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

Abstract

AbstractThe direct utilization of H2S in polymerization is rarely reported. Here step polymerization of H2S 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 1H 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 H2S with diacrylates is stepwise manner. The calculation results show that H2S 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 H2S 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 H2S.