| 摘要 |
1338237 Oxo process UNION CARBIDE CORP 16 Dec 1970 [22 Dec 1969] 59623/70 Heading C2C A continuous hydroformylation process for the production of oxygenated products rich in normal aldehydes comprises reacting (1) an alpha olefin of 2 to 20 carbon atoms; (2) with carbon monoxide and hydrogen; (3) in the presence of a catalytic quantity of a complex catalyst consisting essentially of rhodium in complex combination with carbon monoxide and a triorganophosphorus ligand, each organo moiety being monovalently bonded to the phosphorus atom through a carbon atom or an aliphatic etheric oxygen atom, said phosphorus atom possessing one available pair of electrons, said triorganophosphorus ligand having a #HNP value of at least 425; and (4) at least 2 mols. of free triorganophosphorus ligand as defined above per mol. of rhodium; (5) at a temperature in the range of from 50‹ to 145‹ C.; (6) at a total pressure of carbon monoxide and hydrogen of less than 450 p.s.i.a.; and (7) a partial pressure attributable to carbon monoxide no greater than 75% of said total pressure; the hydroformylation being conducted in the presence of high boiling liquid condensation products resulting from condensation reactions of the C 3-21 alkanol products rich in hydroxylic compounds, as a solvent for said rhodium complex catalyst. The condensation products may be preformed or the reaction may be started in their absence and build-up allowed as the reaction proceeds. A minor amount of co-solvent may be present. In examples, butyraldehydes and decaldehydes with a high n : iso ratio are prepared from propylene and 1-nonene. Example 11 describes a similar process using octene-1 but conducted batchwise, while Examples 1-10 hydroformylate propylene using similar catalysts, but are conducted in other solvents, viz.: xylene, tributylamine, ethyl benzoate, 2-methyl-5-ethylpyridine, diethyl succinate, methyl isobutyl ketone, acetonitrile, t-butanol, n-butanol or N,N-dimethylaniline. |
