Synthesis and Catalytic Applications of Chemically Grafted SiH-Functionalized Tripodal Ti-POSS Complexes in Crosslinked Hyperbranched Poly(siloxysilane)

Abstract

This study investigated the synthesis, activity, epoxide selectivity, H2O2 efficiency, and recyclability of new heterogeneous alkene epoxidation catalysts prepared by chemical grafting of new SiH-functionalized tripodal Ti–polyhedral oligomeric silsesquioxane (Ti-POSS) complexes in hyperbranched poly(siloxysilane) via hydrosilation. Crosslinked hyperbranched poly(siloxysilane)-grafted [{(p-HSiMe2(CH2)2C6H4)(c-C6H11)6Si7O12}Ti(NMe2)] (11) and crosslinked hyperbranched poly(siloxysilane)-grafted [{(HSiMe2(CH2)3)(i-C4H9)6Si7O12}- Ti(NMe2)] (12) displayed high activity, epoxide selectivity (≥98 %), and H2O2 efficiency (≥97 %) in cyclohexene and 1-octene epoxidation with aqueous H2O2. Moreover, these catalysts were highly recyclable with retained activity and durability and proved to be truly heterogeneous. Using chemical grafting for the synthesis of 11 and 12 enhanced their recyclability and durability with retained activity. The high H2O2 efficiency can be attributed to the uniformly non-polar environment provided about Ti in 11 and 12 by the polymer; this results in low water concentrations and higher [alkene] : [H2O2] ratios at the Ti active site than in the rest of the solution. These effects enhance the epoxide selectivity and minimize leaching of titanium.