Kinetics of the hydroformylation of soybean oil by ligand-modified homogeneous rhodium catalysis

摘要

The kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand-modified rhodium catalysts were investigated at 70-130degreesC and 4000-11,000 kPa. The effects of reaction rates on systematic variations in reaction parameters were evaluated in order to develop an industrial process to convert vegetable oils to polyaldehydes. The activation energies in the presence of triphenylphosphine (Ph3P) (61.1+/-0.8 kJ/mol) (mean+/-SD) and triphenyl phosphite [(Pho)(3)P] (77.4+/-5.0 kJ/mol) were determined. The catalyst was deactivated at temperatures higher than 100degreesC. An evaluation of the effects of the reaction parameters on initial rates yielded the rate laws for Ph3P {rate=k [olefin][Rh(CO)(2)Acac](1.1) [Ph3P](-0.5)(pH(2)+pCO)(1.4), where Rh(CO)(2)Acac is (acetylacetonato)dicarbonylrhodium (I)} and (PhO)(3)P {rate=[olefin] [Rh(CO)(2)Acac](1.2) [(PhO)(3)P](-0.8) (pH(2)+PCO)(0.9) at total pressures lower than 7000 kPa, and rate=[olefin] [Rh(CO)(2)Acac](1.2) [(PhO)(3)P](-0.8)(pH(2)+pCO)(1.7) at total pressures higher than 7000 kPa}.