Suspension Polymerization as a Kinetic Control-Free Platform for Constructing Functional Architectures From Polarity-Mismatched Monomers

Suspension polymerization may play a crucial role in synthesizing multiblock copolymers for functional architectures. In this study, water (H 2 O) was employed as the continuous dispersion medium, hydrophobic benzyl methacrylate (BzMA) was initially polymerized in toluene (MB) droplets containing oil-soluble initiator under controlled MB volume. Subsequently, glycidyl methacrylate (GMA) was introduced in a controlled manner, where it preferentially accumulated at the MB droplet interface due to its intrinsic properties and polymerization-modulating effects. Remarkably, the spatially confined segregation enabled sequential polymerization, where initial homopolymerization occurred within BzMA domains prior to initiating GMA polymerization at the interface, ultimately yielding the diblock (PGMA-b-PBzMA, PGB) copolymers and oil-soluble (PBzMA, PB) byproducts. Moreover, the rational functionalization and controlled assembly of the produced PGB copolymers not only effectively eliminated byproduct interference, but also facilitated the construction of versatile advanced architectures with programmable properties. Collectively, the aforementioned continuous feeding suspension polymerization (CFSP) strategy significantly reduces time and cost compared to conventional chain-extension methods requiring strict kinetic control.