Multiblock Poly-ε-Caprolactones: One-Step Synthesis toward Programmable Properties

Control of monomer sequence enables predictable structure-property relationships in versatile polymeric materials. The facile synthesis of multiblock copolymers (MBCPs) with controlled chain structure is highly challenging, particularly for those prepared via one-pot copolymerization of mixed monomers. Herein, poly-ε-caprolactone MBCPs, a series of thermoplastic elastomers with tailored thermal, mechanical, rheological, and degradable properties, are synthesized by Janus polymerization. Melting temperature, tensile strength, ductility, viscosity, and enzymatic degradability are governed by block length which is in turn dictated by the monomer-to-catalyst feed ratio. The relationships between the physicochemical properties and the architectures are investigated in detail.