Synthesis of poly(ester disulfide)s from S<sub>8</sub>-involved step-growth addition polymerization at ambient temperature.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41593067.
- Also identified by DOI 10.1038/s41467-026-68963-7 and PMC identifier 12949229.
- Licence recorded as CC BY-NC-ND.
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Abstract
Elemental sulfur (S<sub>8</sub>), 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), M<sub>n</sub> up to 42.0 kDa, and dual functionality: biodegradable ester units and stimuli-responsive disulfides. Mechanistic studies reveal a chemoselective three-component coupling involving S<sub>8</sub> 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 (T<sub>d,5%</sub> = 248-281 °C), tunable phase behavior (amorphous T<sub>g</sub> = -64 °C to semicrystalline T<sub>m</sub> = 142 °C), and reductive degradation. By overcoming traditional limitations of harsh conditions and monomer scope, this strategy establishes S<sub>8</sub> as a versatile feedstock for functional polymers, opening avenues for dynamic materials in biomedicine and environmental remediation.