WO1996003363A1 - Procede d'hydroformylation de composes olefiniquement insatures - Google Patents

Procede d'hydroformylation de composes olefiniquement insatures Download PDF

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Publication number
WO1996003363A1
WO1996003363A1 PCT/EP1995/002910 EP9502910W WO9603363A1 WO 1996003363 A1 WO1996003363 A1 WO 1996003363A1 EP 9502910 W EP9502910 W EP 9502910W WO 9603363 A1 WO9603363 A1 WO 9603363A1
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WIPO (PCT)
Prior art keywords
rhodium
diphosphines
rhc
hydroformylation
angle
Prior art date
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PCT/EP1995/002910
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German (de)
English (en)
Inventor
Helmut Bahrmann
Christian W. Kohlpaintner
Wolfgang A. Herrmann
Rochus Schmid
Guido Albanese
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Hoechst Aktiengesellschaft
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Publication of WO1996003363A1 publication Critical patent/WO1996003363A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/20—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxo-reaction
    • C07C27/22—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxo-reaction with the use of catalysts which are specific for this process
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • 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

Definitions

  • the invention relates to a process for the hydroformylation of olefinically unsaturated compounds in the presence of rhodium complex compounds as catalysts which contain diphosphines as complex ligands.
  • the rhodium catalyst is used in the form of modified hydridorhodium carbonyls which contain additional ligands, in particular tertiary, organic phosphines or phosphites.
  • additional ligands in particular tertiary, organic phosphines or phosphites.
  • the ligands are usually present in excess in relation to the metal atom, so that the catalyst system consists of complex compound and free ligand.
  • the hydroformylation of olefinically unsaturated compounds under the catalytic action of rhodium-phosphine complex compounds is essentially realized in two variants.
  • the catalyst is homogeneously dissolved in the reaction mixture, in the other it, when dissolved in water, forms its own phase.
  • Both processes have been described many times in the literature, for example by B. Cornils in New Syntheses with Carbon Monoxide Berlin, Heidelberg, New York 1980, also in DE-C-26 27 354 and EP-B-01 03 810.
  • the reaction has different characteristics among others Influence on the level of sales of raw materials and the formation of by-products. In general, the heterogeneous process achieves better conversions with higher selectivity compared to the homogeneous process.
  • a particular advantage of the implementation in the system with a separate catalyst phase is the problem-free separation of the catalyst. It is done by simply separating the aqueous and organic phases, i.e. without distillation and thus without thermal process steps. In contrast, in homogeneously catalyzed processes, the reaction product has to be distilled off from the catalyst, a measure which is often associated with losses in yield due to the thermal sensitivity of the reaction products.
  • phosphine ligands are triphenylphosphine in the homogeneously catalyzed process and trisodium tri (m-sulfophenyl) phosphine in the heterogeneous catalyst system. Further developments of both processes strive for technical and economic reasons, among others. an increase in the activity and life of the catalytic converter
  • diphosphines As complex ligands by diphosphines, in particular by diphosphines, which react with the central atom of the complex compound to form chelates.
  • diphosphines for catalysts which are used in the low-pressure hydroformylation of olefins and in the molecule modified 3 -> 01efins by heteroatom substitution.
  • diphosphines which are derived from biphenyl, phenylnaphthalene and binaphthalene as the base body.
  • the demands for high activity ie the amount of aldehyde, which is formed for each amount of catalyst and unit of time, and for long-term stability are of outstanding importance.
  • the aim is to achieve the desired results with the lowest possible ligand / rhodium ratio.
  • the object of the invention is to improve the hydroformylation process by selecting suitable diphosphine ligands as constituents of the catalyst.
  • the invention consists in a process for the hydroformylation of olefinically unsaturated compounds at temperatures from 20 to 150 ° C. and pressures from 0.1 to 20 MPa in the presence of diphosphines in rhodium compounds containing complex bonds. It is characterized in that the diphosphines have a bite angle (according to Casey) of 100 to 160 ° and a cone angle (according to Tolman) from 120 to 240 ° and the isomer energy difference ⁇ E is at least 2.0 kcal / mol.
  • the new process allows the selection of diphosphines as a catalyst component, among others. with the aim of controlling the catalytic activity and, when using terminal olefins, the ratio of n- and iso-aldehyde in the reaction product.
  • a key feature of the new process is the use of diphosphines, whose natural bite angle is 100 is up to 160 °.
  • the natural bite angle results from the graphical representation of the energy content of the chelate complex compared to the associated bite angle.
  • the natural bite angle corresponds to the bite angle with the lowest energy content of the complex (minimum energy; see Casey et al., Isr.J.Chem., 30 (4), 299 ff (1990).
  • cone angle “ ⁇ ” Another measure of the space requirement of phosphine ligands is the cone angle “ ⁇ ” according to Tolman (CA. Tolman, Chem. Rev. 1977, 77, 313 ff). It is defined as the opening angle of a cone, the tip of which is 2.28 8 from the phosphorus atom and whose surface lines are described by the tangents to the van der Waals radii of the substituents on the phosphorus atom. This definition can also be applied to diphosphines if they attack the metal like a chelate. In this case, the cone angle of the diphosphine is made up of the half-angle of neither of the two PM fragments and the PMP angle.
  • the cone angle is 120 to 240 °, in particular 180 to 210 °. Diphosphines with a large cone angle lead to the preferred formation of unbranched products as catalyst components for steric reasons. Conversely, phosphines with a small space requirement increasingly result in iso compounds. Since the PMP angle is included in the calculation of the cone angle for diphosphines, the cone and bite angles have a direct influence on the space requirement of these ligands. Both angles are purely geometrical sizes and are therefore accessible for arithmetic treatment.
  • Diphosphine is the energy difference ⁇ .
  • E Ei.so - En of the two isomeric intermediates I and II, which are formed by the insertion reaction of the olefin into the catalytically active rhodium hydridocarbonyl complex. This is the first, product-determining step of hydroformylation (see e.g. Evans et al. J. Chem.Soc [AI 1968, 3133).
  • the space requirement of the phosphine ligands is determined on the assumption that the metal atom is not connected to any other ligand.
  • the calculation of the energy difference of the isomers according to formulas I and II also takes into account the influence of other ligands that are active metal complex compound are bound.
  • the space requirement of the diphosphines can be determined much more precisely and the catalytic properties of the rhodium / diphosphine complex compounds can be adjusted much more precisely to the desired result.
  • the computational simulation moves much closer to the real conditions during the catalytic cycle.
  • the isomer energy difference is at least 2 kcal / mol, preferably at least 2.5 kcal / mol.
  • the energy content is calculated as follows:
  • Diphosphine built up as a ligand.
  • the rhodium atom at the origin of the Cartesian coordinate system and the ligand atoms directly linked to the rhodium (both phosphorus atoms, carbonyl and alkyl carbon) are in the xy plane.
  • Diphosphine ligands whose terminal bridging carbon atoms (these are the carbon atoms at the two ends of the carbon chain which are bonded to one of the phosphorus atoms of the diphosphine in each case) are at least 0.33 nm apart. This distance is characterized by bridges made of carbon atoms that are linked together by single bonds Entropy reasons not reached (no chelating coordination). In contrast, it is possible to set such distances with carbon atom bridges in which the mobility of the carbon atoms is restricted by multiple bonds between them. Examples of this are the 2,2'-dimethylbiaryl systems, which lead to a distance of the terminal bridging carbon atoms of more than 0.4 nm.
  • the diphosphines used as catalyst components in the new process give the catalysts remarkably high flexibility and effectiveness.
  • the formation of normal aldehydes can be increased further compared to known processes, but it is also possible to adapt the ratio of n- and iso-compound in the reaction product to the respective requirements.
  • the discharge of noble metal and phosphine with the reaction product is further reduced compared to the prior art.
  • these results are achieved with catalysts which have a significantly lower ligand / rhodium ratio than those previously used.
  • the new process can be carried out with catalysts homogeneously dissolved in the reaction medium.
  • complex compounds dissolved in water which form a separate catalyst phase, can be used with equally good success, a possibility which is surprising because by introducing hydrophilic residues such as the sulfonate - (- SO..H) or the carboxylate - (- COOH ) Group in the diphosphine molecule compared to the unsubstituted molecule, both the steric and the electronic conditions can be changed significantly.
  • rhodium is used either as a metal or as a compound.
  • metallic Form it is used in the form of finely divided particles or in a thin layer on a support such as activated carbon, calcium carbonate, aluminum silicate, alumina.
  • the type of rhodium compound depends on whether the reactants are reacted in a homogeneous or heterogeneous liquid phase. Substances which are soluble from the start in the organic phase or in water or which become soluble under the reaction conditions are therefore suitable.
  • rhodium oxides salts of inorganic hydro- or oxygen acids, and salts of aliphatic mono- or polycarboxylic acids are suitable.
  • rhodium salts are rhodium nitrate, rhodium sulfate, rhodium acetate, rhodium 2-ethylhexanoate, rhodium malonate.
  • Rhodium halogen compounds are less useful because of the corrosive behavior of the halide ions.
  • Rhodium carbonyl compounds such as Rh 3 (CO), 2 or Rhg (CO) .g or complex salts of rhodium, for example cycloocadienylrhodium compounds, can also be used.
  • Rhodium 2-ethylhexanoate Under the conditions of the hydroformylation reaction, lipophilic or hydrophilic rhodium complex compounds are formed which contain carbon monoxide and the diphosphine which is soluble in organic medium or in water as ligands.
  • diphosphines it is not necessary to use the diphosphines as uniform compounds.
  • Mixtures of different diphosphines or, in the case of water-soluble ligands, diphosphines of different sulfonation or carboxylation stages can be used.
  • rhodium and diphosphine are not in a stoichiometric ratio, i.e. according to the to use chemical composition of the rhodium complex compound, which forms in the course of the hydroformylation reaction, but to use the diphosphine in excess.
  • the ratio of rhodium and diphosphine can be varied within wide limits and about 1 to 130 mol of diphosphine can be used per mole of rhodium.
  • a ratio of rhodium to diphosphine in the range from 1: 2 to 1:25 and in particular 1: 2 to 1:10 mol is preferred.
  • the solution of the catalyst in the organic solvent or in water is prepared from the components either in the hydroformylation reactor or beforehand in a separate device and then fed to the hydroformylation reactor.
  • the concentration of the rhodium in the reaction mixture or in the aqueous catalyst solution is 20 to 1000 ppm by weight (based on the solution), preferably 100 to 600 ppm by weight and in particular 200 to 400 ppm by weight.
  • the reaction of the olefin with carbon monoxide and hydrogen takes place at pressures of approximately 0.1 to approximately 30 MPa, preferably 1 to 12 MPa and in particular 3 to 7 MPa.
  • the composition of the synthesis gas i.e. the volume ratio of carbon monoxide and hydrogen can extend over wide ranges and e.g. can be varied between 1:10 and 10: 1. Generally you bet
  • the reaction temperature is between about 20 to 150 ° C, preferably 80 to 140 C ⁇ us in particular 100 to 125 ° C.
  • the reaction partners present in the liquid and gaseous phase are converted in conventional reactors.
  • the course of the reaction in the liquid two-phase system is significantly influenced by the fact that the aqueous catalyst solution must be saturated with the liquid or gaseous, hydrophobic olefin and the synthesis gas. It is therefore necessary to create the largest possible contact area between the phases. It has proven useful to stir the liquid reactor contents - catalyst solution, optionally liquid olefin and reaction product - intensively and to feed the gaseous reactants - synthesis gas and optionally olefin - via distribution devices to the liquid phase. It has proven very useful to keep the proportion of the organic phase in the reaction mixture low.
  • a volume ratio of aqueous to organic phase is accordingly set from 1: 1 to 100: 1, preferably 10: 1 to 100: 1.
  • a corresponding part of the reaction mixture can be continuously removed from the reactor, aqueous and organic phases separated from one another and the aqueous phase returned to the reactor.
  • the reaction can be carried out batchwise or, preferably, continuously.
  • the process according to the invention is successfully applicable to the conversion of monoolefins, non-conjugated polyolefins, cyclic olefins and derivatives of these unsaturated compounds.
  • the olefins used are not subject to any restrictions, the procedure has proven successful for compounds having 2 to 40 carbon atoms.
  • the olefinically unsaturated compounds can be straight-chain or branched, the double bonds can be terminal or internal.
  • olefins examples include ethylene, propylene, butene-1, butene-2, pentene-1, 2-methylbutene-1, hexene-1, hexene-2, heptene-1, octene-1 , Octen-3, 3-ethylhexene-1, decene-1, undecene-3, 4,4-dimethylnone-1, dicyclopentadiene, vinylcyclohexene, cyclooctadiene, styrene.
  • Derivatives of the olefins mentioned which can be hydroformylated according to the claimed procedure are, for example, alcohols, aldehydes, carboxylic acids, esters, nitriles and halogen compounds, allyl alcohol, acrolein, methacrolein, crotonaldehyde, methyl acrylate, ethyl crotonate, diethyl fumarate , Diethyl maleate, acrylonitrile.
  • the process for the hydroformylation of olefins and olefin derivatives having 2 to 20 and in particular 2 to 8 carbon atoms is used with particular success.

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

Abstract

L'hydroformylation d'oléfines s'effectue en présence de complexes rhodium-diphosphine utilisés comme catalyseurs. Les diphosphines présentent un angle de morsure (selon Casey) compris entre 100 et 160° et un angle d'entrée (selon Tolman) compris entre 120 et 240 °C et la différence d'énergie isomère s'élève à au moins 2 kcal/mole.
PCT/EP1995/002910 1994-07-27 1995-07-22 Procede d'hydroformylation de composes olefiniquement insatures WO1996003363A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4426577A DE4426577C2 (de) 1994-07-27 1994-07-27 Verfahren zur Hydroformylierung olefinisch ungesättigter Verbindungen
DEP4426577.8 1994-07-27

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WO1996003363A1 true WO1996003363A1 (fr) 1996-02-08

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WO (1) WO1996003363A1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1244608A1 (fr) * 2000-01-06 2002-10-02 ARCO Chemical Technology, L.P. Hydroformylation d'alcool allylique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0311092D0 (en) * 2003-05-14 2003-06-18 Bp Chem Int Ltd Process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2385671A1 (fr) * 1977-03-31 1978-10-27 Celanese Corp Procede d'hydroformylation utilisant un complexe catalytique a base de rhodium et de ligands diphosphino
US4169861A (en) * 1977-08-19 1979-10-02 Celanese Corporation Hydroformylation process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2385671A1 (fr) * 1977-03-31 1978-10-27 Celanese Corp Procede d'hydroformylation utilisant un complexe catalytique a base de rhodium et de ligands diphosphino
US4169861A (en) * 1977-08-19 1979-10-02 Celanese Corporation Hydroformylation process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C.P.CASEY ET AL.: "Diphosphines with Natural Bite Angles near 120Ÿ Increase Selectivity for n-Aldehyde Formation in Rhodium-Catalyzed Hydroformylation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 114, DC US, pages 5535 - 5543 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1244608A1 (fr) * 2000-01-06 2002-10-02 ARCO Chemical Technology, L.P. Hydroformylation d'alcool allylique
JP2003519203A (ja) * 2000-01-06 2003-06-17 アルコ ケミカル テクノロジィ， エル．ピー． アリルアルコールのヒドロホルミル化
EP1244608A4 (fr) * 2000-01-06 2005-08-03 Arco Chem Tech Hydroformylation d'alcool allylique
JP4657555B2 (ja) * 2000-01-06 2011-03-23 ライオンデル ケミカル テクノロジー、 エル．ピー． アリルアルコールをヒドロホルミル化する方法

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ZA956232B (en) 1996-01-29
DE4426577A1 (de) 1996-02-01
DE4426577C2 (de) 1998-01-22

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