Dithiophosphoric Acids for Polymer Functionalization

Dithiophosphoric acids (DTPAs) are an intriguing class of compounds that are sourced from elemental sulfur and white phosphorus and are prepared from the reaction of phosphorus pentasulfide with alcohols. The electrophilic addition of DTPAs to alkenes and unsaturated olefinic substrates is a known reaction, but has not been applied to polymer synthesis and polymer functionalization. We report on the synthesis and application of DTPAs for the functionalization of challenging poly‐enes, namely polyisoprene (PI) and polynorbornene (pNB) prepared by ring‐opening metathesis polymerization (ROMP). The high heteroatom content within DTPA moieties impart intriguing bulk properties to poly‐ene materials after direct electrophilic addition reactions to the polymer backbone introducing DTPAs as side chain groups. The resulting materials possess both enhanced optical and flame retardant properties vs the poly‐ene starting materials. Finally, we demonstrate the ability to prepare crosslinked polydiene films with di‐functional DTPAs, where the crosslinking density and thermomechanical properties can be directly tuned by DTPA feed ratios. We reporton a new polymer functionalization method for challenging poly‐enes substates through a regioselective electrophilic Markovnikov addition with dithiophosphoric acids, which are derived from elemental sulfur and phosphorus feedstocks. DTPA functionalization to these poly‐enes confer enhanced thermomechanical, optical and flame retardant properties using inexpensive reagents.