Fast synthesis of crosslinked self-blowing poly(β-hydroxythioether) foams by decarboxylative-alkylation of thiols at room temperature

A novel strategy was developed to prepare a self-blowing poly(β-hydroxythioether) foam at room temperature by S-alkylation of 5-membered bis-cyclic carbonate using multifunctional thiol monomers. Two different thiol compounds, trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropanoic acid) were used for the decarboxylative s-alkylation reaction. The thiol compounds simultaneously act as crosslinking agents and generate carbon dioxide during the decarboxylative s-alkylation reaction. This enables foam preparation without an external blowing agent. The use of tetrathiol monomer improves thermal stability, provides flexibility to the foams, and induces an increase in the glass transition temperature (Tg) due to a higher degree of cross-linking. The apparent density of the foams decreases with the increase of the tetrathiol ratio. This novel solvent-free approach paves the way to design sustainable foams with modular properties using accessible components and additives, as well as provides an alternative to non-isocyanate polyurethane foams.