Hydroformylation using low volatile phosphine ligands

In a non-aqueous hydroformylation process for producing aldehydes which comprises reacting an alpha-olefin containing from 2 to 5 carbon atoms, with carbon monoxide and hydrogen, in a non-aqueous hydroformylation reaction medium containing the olefinically unsaturated organic compound, aldehyde product, solubilized rhodium-phosphorus ligand complex catalyst and solubilized free phosphorus ligand, and wherein the hydroformylation reaction conditions comprise a reaction temperature of from about 45.degree. C. to about 200.degree. C., a total gas pressure of hydrogen, carbon monoxide and olefinically unsaturated compound of less than about 500 psia;

• a carbon monoxide partial pressure of from about 1 to 120 psia, a hydrogen partial pressure of about 10 to 160 psia and wherein said reaction medium contains at least about 2 moles of total free phosphorus ligand per mole of rhodium in said medium, the improvement comprising employing as the phosphorus ligand of said complex catalyst and as said free phosphorus ligand, a monosulfonated tertiary phosphine metal salt the general formula ##STR31## wherein M represents a metal cation selected from the group consisting of sodium, lithium and rubidium, wherein the organic solvent for said complex catalyst and said free ligand is selected from the group consisting of an aldehyde, a higher boiling aldehyde condensation by-product, and mixtures thereof, and wherein said hydroformylation process is carried out in the absence of any added organic solubilizing agent selected from the group consisting of an alkylene oxide oligomer having an average molecular weight of at least 150, an organic nonionic surfactant mono-ol having an average molecular weight of at least 300, a polar organic compound having a molecular weight of less than 150 and having a Hildebrand solubility value of at least 10, and mixtures thereof.

In a non-aqueous hydroformylation process for producing aldehydes which comprises reacting an olefinically unsaturated organic compound containing from 2 to 20 carbon atoms with carbon monoxide and hydrogen, in a non-aqueous hydroformylation reaction medium containing the olefinically unsaturated organic compound, aldehyde product, solubilized rhodium-phosphorus ligand complex catalyst and solubilized free phosphorus ligand, and wherein the hydroformylation reaction conditions comprise a reaction temperature of from about 45.degree. C. to about 200.degree. C., a total gas pressure of hydrogen, carbon monoxide and olefinically unsaturated compound of less than about 500 psia;

• a carbon monoxide partial pressure of from about 1 to 120 psia, a hydrogen partial pressure of about 10 to 160 psia and wherein said reaction medium contains at least about 2 moles of total free phosphorus ligand per mole of rhodium in said medium, the improvement comprising enploying as the phosphorus ligand of said complex catalyst and as said free phosphorus ligand, a monosulfonated tertiary phosphine metal salt the general formula ##STR32## wherein one R group represents a cyclohexyl radical and the other R group represents a phenyl or cyclohexyl radical wherein M represents a metal cation selected from the group consisting of alkali and alkaline earth metals, and wherein n has a value of 1 to 2 corresponding to the valence of the particular metal cation represented by M;
• wherein the organic solvent for said complex catalyst and said free ligand is selected from the group consisting of an aldehyde, a higher boiling aldehyde condensation by-product, and mixtures thereof, and wherein said hydroformylation process is carried out in the absence of any organic solubilizing agent selected from the group consisting of an alkylene oxide oligomer having an average molecular weight of at least 150, an organic nonionic surfactant mono-ol having an average molecular weight of at least 300, a polar organic compound having a molecular weight of less than 150 and having a Hildebrand solubility value of at least 10, and mixtures thereof.