Easy Access to Diverse Multiblock Copolymers with On-Demand Blocks via Thioester-Relayed In-Chain Cascade Copolymerization

Multiblock copolymers are envisioned as promising materials with enhanced properties and functionality compared with their diblock/triblock counterparts. However, the current approaches can construct multiblock copolymers with a limited number of blocks but tedious procedures. Here, we report a thioester-relayed in-chain cascade copolymerization strategy for the easy preparation of multiblock copolymers with on-demand blocks, in which thioester groups with on-demand numbers are built in the polymer backbone by controlled/living polymerizations. These thioester groups further serve as the in-chain initiating centers to trigger the acyl group transfer ring-opening polymerization of episulfides independently and concurrently to extend the polymer backbone into multiblock structures. The compositions, number of blocks, and block degree of polymerization can be easily regulated. This strategy can offer easy access to a library of multiblock copolymers with approximate to 100 blocks in only 2 to 4 steps.

Automated summary

Introduces a thioester-relayed in-chain cascade copolymerization strategy for the preparation of multiblock copolymers with on-demand blocks. The strategy involves building thioester groups in the polymer backbone and using them as initiating centers to trigger the polymerization of episulfides for extending the polymer backbone into multiblock structures. The composition, number of blocks, and block degree of polymerization can be easily regulated.