Polysulfamates as “Macroisosteres” of Polyurethanes with Improved Degradability

Addressing the environmental persistence of plastics requires the development of next-generation polymers that combine high performance with enhanced degradability. Progress toward this grand challenge has been impeded, in part, by the absence of a general blueprint for the macromolecular design of such materials. Herein, we introduce a "macroisostere" design strategy, where the carbonyl group (-CO-) in polyurethanes (PUs) is replaced with a sulfonyl group (-SO₂-), resulting in a virtually unknown family of polymers called polysulfamates. This approach, inspired by the use of bioisosteres in drug discovery, aims to preserve key interchain interactions that contribute to thermomechanical performance while enhancing the hydrolytic lability of the polymer backbone. The optimization of a Sulfur(VI) Fluoride Exchange (SuFEx) polymerization allowed the synthesis of ten polysulfamates structurally analogous to common PUs. Comparative analysis of one PU and its polysulfamate analog showed that this isosteric substitution increases thermal stability, slightly lowers the glass transition temperature, and retains similar hardness and reduced Young's modulus. Notably, the S(VI)-based polysulfamate demonstrated significantly enhanced hydrolytic degradability. These results highlight the potential of the "macroisostere" approach as a generalizable strategy for designing high-performance, degradable alternatives to traditional plastics.