Continuous reactive extraction for selective telomerisation of butadiene with glycerol in a miniplant

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

“…In another work, this catalytic system was compared to an H‐Beta zeolite‐catalyzed etherification with 1‐octene . Another approach towards the selective mono‐telomerization of glycerol is the use of aqueous biphasic reaction mixtures and sulfonated phosphine ligands ,. In these cases, an additional base influences the reactivity of the catalyst …”

Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

“…As the phosphonium salt could not be reacted with dimethylamine by incubation, the authors concluded that phosphonium formation was not reversible and that the species did not participate in the catalytic cycle. In contrast, in both patents from the Kuraray company [61][62][63] and a contribution from the group of Behr [64], phosphonium salts of TPPTS were actually deliberately added to the reaction mixture to serve as ligand reservoirs in the biphasic telomerization of butadiene with water. This implies reversibility and a more prominent role for the phosphonium species.…”

“…8 Product quality with one-time addition (left) and continuous addition (right) of a phosphonium salt and polymerization inhibitor in a continuous reactive extraction set-up for the telomerization of glycerol. Adapted with permission from [64] the section on the mechanistic aspects of the telomerization reaction. From a screening of eight different phosphine ligands, the combination of palladium with the ligand TOMPP emerged as the most active catalyst system (Fig.…”

“…Reactions were run continuously for up to 250 h with a product stream of 10 g h À1 , under which conditions Pd leaching was limited to 20 ppm even at a phase separation temperature of 90 C. Continuous addition of TPPTS, phosphonium salt and polymerization inhibitor (4-t-butylcatechol) was essential for a constant product quality in runs of more than 100 h (Fig. 8) [64]. Catalyst deactivation gradually occurs if TPPTS and its phosphonium salt are only added at the beginning of the reaction, leading to reduction in telomer formation and a concomitant increase in butadiene dimer formation.…”

Neue Trends in der homogenen Übergangsmetallkatalyse

“…Wenn es gelingt, die Ligninkomponente aus der Lignocellulose gezielt in substituierte Phenole abzubauen, könnten diese biobasierten Nucleophile ebenfalls durch Telomerisation in Wertprodukte überführt werden [155]. Das trifunktionelle Nucleophil Glycerin kann durch Anwendung der Zweiphasentechnik fast ausschließlich in das gewünschte Monotelomer überführt werden, das als Ausgangsstoff für Tenside von Interesse ist [157,158]. Einerseits kann auf diese Weise -wie bereits bei der Hydroformylierung vorgestellt -ein einfach durchzuführender Recycle des Ü bergangsmetall-Katalysators erfolgen, andererseits ist durch diese Reaktionsmethode bei Einsatz mehrfunktioneller Nucleophile eine Selektivierung der Telomerisation möglich.…”