Facile Synthesis of Hyperbranched Polymers by Sequential Polycondensation

Hyperbranched polymers are an important class of soft nanomaterial, but the synthesis of hyperbranched polymers with well-defined dendritic structure from readily available monomers remains a challenge in polymer chemistry. We herein report a sequential polycondensation method for the one-pot synthesis of hyperbranched polymers with tunable structure and high degree of branching from commercial available monomers. Specifically, in the polycondensation process of equimolar difunctional haloalkane (A2-type monomers) and trifunctional dihydroxybenzoic acid (CB2-type monomers) using K2CO3 as the base, the aliphatic nucleophilic substitution reactivity sequence of the functional groups derived from CB2 monomers is C > second B > first B ≫ original B, thereby producing hyperbranched poly(ester ether)s with high degree of branching (DB > 0.6). Moreover, the surface functionality of the hyperbranched poly(ester ether)s could be facilely tailored by just introducing A-type monofunctional reagents into the one-pot A2 + CB2 polymerization system.