WO2000058319A1 - Catalyseur d'oligomerisation - Google Patents

Catalyseur d'oligomerisation Download PDF

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Publication number
WO2000058319A1
WO2000058319A1 PCT/EP2000/002660 EP0002660W WO0058319A1 WO 2000058319 A1 WO2000058319 A1 WO 2000058319A1 EP 0002660 W EP0002660 W EP 0002660W WO 0058319 A1 WO0058319 A1 WO 0058319A1
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triazacyclohexane
groups
alkyl
independently
chromium
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PCT/EP2000/002660
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German (de)
English (en)
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Heiko Maas
Shahram Mihan
Randolf KÖHN
Guido Seifert
Jürgen Tropsch
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Basf Aktiengesellschaft
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Priority to EP00920583A priority Critical patent/EP1171445B1/fr
Priority to US09/937,815 priority patent/US6844290B1/en
Priority to AT00920583T priority patent/ATE258184T1/de
Priority to JP2000608019A priority patent/JP2002539945A/ja
Priority to DE50005086T priority patent/DE50005086D1/de
Publication of WO2000058319A1 publication Critical patent/WO2000058319A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
    • 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
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • 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
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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 an oligomerization catalyst for olefins obtainable from
  • groups R 1 to R 9 independently of one another have the following meanings: hydrogen or Si-organic or optionally substituted C-organic groups with 1 to 30 C atoms, two geminal or vicinal radicals R 1 to R 9 also forming a five - Or six-membered ring can be connected and
  • the present invention relates to a process for the preparation of oligomers of olefins using the new catalysts, the oligomers thus obtainable and the oxo alcohols obtainable from these oligomers.
  • Olefin oligomers with up to 30 carbon atoms are of great economic importance as copolymers for plastics (eg 1-hexene) or as precursors for oxo alcohols (eg 1-hexene and the decenes and tetradecenes), the latter in turn being a component of surfactants and plasticizers for plastics.
  • the oligomerization processes are a key step from the large-scale olefin streams, which originate from steam crackers, to everyday products.
  • catalysts which contain compounds of chromium, amines and aluminum compounds in the oligomerization of ⁇ -olefins is generally known: According to EP-A 780 353, olefins can be oligomerized, especially trimerized, in the presence of a chromium source, a pyrrole-containing compound and a metal alkyl. However, the preparation of the catalyst is accompanied by a loss of active 5 components.
  • DE-A 196 07 888 discloses an oligomerization catalyst for ⁇ -olefins which, in addition to a chromium compound and an aluminum compound, also contains at least one nitrogen-containing compound, which can be a pyrrole.
  • the catalyst preparation according to EP-A 780 353 is lossy.
  • EP-A 537 609 teaches a process in which ethylene in the presence of a chromium complex with a coordinating polydentate
  • the present invention was therefore based on the object of obtaining inexpensive and stable catalysts with improved activity and selectivity with regard to low-molecular oligomers of olefins.
  • oligomers of olefins can be obtained in high yields and with a low proportion of by-products, the molecular weight M w of which is greater than 45,500.
  • the catalyst is characterized high selectivity with regard to the trimerization of ⁇ -olefins and especially of ethene.
  • Triazacyclohexane and its derivatives which differ in their substitution patterns on the ring atoms, have been known for a long time and are used in a variety of technical ways, since they can usually be prepared in a simple and inexpensive manner from readily available starting materials.
  • triazacyclohexane derivatives are used in the desulfurization of kerosene.
  • the use of triazacyclohexane and its derivatives as ligands in the preparation of organometallic complexes is hardly widespread. Complexes with these ligands are described only occasionally in the organometallic literature, for example in J. Chem. Soc, Dalton Trans. (1997), 1363-1368; Z.
  • the properties of the catalyst according to the invention can be influenced by varying the substituents on the 1,3,5-triazacyclohexane ring.
  • the catalyst activity can normally be increased by substituents, especially on the nitrogen atoms.
  • the accessibility of the central atom for the ⁇ -olefins to be converted and thus also the selectivity of the reaction with respect to various starting olefins can be controlled by the number and geometry of the substituents.
  • the chemical structure of the substituents R 1 to R 9 can therefore be varied within wide limits in order to obtain a catalyst which is tailored to the particular reaction.
  • 1, 3, 5-triazacyclohexane ring can be considered, for example:
  • Cis alkyl preferably Ci to C ⁇ 2 alkyl such as methyl, ethyl, N, N-dimethylaminoethyl, n-propyl, i-propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, Decyl, dodecyl, 1,1 -dirnethyldodecyl,
  • cycloalkyl which in turn can carry a Ci " to Cio-aryl group as a substituent, such as cyclopentyl and cyclohexyl,
  • aryl such as phenyl, o-tolyl, p-tolyl, m-tolyl, 1-naphthyl and 2-naphthyl or C 6 - to Cis-arylalkyl, preferably C 6 - to Cs-arylalkyl such as benzyl and (1 - phenyl) ethyl.
  • Suitable organic silicon groups are: trialkylsilyl groups having 1 to 10 carbon atoms in the same or different alkyl radicals, in particular trimethylsilyl groups.
  • Substituents in the C-organic groups or Si-organic groups on the 1, 3, 5 -triazacyclohexane ring can in particular be alkyl groups with donor groups.
  • the donor group can be neutral or anionic and contain a hetero atom of groups 15-16 of the periodic table (according to IUPAC proposal 1985) or a carbanion. If it is neutral, it can be coordinated to the chromium. It is preferably coordinated with the chromium. If the donor is formally anionic, it is covalently bound to the metal center.
  • the bonds can be intra- or intermolecular, they are preferably intramolecular. Neutral donors with oxygen and / or nitrogen atoms, which have lone pairs of electrons, are preferred, wherein the oxygen and / or nitrogen atoms can also be inserted into an alkyl chain.
  • Preferred 1, 3, 5-triazacyclohexanes are 1, 3, 5-tritert. -butyl-1,3,5-triazacyclohexane, 1,3,5-riethyl -1,3,5-triazacyclohexane, 1,3,5-tris- [(1-phenyl) ethyl] -1, 3,5-triazacyclohexane, 1,3,5-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 preferably 1,3,5-tri-n-octyl-1,3,5-triazacyclohexane, 1,3,5-tri-n- dodecyl -1, 3,5-triazacyclohexane, 1,3,5-tribenzyl-1,
  • the 1, 3, 5 -triazacyclohexanes of the general formula I in which the groups R 4 to R 9 are hydrogen and the groups R 1 to R 3 are the same, can be prepared in a manner known per se, for example by reacting primary amines type R : L NH 2 with formaldehyde or paraformaldehyde. Accordingly, the 1, 3, 5-triazacyclohexanes, each of which has a methyl group and a hydrogen atom on the carbon atoms of the ring, are accessible via acetaldehyde.
  • the product mixture can be separated as in 1).
  • the separation can be done as in 1).
  • Suitable groups X in the chromium compounds CrX 3 or the chromium complexes CrX 3 L are any abstractable counterions which are suitable for this purpose in organometallic chemistry, in particular
  • Halogen such as fluorine, bromine, iodine and especially chlorine, tosylate, triflate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraphenylborate, - C ⁇ ⁇ to Cio-carboxy, especially 2-ethylhexanoate,
  • Alkyl groups for example methyl, ethyl, i-propyl, phenyl
  • the groups X are selected in particular so that the chromium compounds CrX 3 or chromium complexes CrX 3 L containing them have good solubility in the solvent used in each case.
  • the starting materials used for the chromium compounds CrX and the chromium complexes CrXL are, for example, chromium halides such as CrCl 3 CrBr 3 , Cr (triflate) 3 , Cr (III) alkoxylates such as 2-ethylhexanoate, and complexes of these chromium compounds with weakly bound neutral complex ligands which are caused by the 1, 3, 5-triazacyclohexane and, if appropriate, can be displaced by the five-membered aromatic N-heterocycle, for example 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
  • oligomerization catalysts which have been produced using previously produced and isolated chromium complexes CrX 3 L.
  • the chromium complexes CrX 3 L are otherwise obtainable by methods known to those skilled in the art or analogously to these (see, for example, WA Herrmann, A. Salzer: “Synthetic Methods of Organometallic and Inorganic Chemistry”, Vol. 1 - Literature, Laboratory Techniques, and Common Starting Materials, Thieme Verlag, Stuttgart, 1996).
  • the procedure is generally that the chromium compound CrX 3 is dissolved or suspended in the reaction medium and the 1,3,5-triazacyclohexane is added either in bulk or in dissolved form.
  • X independently of one another: halogen, tosylate, triflate, alkyl
  • R 4 , R 5 , R 6 , R 7 , R 8 and R 9 independently of one another are hydrogen or C 1 -C 4 -alkyl and in particular hydrogen or methyl and in which R 1 , R 2 and R 3 independently of one another are methyl, ethyl, N, N-dimethylaminoethyl, propyl, n-butyl, tert-butyl, hexyl, octyl, dodecyl, 1, 1-dimethyldodecyl or ( 1-phenyl) ethyl.
  • chromium complexes CrX 3 L in which X and L have the following meanings is particularly preferred:
  • the activating additive is composed of an optionally substituted five-membered aromatic
  • Suitable five-membered aromatic N-heterocycles are those with 1, 2, 3 or 4, preferably 1 or 2 nitrogen atoms in the five-membered aromatic ring.
  • the five-membered aromatic N-heterocylene can be substituted on the ring carbon atoms by groups which are inert under the reaction conditions, such as alkyl groups, preferably methyl and / or ethyl, or two adjacent carbon atoms of the five-membered aromatic N-heterocycle can belong together to a condensed aromatic carbocyclic system , wherein the aromatic carbocyclic system can in turn carry inert groups.
  • N-heterocycles examples include the base bodies and the substituted representatives of the pyrroles, pyrazoles, imidazoles, triazoles and tetrazoles such as pyrrole, 2, 5-dimethylpyrrole, indole, carbazole, pyrazole, indazole, imidazole, benzimidazole. It is preferred to use pyrroles and in particular alkyl-substituted pyrroles, especially 2,5-dimethylpyrrole.
  • Aluminum alkyl, the alkyl groups of which can be partially replaced by halogen and / or alkoxy, are aluminum alkyls of the formulas A1R 3 , AlR 2 Hal, AlRHal 2 , A1R 2 0R ', AlRHalOR' and Al 2 R 3 Hal 3 and mixtures thereof, in which R and R 'independently of one another represent methyl, ethyl or a straight-chain or branched C 3 - to Cs-alkyl group and in which shark represents fluorine, bromine iodine and especially chlorine, for example trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum , Tri-iso-propylaluminium, tributylaluminium, diethylaluminium trichloride, diethylaluminium umbromide, diethylaluminium ethoxide, diethylaluminiumphenoxide, ethylaluminiumethoxichlor
  • Suitable cocatalysts are alkyl halides, alkyl silicon halides and Lewis acidic metal halides, preferably n-butyl chloride, n-butyl iodide, trimethylsilyl chloride, trimethysilyl bromide, tin tetrachloride, germanium chloride and especially n-butyl bromide.
  • the two components are in a molar ratio of 1: 3 to 30: 1, preferably 1: 1 to 15: 1.
  • the amount of the chromium compound CrX 3 or the chromium complex CrX 3 L is normally in the range from 1 x 10 "" 7 to 1, preferably from 1 x 10 -6 to 0.1 and in particular from 1 x 10 ⁇ 5 to 0.01 mol per kg of the reaction mixture.
  • the amount of the five-membered aromatic N-heterocycle is normally in the range from 1 x 10 "8 to 100, preferably from 1 x 10 -7 to 1 and in particular from 1 x 10 -5 to 0.05 mol per kg of the reaction mixture.
  • the amount of aluminum alkyl, the alkyl groups of which can be partially replaced by halogen and / or alkoxy, is normally in the range from 1 x 10 -8 to 500, preferably from 1 x 10 -7 to 10 and in particular from 5 x 10 -5 to 0 , 5 mol per kg of the reaction mixture.
  • the molar ratio of components (a), (b) and (c) is 1: 0.1-100: 0.1-500, preferably 1: 0.1-10: 1-100 and in particular 1: 1 -5: 5-50.
  • a catalyst consisting of (a) [(1,3, 5-tri-n-octyl-l, 3,5-triazacyclohexane) CrCl 3 ] or [(1,3, 5-tribenzyl-l, 3, 5-triazacyclohexane) CrCl 3 ], (b) 2, 5-dimethylpyrrole and (c) triethyl aluminum and ethyl aluminum dichloride, these components in a molar ratio of 1: 0.1-10: 0.1-100 and preferably 1: 1-5: 5-50.
  • the molar ver Ratio of triethyl aluminum and ethyl aluminum dichloride in component (c) is 1-50: 1, preferably 3-20: 1.
  • the oligomerization is preferably carried out in a solvent.
  • a solvent Straight-chain, branched or alicyclic saturated hydrocarbons with 1 to 20 carbon atoms such as butane, pentane, 3-methylpentane, hexane, heptane, 2-methylhexane, octane, cyclohexane, methylcyclohexane, 2, 2, 4-trimethylpentane can be used as solvents for the oligomerization ,
  • Decalin, straight-chain or branched halogenated hydrocarbons such as dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene, tetralin and the oligomeric reaction products such as 1-hexene which are liquid under the reaction conditions are used themselves.
  • These solvents can be used either individually or as a mixture.
  • Preferred oligomerization catalysts according to the invention are furthermore those which contain an alkylalumoxane as the activating additive.
  • Ligands L in which the groups R 1 , R 2 and R 3 are partially or wholly and independently of one another are very particularly preferred are a group which is in the ⁇ position or in one of the N atoms of 1, 3, 5-triazacyclohexane ring even further away bears a substituent bonded via a carbon atom, in particular an alkyl, aryl or silyl group.
  • This substituent is particularly preferably in the ⁇ position.
  • this substituent is particularly preferably a ⁇ -alkyl-substituted alkyl, especially 2-ethylhexyl or 2-n-propylheptyl.
  • these ligands L those in which the groups R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are hydrogen are particularly preferred.
  • Suitable alkylalumoxanes are known, for example, from DE-A 30 07 725, their structures being largely unexplained. These are products of the careful partial hydrolysis of aluminum alkyls (cf. DE-A 30 07 725). These products do not appear to be pure, but as mixtures of open-chain and cyclic structures of type II a and Ilb, which are probably in dynamic equilibrium with one another. Ha Ilb
  • the groups R 10 are identical or different and independently of one another are C ⁇ -Ci 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,
  • n-dodecyl 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 -CC 6 ⁇ 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, methyl is particularly preferred, m is an integer from 0 to 40
  • alkylalumoxanes fulfill their effectiveness as an activating additive in the sense of the present invention irrespective of their structural nature.
  • the amount of activating alkylalumoxane used is depen ⁇ gig of its nature.
  • the ratio of chromium compound CrX 3 or chromium complex CrX 3 L to the activating alkylalumoxane is generally 1: 0.1 to 1: 10000, preferably 1: 1 to 1: 1000.
  • Suitable solvents when using an oligomerization catalyst made from CrX 3 , a ligand L and the alkylalumoxane or from CrX 3 L and the alkylalumoxane are aprotic solvents, for example the aliphatic or aromatic hydrocarbons mentioned above as solvents, and above all toluene .
  • an oligomerization catalyst which contains at least one boron compound as the activating additive and contains at least one aluminum alkyl, the alkyl groups of which can be partially replaced by halogen and / or alkoxy.
  • Suitable boron compounds are, for example, those with electron-withdrawing radicals (for example trispentafluorophenylborane, N, N-dimethylanilinium tetrakis-pentafluorophenylborate, tri-n-butyl-ammonium-tetrakis-pentafluorophenylborate, N, N-dimethylanilinium-tetrakis (3, 5) bisperfluor phenylborate, tri-n-butylammonium tetrakis (3,5-bisperfluoromethyl) phenylborate and tritylium tetrakispentafluorophenylborate).
  • electron-withdrawing radicals for example trispentafluorophenylborane, N, N-dimethylanilinium tetrakis-pentafluorophenylborate, tri-n-butyl-ammonium-t
  • Tritylium tetrakispentafluorophenylborate, trispentafluorophenylborane and especially dimethylanilinium tetrakis (pentaflourophenyl) borate are preferred.
  • the amount of activating boron compound used depends on its nature.
  • the ratio of chromium compound CrX 3 or chromium complex CrX 3 L to the activating boron compound is generally 1: 0.1 to 1: 10000, preferably 1: 1 to 1: 1000.
  • the alkyl groups of which can be partially replaced by halogen and / or alkoxy are suitable in the amounts given there based on the chromium compound CrX 3 or the chromium complex CrX 3 L.
  • Suitable solvents are aprotic solvents, e.g. the aliphatic or aromatic hydrocarbons listed above as solvents, and above all toluene.
  • Preferred olefins for the oligomerization by the process according to the invention are straight-chain and branched ⁇ -olefins having preferably 2 to 10, in particular 2 to 6 and especially 2 to 4, carbon atoms and mixtures thereof and very particularly preferably in each case: 1-propene , 1-butene, 1-hexene, 1-decene and especially ethene, 1-butene, especially 1-butene in a mixture with its isomers, such as is present in raffinate II.
  • the oligomerization is generally to be carried out with the greatest possible exclusion of moisture.
  • Well-known working techniques are used. It is preferable to work with heated equipment and under protective gas. All gases which are chemically inert under the reaction conditions, advantageously nitrogen or argon, can be used as protective gases. Besides that, it can ⁇ -olefin to be converted 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 1 to 120 and in particular at 70 to 110 ° C. and preferably at a pressure in the range from 3 to 120 bar.
  • the pressure is expediently chosen so that the feed mixture is in liquid form at the set temperature.
  • the process according to the invention can be carried out batchwise or continuously, preference being given to the continuous procedure on an industrial scale.
  • a number of substances can be used for the catalyst deactivation at the end of the reaction, the common feature of which is that they are able to hydrolyze aluminum alkyl compounds, for example water and monoalcohols having 1 to 10 carbon atoms, it being possible to add mineral acids to these substances.
  • the products of the oligomerization according to the invention are expediently purified by distillation.
  • a decene and a tetradecene fraction can be isolated from the discharge of the ethene oligomerization in addition to the main (-hexene) fraction, which consists predominantly of 1-hexene.
  • the latter two fractions consist primarily of branched, internal olefins.
  • unreacted starting material can be recovered and returned to the reaction.
  • Preferred products of the process according to the invention are atoms trimers of ⁇ -olefins, especially ⁇ -olefins having 2 to 6 carbon and available particularly from 'ethene 1-hexene.
  • the oligomers obtainable by the process according to the invention are particularly suitable for the production of monoalcohols for plasticizers and surfactants.
  • the oligomers are advantageously subjected to hydroformylation, in which mixtures of the aldehydes and alcohols chain-extended by one carbon atom are formed, which are then hydrogenated to the desired alcohols.
  • hydroformylation and hydrogenation are known per se to the person skilled in the art and therefore do not require any further explanation (cf. for example Beller et al., Journal of Molecular Catalysis A 104 (1995) pages 17-85).
  • Chromium- Komp1ex 3 [(1,3, 5-tri-n-dodecyl-1,3,5-triazacyclohexane) CrCl 3 ]
  • Chromium- Komp1ex 7 [(1,3,5-tris [(1,1-dimethyl) dodecyl] -1,3,5-triazacyclohexane) CrCl 3 ]
  • Chromium complex 10 [(1,3,5 -Tris- (2-n-propylheptyl) -1,3,5 -triazacyclohexane) CrCl 3 ]
  • a steel autoclave with a volume of 100 ml was heated in an argon flow at 105 ° C. for 60 minutes.
  • 14.5 mg of “chromium complex 1” were then introduced at 25 ° C. and then 25 ml of n-heptane dried over sodium and 0.5 ml of a solution of 143 mg of 2,5-dimethylpyrrole in 10 ml of n
  • the autoclave was then flushed three times with ethene at atmospheric pressure, followed by the addition of 0.75 ml of a 1 molar solution of triethylaluminum in n-heptane, followed by pressing an ethene pressure of 25 joined bar Hie ⁇ up the temperature was raised to 80 ° C and the ethene pressure to 40 bar, the autoclave was stirred for 2 hours at these conditions;..
  • the autoclave was cooled and depressurized by the addition of.
  • the catalyst was deactivated by 1 ml of water to the reaction mixture, the constituents which were insoluble in the reaction mixture were separated off, dried and weighed, calculated on the basis of 1 g of chromium in the catalyst, the productivity was 18.6 kg rde determined by gas chromatography with n-heptane as internal standard:
  • Examples 2 to 11 were carried out analogously to Example 1.
  • n-Butyl bromide (n-BuBr) and ethyl aluminum dichloride (EADC) were used as 0.1 M solutions in n-heptane.
  • the starting materials, the associated quantities and the results of the tests are summarized in Table 1 below.
  • Example 12 Trimerization of 1-butene in the presence of “chromium complex 9” and methylaluminoxane and hydroformylation of the trimer thus obtained to the corresponding oxo alcohol
  • a steel autoclave with a volume of 2500 ml was heated in a stream of argon at 120 ° C.
  • 750 mg of “chromium complex 9” and 500 g of toluene dried over sodium were introduced into the autoclave at 25 ° C., and the autoclave was then rinsed three times with 1-butene and 500 g of 1-butene were added to the autoclave by means of a sluice, then the temperature in the autoclave was raised to 40 ° C. and the pressure was adjusted to 15 bar with nitrogen gas
  • the catalyst was deactivated by adding 2-propanol.
  • In the reactor discharge (800 g) only isomeric dodecenes were found as oligomers in the subsequent gas chromatographic analysis.
  • the dodecane mixture obtained by hydrogenation had an ISO index of 2.3.
  • the oxo product thus obtained was hydrogenated in a 2500 ml tubular reactor in a trickle mode over a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar H 2 with the addition of 10% by weight of water, based on the organic phase.
  • the resulting alcohol mixture was worked up by distillation, the tridecanol mixture obtained had an OH number of 279 mg KOH / g. i H-NMR spectroscopy measured an average degree of branching of 2.9.
  • trimerizations were carried out in a 1 1 four-necked flask provided with a contact thermometer, stirrer, heating mushroom and gas inlet tube, into which 30 to 50 ⁇ mol "chromium complex 9" in 250 ml of toluene at 40 ° C. were placed under argon.
  • Methylalumoxane (“MAO") was used in the form of a 1.6 M solution in toluene.
  • DMAB dimethylanilinium tetrakis (pentaflourophenyl) borate
  • TIBAL triisobutylaluminum
  • Activation takes place by adding DMAB and TIBAL.
  • Triethyl aluminum was used instead of TIBAL 2, 5 -Dirnethylpyrrol gas was passed through
  • the preparation was carried out analogously to the alternative preparation of chromium complex 9 according to Examples 13-22.
  • Example 26 In contrast, the reaction according to Example 26 was carried out in a 1000 ml autoclave at a pressure of 40 bar, also in toluene.
  • Triethyl aluminum was used instead of TIBAL

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un catalyseur d'oligomérisation pour oléfines, que l'on obtient à partir: a) d'un composé à base de chrome CrX3 et de la quantité au moins équimoléculaire, par rapport au composé CrX3, d'un ligand L ou d'un complexe fini à base de chrome CrX3L, dans lesquels les groupes X représentent indépendamment des contre-ions extractibles et L représente un 1,3,5-triazacyclohexane de formule (I), dans laquelle les groupes R1 à R9 représentent indépendamment l'hydrogène, des groupes organiques Si ou des groupes organiques C éventuellement substitués, renfermant 1 à 30 atomes de C, deux résidus R1 à R9 géminaux ou voisins pouvant aussi être reliés à un noyau à 5 ou 6 éléments; et b) d'au moins un additif d'activation. L'invention concerne également un procédé qui permet de produire des oligomères d'oléfines au moyen desdits catalyseurs, les oligomères ainsi obtenus et les oxoalcools obtenus à partir desdits oligomères.
PCT/EP2000/002660 1999-03-29 2000-03-25 Catalyseur d'oligomerisation WO2000058319A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP00920583A EP1171445B1 (fr) 1999-03-29 2000-03-25 Catalyseur d'oligomerisation
US09/937,815 US6844290B1 (en) 1999-03-29 2000-03-25 Oligomerization catalyst
AT00920583T ATE258184T1 (de) 1999-03-29 2000-03-25 Oligomerisierungskatalysator
JP2000608019A JP2002539945A (ja) 1999-09-11 2000-03-25 オリゴマー化触媒
DE50005086T DE50005086D1 (de) 1999-03-29 2000-03-25 Oligomerisierungskatalysator

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US09/277,823 1999-03-29
DE19922048.4 1999-07-30
DE19943544.8 1999-09-11
DE19943544A DE19943544A1 (de) 1999-09-11 1999-09-11 Oligomerisierungskatalysator

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001098379A1 (fr) * 2000-06-20 2001-12-27 Basf Aktiengesellschaft Pates contenant un solvant et en plus de la cire de polyolefine
WO2001098415A2 (fr) * 2000-06-20 2001-12-27 Basf Aktiengesellschaft Concentre de pigments et son procede de fabrication
WO2003076367A2 (fr) * 2002-03-14 2003-09-18 Basell Polyolefine Gmbh Procede d'oligomerisation d'olefines utilisant un triazacyclohexane substitue par cycloalkylalkyle
WO2003076368A1 (fr) * 2002-03-14 2003-09-18 Basf Aktiengesellschaft Olegomerisation d'olefines comportant au moins trois atomes de carbone
US6858071B2 (en) 2000-06-20 2005-02-22 Basf Aktiengesellschaft Solvent-containing pastes containing in addition polyolefin wax
WO2007039851A2 (fr) * 2005-10-03 2007-04-12 Sasol Technology (Pty) Limited Oligomerisation de composes olefiniques en presence d'un catalyseur d'oligomerisation, et activateur catalytique comprenant un groupe organique halogene
FR3073845A1 (fr) * 2017-11-22 2019-05-24 Total Marketing Services Procede de preparation de trimeres de 1-decene
WO2020049101A1 (fr) * 2018-09-06 2020-03-12 Total Marketing Services Catalyseur au chrome pour la preparation de trimeres d'alpha-olefine(s)
US10646857B2 (en) 2015-09-23 2020-05-12 Lotte Chemical Corporation Catalyst system for olefin oligomerization and method for oligomerizing olefins using the same

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JP2002540260A (ja) * 1999-03-29 2002-11-26 ビーエーエスエフ アクチェンゲゼルシャフト オレフィンの重合
DE10215754A1 (de) 2002-04-10 2003-10-30 Basf Ag Verfahren zur Oligomerisierung von Olefinen
JP5448142B2 (ja) * 2005-03-09 2014-03-19 エクソンモービル・ケミカル・パテンツ・インク オレフィンのオリゴマー化
FR3019064B1 (fr) * 2014-03-25 2020-02-28 IFP Energies Nouvelles Nouvelle composition catalytique et procede pour l'oligomerisation de l'ethylene en hexene-1

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JPH10231317A (ja) * 1997-02-18 1998-09-02 Mitsubishi Chem Corp α−オレフィン重合体の製造方法
WO2000034211A1 (fr) * 1998-12-04 2000-06-15 Bp Chemicals Limited Procede d'oligomerisation

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US6846356B2 (en) 2000-06-20 2005-01-25 Basf Aktiengesellschft Pigment concentrates and method for producing them
WO2001098415A2 (fr) * 2000-06-20 2001-12-27 Basf Aktiengesellschaft Concentre de pigments et son procede de fabrication
WO2001098415A3 (fr) * 2000-06-20 2002-04-04 Basf Ag Concentre de pigments et son procede de fabrication
WO2001098379A1 (fr) * 2000-06-20 2001-12-27 Basf Aktiengesellschaft Pates contenant un solvant et en plus de la cire de polyolefine
US6858071B2 (en) 2000-06-20 2005-02-22 Basf Aktiengesellschaft Solvent-containing pastes containing in addition polyolefin wax
US7081557B2 (en) 2002-03-14 2006-07-25 Basell Polyolefine Gmbh Method for the oligomerization of olefins using a cycloalkylalkyl-substituted triazacyclohexane
WO2003076367A3 (fr) * 2002-03-14 2003-12-18 Basell Polyolefine Gmbh Procede d'oligomerisation d'olefines utilisant un triazacyclohexane substitue par cycloalkylalkyle
WO2003076368A1 (fr) * 2002-03-14 2003-09-18 Basf Aktiengesellschaft Olegomerisation d'olefines comportant au moins trois atomes de carbone
WO2003076367A2 (fr) * 2002-03-14 2003-09-18 Basell Polyolefine Gmbh Procede d'oligomerisation d'olefines utilisant un triazacyclohexane substitue par cycloalkylalkyle
CN100340533C (zh) * 2002-03-14 2007-10-03 巴斯福股份公司 含有至少3个碳原子的烯烃的低聚反应
WO2007039851A2 (fr) * 2005-10-03 2007-04-12 Sasol Technology (Pty) Limited Oligomerisation de composes olefiniques en presence d'un catalyseur d'oligomerisation, et activateur catalytique comprenant un groupe organique halogene
WO2007039851A3 (fr) * 2005-10-03 2008-05-22 Sasol Tech Pty Ltd Oligomerisation de composes olefiniques en presence d'un catalyseur d'oligomerisation, et activateur catalytique comprenant un groupe organique halogene
US8134038B2 (en) 2005-10-03 2012-03-13 Sasol Technology (Pty) Limited Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated organic group
US10646857B2 (en) 2015-09-23 2020-05-12 Lotte Chemical Corporation Catalyst system for olefin oligomerization and method for oligomerizing olefins using the same
FR3073845A1 (fr) * 2017-11-22 2019-05-24 Total Marketing Services Procede de preparation de trimeres de 1-decene
WO2019102152A1 (fr) * 2017-11-22 2019-05-31 Total Marketing Services Procede de preparation de trimeres de 1-decene
WO2020049101A1 (fr) * 2018-09-06 2020-03-12 Total Marketing Services Catalyseur au chrome pour la preparation de trimeres d'alpha-olefine(s)

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