Synthesis of a series of octaalkoxy-substituted cage silsesquioxanes catalyzed by zinc acetate

Abstract

Octaalkoxy-substituted polyhedral oligomeric silsesquioxane (8RO-POSS) is an attractive starting material for producing silicone resins. However, polymers derived from 8RO-POSS via the sol–gel process have seldom been reported owing to their synthetic difficulty. In this study, we attempted to use zinc acetate (Zn(OAc)₂) as the catalyst for the synthesis of a series of 8RO-POSS from octahydrido-POSS (8H-POSS). The reaction conditions were optimized using heptaisobutyl monohydride-POSS (7iBu1H-POSS) as a model reaction. The desired product was obtained in 96% yield under optimized conditions. The alkoxylation of 8H-POSS was performed using methanol (MeOH), ethanol (EtOH), isopropyl alcohol (i-PrOH), and tert-butyl alcohol (t-BuOH) in the presence of Zn(OAc)₂ as the catalyst. Although octamethoxy-POSS (8MeO-POSS) was isolated in the presence of a byproduct, octaethoxy-POSS (8EtO-POSS) and octaisopropoxy-POSS (8iPrO-POSS) were obtained in high yields. The degree of alkoxylation was 55% in the case of using t-BuOH. The structures of 8MeO-POSS, 8EtO-POSS, and 8iPrO-POSS were confirmed by FT-IR, ¹H-, and ²⁹Si-NMR and MALDI-TOF-MS analyses. Compared to the random silicate obtained by base-treated tetramethoxysilane (TMOS), base-treated 8EtO-POSS and 8iPrO-POSS showed that the cage structures were maintained even after the formation of condensed silicate structures via a condensation reaction.