Polymers with dynamic covalent bonds have the ability to self-heal, to adapt, and to show regulated life-cycle, helping lower the economic burden and minimize human’s impact on the environment. The reversibility of dynamic covalent bonds limits our ability to synthesize large molecular weight polymers with these bonds in the main chain. Here, we exploit a new scheme of anionic ring-opening polymerization that enables high molar mass polymers (&gt;100 KDa) to be synthesized with dynamic S–S bonds. The choice of Lewis base, initiator, and solvent are critical to achieve high (&gt;70%) and rapid (~2 hrs) conversion, opening doors to block copolymers and cross-linked networks. Polydispersity of 1.5 was obtained by optimizing reaction temperature, concentration, and targeted conversion, which is lower than typical dynamic covalent polymers (&gt;2.0). Our work provides a new opportunity for stimuli-responsive polymers with high strength, programmable composition, and improved recyclability.

Lewis pair-mediated ring-opening polymerization of cyclic disulfides: Building high molar mass polymers with dynamic s–s bonds

2019 Fall National Meeting

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