Organic catalyst-mediated ring-opening polymerization for the highly efficient synthesis of polyester-based star polymers

Abstract

A facile, highly efficient, and metal-free synthesis of well-defined polyester-based core cross-linked star (CCS) polymers with yields of up to 96 % was achieved via an organic catalyst (i.e., methanesulfonic acid) mediated ring-opening polymerization (ROP) at room temperature, through either a two-pot or a one-pot, two-step strategy. CCS polymers with narrow molecular weight distributions (PDI ≤ 1.3) and macroinitiator (MI) conversions of 90.96% were prepared using poly(ε-caprolactone) (PCL) MIs with molecular weights ranging from 9.9 to 36.2 kDa and [4,4'-bioxepane]-7,7'-dione (BOD) as the cross-linker. Furthermore, transesterification was identified as being responsible for the small perc..