Dithiophosphoric Acids for Polymer Functionalization

Jianhua Bao, Kyung Seok Kang, Jake Molineux, Derek J. Bischoff, Michael E. Mackay, Jeffrey Pyun, Jon T. Njardarson

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish (US)
Article numbere202315963
JournalAngewandte Chemie - International Edition
Issue number7
StatePublished - Feb 12 2024
Externally publishedYes


  • Polyisoprene
  • Polymer Functionalization
  • Ring-Opening Metathesis Polymerization

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry


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