one of the preceding claims, wherein the ligand used is l, 3,5-tri-n-dodecyl-l, 3,5-triazacyclohexane
40 det.40 det.
12. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Borverbindung die Formel BZ3 und/oder Kat® BZ4® aufweist, worin Z für einen elektronenziehenden Rest und Kat® für ein12. The method according to any one of the preceding claims, wherein the boron compound has the formula BZ 3 and / or Kat® BZ 4 ®, wherein Z for an electron-withdrawing radical and Kat® for a
45 Kation steht. 45 cation stands.
13. Verfahren nach Anspruch 5, wobei die Borverbindung unter Trispentafluorphenylboran, N,N-Dimethylanilinium-tetrakispen- tafluorphenylborat, Tri-n-butylammonium-tetrakispentafluorphenylborat, N,N-Dimethylanilinium-tetrakis- ( 3 , 5-bisperfluor- methyl) -phenylborat, Tri-n-butylammonium-tetrakis-(3,5-bis- perfluormethyl) -phenylborat und Tritylium-tetrakispentafluorphenylborat ausgewählt ist.13. The method according to claim 5, wherein the boron compound among trispentafluorophenylborane, N, N-dimethylanilinium tetrakispenetafluorophenylborate, tri-n-butylammonium tetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakis (3, 5-bisperfluoromethyl) phenol , Tri-n-butylammonium tetrakis (3,5-bis-perfluoromethyl) phenylborate and tritylium tetrakispentafluorophenylborate is selected.
14. Verfahren nach einem der vorhergehenden Ansprüche, wobei man als Olefin 1-Buten einsetzt. 14. The method according to any one of the preceding claims, wherein 1-butene is used as olefin.
EP03743871A 2002-03-14 2003-03-11 Oligomerization of olefins comprising at least three carbon atoms Withdrawn EP1487764A1 (en)

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