Catalysis of Organic..

380 Polyurethane from Natural Oilcomposed of a mixture of internal olefins. The differences in the placement of ahydroxymethyl group on the 9 vs 10 position has little impact on the polyol product.The rhodium catalyst currently used for this step utilizes a monosulfonatedphosphine ligand, dissolved N-methyl-2-pyrrolidinone (NMP).(6) This catalystsystem has shown adequate activity and stability. More importantly, it enablesproduct-catalyst phase separation.(7)Each olefin component in the feed behaves somewhat differently during thecourse of hydroformylation. For the hydroformylation of methyl linoleate (shown inFigure 4) the reaction of olefin at the 9,10 or 12,13 positions occur at a similar rate(k 1 ). The hydroformylation rate (k 2 ) of the remaining olefin, however, is generallyslower.Ok 1[CO][H 2 ]OMeHOOHOOOMek 2[CO][H 2 ]OMeHOOOMeHOFigure 4. Hydroformylation products of methyl linoleate (excluding isomers)HydrogenationAfter hydroformylation, the resulting mixture of saturates, unsaturates, andaldehydes, are hydrogenated over a fixed-bed commercial hydrogenation catalyst.Unreacted olefins are converted to saturates, and aldehydes are converted to the