Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s.

A strategy is reported for controlling the architecture of poly(disulfide)s by ring-opening polymerization. Aryl thiol initiators shift the ring-chain equilibrium to yield cyclic polymers, while alkyl thiols favor linear ones. Control over polymerization enables synthesis of large polymers (630 kDa) and catalytic depolymerization to recycle monomers. This work provides a new avenue to create dynamic covalent polymers with controlled geometry and length, allowing better characterization of structure-property relationships to expand their materials potentials.