Katalysatorvergleich bei der Hydroesterifizierung von 10‐Undecensäuremethylester in thermomorphen Lösungsmittelsystemen

Abstract

Zwei homogene Palladium‐Katalysatoren zur Hydroesterifizierung des nachwachsenden Rohstoffs 10‐Undecensäuremethylester zum Monomer Dodecandisäuredimethylester werden verglichen. Die Katalysatoren wurden auf ihre Reaktionsraten in thermomorphen Lösungsmittelsystemen untersucht und die Reaktionsparameter optimiert. Anschließend wurde die Abtrennbarkeit der Katalysatoren vom Produkt untersucht und schließlich die Anwendbarkeit des Konzeptes der thermomorphen Lösungsmittelsysteme in dieser Reaktion durch Recyclingexperimente mit beiden Katalysatoren validiert.

Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

“…). For all reaction conditions a constant l / b ratio of 94/6 was determined according to the literature , , , . A comparison of concentration profiles for different CO pressures indicated an inhibition of the isomerization with increasing CO pressure.…”

“…Unsaturated oleochemicals from renewables like glycerides, methyl oleate and methyl 10‐undecenoate (UME) have also been proven to be attractive substitutes for petrochemical substrates in the palladium‐catalyzed methoxycarbonylation producing α , ω ‐functionalized intermediates for the production of polyesters and polyamides . For a sustainable and economic catalytic process, the reuse of the catalyst plays a key role.…”

“…For a sustainable and economic catalytic process, the reuse of the catalyst plays a key role. In this context, Gaide et al , successfully demonstrated the Pd/DTBPMB‐catalyzed methoxycarbonylation of UME with high yields of the desired diester using a thermomorphic solvent system (TMS) to recycle the homogeneous catalyst. Thus, a temperature‐dependent miscibility gap enables phase separation at low temperature and an efficient reaction without mass transport limitations at elevated temperature .…”

“…1‐Decene was used as model substrate for long chain unsaturated oleochemicals. The composition of the TMS and the highly active and selective catalytic system refers to reported results of Gaide et al , .…”

Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes

“…Behr [89][90][91] pp -- , while the corresponding hydrogenation product n-dodecane was selectively dissolved in the n-heptane phase. At ar eaction temperature of 70 8C, the aqueous mixture of ethanol/n-heptane (1:1) was monophasic.A fter lowering the temperature and subsequent phase separation, the catalyst was successfully recycled fourt imes with stable conversions and catalysta ctivities, as shown through H 2 uptake of around 10 mL per run.…”