WO2001002323A1 - Donor ligand-substituted cyclopentadienyl-chrome compounds used as catalysts for oligomerizing alkenes - Google Patents

Donor ligand-substituted cyclopentadienyl-chrome compounds used as catalysts for oligomerizing alkenes Download PDF

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WO2001002323A1
WO2001002323A1 PCT/EP2000/004362 EP0004362W WO0102323A1 WO 2001002323 A1 WO2001002323 A1 WO 2001002323A1 EP 0004362 W EP0004362 W EP 0004362W WO 0102323 A1 WO0102323 A1 WO 0102323A1
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alkyl
ethylene
alkenes
catalysts
aryl
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French (fr)
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Peter Walther Jolly
Arno DÖHRING
Jan Christoph Weber
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Studiengesellschaft Kohle Mbh
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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
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • 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
    • 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
    • C07C2531/24—Phosphines

Definitions

  • the invention describes a new process for the catalytic oligomerization of alkenes with the aid of Lewis acid-activated organochrome compounds.
  • catalysts have also become known which act on nickel diimine through the action of Lewis acids, in particular alkylalumoxanes Complexes (see Killian, CM; Johnson, LK; Brokhart, M., Organometallics 1997, 16, 2005; Du Pont WO 96/23010, 1996; Du Pont US Pat. No. 5,880,241, 1999), boratobenzene-zirconium complexes (see Barnhart, RW; Bazon, G .; Mourey, T., J. Am. Chem. Soc. 1998, 120, 1082) and pyridine bisimine iron and cobalt complexes (see Britovsek, GJP et al, Chem.
  • Organochrome compounds which preferentially trimerize ethylene are also known and are formed by the action of Lewis acids on chromium salts in the presence of donor ligands, the use of P-donor ligands such as
  • N-donor ligands such as 2,5-dimethylpyrrole (see e.g. Phillips Petroleum US Pat. No. 5,689,028, 1997; Ethyl Corp. EP 0 537 609 , 1993; Idemitsu Kosan WO 94 / 15,940, 1994) and O-donor ligands, such as monoglyme (see Briggs, JR, Chem. Commun. 1989, 674; Union Carbide US Pat. No. 4,668,838, 1987).
  • organo-chromium compounds activated by Lewis acids, such as methylalumoxane (MAO)
  • MAO methylalumoxane
  • R 1 is a delocalized ⁇ 5 -coordinated ⁇ system, such as cyclopentadienyl,
  • X is an electronegative atom or group, such as halide or amide, or an organyl group, such as alkyl or aryl,
  • Y is a donor atom of the 15th group of the periodic table
  • Z is an atom of the 14th group (C, Si, Ge, Sn, Pb) of the periodic table
  • R H alkyl or organyl groups
  • R is H, alkyl or organyl groups, and n> 1.
  • the organochrome compounds are preferably activated with methylalumoxane as Lewis acid.
  • the molar ratio of Al: Cr in the catalyst is preferably between 40: 1 and 10000: 1. Cyclopentadienyl, substituted cyclopentadienyl or indenyl are used as the preferred delocalized ⁇ -coordinated ⁇ system.
  • the process also serves for the cooligomerization of various alkenes, e.g. B. also for the cooligomerization of ethylene with other, also substituted alkenes.
  • the butene-hexene mixture can be copolymerized with ethylene to linear low-density polyethylene (LLDPE), while the long-chain olefin mixtures, in the sense of the Shell Higher Olefin Process (SHOP) long-chain alcohols or aldehydes can be processed.
  • LLCPE linear low-density polyethylene
  • SHOP Shell Higher Olefin Process
  • phosphino and arsino substituted cyclopentadienyl ligands were prepared by methods known from the literature (see, for example, Bensley, DM et al J. Org. Chem 53, 4417, 1988; Kaufftnann, T. et al Angew. Chem. 92, 321, 1980; Kettenbach, RT et al Chem. Ber 126, 1657, 1993; Kataoka, Y. et al Chem Letters 621, 1997) e.g. B. Eq 1-4
  • Crystal structure determinations of IV, V, and VI confirm that the donor atom is bound to the chromium.
  • EtsP HH t Li prepared from Spiro [2.4]] hepta-4,6-diene (1.27g, 13.8mmol) and LiPEt 2 (1.32g, 13.8mmol) in THF was dissolved in THF (20ml) and at -78 ° C was added dropwise to Cr (THF) 3 Cl 3 (4.70g, 12.6 mmol) in THF (100ml). The solution the mixture was stirred for a further 4 h at room temperature, the blue solution was concentrated and the residue was extracted with boiling toluene (500 ml). The compound precipitated out of solution in the form of blue needles at room temperature. Yield: 1.54g (40% theory).
  • Ph2PC 3 H 6 C5Me 4 Li (1.64g, 4.7mmol; prepared from Tosyl OC 3 H 6 C 5 H 5 and KPPh 2 with subsequent protonolysis and reaction with BuLi) was dissolved in THF (20ml) and at room temperature to Cr (THF ) 3 Cl 3 (1.81g, 4.7mmol) in THF (20ml) added dropwise.
  • the green reaction solution was concentrated and the residue extracted with toluene (300ml) and the solution filtered through a Celite column (20x2cm) to remove the green impurity.
  • the blue solution thus obtained was concentrated and the residue was extracted with toluene at room temperature.
  • the compound was recrystallized from toluene. Yield: 0.6g (27% theory).
  • Table 1 The oligomerization / polymerization of ethylene under ⁇ T conditions with MAO-activated, phosphino- and arsino-substituted cyclopentadienyl-chromium catalysts a
  • the same catalysts can also be used in the cooligomerization of ethylene with other alkenes (e.g. norbornene, example 22).
  • alkenes e.g. norbornene, example 22.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a method for catalytically oligomerizing alkenes, especially ethylene, whereby Lewis acid-activated donor ligand-substituted eta <5>-organyl-chrome complexes are used as catalysts, especially phosphino-substituted or arsino-substituted cyclopentadienyl complexes.

Description

Donor-Ligand-Substituierte Cyclopentadienyl- Chrom- Verbindungen als Katalysatoren für die Oligomerisation von Alkenen Donor-ligand-substituted cyclopentadienyl-chromium compounds as catalysts for the oligomerization of alkenes
Die Erfindung beschreibt ein neues Verfahren zur katalytischen Oligomerisierung von Alkenen mit Hilfe von Lewis-Säuren-aktivierten Organochrom- Verbindungen.The invention describes a new process for the catalytic oligomerization of alkenes with the aid of Lewis acid-activated organochrome compounds.
Die Oligomerisierung von Alkenen, insbesondere von Ethylen, ist von großer technischer Bedeutung und die Produkte (Dimere, Trimere oder höhere Oligomere) werden großtechnisch hergestellt. Besondere Bedeutung haben Prozesse erlangt, die als Katalysatoren Alkylaluminium (Aufbaureaktion) und Nickel- Yliden (Shell Higher Olefin Process) verwenden: Für eine aktuelle Zusammenfassung des Standes der Technik siehe Cornils, B.; Herrmann, W. A., Eds. in 'Applied Homo- geneous Catalysis with Organometallic Compounds, Vol. 1, Chapter 2.3', VCH- Verlag, 1996. In der letzten Zeit sind auch Katalysatoren bekannt geworden, die durch Einwirken von Lewis-Säuren, insbesondere Alkylalumoxane, auf Nickel- Diimin-Komplexe (s. Killian, C. M.; Johnson, L. K.; Brokhart, M., Organometallics 1997, 16, 2005; Du Pont WO 96/23010, 1996; Du Pont US PS 5,880,241, 1999), Boratobenzol-Zirkonium-Komplexe (s. Barnhart, R. W.; Bazon, G.; Mourey, T., J. Am. Chem. Soc. 1998, 120, 1082) und Pyridinbisimin-Eisen und -Cobalt- Komplexe (s. Britovsek, G. J. P. et al, Chem. Commun., 1998, 849; S all, B. L^Brookhart, M., J. Am. Chem. Soc, 1998, 120, 7143) hergestellt wurden. Organochromverbindungen, die Ethylen bevorzugt trimerisieren, sind auch bekannt und werden durch die Einwirkung von Lewis-Säuren auf Chromsalze in Gegenwart von Donor-Liganden gebildet, wobei die Verwendung von P-Donor-Liganden, wieThe oligomerization of alkenes, especially ethylene, is of great technical importance and the products (dimers, trimers or higher oligomers) are produced on an industrial scale. Processes that use alkyl aluminum (build-up reaction) and nickel ylidene (Shell Higher Olefin Process) as catalysts have gained particular importance: For a current summary of the prior art, see Cornils, B .; Herrmann, W.A., Eds. in 'Applied Homogeneous Catalysis with Organometallic Compounds, Vol. 1, Chapter 2.3', VCH-Verlag, 1996. In recent times, catalysts have also become known which act on nickel diimine through the action of Lewis acids, in particular alkylalumoxanes Complexes (see Killian, CM; Johnson, LK; Brokhart, M., Organometallics 1997, 16, 2005; Du Pont WO 96/23010, 1996; Du Pont US Pat. No. 5,880,241, 1999), boratobenzene-zirconium complexes (see Barnhart, RW; Bazon, G .; Mourey, T., J. Am. Chem. Soc. 1998, 120, 1082) and pyridine bisimine iron and cobalt complexes (see Britovsek, GJP et al, Chem. Commun ., 1998, 849; S all, B. L ^ Brookhart, M., J. Am. Chem. Soc, 1998, 120, 7143). Organochrome compounds which preferentially trimerize ethylene are also known and are formed by the action of Lewis acids on chromium salts in the presence of donor ligands, the use of P-donor ligands such as
C3H7P(C2H4PEt2)2 (Amoco Corp. US PS 5,811,618, 1998) N-Donor-Liganden, wie 2,5-Dimethylpyrrol (s. z. B. Phillips Petroleum US PS 5,689,028, 1997; Ethyl Corp. EP 0 537 609, 1993; Idemitsu Kosan WO 94/15,940, 1994) und O-Donor- Liganden, wie Monoglyme (s. Briggs, J. R., Chem. Commun. 1989, 674; Union Carbide US PS 4,668,838, 1987) beschrieben ist. Es ist bekannt, daß Organo-Chrom- Verbindungen, aktiviert durch Lewis-Säuren, wie Methylalumoxan (MAO), zur Polymerisation von Alkenen, insbesondere von Ethylen eingesetzt werden können. (Studiengesellschaft Kohle mbH, PCT WO 97/03868)C 3 H 7 P (C2H4PEt2) 2 (Amoco Corp. US Pat. No. 5,811,618, 1998) N-donor ligands such as 2,5-dimethylpyrrole (see e.g. Phillips Petroleum US Pat. No. 5,689,028, 1997; Ethyl Corp. EP 0 537 609 , 1993; Idemitsu Kosan WO 94 / 15,940, 1994) and O-donor ligands, such as monoglyme (see Briggs, JR, Chem. Commun. 1989, 674; Union Carbide US Pat. No. 4,668,838, 1987). It is known that organo-chromium compounds, activated by Lewis acids, such as methylalumoxane (MAO), can be used for the polymerization of alkenes, in particular ethylene. (Studiengesellschaft kohl mbH, PCT WO 97/03868)
Überraschenderweise haben wir jetzt festgestellt, daß die gleichen Lewis-Säure- aktivierten Organochromverbindungen der allgemeinen Formel I auch zur Oligo- merisation von Alkenen eingesetzt werden können,Surprisingly, we have now found that the same Lewis acid-activated organochrome compounds of the general formula I can also be used for the oligomerization of alkenes.
Figure imgf000003_0001
Figure imgf000003_0001
I wobei R1 ein delokalisiertes η5-koordiniertes π-System wie z.B. Cyclopentadienyl,I where R 1 is a delocalized η 5 -coordinated π system, such as cyclopentadienyl,
Indenyl oder Fluorenyl, enthält, wobei X ein elektronegatives Atom oder Gruppe, wie Halogenid oder Amid, oder eine Organylgruppe, wie Alkyl oder Aryl,Contains indenyl or fluorenyl, where X is an electronegative atom or group, such as halide or amide, or an organyl group, such as alkyl or aryl,
Y ein Donoratom der 15. Gruppe des Periodensystems,Y is a donor atom of the 15th group of the periodic table,
Z ein Atom der 14. Gruppe (C, Si, Ge, Sn, Pb) des Periodensystems,Z is an atom of the 14th group (C, Si, Ge, Sn, Pb) of the periodic table,
R H, Alkyl oder Organylgruppen,R H, alkyl or organyl groups,
R H, Alkyl oder Organylgruppen, und n >1 ist.R is H, alkyl or organyl groups, and n> 1.
Insbesondere führt der Einsatz von phosphino- oder arsino-substituierten Cyclopentadienyl-Chrom-Komplexen (In I: Y = P, As) in Gegenwart kleinerer Substituenten, z. B. Methyl (Me) oder Ethyl (Et), am P- bzw. As-Atom zu Oligomeren als überwiegenden Reaktionsprodukten. Demgegenüber führen größere Substituenten, z. B. Cyclohexyl (Cy), wie in Verbindung II überwiegend oder ausschließlich zu Polymeren, z. B. zu Polyethylen, wenn als Alken Ethylen eingesetzt wird. (PCT WO97/03868) Es besteht ein Zusammenhang zwischen den sterischen Ansprüchen der Substituenten am P- oder As-Atom und des Molekulargewichtes des entstandenen Oligomerengemisches: In Gegenwart kleinster Substituenten, wie z.B. Methyl, werden hauptsächlich niedrige Oligomere (Buten, Hexen) gebildet, während in Gegenwart größerer Substituenten, wie Ethyl, oder Phenyl, hauptsächlich höhere Oligomere (C14 - C40) gebildet werden. Beispiele sind in Tabelle 1 aufgeführt.In particular, the use of phosphino- or arsino-substituted cyclopentadienyl-chromium complexes (In I: Y = P, As) in the presence of smaller substituents, e.g. As methyl (Me) or ethyl (Et), on the P or As atom to oligomers as the predominant reaction products. In contrast, larger substituents, e.g. B. Cyclohexyl (Cy), as in compound II predominantly or exclusively to polymers, e.g. B. to polyethylene if ethylene is used as alkene. (PCT WO97 / 03868) There is a connection between the steric requirements of the substituents on the P or As atom and the molecular weight of the resulting oligomer mixture: in the presence of very small substituents, such as methyl, mainly low oligomers (butene, hexene) are formed, while in the presence of larger substituents, such as ethyl or phenyl, mainly higher oligomers (C 14 - C 40 ) are formed. Examples are listed in Table 1.
Figure imgf000004_0001
Figure imgf000004_0001
IIII
Die Organochromverbindungen werden vorzugsweise mit Methylalumoxan als Lewissäure aktiviert. Das Molverhältnis von Al:Cr im Katalysator liegt hierbei bevorzugt zwischen 40:1 und 10000:1. Als bevorzugtes delokalisiertes η - koordininiertes π-System wird Cyclopentadienyl, substituiertes Cyclopentadienyl oder Indenyl eingesetzt. Das Verfahren dient auch zur Cooligomerisation von verschiedenen Alkenen, z. B. auch zur Cooligomerisation von Ethylen mit anderen, auch substituierten Alkenen.The organochrome compounds are preferably activated with methylalumoxane as Lewis acid. The molar ratio of Al: Cr in the catalyst is preferably between 40: 1 and 10000: 1. Cyclopentadienyl, substituted cyclopentadienyl or indenyl are used as the preferred delocalized η-coordinated π system. The process also serves for the cooligomerization of various alkenes, e.g. B. also for the cooligomerization of ethylene with other, also substituted alkenes.
Die entstandenen Oligomeren und Cooligomeren sind von erheblichem industriellen Interesse: das Buten Hexen-Gemisch kann mit Ethylen zu Linear-Low-Density- Polyethylene (LLDPE) copolymerisiert werden, während die langkettigen Olefingemische, im Sinne des Shell Higher Olefin Process (SHOP), zu langkettigen Alkoholen oder zu Aldehyden weiterverarbeitet werden können. Beispiele:The resulting oligomers and cooligomers are of considerable industrial interest: the butene-hexene mixture can be copolymerized with ethylene to linear low-density polyethylene (LLDPE), while the long-chain olefin mixtures, in the sense of the Shell Higher Olefin Process (SHOP) long-chain alcohols or aldehydes can be processed. Examples:
Die phosphino- und arsino-substituierten Cyclopentadienyl-Liganden wurden durch literaturbekannte Methoden hergestellt (siehe z.B. Bensley, D. M. et al J. Org. Chem 53, 4417, 1988; Kaufftnann, T. et al Angew. Chem. 92, 321, 1980; Kettenbach, R. T. et al Chem. Ber 126, 1657, 1993; Kataoka, Y. et al Chem Letters 621, 1997) z. B. Gl 1-4The phosphino and arsino substituted cyclopentadienyl ligands were prepared by methods known from the literature (see, for example, Bensley, DM et al J. Org. Chem 53, 4417, 1988; Kaufftnann, T. et al Angew. Chem. 92, 321, 1980; Kettenbach, RT et al Chem. Ber 126, 1657, 1993; Kataoka, Y. et al Chem Letters 621, 1997) e.g. B. Eq 1-4
Figure imgf000005_0001
Figure imgf000005_0001
Die Weiterreaktion der Alkali-Metall-Salze mit CrCl3 führte zu den gewünschten CrCl2- Verbindungen als dunkelblaue Nadeln, z.B. Gl. 5-7 The further reaction of the alkali metal salts with CrCl 3 led to the desired CrCl 2 compounds as dark blue needles, for example Eq. 5-7
(Ph2PC2H4C5H4)CrCl2 (5)
Figure imgf000006_0001
(Ph 2 PC 2 H 4 C 5 H 4 ) CrCl 2 (5)
Figure imgf000006_0001
IVIV
C5Me4)CrCl2 (6)C 5 Me 4 ) CrCl 2 (6)
Figure imgf000006_0002
Figure imgf000006_0002
(Cy2AsC2H4C5H4)CrCl2 (7)
Figure imgf000006_0003
(Cy 2 AsC 2 H 4 C 5 H 4 ) CrCl 2 (7)
Figure imgf000006_0003
VIVI
Kristallstrukturbestimmungen von IV, V, und VI ( Abb. 1) bestätigen, daß das Donor-Atom am Chrom gebunden ist.Crystal structure determinations of IV, V, and VI (Fig. 1) confirm that the donor atom is bound to the chromium.
Reaktion der CrCl2- Verbindungen mit Organomagnesium- bzw. -Alkalimetal- Reagenzien führt zur Bildung der entsprechenden Alkyl- bzw. Aryl-Chrom- Derivate (z.B. Gl. 8).Reaction of the CrCl 2 compounds with organomagnesium or alkali metal reagents leads to the formation of the corresponding alkyl or aryl chromium derivatives (eg Eq. 8).
2MeMgQ (Et^C^4C5H^CrCl2 " (Et^C^C^CrM^ (8)2MeMgQ (Et ^ C ^ 4 C 5 H ^ CrCl 2 "(Et ^ C ^ C ^ CrM ^ (8)
Beispiel 1example 1
Darstellung von (Et2PC2H4C5H4)CrCl2.Preparation of (Et2PC 2 H 4 C 5 H 4 ) CrCl2.
EtsP H HtLi (dargestellt aus Spiro[2.4]]hepta-4,6-diene (1.27g, 13.8mmol) und LiPEt2 (1.32g, 13.8mmol) in THF) wurde in THF (20ml) gelöst und bei -78°C zu Cr(THF)3Cl3 (4.70g, 12.6 mmol) in THF (100ml) zugetropft. Die Lösung wurde weitere 4h bei Raumtemperatur gerührt, die blaue Lösung eingeengt und der Rückstand mit siedendem Toluol (500ml) extrahiert. Die Verbindung fiel bei Raumtemperatur aus der Lösung in Form von blauen Nadeln aus. Ausbeute: 1.54g (40% Theorie).EtsP HH t Li (prepared from Spiro [2.4]] hepta-4,6-diene (1.27g, 13.8mmol) and LiPEt 2 (1.32g, 13.8mmol) in THF) was dissolved in THF (20ml) and at -78 ° C was added dropwise to Cr (THF) 3 Cl 3 (4.70g, 12.6 mmol) in THF (100ml). The solution the mixture was stirred for a further 4 h at room temperature, the blue solution was concentrated and the residue was extracted with boiling toluene (500 ml). The compound precipitated out of solution in the form of blue needles at room temperature. Yield: 1.54g (40% theory).
Analytische Daten, Ber. für CnH18Cl2CrP: C, 43.6; H, 6.1; Cl, 23.3; Cr, 17.2; P, 10.1% Gef.: C, 43.4; H, 6.0; Cl, 23.3; Cr, 17.1; P, 10.2%. MS (135°C): m/e 303 ([M-H]+, 27%), 268 (8%).Analytical data, calc. for CnH 18 Cl 2 CrP: C, 43.6; H, 6.1; Cl, 23.3; Cr, 17.2; P, 10.1% Found: C, 43.4; H, 6.0; Cl, 23.3; Cr, 17.1; P, 10.2%. MS (135 ° C): m / e 303 ([MH] + , 27%), 268 (8%).
Folgende Verbindungen wurden auf ähnliche Weise hergestellt:The following connections were made in a similar manner:
Beispiele 2-6Examples 2-6
(Me2PC2H4C5H4)CrCl2 (Me 2 PC 2 H 4 C 5 H 4 ) CrCl 2
Ber. für C9H14Cl2CrP: C, 39.2; H, 5.1; Cl, 25.7; Cr, 18.8; P, 11.2% Gef: C, 39.3;Ber. for C 9 H 14 Cl 2 CrP: C, 39.2; H, 5.1; Cl, 25.7; Cr, 18.8; P, 11.2% Found: C, 39.3;
H, 5.0; Cl, 25.5; Cr, 18.7; P, 11.2%. MS (140°C): m/e 275 ([M-H]+, 41%), 240H, 5.0; Cl, 25.5; Cr, 18.7; P, 11.2%. MS (140 ° C): m / e 275 ([MH] + , 41%), 240
(9.3%).(9.3%).
(Ph2PC2H4C5H4)CrCl2.Toluol (Ausbeute: 84%)(Ph 2 PC 2 H 4 C 5 H 4 ) CrCl 2 .Toluene (yield: 84%)
Ber. für Cι9H18Cl2CrP.Toluol: C, 63.4; H, 5.3; Cl, 14.4; Cr, 10.6; P, 6.3% Gef.: C,Ber. for Cι 9 H 18 Cl 2 CrP.Toluene: C, 63.4; H, 5.3; Cl, 14.4; Cr, 10.6; P, 6.3% Found: C,
63.4; H, 5.4; Cl, 14.4; Cr, 10.5; P, 6.2%. MS (170°C): m/e 399 ([M-H]+, 30%),63.4; H, 5.4; Cl, 14.4; Cr, 10.5; P, 6.2%. MS (170 ° C): m / e 399 ([MH] + , 30%),
364 (1.8%). Kristallstruktur: siehe Figur 1.364 (1.8%). Crystal structure: see Figure 1.
(Cy2PC2H4C5H4)CrCl2 (Ausbeute: 85%)(Cy 2 PC 2 H 4 C 5 H 4 ) CrCl 2 (yield: 85%)
Ber.für C19H30Cl2CrP: C, 55.4; H, 7.3; Cl, 17.2; Cr, 12.6; P, 7.5%. Gef.: C. 55.2;Calc. For C 19 H 30 Cl 2 CrP: C, 55.4; H, 7.3; Cl, 17.2; Cr, 12.6; P, 7.5%. Found: C. 55.2;
H, 7.3; Cl, 17.1; Cr, 12.7; P, 7.7%. MS(150°C): m/e 411 ([M-H]+, 27%), 367H, 7.3; Cl, 17.1; Cr, 12.7; P, 7.7%. MS (150 ° C): m / e 411 ([MH] + , 27%), 367
(4.4%).(4.4%).
(CyzPCzHUindeny CrCk (Ausbeute: 23%)(CyzPCzHUindeny CrCk (yield: 23%)
Ber. für C23H32Cl2CrP: C, 59.8; H, 7.0; Cl, 15.3; Cr, 11.3; P, 6.7%. Gef.: C, 59.9;Ber. for C 23 H 32 Cl 2 CrP: C, 59.8; H, 7.0; Cl, 15.3; Cr, 11.3; P, 6.7%. Found: C, 59.9;
H, 7.1; Cl, 15.3; Cr, 11.2; P, 6.6%. MS (185°C): m/e 461 ([M-H]+, 39%) 425H, 7.1; Cl, 15.3; Cr, 11.2; P, 6.6%. MS (185 ° C): m / e 461 ([MH] + , 39%) 425
(31%).(31%).
(Cy2AsC2H4C5H4)CrCl2 (Ausbeute: 73%) Ber. für C,9H30AsCl2Cr: C, 50.0; H, 6.7; As, 16.4; Cl, 15.5; Cr, 1 1.4%. Gef: C, 50.1; H, 6.6; As, 16.4; Cl, 15.5; Cr, 11.5%. MS(160°C): m/e 455([M-H]+, 7.3%) 420 (6.4%). Kristallstruktur: siehe Abb. 1.(Cy 2 AsC 2 H 4 C 5 H 4 ) CrCl 2 (yield: 73%) Ber. for C, 9 H 30 AsCl 2 Cr: C, 50.0; H, 6.7; As, 16.4; Cl, 15.5; Cr, 1 1.4%. Found: C, 50.1; H, 6.6; As, 16.4; Cl, 15.5; Cr, 11.5%. MS (160 ° C): m / e 455 ([MH] + , 7.3%) 420 (6.4%). Crystal structure: see Fig. 1.
Beispiel 7Example 7
(Ph2PC3H6C5H4)CrCl2
Figure imgf000008_0001
(dargestellt aus ClC3H6PPh2 (1.3g, 4.9mmol) und NaCp (4.3g,(Ph 2 PC 3 H 6 C 5 H 4 ) CrCl 2
Figure imgf000008_0001
(shown from ClC 3 H 6 PPh 2 (1.3g, 4.9mmol) and NaCp (4.3g,
49mmol) und nachfolgende Protonolyse und Behandlung mit BuLi) wurde mit49mmol) and subsequent protonolysis and treatment with BuLi) was performed with
Cr(THF)3Cl3 (1.84g, 4.9mmol) in THF (100ml) bei Raumtemperatur umgesetzt.Cr (THF) 3 Cl 3 (1.84g, 4.9mmol) in THF (100ml) at room temperature.
Die blaue Lösung wurde eingeengt und der Rückstand mit siedendem ToluolThe blue solution was concentrated and the residue with boiling toluene
(100ml) extrahiert. Die Verbindung kristallisiert bei Raumtemperatur in Form von blauen Nadeln. Ausbeute: 1.48g ( 73% Theorie).(100ml) extracted. The compound crystallizes at room temperature in the form of blue needles. Yield: 1.48g (73% theory).
Analytische Daten, Ber. für C20H20Cl2CrP: C, 58.1; H, 5.0; Cl, 17.1; Cr, 12.4; P,Analytical data, calc. for C 20 H 20 Cl 2 CrP: C, 58.1; H, 5.0; Cl, 17.1; Cr, 12.4; P,
7.3%. Gef.: C, 58.0; H, 4.9; Cl, 17.1; Cr, 12.6; P, 7.5%. MS (170°C): m/e 4137.3%. Found: C, 58.0; H, 4.9; Cl, 17.1; Cr, 12.6; P, 7.5%. MS (170 ° C): m / e 413
([M-H]+, 18%), 378 (1.5%). Kristallstruktur: siehe Abb. 1.([MH] + , 18%), 378 (1.5%). Crystal structure: see Fig. 1.
Beispiel 8Example 8
(Ph2PC3H6C5Me4)CrCl2 (Ph 2 PC 3 H 6 C 5 Me 4 ) CrCl 2
Ph2PC3H6C5Me4Li (1.64g, 4.7mmol; dargestellt aus Tosyl OC3H6C5H5 und KPPh2 mit nachfolgender Protonolyse und Reaktion mit BuLi) wurde in THF (20ml) gelöst und bei Raumtemperatur zu Cr(THF)3Cl3 (1.81g, 4.7mmol) in THF (20ml) zugetropft. Die grüne Reaktionslösung wurde eingeengt und der Rückstand mit Toluol (300ml) extrahiert und die Lösung durch eine Celite-Säule (20x2cm) filtriert, um die grüne Verunreinigung zu entfernen. Die so erhaltene blaue Lösung wurde eingeengt und der Rückstand mit Toluol bei Raumtemperatur extrahiert. Die Verbindung wurde aus Toluol umkristallisiert. Ausbeute: 0.6g (27% Theorie). Analytische Daten, Ber. für C24H2gCl2CrP: C, 61.3; H, 6.0; Cl, 15.1; Cr, 11.1; P, 6.6%. Gef.: C, 61.1; H, 6.1; Cl, 15.0; Cr, 10.8; P, 6.4%. MS (140°C): m/e 469 ([M-HJ 25%) 434 (5.5%). Kristallstruktur: siehe Abb. 1. Beispiel 9Ph2PC 3 H 6 C5Me 4 Li (1.64g, 4.7mmol; prepared from Tosyl OC 3 H 6 C 5 H 5 and KPPh 2 with subsequent protonolysis and reaction with BuLi) was dissolved in THF (20ml) and at room temperature to Cr (THF ) 3 Cl 3 (1.81g, 4.7mmol) in THF (20ml) added dropwise. The green reaction solution was concentrated and the residue extracted with toluene (300ml) and the solution filtered through a Celite column (20x2cm) to remove the green impurity. The blue solution thus obtained was concentrated and the residue was extracted with toluene at room temperature. The compound was recrystallized from toluene. Yield: 0.6g (27% theory). Analytical data, calc. for C 24 H 2g Cl 2 CrP: C, 61.3; H, 6.0; Cl, 15.1; Cr, 11.1; P, 6.6%. Found: C, 61.1; H, 6.1; Cl, 15.0; Cr, 10.8; P, 6.4%. MS (140 ° C): m / e 469 ([M-HJ 25%) 434 (5.5%). Crystal structure: see Fig. 1. Example 9
(Et2PC2H4C5H4)CrMe2 (Et 2 PC 2 H 4 C 5 H 4 ) CrMe 2
(Et2PC2H4C5H4)CrCl2 (0.9g, 3mmol) wurde in THF (20ml) bei -30°C gelöst und mit MeMgCl (11ml eine 2.70mol Lösung in THF) umgesetzt. Die dunkelgrüne(Et 2 PC 2 H 4 C 5 H 4 ) CrCl 2 (0.9g, 3mmol) was dissolved in THF (20ml) at -30 ° C and reacted with MeMgCl (11ml a 2.70mol solution in THF). The dark green
Lösung wurde bei Raumtemperatur eingeengt und der Rückstand mit PentanSolution was concentrated at room temperature and the residue with pentane
(2x50ml) extrahiert. Die Verbindung fiel in Form von dunkelblau-violetten Nadeln bei -78°C aus der Lösung aus. Ausbeute: ca. 10%.(2x50ml) extracted. The compound precipitated out of solution in the form of dark blue-violet needles at -78 ° C. Yield: approx. 10%.
Analytische Daten, Ber. für C13H24CrP: C, 59.3; H, 9.2; Cr, 19.8; P, 11.8%. Gef.:Analytical data, calc. for C 13 H 24 CrP: C, 59.3; H, 9.2; Cr, 19.8; P, 11.8%. Found .:
C, 59.4; H, 9.3; Cr, 19.6; P, 11.7%. MS(75°C): m/e 263 (M+, 3%), 249 (12%).C, 59.4; H, 9.3; Cr, 19.6; P, 11.7%. MS (75 ° C): m / e 263 (M + , 3%), 249 (12%).
Katalytische Alken-OligomerisationCatalytic alkene oligomerization
Beispiel 10-18Example 10-18
Die folgenden Beispiele der Oligomerisation von Ethylen wurden bei isothermerThe following examples of oligomerization of ethylene have been shown to be isothermal
Reaktionsführung, d. h. ΔT < 4 °C, in einem Glasautoklav, ausgestattet mit einemReaction management, d. H. ΔT <4 ° C, in a glass autoclave, equipped with a
Glasflügelrührer, bei 1200U/min ausgeführt (Tabelle 1). Glass paddle stirrer, executed at 1200rpm (Table 1).
Tabelle 1 : Die Oligomerisation / Polymerisation von Ethylen unter ΔT Bedingungen mit MAO-aktivierten, phosphino- und arsino- substituierten Cyclopentadienyl-Chrom-Katalysatoren a Table 1: The oligomerization / polymerization of ethylene under ΔT conditions with MAO-activated, phosphino- and arsino-substituted cyclopentadienyl-chromium catalysts a
Figure imgf000010_0001
Figure imgf000010_0001
Tabelle 1: FortsetzungTable 1: continued
Figure imgf000011_0001
Figure imgf000011_0001
2 Standard Bedingungen : Lösungsmittel, Toluol(250 ml) ; PEthyien 2 bar ; Cr : MAO = 1 : 100 ; t = 4 min, ΔT < 4 °C fe Cr - Komplex gelöst in CH2C12(2 ml) ; t = 22 min ; nicht isotherm (ΔT = 12 °C) und nicht vergleichbar, 2 standard conditions: solvent, toluene (250 ml); P Ethy i s 2 bar; Cr: MAO = 1: 100; t = 4 min, ΔT <4 ° C fe Cr complex dissolved in CH 2 C1 2 (2 ml); t = 22 min; not isothermal (ΔT = 12 ° C) and not comparable,
- Cr - Komplex gelöst in CH2Cl2(lml), ä Cr - Komplex gelöst in CH2C12(2.5 ml) ; t = 62 min, - Cr complex dissolved in CH 2 Cl 2 (lml), ä Cr complex dissolved in CH 2 C1 2 (2.5 ml); t = 62 min,
Beispiel 19Example 19
Obwohl ausgezeichnete Aktivitäten bereits bei einem Cr: AI- Verhältnis von 1:100 erzielt wurden sind, stieg die Aktivität noch erheblich bei der Anwendung von höheren AI-Konzentrationen (Tabelle 2).Although excellent activities have already been achieved at a Cr: Al ratio of 1: 100, the activity increased considerably when higher Al concentrations were used (Table 2).
Tabelle 2Table 2
(Ph2PC3H6C5Me4)CrCl2/MAO-katalysierte Oügomerisierung von Ethylen (Lösungsmittel: Toluol; T=21°C; p(Ethylen) 2 bar) unter isothermischen Bedingungen (ΔT= < 3°C).(Ph2PC 3 H 6 C5Me4) CrCl 2 / MAO-catalyzed ougomerization of ethylene (solvent: toluene; T = 21 ° C; p (ethylene) 2 bar) under isothermal conditions (ΔT = <3 ° C).
CπMAO Aktivität (Kg-Produkt / mol-Cr.h)CπMAO activity (kg product / mol-Cr.h)
0 00 0
100 5500100 5500
500 21000500 21000
1000 279001000 27900
5000 518005000 51800
10000 7470010000 74700
Die Ergebnisse in Tabelle 1 sind bei Raumtemperatur und 2 bar Ethylen in Toluol erzielt worden, jedoch kann die Katalyse auch bei höheren Temperaturen (z.B. 80°C, Beispiel 20) und in anderen Lösungsmitteln (z.B. Heptan, Beispiel 21) durchgeführt werden.The results in Table 1 were achieved at room temperature and 2 bar ethylene in toluene, but the catalysis can also be carried out at higher temperatures (e.g. 80 ° C, example 20) and in other solvents (e.g. heptane, example 21).
Beispiel 20Example 20
Katalysator:(Et2PC2H4C5H4)CrC12 (4.48 μmol)/ MAO (Cr:MAO=l:500) in CH2C12 (1.2ml). Oligomerisation: Lösungsmittel, Toluol (250ml); PCCJrL , 2bar; T, 76.7-84.7°C; Zeit, 4min; Produkt, 9.39g (C4-C]2 Alkene, GC); Aktivität, 3000 Kg Produkt/mol Cr.h. Beispiel 21Catalyst: (Et 2 PC 2 H 4 C 5 H 4 ) CrC12 (4.48 μmol) / MAO (Cr: MAO = l: 500) in CH 2 C1 2 (1.2ml). Oligomerization: solvent, toluene (250ml); PCCJrL, 2bar; T, 76.7-84.7 ° C; Time, 4min; Product, 9.39g (C 4 -C] 2 alkenes, GC); Activity, 3000 kg product / mol Cr.h. Example 21
Katalysator: (Et2PC2H4C5H4)CrCl2 (16.77 μmol)/ MAO (Cr:MAO= l: 100)inCatalyst: (Et 2 PC 2 H 4 C 5 H 4 ) CrCl 2 (16.77 μmol) / MAO (Cr: MAO = l: 100) in
CH2C12 (2ml). Oligomerisation: Lösungsmittel, Heptan (250ml); P(C2H4), 2bar; T,CH 2 C1 2 (2ml). Oligomerization: solvent, heptane (250ml); P (C 2 H 4 ), 2bar; T
21.0-27.2; Zeit, 4min; Produkt, 6.73g (C4-C20 Alkene, GC); Aktivität, 1,800 Kg21.0-27.2; Time, 4min; Product, 6.73g (C 4 -C 20 alkenes, GC); Activity, 1,800 kg
Produkt/molCr.h.Product / molCr.h.
Die gleichen Katalysatoren können auch bei der Cooligomerisation von Ethylen mit anderen Alkenen (z.B. Norbornen, Beispiel 22) verwendet werden.The same catalysts can also be used in the cooligomerization of ethylene with other alkenes (e.g. norbornene, example 22).
Beispiel 22Example 22
Katalysator: (Et2PC2H4C5H4)CrCl2 (23,34 μmol)/MAO (CπMAO = 1:100) in CH2C12 Catalyst: (Et 2 PC 2 H 4 C 5 H 4 ) CrCl 2 (23.34 μmol) / MAO (CπMAO = 1: 100) in CH 2 C1 2
(2 ml). Oligomerisation: Lösungsmittel Toluol (200 ml)/Norbornen (50ml); P(C2rΪ4), 2 bar, T 21.0; Zeit 52 min.; Produkt 34 g (Ethylen-Norbornen Cooligomer), (2 ml). Oligomerization: solvent toluene (200 ml) / norbornene (50 ml); P (C2rΪ4), 2 bar, T 21.0; Time 52 min .; Product 34 g (ethylene norbornene cooligomer),

Claims

Patentansp rüche Claims
1. Verfahren zur katalytischen Oügomerisierung oder Cooügomerisierung von Alkenen, dadurch gekennzeichnet, daß der Katalysator mindestens eine Organochrom- Verbindung der aUgemeinen Formel I enthält,1. A process for the catalytic ougomerization or coougomerization of alkenes, characterized in that the catalyst contains at least one organochrome compound of the general formula I,
Figure imgf000014_0001
Figure imgf000014_0001
wobeiin which
R1 ein delokaüsiertes η5-koordiniertes π-System enthält,R 1 contains a delta-cured η 5 -coordinated π system,
X ein elektronegatives Atom, Halogen, Amid oder Organylgruppe,X is an electronegative atom, halogen, amide or organyl group,
Y ein Donoratom der 15. Gruppe des Periodensystems,Y is a donor atom of the 15th group of the periodic table,
Z ein Atom der 14. oder 16. Gruppe des Periodensystems ist,Z is an atom of the 14th or 16th group of the periodic table,
R' und R' ' gleich oder verschieden sein können und H, Alkyl, Aryl,R 'and R' 'can be the same or different and H, alkyl, aryl,
Organylgruppen, OR, oder NR2 (R=Alkyl, Aryl) sind und n >1 ist.Organylgruppen, OR, or NR 2 (R = alkyl, aryl) and n> 1.
2. Verfahren nach Anspruch 1, wobei Y = P oder As ist.2. The method of claim 1, wherein Y = P or As.
3. Verfahren nach Anspruch 1, wobei der Organochromverbindung eine Lewis- Säure zugesetzt ist.3. The method of claim 1, wherein a Lewis acid is added to the organochrome compound.
4. Verfahren nach Anspruch 3, wobei die Lewis-Säure Methylalumoxan ist 4. The method of claim 3, wherein the Lewis acid is methylalumoxane
5. Verfahren nach Anspruch 4, wobei das Molverhältnis von Al:Cr im Katalysator zwischen 40: 1 und 10000: 1 üegt.5. The method according to claim 4, wherein the molar ratio of Al: Cr in the catalyst ranges between 40: 1 and 10000: 1.
6. Verfahren nach Ansprüchen 1-5, wobei das delokaüsierte η5-koordinierte π- System Cyclopentadienyl, substituiertes Cyclopentadienyl oder Indenyl ist.6. The method according to claims 1-5, wherein the delocated η 5 -coordinated π- system is cyclopentadienyl, substituted cyclopentadienyl or indenyl.
7. Verfahren nach Ansprüchen 1-6, wobei R"= H, Alkyl, Aryl, OR oder NR2 und R= Alkyl oder Aryl ist.7. The method according to claims 1-6, wherein R "= H, alkyl, aryl, OR or NR 2 and R = alkyl or aryl.
8. Verfahren nach Ansprüchen 1-7, wobei über die Größe des Substituenten R" das Molekulargewicht des Oügomerisationsproduktes gesteuert wird, wobei größere Substituenten zu höherem Molekulargewicht führen.8. The method according to claims 1-7, wherein the molecular weight of the ougomerization product is controlled via the size of the substituent R ", larger substituents leading to higher molecular weight.
9. Verfahren nach Ansprüchen 1-8, wobei als Alken Ethylen eingesetzt wird.9. The method according to claims 1-8, wherein ethylene is used as alkene.
10. Verfahren nach Ansprüchen 1-8, wobei Ethylen und ein substituiertes Alken cooügomerisiert werden. 10. The method according to claims 1-8, wherein ethylene and a substituted alkene are coougomerized.
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