Copolymerization is a versatile strategy to produce materials combining properties of different homopolymers. It is a challenge when monomers give incompatible propagating chain ends. Janus polymerization is a novel strategy that combines cationic and anionic polymerizations at two ends of a single propagating chain followed by self-triggered coupling reaction and thus provides a facile methodology to synthesize multiblock copolymers with mechanically incompatible blocks in one step. For instance, high molecular weight poly(ε-caprolactone) (PCL) is usually produced by anionic (coordinated) ring-opening polymerization (AROP), while tetrahydrofuran (THF), 3,3-bis(chloromethyl) oxacyclobutane (CO) and 1,3-dioxolane (DO) are reported to be polymerized via cationic polymerization only. Janus polymerization catalyzed by rare earth triflates and epoxides comprises AROP of CL and cationic copolymerization of CL with THF, CO or DO at two ends of a propagating chain, producing corresponding multiblock copolymers in one-step procedure.

Janus polymerization: A direct way towards multiblock copolymers

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