Abstract
We have studied synthesis, activity, epoxide selectivity, H2O2 efficiency, and recyclability of new robust heterogeneous alkene epoxidation catalysts of grafted tripodal (phenoxy) Ti-polyhedral oligomeric silsesquioxane (Ti-POSS) complexes in hyperbranched poly(siloxysilane) matrix. Crosslinked hyperbranched (CHB) poly(siloxysilane)-grafted [Ti(OC6H4CN-p){(HSiMe2(CH2)3)-(i-C4H9)6Si7O12}] (5) and CHB-poly(siloxysilane)-grafted [Ti(OC6H5){(HSiMe2(CH2)3)(i-C4H9)6Si7O12}] (6) have demonstrated high activity, epoxide selectivity (≥99%) and H2O2 efficiency (≥98%) in cyclohexene and 1-octene epoxidation with aqueous H2O2 higher than titanosilicate catalysts such as TS-1 and Ti-β, due to high Lewis acidity of the Ti-center and to the use of CHB-poly(siloxysilane) matrix. The catalysts are readily recyclable with retained activity.
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