Synthesis of Copolymers from Phenylboronic Acid-Installed Cyclic Carbonates

Organoboron polymers play important roles in biomedical applications. An ample number of monomers bearing boronic acid derivatives have been synthesized, particularly focusing on controlled free radical polymerization methods. Organoboron polymers synthesized by ring-opening polymerization (ROP) routes are far less explored. We report on the ROP of boronic acid-installed cyclic carbonates, catalyzed by DBU from a poly(ethylene glycol) macroinitiator. Controlled polymerization proceeded to relatively high conversions (∼70%) with low polydispersity. Deprotection of the copolymer to generate the boronic acid pendant group was readily achieved by displacement of the protecting group with free diboronic acid. The resulting amphiphilic copolymers self-assembled in water into spherical nanoparticles or vesicles, depending on hydrophilic/hydrophobic ratio. We envision these functional carbonates finding direct applications for core stabilization of biodegradable amphiphilic assemblies or in drug and protein encapsulation.