Sulfur-based hyper cross-linked polymers

Abstract

Various hyper cross-linked polymers (HCPs) based on tetrakis(thiylphenyl)methane were generated by sulphur-relevant chemistry. Disulfide and thioether connections were exploited as a direct route to produce three-dimensional polymers. HCPs based on a thio-ether connection were quantitatively generated in the presence of triethylamine and di-iodo derivatives by a nucleophilic substitution reaction. They exhibited a Brunauer–Emmett–Teller surface area of 177 m² g⁻¹ for N₂ adsorption at 77 K while disulfide HCPs directly generated by oxidation of the corresponding polythiophenol monomers did not exhibit any ability to store gaseous molecules. Thia-Michael addition between tetrakis(thiylphenyl)methane and N-aryl-bismaleimide derivatives was next realized and led to porous HCPs presenting a specific surface area up to 1675 m² g⁻¹ in sorption measurements using nitrogen gas at 77 K. These organic frameworks were insoluble in common organic solvents and showed a high thermal stability up to 500 °C.