Polysulfide-ene polymerization of bisacrylamides and bismaleimides toward sulphur-rich polymers

Abstract

Given the ever-increasing importance of developing more sustainable solutions for the fabrication and engineering of polymeric materials, alternative building blocks to the petroleum-derived chemicals are gaining growing interest. In addition to its natural abundance, elemental sulfur is produced industrially in vast quantities which is primarily obtained as a side product from oil refineries and gas purification plants. Thus, elemental sulfur has been prospected as a sustainable resource for the fabrication of structurally diverse polymers. In this study an efficient methodology to obtain sulfur-rich polymers from elemental sulfur-derived polysulfide salts is reported. Polysulfide-ene step growth polymerization of bisacrylamide and bismaleimide-based monomers with bifunctional disodium pentasulfide (Na2S5) generated structurally diverse polyamide and polyimide copolymers incorporating polysulfide chains on the polymer backbones. Copolymers up to 31.8 kDa molecular weight (Mn) and 94% monomerconversions were efficiently obtained under ambient temperature conditions and without the need of any metal or organo-catalyst. By choosing various bifunctional ene monomers, structurally diverse and tailorable linear copolymers were obtained. The methodology was also extended to the fabrication of sulfur-rich crosslinked polymers by employing a multifunctional thiolate-based crosslinker. As a potential application, fabricated crosslinked polymers were employed as adsorbents to remove toxic mercury ions from water. The reported synthetic strategy demonstrated the efficiency of polysulfide-ene reaction to synthesize sulfur-rich polyamide and polyimide polymers and could broaden the available polymerization reaction tools that employelemental sulfur-derived polysulfide salts in functional polymer synthesis.