Isomerization of methylenedianilines using shape-selective zeolites
Methylenedianilines (MDA) are widely used as intermediates in the production of polyurethanes and polyisocyanurates.The current routes for the production of MDA offer only limited control of the isomer ratio (4,4'/(2,4'+2,2')),with 4,4'-MDA being the most valuable isomer.While 2,4'-MDA is also marketed,significant added value could be unlocked upon further steering the production towards 4,4'-MDA.We here show that zeolites such as Beta can selectively isomerize 2,4'-MDA to-wards the desired 4,4'-MDA via a bimolecular mechanism,in an aniline background.While several acid zeolites were found to be active isomerization catalysts,MCM-68 (MSE topology) in particular combines high isomerization activity with efficient shape-selective suppression of the formation of unwanted 2,2'-MDA and oligomers.The origin of this shape-selectivity was studied,highlighting the crucial role of the acid site location in the pore confinement of MSE zeolites.
Sam Van Minnebruggen、Ka Yan Cheung、Trees De Baerdemaeker、Niels Van Velthoven、Matthias Degelin、Galahad O'Rourke、Hiroto Toyoda、Andree Iemhoff、Imke Muller、Andrei-Nicolae Parvulescu、Torsten Mattke、Jens Ferbitz、吴勤明、肖丰收、Toshiyuki Yokoi、Nils Bottke、Dirk De Vos
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