Process for the hydroformylation of an olefin in a two-phase med

Details Process for the hydroformylation of an olefin in a two-phase med Process for the hydroformylation of an olefin in a two-phase med

1997-07-17

1998-12-08

Burn, Brian M.

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

568451, C07C 4550

Patent

active

058472282

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

(i) Field of the Invention
This is the U.S. National Stage Application of PCT/FR96/00069 filed Jan. 16, 1996 now WO 96/22267 published Jul. 25, 1996.
The present invention relates to a process for the hydroformylation of an olefin.
(ii) Description of Related Art
It is known that the hydroformylation of olefins may be carried out in a homogeneous medium in the presence of solvents, in very good yield. However, the addition of solvents complicates the process, in particular in the case of olefins of high molar mass. The reason for this is that, in such a medium, the aldehydes can only be separated from the catalyst by distillation of the crude reaction mixture. In the case of heavy olefins, given the boiling points of the olefins and of the products formed, this distillation must be carried out at high temperatures, which causes, in the medium or long term, considerable degradation of the catalyst, which is economically unacceptable in particular when the catalyst is based on noble metals (Rh, Pt, etc).
To overcome this drawback, the hydroformylation of higher olefins has been carried out with CO/H.sub.2 in a two-phase medium. The aim was to allow the ready separation of the catalyst (found in one phase) from the products obtained (which are in the other phase) by carrying out a simple separation by settling. Two main types of two-phase systems have been described: the water/organic phase system (the more common) and, more recently, the perfluoroalkane/organic phase system.
Various solutions have been proposed to dissolve the catalyst in perfluoroalkanes or in water, these consisting essentially in using fluorophosphines in the first case and water-soluble phosphines in the second case.
Thus, I. T. Horvath et al., (Science 1994 Vol. 266, 72) describe the hydroformylation of 1-decene dissolved in toluene, catalyzed by the which is dissolved in C.sub.6 F.sub.11 CF.sub.3 and in the presence of P{CH.sub.2 CH.sub.2 (CF.sub.2).sub.5 CF.sub.3 }.sub.3. In this process, the catalyst is easily recycled since it is found in the perfluoro phase, whereas the aldehyde is in the toluene phase, which is immiscible with the former. However, the main difficulty lies in the synthesis of the very specific phosphine used. Moreover, the amount of rhodium present in the toluene phase is not specified.
The use of water/organic phase two-phase systems is much more common. Thus, E. Kuntz (Rhone-Poulenc) has proposed using triphenylphosphine trisulfonate (TPPTS) to dissolve metal complexes in water. This technique has been carried out industrially, in particular to perform the hydroformylation of propene into butanal with catalytic systems based on rhodium and TPPTS in aqueous solution (see for example Angewandte Chemie, Int. Ed. Eng. 1993, 1524-1544).
Admittedly, the use of a water-soluble phosphine does improve the hydroformylation process, but only in the case of light olefins that are partially soluble in an aqueous medium, the yield being very low with fatty olefins.
Thus, various studies have been targeted toward increasing the solubility of fatty olefins in an aqueous phase so as to be able to apply the two-phase process to them. The solutions proposed consisted mainly in adding a surfactant to the reaction medium containing a rhodium complex, a water-soluble phosphine and the olefin.
For example, in U.S. Pat. No. 4,399,312, 1981, Russel describes the use of dodecyltrimethylammonium bromide as surfactant, the aim of which is to make a fatty olefin, 1-decene, soluble in an aqueous medium. However, the yield still remains modest. In WO 93/04029, the same catalytic system was used, but with the catalyst being recovered by filtration through a membrane, which makes it possible to achieve extremely low residual rhodium concentrations in the organic phase. Nevertheless, this technique complicates the recovery of the catalyst considerably.
Hanson et al., (J. Mol. Catal. 1994 Vol. 88 43-56), describes the use of sodium dodecylbenzenesulfonate in the presence of various water-soluble phosphines for the hydr

REFERENCES:
patent: 4399312 (1983-08-01), Russell et al.
patent: 5091350 (1992-02-01), Cornils et al.
Angewandte Chemie. International Edition, vol. 34, No. 20, Nov. 3, 1995, pp. 2269-2271, Monflier et al., "Molecular Recognition Between Chemically Modified Beta-Cyclodextrin and Dec-1-Ene: new Prospects for Biphasic Hydroformylation of Water-Insoluble Olefins".
Tetrahedron Letters, vol. 36, No. 52, pp. 9481-9484, Monflier et al., "A further Breathrough in Biphasic Rhodium-Catalyzed Hydroformylation: Use of per(2,6-di-O-methyl)-.beta.-cyclodextrin as Inverse Phase Transfer Catalyst" (1995).
Catalysis Letters, 9 (1991) 55-58, Anderson, et al., Hydroformylation of Olefins with Water-Soluble Rhodium Catalysts in the Presence of .alpha.-Cyclodextrin.
Angewandte Chemie. International Edition, vol. 33, No. 20, pp. 2100-2102, Monflier, et al.,; "Wacker Oxidation of 1-Decene to 2-Decanone in the Presence of a Chemcially Modified Cyclodextrin System: a Happy Union of Host--Guest Chemistry and Homogenous Catalysis" (1994).

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