ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

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)