The catalytic properties of Ti-MWW in the epoxidation of allyl alcohol (AAL) with hydrogen peroxide to glycidol (GLY) have been studied in detail by a comparison with those of TS-1 and pure silica Ti-Beta, and mechanical considerations have been given to the relation between the catalytic performance and the structural, acidic, and hydrophilic/hydrophobic nature of titanosilicates. Ti-MWW catalyzed the AAL epoxidation more actively and selectively than TS-1 and Ti-Beta in the presence of H2O or MeCN, and exhibited a conversion of 95% for AAL and a selectivity of 99% for GLY when the AAL epoxidation was carried out at 333K for 30min and at 12wt% of catalyst to substrate. Ti-MWWproved to be a reusable and sustainable catalyst as it stood up to Ti leaching and maintained the catalytic activity and the product selectivity in the reaction-regeneration cycles. The acidic character due to the boron framework was very weak, and thus contributed negligibly to the solvolysis of GLY. The AAL epoxidation proceeded mainly within the intralayer sinusoid 10-MR channels which supplied more steric fitness to the substrate molecules than the tunnel-like channels of TS-1 ad Ti-Beta. Ti-MWW was more hydrophilic than TS-1, but much more hydrophobic than Ti-Beta. The hydrophilicity of Ti-MWW was presumed to derive mainly from the defect sites due to the incomplete dehydroxylation between the layers and partially as a result of deboronation. The sinusoidal 10-MR channels serving as the reaction space for the AAL epoxidation were considered to be hydrophobic, thus rendering the Ti-MWWcatalyst applicable to the substrates and solvents, both of a polar nature.

The catalytic activity and selectivity of Ti-MWW in the epoxidation of diallyl ether (DAE) with hydrogen peroxide to allyl glycidyl ether (AGE) and diglycidyl ether (DGE) have been studied by a comparison with those of TS-1, and the issues concerning the consecutive reaction and the selective production of AGE have been considered. Ti-MWW catalyzed the DAE epoxidation in the presence of aprotic solvents such as acetonitrile or acetone, and produced only minor levels of solvolysis products. Ti-MWW proved to be a reusable catalyst standing up to the Ti leaching and maintaining the catalytic activity and the product selectivity in the reaction-regeneration cycles. Studies with different solvents, Ti contents, reaction times, temperature, and catalyst amounts confirmed that the DAE epoxidation was a typical consecutive reaction with AGE as an intermediate product and DGE as a secondary one. The reaction rate for AGE formation was much faster than that for DGE, making the selective production of AGE possible by controlling the reaction up to a DAE conversion level of ca. 30%.