Epoxidation of olefines with PDMS membranes containing zeolite occluded manganese diimine complexes

A new composite catalyst for selective epoxidation of olefins with tert-butyl hydroperoxide (tBHP) is reported. The catalyst contains manganese diimine complexes (cis-Mn bis-2,2′-Bipyridyl), occluded within a NaY zeolite, in turn incorporated in a polydimethylsiloxane membrane (cis-[Mn(bpy)₂]²⁺-NaY-PDMS). The three-step synthesis consists of a Mn²⁺exchange of NaY, ligand sorption to form cis-[Mn(bpy)₂]²⁺-NaY and incorporation of the latter in a PDMS membrane. The major differences between [Mn(bpy)₂]²⁺-NaY as such and occluded in PDMS are observed in the sorption and catalytic characteristics. With the membrane system, the use of a solvent becomes obsolete. Whereas optimal cyclohexene oxidation with [Mn(bpy)₂]²⁺-NaY occurs with hydrogen peroxide in acetone, tBuOOH proves to be a better oxidant for [Mn(bpy)₂]²⁺-NaY-PDMS. The reactions in batch and fed-batch reactors are discussed. A simple regeneration procedure, monitored by FT-IR spectroscopy is proposed.