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The effect of diolefins on the oxo synthesis

V. Macho, E. J. Mistrik, and J. Střešinka

Forschungsinstitut für Petrochemie, Nováky


Abstract: By discontinuous expts. of propylene oxonation at 150°, the inhibitive effect of conjugated diolefins was detd. By using 0.2% by wt. Co (calcd. on propylene) and toluene as solvent, the inhibition time was linearly increased with an increased amt. of isoprene; at 0.2% by wt. isoprene, the inhibition time was 25 min., and at 2.0%, 240 min. With increasing temp., the inhibition was decreased and ceased at >190°. The inhibition time was decreased by using alcs. as solvent. The nature of the catalyst had a considerable effect on the inhibition time. Co stearate gave inhibition times of 295 and 290 min. as compared with 15 and 10 min. for Co2(CO)8. In the presence of diolefins and Co stearate, more than 95% of the inhibition time was used for the formation of the catalytically active carbonyls of Co and only up to 5% for the reactions between the diolefins and carbonyls. At a const. amt. of diolefins and 150°, the relative time of inhibition for Co2(CO)8, powd. metallic Co, and Co stearate was 1:8-10:30-90. The mechanism of the effect of conjugated diolefins, which caused inhibition, and of diolefins with isolated double bonds (1,5-hexadiene) or with aromatic character (thiophene), which did not inhibit Oxo synthesis, was discussed.

Full paper in Portable Document Format: 179a629.pdf (in Slovak)


Chemical Papers 17 (9) 629–639 (1963)

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