EP2542561A1 - Polyhedral oligomeric silsequioxane (poss) bonded ligands and the use thereof - Google Patents

Polyhedral oligomeric silsequioxane (poss) bonded ligands and the use thereof

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Publication number
EP2542561A1
EP2542561A1 EP11705890A EP11705890A EP2542561A1 EP 2542561 A1 EP2542561 A1 EP 2542561A1 EP 11705890 A EP11705890 A EP 11705890A EP 11705890 A EP11705890 A EP 11705890A EP 2542561 A1 EP2542561 A1 EP 2542561A1
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EP
European Patent Office
Prior art keywords
olefin
hydroformylation
catalytically active
group
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11705890A
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German (de)
French (fr)
Inventor
Andrea Christiansen
Robert Franke
Dieter Hess
Dirk Fridag
Dieter Vogt
Christian Müller
Michèle Janssen
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Evonik Operations GmbH
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Evonik Oxeno GmbH and Co KG
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Priority to EP11705890A priority Critical patent/EP2542561A1/en
Publication of EP2542561A1 publication Critical patent/EP2542561A1/en
Withdrawn legal-status Critical Current

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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
    • B01J31/124—Silicones or siloxanes or comprising such units
    • B01J31/125—Cyclic siloxanes
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B01J31/1683—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4061—Regeneration or reactivation of catalysts containing metals involving membrane separation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the hydroformylation of olefins and olefin-containing mixtures is a research topic of the chemical industry.
  • a permanent problem in the case of catalytic hydroformylation is the maintenance of the activity and the selectivity of the catalytically active compositions used in each case in comparison with the olefins to be hydroformylated and olefin-containing mixtures under the reaction conditions.
  • transition metal-containing, catalytically active compositions it is an object of research to at least significantly limit the inhibition of the catalytic activity, the formation of transition metal clusters and the failure of the transition metal itself.
  • the present invention provides a contribution to this problem by providing a way in which, while avoiding thermal stress on the reaction mixture, the desired target products can be easily separated from the catalytically active composition while retaining its catalytic activity.
  • An object of the present invention are POSS-modified ligands, wherein POSS are understood as meaning polyhedral oligomers silsesquioxane derivatives.
  • the polyhedral oligomers silsesquioxane derivatives used are reacted with per se known ligand precursors.
  • the resulting POSS-modified ligands have dramatically increased molecular weight compared to unmodified ligands.
  • triphenylphosphine for example, alkylphenyl-substituted, in particular an ethylphenyl-substituted, POSS-substituted triphenylphosphine derivative are prepared: Si 8
  • Another object of the present invention in the hydroformylation of olefins and olefin-containing mixtures catalytically active, transition metal-containing compositions obtainable by reacting the POSS-modified ligands with suitable transition metal precursors.
  • Characteristic of these novel transition-metal complexes prepared in the catalytically active compositions with POSS-modified ligands is that the activity and selectivity for the non-POSS-modified transition metal complexes are maintained.
  • the catalytically active compositions according to the invention are completely separable from the reaction mixture by means of organic nanofiltration and can be recycled to the hydroformylation reaction.
  • the previously described POSS-substituted triphenylphosphine is reacted with a rhodium-containing, suitable transition metal precursor, such as e.g. B. [Rh (acac) (CO) 2], converted to the catalytically active composition.
  • a rhodium-containing, suitable transition metal precursor such as e.g. B. [Rh (acac) (CO) 2]
  • Another object of the present invention is the use of POSS-modified ligands in catalytically active compositions in the hydroformylation of olefins and olefin-containing mixtures.
  • the above-described POSS-substituted triphenylphosphine is reacted with a rhodium-containing, suitable transition metal precursor, such as e.g. [Rh (acac) (CO) 2], converted to the catalytically active composition which in the hydroformylation of olefins, such.
  • a rhodium-containing, suitable transition metal precursor such as e.g. [Rh (acac) (CO) 2]
  • Example 1 Hydroformylation of 1-octene in a continuously operated membrane reactor
  • the hydroformylation experiments were carried out in a continuously operated pilot plant; s. Plant sketch.
  • This pilot plant consisted of a reaction part and a membrane part.
  • the reaction section comprised a 100 mL autoclave b with a circulation pump c.
  • the autoclave b was equipped with a pressure hold A for the synthesis gas. By this pressure A During the reaction, the synthesis gas pressure was kept constant throughout the system.
  • the synthesis gas uptake of the system was determined by a flow measurement C.
  • the reactor was equipped with a pressure burette a, which could be charged with syngas and thus allowed a dosage of the educt and catalyst solutions under reaction conditions.
  • the autoclave b was also equipped with a level control B.
  • the Eduktpumpe e was controlled, which then pumped from a template h Edukthus comprising the olefin-containing mixture, optionally solvent, in the autoclave b, so as to keep the state constant in the autoclave.
  • This educt template h was covered with argon to avoid contact with air.
  • the necessary turbulence in the autoclave was generated by the circulation pump c, which was specially designed for this application.
  • the pump c built a loop of the reaction solution through a nozzle in the head of the autoclave b and thus provided for a corresponding gas / liquid exchange.
  • the synthesis gas and the educt were also metered into the nozzle.
  • a cross-flow chamber f was also installed.
  • the cross flow chamber f separates the reaction part from the membrane part of the plant.
  • the cross-flow chamber f ensures the mixing of the membrane circulation with the reactor discharge and ensured that the free gas fraction in the outlet of the reactor could not get into the membrane part, but was returned to the reaction cycle.
  • the membrane part consisted of a pressure tube containing a ceramic membrane j of 200mm length with a specific filter area of 0.0217m2 / m and a cut-off of 450D, and a circulation pump g which created a loop across the membrane.
  • the connection to the reaction part was realized via the already described cross flow chamber f.
  • the permeate flow through the membrane j was realized by a pressure maintenance F on the permeate side.
  • a pressure maintenance F on the permeate side.
  • the preparation of the catalyst solution was carried out under an argon atmosphere. Subsequently, a differential pressure TMP of 0.35 MPa was set on the membrane j via the permeate pressure control F in order to remove the generated product i, aldehydes, from the system.
  • Example 2 Hydroformylation of 1-Butene in a Continuously Operated Membrane Reactor The hydroformylation experiments were carried out in a continuously operated pilot plant; s. Plant sketch. This pilot plant consisted of a reaction part and a membrane part.
  • the reaction section comprised a 1 00 mL autoclave b with a circulation pump c.
  • the autoclave b was with a Pressure maintenance A equipped for the synthesis gas. Through this pressure A, the synthesis gas pressure was kept constant during the reaction throughout the system.
  • the synthesis gas uptake of the system was determined by a flow measurement C.
  • the reactor was equipped with a pressure burette a, which could be charged with syngas and thus allowed a dosage of the educt and catalyst solutions under reaction conditions.
  • the autoclave b was also equipped with a level control B.
  • the Eduktpumpe e was controlled, which then pumped from a template h Eduktsignificant comprising the olefin-containing mixture, optionally solvent, in the autoclave b, so as to keep the state constant in the autoclave.
  • This educt template h was covered with argon to avoid contact with air.
  • the necessary turbulence in the autoclave was generated by the circulation pump c, which was specially designed for this application.
  • the pump c built a loop of the reaction solution through a nozzle in the head of the autoclave b and thus provided for a corresponding gas / liquid exchange.
  • the synthesis gas and the educt were also metered into the nozzle.
  • a cross-flow chamber f was also installed.
  • the cross flow chamber f separates the reaction part from the membrane part of the plant.
  • the cross-flow chamber f ensures the mixing of the membrane circulation with the reactor discharge and ensured that the free gas fraction in the outlet of the reactor could not get into the membrane part, but was returned to the reaction cycle.
  • the membrane part consisted of a pressure tube which contained a ceramic membrane j of 200 mm length with a specific filter area of 0.0217 m 2 / m and a cut-off of 450 D, and a circulation pump g which generated a circulation across the membrane.
  • the connection to the reaction part was realized via the already described cross flow chamber f.
  • the permeate flow through the membrane j was realized by a pressure maintenance F on the permeate side.
  • a pressure maintenance F on the permeate side.
  • the preparation of the catalyst solution was carried out under an argon atmosphere. Subsequently, a differential pressure of 0.30 MPa was set on the membrane j via the permeate pressure control F in order to remove the generated product i, aldehydes, from the system.
  • Raffinates such as. As raffinate I, raffinate II, but also mixtures containing olefins having 3 to 20 carbon atoms used.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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  • Catalysts (AREA)

Abstract

The present invention relates to POSS-modified ligands and to the use thereof in catalytically effective compositions in hydroformylation.

Description

Polyhedrale Oligomere Silsesquioxan (POSS)-verbundene Liganden und deren Verwendung  Polyhedral oligomeric silsesquioxane (POSS) -linked ligands and their use
Die Hydroformylierung von Olefinen und olefinhaltigen Gemischen sind ein Forschungsgegenstand der chemischen Industrie. Eine dauerhafte Problemstellung ist bei der katalytischen Hydroformylierung der Erhalt der Aktivität und der Selektivität der jeweils verwendeten katalytisch wirksamen Zusammensetzungen gegenüber den zu hydroformylierenden Olefinen und olefinhaltigen Gemischen unter den Reaktionsbedingungen. Insbesondere bei Übergangsmetallhaltigen, katalytisch wirksamen Zusammensetzungen ist es ein Ziel der Forschung die Inhibie- rung der katalytischen Wirkung, die Bildung von Übergangsmetall-Clustern und den Ausfall des Übergangsmetalls selbst zu verhindern, zumindest deutlich einzuschränken. Die vorliegende Erfindung liefert einen Beitrag zu dieser Problemstellung, indem sie einen Weg aufzeigt, wie unter Vermeidung von thermischer Belastung des Reaktionsgemisches auf einfache Weise die gewünschten Zielpro- dukte abgetrennt werden von der katalytisch wirksamen Zusammensetzung, wobei dessen katalytische Aktivität erhalten bleibt. The hydroformylation of olefins and olefin-containing mixtures is a research topic of the chemical industry. A permanent problem in the case of catalytic hydroformylation is the maintenance of the activity and the selectivity of the catalytically active compositions used in each case in comparison with the olefins to be hydroformylated and olefin-containing mixtures under the reaction conditions. Particularly in the case of transition metal-containing, catalytically active compositions, it is an object of research to at least significantly limit the inhibition of the catalytic activity, the formation of transition metal clusters and the failure of the transition metal itself. The present invention provides a contribution to this problem by providing a way in which, while avoiding thermal stress on the reaction mixture, the desired target products can be easily separated from the catalytically active composition while retaining its catalytic activity.
Ein Gegenstand der vorliegenden Erfindung sind POSS-modifizierte Liganden, wobei unter POSS Polyhedrale Oligomere Silsesquioxan-Derivate verstanden werden. Die verwendeten Polyhedralen Oligomeren Silsesquioxan-Derivate wer- den mit an sich bekannten Ligandenvorstufen umgesetzt. Die daraus resultierenden POSS-modifizierten Liganden weisen ein drastisch erhöhtes Molekulargewicht im Vergleich zu unmodifizierten Liganden auf. In einer Ausführungsform der Erfindung werden auf Basis von Triorganophosphinen, wie Triphenylphosphin beispielsweise Alkylphenyl-substituierte, insbesondere ein Ethylphenyl-substituiertes, mit POSS substituiertes Triphenylphosphinderivat hergestellt: Si8 An object of the present invention are POSS-modified ligands, wherein POSS are understood as meaning polyhedral oligomers silsesquioxane derivatives. The polyhedral oligomers silsesquioxane derivatives used are reacted with per se known ligand precursors. The resulting POSS-modified ligands have dramatically increased molecular weight compared to unmodified ligands. In one embodiment of the invention, on the basis of triorganophosphines, such as triphenylphosphine, for example, alkylphenyl-substituted, in particular an ethylphenyl-substituted, POSS-substituted triphenylphosphine derivative are prepared: Si 8
Herstellung von POSS-substituierten Triphenylphosphin Preparation of POSS-substituted triphenylphosphine
4-Bromophenylethyl-POSS (1 1 g, 10.92 mmol) wird gelöst in 100 mL THF und auf -78°C gekühlt. n-BuLi (2.5 M in hexanes, 4.8 mL, 12 mmol) wird tropfenweise zugefügt und die Reaktionsmischung wird bei dieser Temperatur 1 h gerührt. PCI3 (0.5 g, 3.64 mmol) wird tropfenweise hinzugegeben. Man lässt die Reaktionsmischung auf Raumtemperatur erwärmen und rührt über Nacht. Das Lösungsmittel wird im Vakuum entfernt. Das Reaktionsprodukt wird aus dem verbleibenden Feststoff mit Toluol/Hexan (1 :1 , 1 50 mL) extrahiert und mit entgastem Wasser gewaschen. Die organische Phase wird über MgSO4 getrocknet. Die Lösungsmittel werden im Vakuum entfernt. Das Produkt wird erhalten als ein weißer Feststoff in 78% Ausbeute (8 g, 2.84 mmol). 4-Bromophenylethyl-POSS (1 1 g, 10.92 mmol) is dissolved in 100 mL of THF and cooled to -78 ° C. n-BuLi (2.5 M in hexanes, 4.8 mL, 12 mmol) is added dropwise and the reaction mixture is stirred at this temperature for 1 h. PCI3 (0.5 g, 3.64 mmol) is added dropwise. The reaction mixture is allowed to warm to room temperature and stirred overnight. The solvent is removed in vacuo. The reaction product is extracted from the remaining solid with toluene / hexane (1: 1, 1 50 mL) and washed with degassed water. The organic phase is dried over MgSO 4 . The solvents are removed in vacuo. The product is obtained as a white solid in 78% yield (8 g, 2.84 mmol).
1 H NMR δ (ppm): 7.24 (dd, J = 12.4 Hz, J = 14.4 Hz, 12H), 2.69 (m. 6H), 1 .87 (sept, J = 6.7 Hz, 7H), 0.97 (d, J = 6.6 Hz, 42H), 0.62 (d, J = 7 Hz, 14H) 1 H NMR δ (ppm): 7.24 (dd, J = 12.4 Hz, J = 14.4 Hz, 12H), 2.69 (m 6H), 1 .87 (sept, J = 6.7 Hz, 7H), 0.97 (d, J = 6.6 Hz, 42H), 0.62 (d, J = 7 Hz, 14H)
13C NMR δ (ppm): 145.15, 133.83, 127.94, 125.61 , 28.97, 25.70, 23.88, 22.53, 14.07 13C NMR δ (ppm): 145.15, 133.83, 127.94, 125.61, 28.97, 25.70, 23.88, 22.53, 14.07
31 P NMR δ (ppm): - 7.76 (s)  31 P NMR δ (ppm): - 7.76 (s)
Maldi-Tof: m/z = 2809.07 (M+Na) Elementaranalyse: berechnet (gefunden): C 46.45 (46.54), H 7.69 (7.77) Maldi-Tof: m / z = 2809.07 (M + Na) Elemental analysis: calculated (found): C 46.45 (46.54), H 7.69 (7.77)
Ein weiterer Gegenstand der vorliegenden Erfindung sind in der Hydroformylie- rung von Olefinen und olefinhaltigen Gemischen katalytisch wirksame, Übergangsmetallhaltige Zusammensetzungen, die durch Umsetzung der POSS- modifizierten Liganden mit geeigneten Übergangsmetallvorstufen erhältlich sind. Kennzeichnend für diese neuartigen, mit POSS-modifizierten Liganden hergestellten Übergangsmetallkomplexe in den katalytisch wirksamen Zusammensetzungen ist, dass d ie Aktivität sowie Selektivität gegenü ber den n icht m it POSS- modifizierten Übergangsmetallkomplexen erhalten bleibt. Zugleich sind die erfin- dungsgemäßen, katalytisch wirksamen Zusammensetzungen vollständig aus dem Reaktionsgemisch mittels organischer Nanofiltration abtrennbar und können in die Hydroformylierungsreaktion zurückgeführt werden. In einer Ausführungsform der Erfindung wird das zuvor beschriebene POSS-substituierte Triphenylphoshin mit einer Rhodiumhaitigen, geeigneten Übergangsmetallvorstufe, wie z. B. [Rh(acac)(CO)2] , zu der katalytisch wirksamen Zusammensetzung umgesetzt. Another object of the present invention in the hydroformylation of olefins and olefin-containing mixtures catalytically active, transition metal-containing compositions obtainable by reacting the POSS-modified ligands with suitable transition metal precursors. Characteristic of these novel transition-metal complexes prepared in the catalytically active compositions with POSS-modified ligands is that the activity and selectivity for the non-POSS-modified transition metal complexes are maintained. At the same time, the catalytically active compositions according to the invention are completely separable from the reaction mixture by means of organic nanofiltration and can be recycled to the hydroformylation reaction. In one embodiment of the invention, the previously described POSS-substituted triphenylphosphine is reacted with a rhodium-containing, suitable transition metal precursor, such as e.g. B. [Rh (acac) (CO) 2], converted to the catalytically active composition.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von POSS-modifizierten Liganden in katalytisch wirksamen Zusammensetzungen in der Hydroformylierung von Olefinen und olefinhaltigen Gemischen. In einer Aus- führungsform der Erfindung wird das zuvor beschriebene POSS-substituierte Triphenylphosphin mit einer Rhodiumhaitigen, geeigneten Übergangsmetallvorstufe, wie z.B. [Rh(acac)(CO)2] , zu der katalytisch wirksamen Zusammensetzung umgesetzt, welche in der Hydroformylierung von Olefinen, wie z. B. 1 -Okten, eingesetzt wird: Another object of the present invention is the use of POSS-modified ligands in catalytically active compositions in the hydroformylation of olefins and olefin-containing mixtures. In one embodiment of the invention, the above-described POSS-substituted triphenylphosphine is reacted with a rhodium-containing, suitable transition metal precursor, such as e.g. [Rh (acac) (CO) 2], converted to the catalytically active composition which in the hydroformylation of olefins, such. B. 1 -Okten, is used:
Beispiel 1 : Hydroformylierung von 1 -Okten in einem kontinuierlich betriebenen Membranreaktor Example 1: Hydroformylation of 1-octene in a continuously operated membrane reactor
Die Hydroformylierungsversuche wurden in einer kontinuierlich betriebenen Versuchsanlage durchgeführt; s. Anlagenskizze. Diese Versuchsanlage bestand aus einem Reaktionsteil und einem Membranteil. Der Reaktionsteil umfasste einen 100 mL Autoklaven b mit einer Kreislaufpumpe c. Der Autoklav b war mit einer Druckhaltung A für das Synthesegas ausgestattet. Durch diese Druckhaltung A wurde der Synthesegasdruck während der Reaktion im gesamten System konstant gehalten. Die Synthesegasaufnahme des Systems wurde mit einer Durchflussmessung C bestimmt. Für die Dosierung von Edukt- und Katalysatorlösungen vor Reaktionsstart war der Reaktor mit einer Druckbürette a ausgestattet, die mit Synthesegas beaufschlagt werden konnte und so eine Dosierung der Edukt- und Katalysatorlösungen unter Reaktionsbedingungen erlaubte. Der Autoklav b war zusätzlich mit einer Standregelung B ausgestattet. Durch diese Standregelung B wurde die Eduktpumpe e angesteuert, die dann aus einer Vorlage h Eduktlösung, umfassend das olefinhaltige Gemisch, optional Lösungsmittel, in den Autoklaven b pumpte, um so den Stand im Autoklaven konstant zu halten. Diese Eduktvorlage h war mit Argon überdeckt, um einen Kontakt mit Luft zu vermeiden. Die nötige Turbulenz in dem Autoklaven wurde durch die Kreislaufpumpe c, die eigens für diesen Anwendungsfall konstruiert wurde, erzeugt. Die Pumpe c baute einen Kreislauf der Reaktionslösung über eine Düse im Kopf des Autoklaven b auf und sorgte somit für einen entsprechenden Gas/Flüssigaustausch. Das Synthesegas und das Edukt wurden ebenfalls in die Düse eindosiert. The hydroformylation experiments were carried out in a continuously operated pilot plant; s. Plant sketch. This pilot plant consisted of a reaction part and a membrane part. The reaction section comprised a 100 mL autoclave b with a circulation pump c. The autoclave b was equipped with a pressure hold A for the synthesis gas. By this pressure A During the reaction, the synthesis gas pressure was kept constant throughout the system. The synthesis gas uptake of the system was determined by a flow measurement C. For the metering of reactant and catalyst solutions before the start of the reaction, the reactor was equipped with a pressure burette a, which could be charged with syngas and thus allowed a dosage of the educt and catalyst solutions under reaction conditions. The autoclave b was also equipped with a level control B. By this state control B, the Eduktpumpe e was controlled, which then pumped from a template h Eduktlösung comprising the olefin-containing mixture, optionally solvent, in the autoclave b, so as to keep the state constant in the autoclave. This educt template h was covered with argon to avoid contact with air. The necessary turbulence in the autoclave was generated by the circulation pump c, which was specially designed for this application. The pump c built a loop of the reaction solution through a nozzle in the head of the autoclave b and thus provided for a corresponding gas / liquid exchange. The synthesis gas and the educt were also metered into the nozzle.
In diesem Kreislauf war ebenfalls eine Kreuzstromkammer f eingebaut. Die Kreuzstromkammer f trennt den Reaktionsteil von dem Membranteil der Anlage.  In this cycle, a cross-flow chamber f was also installed. The cross flow chamber f separates the reaction part from the membrane part of the plant.
Die Kreuzstromkammer f sorgt für die Vermischung des Membrankreislaufes mit dem Reaktoraustrag und stellte sicher, dass der freie Gasanteil im Ausgang des Reaktors nicht in den Membranteil gelangen konnte, sondern wieder in den Reaktionskreislauf zurückgeführt wurde. The cross-flow chamber f ensures the mixing of the membrane circulation with the reactor discharge and ensured that the free gas fraction in the outlet of the reactor could not get into the membrane part, but was returned to the reaction cycle.
Der Membranteil bestand aus einem Druckrohr, welches eine keramische Membran j von 200mm Länge mit einer spezifischen Filterfläche von 0,0217m2/m und einen Cut-Off von 450D, beinhaltete und einer Kreislaufpumpe g, die einen Kreislauf über die Membran erzeugte. Die Verbindung zum Reaktionsteil wurde über die schon beschriebene Kreuzstromkammer f realisiert.  The membrane part consisted of a pressure tube containing a ceramic membrane j of 200mm length with a specific filter area of 0.0217m2 / m and a cut-off of 450D, and a circulation pump g which created a loop across the membrane. The connection to the reaction part was realized via the already described cross flow chamber f.
Der Permeatfluss durch die Membran j wurde durch eine Druckhaltung F auf der Permeatseite realisiert. Durch diese Regeleinrichtung war es möglich eine Druck- differenz über der Membranfläche aufzubauen und somit einen Produktfluss i an Aldehyden zu erzeugen. Vor dem Start wurde das Reaktionssystem fünfmal mit 2,0 MPa Synthesegas CO/H2 (1 :1 ) aufgedrückt und entspannt. Danach wurde die Eduktlosung (1 .9 M 1 - Okten in Toluol) mittels HPLC Pumpe aus der beschriebenen Eduktvorlage h in die Versuchsanlage b, bis auf 90% des angestrebten Füllstandniveaus, überführt. Nach in Betriebnahme des Reaktorkreislaufes, wurde der Reaktionsteil auf 80°C erhitzt und ein Druck von 2,0 MPa CO/H2 (1 :1 ) eingestellt. Das Reaktionssystem wurde über 1 h äquilibriert, bevor die katalytisch wirksame Zusammensetzung, enthaltend 1 5 mg (58 μιτιοΙ) Rh(acac)(CO)2 und 81 5 mg (290 μιτιοΙ) des erfindungsgemäßen POSS-substituierten PPh3, entsprechend einem L:Rh - Verhältnis von 5:1 , in 14 mL Toluol, über die beschriebene Druckbürette a (t =0), unter Reaktionsdruck hinzugegeben wurde. Das Ansetzen der Katalysatorlösung erfolgte unter einer Argonatmosphäre. Anschließend wurde an der Membran j über die Permeatdruckregelung F ein Differenzdruck TMP von 0,35 MPa eingestellt, um das erzeugte Produkt i, Aldehyde, aus dem System zu entfernen. Durch die be- schriebene Standregelung B am Autoklaven, wurde dann die ausgefahrene Menge an Produkt i durch Eduktlosung aus der Vorlage h ersetzt und somit das Füllstandsniveau im Reaktionssystem konstant gehalten. Die Reaktion wurde über einen Zeitraum von 14 Tagen durchgeführt, in dieser Zeit wurden in regelmäßigen Abständen Proben gezogen und analysiert.. Der Umsatz von 1 -Okten und die Regioselektivität (l/b- Verhältnis) wurden mittels GC-Analyse bestimmt. Rh- und P- Rückhalte der Membran wurden über ICP-OES Analytik vom Permeat bestimmt. Sowohl die Rh- als auch die P-Verluste waren sehr gering. Bezogen auf die Gesamtmenge Rhodium und Phosphor lagen diese Verluste bei 0.07%(Rh) bzw. 0.97%(P). The permeate flow through the membrane j was realized by a pressure maintenance F on the permeate side. By means of this control device, it was possible to build up a pressure difference across the membrane surface and thus to produce a product flow i to aldehydes. Before startup, the reaction system was pressurized and expanded five times with 2.0 MPa synthesis gas CO / H 2 (1: 1). Thereafter, the Eduktlosung (1 .9 M 1 - octene in toluene) by means of HPLC pump from the educt template described h in the pilot plant b, up to 90% of the desired level, transferred. After putting the reactor circuit into operation, the reaction part was heated to 80 ° C and a pressure of 2.0 MPa CO / H 2 (1: 1) was set. The reaction system was equilibrated for 1 h before the catalytically active composition containing 1 5 mg (58 μιτιοΙ) Rh (acac) (CO) 2 and 81 5 mg (290 μιτιοΙ) of the POSS-substituted PPh 3 according to the invention, corresponding to a L: Rh - ratio of 5: 1, in 14 mL of toluene, over the described pressure burette a (t = 0), was added under reaction pressure. The preparation of the catalyst solution was carried out under an argon atmosphere. Subsequently, a differential pressure TMP of 0.35 MPa was set on the membrane j via the permeate pressure control F in order to remove the generated product i, aldehydes, from the system. By the described level control B on the autoclave, then the extended amount of product i was replaced by Eduktlosung from the original h and thus kept the level in the reaction system constant. The reaction was carried out over a period of 14 days in which samples were taken and analyzed at regular intervals. The conversion of 1-octene and the regioselectivity (l / b ratio) were determined by GC analysis. Rh and P retention of the membrane were determined by ICP-OES analysis of the permeate. Both Rh and P losses were very low. Based on the total amount of rhodium and phosphorus, these losses were 0.07% (Rh) and 0.97% (P), respectively.
Kontinuierliche Hydroformylierung von 1 -Okten; Spezifikationen Continuous hydroformylation of 1-octene; specifications
Reaktionsvolumen 220 mL  Reaction volume 220 mL
Reaktionstemperatur 80°C  Reaction temperature 80 ° C
Reaktionsdruck 2,0 MPa CO/H2 (1 /1 ) Reaction pressure 2.0 MPa CO / H 2 (1/1)
[Rh] 0.26 mM  [Rh] 0.26 mM
[1 -Okten] 1 .9 M  [1 -Octs] 1 .9 M
Lösungsmittel Toluol Kontinuierliche Hydroformylierung von 1 -Okten; Spezifikationen Solvent toluene Continuous hydroformylation of 1-octene; specifications
L:Rh 5:1  L: Rh 5: 1
Reaktorkreislauf 0,45 l/min  Reactor circulation 0.45 l / min
Membrankreislauf 2,27 l/min  Diaphragm circulation 2.27 l / min
Membran Hersteller Inopor  Membrane manufacturer Inopor
Material= ΤΊΟ2  Material = ΤΊΟ2
Länge= 200mm  Length = 200mm
di=7mm  di = 7mm
da=10mm  da = 10mm
Porengröße=0.9nm  Pore size = 0.9Nm
Filtrationsfläche=0.0217m2/m  Filtration area = 0.0217m2 / m
cut-off=450D  cut-off = 450D
TMP 0,35 MPa  TMP 0.35 MPa
Permeatfluss 10 g/h  Permeate flow 10 g / h
Kontinuierliche Hydroformylierung von 1 -Okten mit POSS-substituierten PPh3 /RhContinuous hydroformylation of 1-octene with POSS-substituted PPh 3 / Rh
Probe Zeit (min) Ausbeute (%) l/b Sample Time (min) Yield (%) l / b
1 0 0  1 0 0
2 10 0.0  2 10 0.0
3 20 1 .3  3 20 1 .3
4 30 4.0 2.8  4 30 4.0 2.8
5 40 6.9 2.8  5 40 6.9 2.8
6 50 10.3 2.8  6 50 10.3 2.8
7 60 13.6 2.8  7 60 13.6 2.8
8 70 17.3 2.8  8 70 17.3 2.8
9 80 20.8 2.8  9 80 20.8 2.8
10 90 23.5 2.8  10 90 23.5 2.8
1 1 100 27.4 2.8  1 1 100 27.4 2.8
12 1 10 30.5 2.8  12 1 10 30.5 2.8
13 120 34.2 2.8 Probe Zeit (min) Ausbeute (%) l/b 13 120 34.2 2.8 Sample Time (min) Yield (%) l / b
14 140 40.7 2.8  14 140 40.7 2.8
15 160 46.8 2.8  15 160 46.8 2.8
16 180 52.1 2.8  16 180 52.1 2.8
17 240 67.6 2.8  17 240 67.6 2.8
18 300 79.9 2.8  18 300 79.9 2.8
19 360 89.7 2.8  19 360 89.7 2.8
20 420 90.3 2.8  20 420 90.3 2.8
21 1020 95.8 2.5  21 1020 95.8 2.5
22 1080 95.7 2.5  22 1080 95.7 2.5
23 1 140 95.6 2.5  23 1 140 95.6 2.5
24 1200 95.7 2.5  24 1200 95.7 2.5
25 1260 95.8 2.5  25 1260 95.8 2.5
26 1620 96.0 2.5  26 1620 96.0 2.5
27 2490 96.3 2.4  27 2490 96.3 2.4
28 3030 96.1 2.3  28 3030 96.1 2.3
29 3930 96.2 2.3  29 3930 96.2 2.3
30 5650 96.4 2.3  30 5650 96.4 2.3
31 7050 96.5 2.3  31 7050 96.5 2.3
32 8680 96.7 2.3  32 8680 96.7 2.3
33 1 1590 96.4 2.4  33 1 1590 96.4 2.4
34 14260 95.2 2.3  34 14260 95.2 2.3
35 17450 93.5 2.3  35 17450 93.5 2.3
36 19620 90.5 2.3  36 19620 90.5 2.3
Beispiel 2: Hydroformylierung von 1 -Buten in einem kontinuierlich betriebenen Membranreaktor Die Hydroformylierungsversuche wurden in einer kontinuierlich betriebenen Versuchsanlage durchgeführt; s. Anlagenskizze. Diese Versuchsanlage bestand aus einem Reaktionsteil und einem Membranteil. Der Reaktionsteil umfasste einen 1 00 mL Autoklaven b mit einer Kreislaufpumpe c. Der Autoklav b war mit einer Druckhaltung A für das Synthesegas ausgestattet. Durch diese Druckhaltung A wurde der Synthesegasdruck während der Reaktion im gesamten System konstant gehalten. Die Synthesegasaufnahme des Systems wurde mit einer Durchflussmessung C bestimmt. Für die Dosierung von Edukt- und Katalysatorlösungen vor Reaktionsstart war der Reaktor mit einer Druckbürette a ausgestattet, die mit Synthesegas beaufschlagt werden konnte und so eine Dosierung der Edukt- und Katalysatorlösungen unter Reaktionsbedingungen erlaubte. Der Autoklav b war zusätzlich mit einer Standregelung B ausgestattet. Durch diese Standregelung B wurde die Eduktpumpe e angesteuert, die dann aus einer Vorlage h Eduktlösung, umfassend das olefinhaltige Gemisch, optional Lösungsmittel, in den Autoklaven b pumpte, um so den Stand im Autoklaven konstant zu halten. Diese Eduktvorlage h war mit Argon überdeckt, um einen Kontakt mit Luft zu vermeiden. Die nötige Turbulenz in dem Autoklaven wurde durch die Kreislaufpumpe c, die eigens für diesen Anwendungsfall konstruiert wurde, erzeugt. Die Pumpe c baute einen Kreislauf der Reaktionslösung über eine Düse im Kopf des Autoklaven b auf und sorgte somit für einen entsprechenden Gas/Flüssigaustausch. Das Synthesegas und das Edukt wurden ebenfalls in die Düse eindosiert. Example 2 Hydroformylation of 1-Butene in a Continuously Operated Membrane Reactor The hydroformylation experiments were carried out in a continuously operated pilot plant; s. Plant sketch. This pilot plant consisted of a reaction part and a membrane part. The reaction section comprised a 1 00 mL autoclave b with a circulation pump c. The autoclave b was with a Pressure maintenance A equipped for the synthesis gas. Through this pressure A, the synthesis gas pressure was kept constant during the reaction throughout the system. The synthesis gas uptake of the system was determined by a flow measurement C. For the metering of reactant and catalyst solutions before the start of the reaction, the reactor was equipped with a pressure burette a, which could be charged with syngas and thus allowed a dosage of the educt and catalyst solutions under reaction conditions. The autoclave b was also equipped with a level control B. By this state control B, the Eduktpumpe e was controlled, which then pumped from a template h Eduktlösung comprising the olefin-containing mixture, optionally solvent, in the autoclave b, so as to keep the state constant in the autoclave. This educt template h was covered with argon to avoid contact with air. The necessary turbulence in the autoclave was generated by the circulation pump c, which was specially designed for this application. The pump c built a loop of the reaction solution through a nozzle in the head of the autoclave b and thus provided for a corresponding gas / liquid exchange. The synthesis gas and the educt were also metered into the nozzle.
In diesem Kreislauf war ebenfalls eine Kreuzstromkammer f eingebaut. Die Kreuzstromkammer f trennt den Reaktionsteil von dem Membranteil der Anlage.  In this cycle, a cross-flow chamber f was also installed. The cross flow chamber f separates the reaction part from the membrane part of the plant.
Die Kreuzstromkammer f sorgt für die Vermischung des Membrankreislaufes mit dem Reaktoraustrag und stellte sicher, dass der freie Gasanteil im Ausgang des Reaktors nicht in den Membranteil gelangen konnte, sondern wieder in den Reaktionskreislauf zurückgeführt wurde. The cross-flow chamber f ensures the mixing of the membrane circulation with the reactor discharge and ensured that the free gas fraction in the outlet of the reactor could not get into the membrane part, but was returned to the reaction cycle.
Der Membranteil bestand aus einem Druckrohr, welches eine keramische Memb- ran j von 200mm Länge mit einer spezifischen Filterfläche von 0,0217m2/m und einen Cut-Off von 450D, beinhaltete und einer Kreislaufpumpe g, die einen Kreislauf über die Membran erzeugte. Die Verbindung zum Reaktionsteil wurde über die schon beschriebene Kreuzstromkammer f realisiert.  The membrane part consisted of a pressure tube which contained a ceramic membrane j of 200 mm length with a specific filter area of 0.0217 m 2 / m and a cut-off of 450 D, and a circulation pump g which generated a circulation across the membrane. The connection to the reaction part was realized via the already described cross flow chamber f.
Der Permeatfluss durch die Membran j wurde durch eine Druckhaltung F auf der Permeatseite realisiert. Durch diese Regeleinrichtung war es möglich eine Druckdifferenz über der Membranfläche aufzubauen und somit einen Produktfluss i an Aldehyden zu erzeugen. Vor dem Start wurde das Reaktionssystem fünfmal mit 2,0 MPa Synthesegas CO/H2 (1 :1 ) aufgedrückt und entspannt. Danach wurde die Eduktlösung (1 .9 M 1 - Buten in Toluol) mittels HPLC Pumpe aus der beschriebenen Eduktvorlage h in die Versuchsanlage, bis auf 90% des angestrebten Füllstandniveaus, überführt. Nach in Betriebnahme des Reaktorkreislaufes, wurde der Reaktionsteil auf 80°C erhitzt und ein Druck von 20 bar CO/H2 (1 :1 ) eingestellt. Das Reaktionssystem wurde über 1 h äquilibriert, bevor die katalytisch wirksame Zusammensetzung, enthaltend 1 5 mg (58 μιτιοΙ) Rh(acac)(CO)2 und 81 5 mg (290 μιτιοΙ) des erfin- dungsgemäßen POSS-substituierten PPh3, entsprechend einem L:Rh - Verhältnis von 5:1 , in 14 ml_ Toluol, über die beschriebene Druckbürette a (t =0), unter Reaktionsdruck hinzugegeben wurde. Das Ansetzen der Katalysatorlösung erfolgte unter einer Argonatmosphäre. Anschließend wurde an der Membran j über die Permeatdruckregelung F ein Differenzdruck von 0,30 MPa eingestellt, um das erzeugte Produkt i, Aldehyde, aus dem System zu entfernen. Durch die beschriebene Standregelung B am Autoklaven, wurde dann die ausgefahrene Menge an Produkt i durch Eduktlösung aus der Vorlage h ersetzt und somit das Füllstandsniveau im Reaktionssystem konstant gehalten. Die Reaktion wurde über einen Zeitraum von 14 Tagen durchgeführt, in dieser Zeit wurden in regelmäßigen Abständen Proben gezogen und analysiert. Der Umsatz von 1 -Okten und die Regioselektivität (l/b- Verhältnis) wurden mittels GC-Analyse bestimmt. Rh- und P- Rückhalte der Membran wurden über ICP-OES Analytik vom Permeat bestimmt. Sowohl die Rh- als auch die P-Verluste waren sehr gering . Bezogen auf die Gesamtmenge Rhodium und Phosphor lagen diese Verluste bei 0.08%(Rh) bzw. 0.95%(P). The permeate flow through the membrane j was realized by a pressure maintenance F on the permeate side. By this control device, it was possible to build a pressure difference across the membrane surface and thus to produce a product flow of aldehydes i. Before startup, the reaction system was pressurized and expanded five times with 2.0 MPa synthesis gas CO / H 2 (1: 1). Thereafter, the educt solution (1 .9 M 1 - butene in toluene) by means of HPLC pump from the Eduktvorlage described h in the pilot plant, up to 90% of the desired level, transferred. After commissioning the reactor circuit, the reaction part was heated to 80 ° C and a pressure of 20 bar CO / H 2 (1: 1) was set. The reaction system was equilibrated for 1 h before the catalytically active composition containing 1 5 mg (58 μιτιοΙ) of Rh (acac) (CO) 2 and 81 5 mg (290 μιτιοΙ) of the inventive POSS-substituted PPh 3 , corresponding to one L: Rh ratio of 5: 1, in 14 mL toluene, was added via the described pressure burette a (t = 0) under reaction pressure. The preparation of the catalyst solution was carried out under an argon atmosphere. Subsequently, a differential pressure of 0.30 MPa was set on the membrane j via the permeate pressure control F in order to remove the generated product i, aldehydes, from the system. By the described level control B on the autoclave, then the extended amount of product i was replaced by educt solution from the original h and thus kept constant the level in the reaction system. The reaction was carried out over a period of 14 days, during which time samples were taken and analyzed at regular intervals. The turnover of 1-octene and the regioselectivity (l / b ratio) were determined by GC analysis. Rh and P retention of the membrane were determined by ICP-OES analysis of the permeate. Both Rh and P losses were very low. Based on the total amount of rhodium and phosphorus, these losses were 0.08% (Rh) and 0.95% (P), respectively.
Kontinuierliche Hydroformylierungsversuche; Reaktor/ReaktionsspezifikationenContinuous hydroformylation experiments; Reactor / reaction specifications
Reaktionsvolumen 220 ml_ Reaction volume 220 ml_
Reaktionstemperatur 80°C  Reaction temperature 80 ° C
Reaktionsdruck 2,0 MPa CO/H2 (1 /1 ) Reaction pressure 2.0 MPa CO / H 2 (1/1)
[Rh] 0.28 mM Kontinuierliche Hydroformylierungsversuche; Reaktor/Reaktionsspezifikationen [Rh] 0.28 mM Continuous hydroformylation experiments; Reactor / reaction specifications
[1 -Buten] 1 .9 M  [1-butt] 1 .9 M
Lösungsmittel Toluol  Solvent toluene
L:Rh 5:1  L: Rh 5: 1
Reaktorlkreislauf 0,45 l/min  Reactor cycle 0.45 l / min
Membrankreislauf 2,27 l/min  Diaphragm circulation 2.27 l / min
Membran Hersteller Inopor  Membrane manufacturer Inopor
Material= TiO2  Material = TiO2
Länge= 200mm  Length = 200mm
di=7mm  di = 7mm
da=10mm  da = 10mm
Porengröße=0.9nm  Pore size = 0.9Nm
Filtrationsfläche=0.0217m2/m  Filtration area = 0.0217m2 / m
cut-off=450D  cut-off = 450D
TMP 0,3 MPa  TMP 0.3 MPa
Permeatfluss 10 g/h  Permeate flow 10 g / h
Kontinuierliche Hydroformylierung von 1 -Buten mit POSS-substituierten PPh3 /RhContinuous hydroformylation of 1-butene with POSS-substituted PPh 3 / Rh
Probe Zeit (min) Ausbeute (%) Ϊ75 Sample Time (min) Yield (%) Ϊ75
Ϊ Ö Ö  Ϊ Ö Ö
2 10 0.5  2 10 0.5
3 20 1 .8  3 20 1 .8
4 30 6.1 2.9  4 30 6.1 2.9
5 40 9.4 3.0  5 40 9.4 3.0
6 50 13.5 3.1  6 50 13.5 3.1
7 60 17.8 3.0  7 60 17.8 3.0
8 90 27.8 3.0  8 90 27.8 3.0
9 120 38.1 2.9  9 120 38.1 2.9
10 180 58.4 3.0  10 180 58.4 3.0
1 1 240 70.7 2.9  1 1 240 70.7 2.9
12 300 82.4 2.9 Probe Zeit (min) Ausbeute (%) l/b 12 300 82.4 2.9 Sample Time (min) Yield (%) l / b
13 360 85.9 2.9  13 360 85.9 2.9
14 720 92.0 2.8  14 720 92.0 2.8
15 1080 94.3 2.7  15 1080 94.3 2.7
16 1200 94.3 2.8  16 1200 94.3 2.8
17 1440 94.5 2.7  17 1440 94.5 2.7
18 2880 95.6 2.6  18 2880 95.6 2.6
19 4320 95.7 2.3  19 4320 95.7 2.3
20 5760 95.4 2.4  20 5760 95.4 2.4
21 8640 95.3 2.3  21 8640 95.3 2.3
22 1 1520 95.8 2.3  22 1 1520 95.8 2.3
23 14400 95.7 2.2  23 14400 95.7 2.2
24 17280 95.0 2.4  24 17280 95.0 2.4
25 20160 93.7 2.3  25 20160 93.7 2.3
26 23040 92.8 2.3  26 23040 92.8 2.3
27 25920 91 .8 2.3  27 25920 91 .8 2.3
28 28800 89.4 2.3  28 28800 89.4 2.3
In weiteren Ausführungsformen der Erfindung zu der Verwendung von POSS- modifizierten Liganden in katalytisch wirksamen Zusammensetzungen in der Hydroformylierung werden als olefinhaltige Gemische u. a. Raffinate, wie z. B. Raffinat I, Raffinat II, aber auch Mischungen, die Olefine mit 3 bis 20 Kohlenstoffatomen enthalten, eingesetzt. In further embodiments of the invention for the use of POSS-modified ligands in catalytically active compositions in the hydroformylation are used as olefin-containing mixtures u. a. Raffinates, such as. As raffinate I, raffinate II, but also mixtures containing olefins having 3 to 20 carbon atoms used.

Claims

Patentansprüche: claims:
1 . Organische Phosphorhaltige Verbindung, kovalent verbunden mit Polyhedralen Oligomeren Silsesquioxanderivaten gemäß Formel 1 1 . Organic phosphorus-containing compound covalently linked to polyhedral oligomer silsesquioxane derivatives according to formula 1
[(R^^SiO^n R2c]m G3 P G1 [ 2a(SiO1 i5)n (R1 a)n-1]k [(R ^^ SiO ^ n R 2c ] m G 3 PG 1 [ 2a (SiO 1 i5 ) n (R 1 a ) n-1 ] k
[(R1bki(Si01.5)n R2 ]i 1 wobei (R1a,b,c)n-i(SiOi,5)nR2a'b'c Polyhedrale Oligomere Silsesquioxanderivate darstellen mit n > 4; [(R 1b ki (Si0 1 5) n R. 2] i 1 wherein (R 1a, b, c) ni (SIOI, 5) nR 2a 'b' c polyhedral oligomers represent Silsesquioxanderivate with n>4;
in denen R1a, R1b,R1c jeweils unabhängig ausgewählt sind aus der Gruppe bestehend aus gleichen oder unterschiedlichen, verzweigten oder linearen C1-C20 Alkylketten, Cyclo- alkyl-, C1-C20 Alkoxy-, Aryl-, Aryloxy-, Heteroaryl- und Arylalkylgruppen, in which R 1a , R 1b , R 1c are each independently selected from the group consisting of identical or different, branched or linear C 1 -C 2 0 alkyl chains, cycloalkyl, C 1 -C 2 0 alkoxy, aryl, aryloxy, Heteroaryl and arylalkyl groups,
worin k, I, m 0 oder 1 ist, unter der Voraussetzung, dass k+l+m > 1 ,  where k, l, m is 0 or 1, provided that k + l + m> 1,
in denen R2a, R2b, R2c die Verknüpfung zwischen Polyhedralen Oligomeren Silsesquioxanderivaten zu G1 , G2 und/oder G3 darstellen, in which R 2a , R 2b , R 2c represent the linkage between polyhedral oligomers silsesquioxane derivatives to G1, G2 and / or G3,
wobei R2a, R2b, R2c jeweils unabhängig voneinander ausgewählt sind aus der Grup- pe bestehend aus linearen oder verzweigten C1-C20 Alkylketten, C3-C10 Cycloalkyl-,wherein R 2a, R 2b, R 2c are each independently selected from the group-pe consisting of linear or branched C1-C2 0 alkyl chains, C3-C1 0 cycloalkyl,
Ci-C20 Alkoxy-, C2-C20 Alkenyl-, C2-C20 Alkenyloxy-, Aryloxy-, C C2o Alkylthio-, C C20 Carboxylat-, Aryl or Heteroaryl-, C1-C20 Alkylhalogenid-, anellierten Aryl- oder Heteroaryl-, C3-C10 Cycloalkylgruppen, Ethern, Polyethern, Polythioethern, Aminen, Amiden, Carboxylaten, Aryl-verbrückten Alkylketten, in denen die Arylstruktur weite- re Substituenten aufweisen kann; Ci-C20 alkoxy, C2-C20 alkenyl, C 2 -C 20 alkenyloxy, aryloxy, CC 2 o alkylthio, C C2 0 carboxylate, aryl or heteroaryl, C1-C2 0 alkyl halide, fused aryl may have substituents or re heteroaryl, C3-C1 0 cycloalkyl groups, ethers, polyethers, polythioethers, amines, amides, carboxylates, aryl-bridged alkyl chains, where the aryl structure weite- -;
wobei G1 , G2 und G3 jeweils gleiche oder verschiedene monovalent mit Phosphor verbundene Einheiten darstellen, ausgewählt aus der Gruppe bestehend aus un- substituierten und/oder substituierten aliphatischen, cycloaliphatischen, heterocyc- loaliphatischen, perfluoralkylierten, aromatischen, heteroaromatischen,  where G1, G2 and G3 each represent identical or different monovalent phosphorus-bonded units selected from the group consisting of unsubstituted and / or substituted aliphatic, cycloaliphatic, heterocycloaliphatic, perfluoroalkylated, aromatic, heteroaromatic,
kondensierten aromatischen, kondensierten heteroaromatischen Einheiten.  condensed aromatic condensed heteroaromatic units.
2. Organische Phosphorhaltige Verbindung nach Anspruch 1 , 2. Organic phosphorus-containing compound according to claim 1,
wobei n die Werte von 6 bis 12 annimmt,  where n assumes the values of 6 to 12,
in denen R1a, R1b, R1c jeweils gleich und CrC8 Alkylketten, oder Phenylgruppen sind, und worin G1 , G2 und/oder G3 jeweils gleiche oder verschiedene monovalent mit Phosphor verbundene Einheiten darstellen, ausgewählt aus der Gruppe Acyl, Alkyl, Aryl, Heteroaryl, Cycloalkyl. in which R 1a , R 1b , R 1c are each the same and C 1 -C 8 are alkyl chains, or phenyl groups, and wherein G1, G2 and / or G3 each represent the same or different monovalent phosphorus-linked units selected from the group acyl, alkyl, aryl, heteroaryl, cycloalkyl.
3. Organische Phosphorhaltige Verbindung nach Anspruch 2, wobei n = 8 ist und R1a, R1b, R1c jeweils gleich und C4 Alkyl ketten sind, 3. The organic phosphorus-containing compound according to claim 2, wherein n = 8 and R 1a , R 1b , R 1c are each the same and C 4 alkyl chains,
worin R2a, R2b, R2c jeweils gleich und C2-Alkyl ketten sind, wherein R 2a , R 2b , R 2c are each the same and C 2 alkyl chains,
wobei G1 , G2 und G3 gleich und jeweils monovalent mit Phosphor verknüpfte Phe- nylgruppen sind.  where G1, G2 and G3 are the same and in each case monovalent phosphorus-linked phenyl groups.
4. Katalytisch wirksame Zusammensetzung, enthaltend mindestens eine organische Phosphorhaltige Verbindung gemäß der Ansprüche 1 - 3 und mindestens ein Metall, ausgewählt aus der 8., 9. oder 10. Gruppe des Periodensystems der Elemente. 4. A catalytically active composition comprising at least one organic phosphorus-containing compound according to claims 1-3 and at least one metal selected from the 8th, 9th or 10th group of the Periodic Table of the Elements.
5. Katalytisch wirksame Zusammensetzung nach Anspruch 4, dadurch gekennzeichnet, dass das Metall ausgewählt ist aus der 9. Gruppe des Periodensystems der Elemente. 5. A catalytically active composition according to claim 4, characterized in that the metal is selected from the ninth group of the Periodic Table of the Elements.
6. Katalytisch wirksame Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, dass das Metall Rhodium ist. 6. Catalytically active composition according to claim 5, characterized in that the metal is rhodium.
7. Verfahren zur Hydroformylierung von olefinhaltigen Gemischen, enthaltend eine katalytisch wirksame Mischung gemäß der Ansprüche 4 - 6. 7. A process for the hydroformylation of olefin-containing mixtures containing a catalytically active mixture according to claims 4-6.
8. Verfahren zur Hydroformylierung von olefinhaltigen Gemischen nach Anspruch 7, dadurch gekennzeichnet, dass das olefinhaltige Gemisch Olefine mit 3 bis 20 Kohlenstoffatomen enthält. 8. A process for the hydroformylation of olefin-containing mixtures according to claim 7, characterized in that the olefin-containing mixture contains olefins having 3 to 20 carbon atoms.
9. Verfahren zur Hydroformylierung von olefinhaltigen Gemischen nach Anspruch 8, dadurch gekennzeichnet, dass das olefinhaltige Gemisch ausgewählt ist aus der Gruppe bestehend aus Propen, Raffinat I, Rafffinat II, Raffinat III. 9. A process for the hydroformylation of olefin-containing mixtures according to claim 8, characterized in that the olefin-containing mixture is selected from the group consisting of propene, raffinate I, rafffinate II, raffinate III.
10. Verfahren zur Hydroformylierung von olefinhaltigen Gemischen nach Anspruch 8, dadurch gekennzeichnet, dass das olefinhaltige Gemisch 1 -Buten enthält. 10. A process for the hydroformylation of olefin-containing mixtures according to claim 8, characterized in that the olefin-containing mixture contains 1-butene.
1 1 . Verfahren zur Hydroformylierung von olefinhaltigen Gemischen nach Anspruch 8, dadurch gekennzeichnet, dass das olefinhaltige Gemisch 1 -Okten enthält. 1 1. A process for the hydroformylation of olefin-containing mixtures according to claim 8, characterized in that the olefin-containing mixture contains 1 -Okten.
12. Verfahren zur Hydroformylierung von olefinhaltigen Gemischen nach den Ansprüchen 7 - 1 1 , dadurch gekennzeichnet, dass die katalytisch wirksame Zusammensetzung unter Verzicht auf thermische Trennverfahren mittels organischer 12. A process for the hydroformylation of olefin-containing mixtures according to claims 7 - 1 1, characterized in that the catalytically active composition waiving thermal separation processes by means of organic
Nanofiltration von einem das Produkt enthaltenden Strom abgetrennt wird.  Nanofiltration is separated from a product-containing stream.
13. Mehrphasiges Reaktionsgemisch, umfassend: 13. A multi-phase reaction mixture comprising:
a) ein olefinhaltiges Gemisch nach den Ansprüchen 8 - 1 1 ,  a) an olefin-containing mixture according to claims 8 - 1 1,
b) ein Gasgemisch enthaltend Kohlenmonoxid, Wasserstoff sowie  b) a gas mixture containing carbon monoxide, hydrogen and
c) Aldehyde,  c) aldehydes,
gekennzeichnet durch die Anwesenheit einer katalytisch wirksame Zusammensetzung nach den Ansprüchen 4 -6.  characterized by the presence of a catalytically active composition according to claims 4-6.
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