Directly using H₂S to Synthesize Crystalline Poly(thioether‐ester)s via Organocatalysis

The direct utilization of H 2 S in polymerization is rarely reported. Here step polymerization of H 2 S and diacrylates using commercially available organic bases as the catalysts is reported. Poly(thioether‐ester)s are successfully synthesized in an atom‐economical way, as confirmed by 1 H NMR spectra, and the molecular weights of these poly(thioether‐ester)s can be up to 64.7 kDa as determined by the gel permeation chromatography, which also shows the polymerization of H 2 S with diacrylates is stepwise manner. The calculation results show that H 2 S is first deprotonated by organic base, and the generated HS ‐ attacks the double bond of diacrylates through anionic Michael addition, to form the intermediate with double bond and ─SH ends or two ─SH ends (slight excess H 2 S used). The continuous self‐Michael addition of the polymer species with double bond and ─SH ends is the main manner for chain growth. The resultant polymers exhibit tensile strength and elongation at breaks of as high as 21.6 MPa and 1031%, respectively and can be chemically recycled. This work provides a facile and atom‐economical method to produce sulfur‐containing polymers by directly using commercially available H 2 S.