Cyclic polymers or ring-based macromolecular architectures have attracted attentions due to the unique fundamental properties derived from less entanglement, more compact volume, and lack of terminal groups. In sharp contrast to the conventional macrocyclization approach where terminal groups of telechelic linear polymer are connected under highly diluted condition, “ring-expansion polymerization” is definitely useful to construct cyclic polymers. However, examples on control of ring-expansion polymerization have been limited to ring-opening polymerizations of cyclic monomers. We have recently realized ring-expansion cationic polymerization of vinyl ethers by using a hemiacetal ester embedded cyclic initiator. The propagation can proceed without irreversible side-reactions to give well-defined cyclic polymer and ring-expansion block copolymerization can be also controlled. Design of the vinyl ether pendant group and post reactions allows precise construction of ring-based architectures.

Controlled ring-expansion cationic polymerization: Precise construction of ring-based architectures

255th National Meeting (2018)

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