Post-Polymerization Modification of Polystyrene through Mn-Catalyzed Phosphorylation of Aromatic C(sp²)–H Bonds

The high flammability and lack of charrability of polystyrene (PS) pose significant limitations on its broader applications. Therefore, there is an urgent need for a straightforward and efficient method for the synthesis of flame-retardant PS, which still poses a considerable challenge. In this study, we present an efficient approach to enhance the flame-retardant properties of PS through direct phosphorylation of aromatic C(sp2)–H bonds using commercially available and inexpensive manganese catalyst. A range of phosphonates served as reactive substrates to enable a tunable degree of polymer functionalization. The corresponding phosphorylated PS specimens were determined by means of 1H NMR, 31P NMR, FTIR spectroscopy, and size exclusion chromatography. Microscale combustion calorimetry tests indicate that this protocol indeed enhances the flame-retardant performance of PS. Moreover, other advantages associated with the incorporation of the phosphonate group have been observed, including maintained thermal resistance and improved wettability. This cost-effective strategy of Mn-catalyzed C–H can also be utilized to directly obtain phosphonate modification of waste foamed PS and styrene acrylonitrile copolymer, providing a method for the purpose of recycling and upgrading PS plastics.