Abstract
Elemental sulfur (S8), an abundant petroleum byproduct, is leveraged as a linchpin monomer in an organobase-catalyzed step-growth addition polymerization with dithiols and diacrylates at ambient temperature. This method enables the scalable synthesis of poly(ester disulfide)s—featuring alternating ester and disulfide linkages—with exceptional atom economy ( > 95% yield), Mn up to 42.0 kDa, and dual functionality: biodegradable ester units and stimuli-responsive disulfides. Mechanistic studies reveal a chemoselective three-component coupling involving S8 ring-opening, disulfide anion formation, and Michael addition, quantitatively generating symmetric and asymmetric disulfides in near-equimolar ratios. Thermal and mechanical characterizations of the poly(ester disulfide)s reveal programmable properties: High thermal stability (Td,5% = 248–281 °C), tunable phase behavior (amorphous Tg = −64 °C to semicrystalline Tm = 142 °C), and reductive degradation. By overcoming traditional limitations of harsh conditions and monomer scope, this strategy establishes S8 as a versatile feedstock for functional polymers, opening avenues for dynamic materials in biomedicine and environmental remediation.
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Data supporting the findings of this study are available within the article (and its Supplementary information files). All data were available from the corresponding author upon request.
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Acknowledgements
We gratefully acknowledge the financial support of the Natural Science Foundation of Zhejiang Province (LR26E030001, received by Chengjian Zhang) and the National Natural Science Foundation of China (52373014, received by Chengjian Zhang).
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Y.S. carried out most of the experiments and wrote the draft. Y.C. carried out the analysis of polymer structure. X.L. carried out the analysis of the polymerization mechanism. C.Z. conceived, designed, and directed the investigation and revised the manuscript. X.Z. directed the investigation and revised the manuscript.
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Sun, Y., Cao, Y., Liu, X. et al. Synthesis of poly(ester disulfide)s from S8-involved step-growth addition polymerization at ambient temperature. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68963-7
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DOI: https://doi.org/10.1038/s41467-026-68963-7
