Epoxy-Selective Polymerization of Glycidyl Acrylate Derivatives through Organocatalysis

Incorporation of reactive functionalities is often indispensable for achieving optimal polymer properties but heavily challenged by the stringent chemoselectivity requirements on polymerization techniques. Here, polymers bearing multiple acrylate functionalities are synthesized directly by ring-opening (co)polymerization of epoxides comprising mono- or bisubstituted acrylate moieties. The acid-excess Lewis pair type organocatalyst, together with a refined monomer purification protocol, allows alcohol-initiated homopolymerization of glycidyl methacrylate (GMA), glycidyl sorbate (GS), and glycidyl cinnamate (GC) to occur in a perfectly epoxy-selective fashion, affording polyethers with 100% pendant-group fidelity, controlled molar mass (up to 63.9 kg mol–1), and low dispersity. The control and chemoselectivity are readily extended to statistical copolymerization with propylene oxide, "n + m" or "n + 1" type block copolymerization with ethylene oxide, and alternating copolymerization with cyclic anhydrides, generating a rich array of (multi)acrylate copolyethers and polyesters. Our results have underscored the potency of this catalytic method as a versatile platform for expeditious and precision synthesis of functionalized polymers.