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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\u2010enes, namely polyisoprene (PI) and polynorbornene (pNB) prepared by ring\u2010opening metathesis polymerization (ROMP). The high heteroatom content within DTPA moieties impart intriguing bulk properties to poly\u2010ene 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\u2010ene starting materials. Finally, we demonstrate the ability to prepare crosslinked polydiene films with di\u2010functional DTPAs, where the crosslinking density and thermomechanical properties can be directly tuned by DTPA feed ratios.<\/jats:p>","DOI":"10.1002\/anie.202315963","type":"journal-article","created":{"date-parts":[[2024,1,15]],"date-time":"2024-01-15T23:44:47Z","timestamp":1705362287000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["Dithiophosphoric Acids for Polymer Functionalization"],"prefix":"10.1002","volume":"63","author":[{"given":"Jianhua","family":"Bao","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry The University of Arizona  Tucson AZ 85721 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kyung\u2010Seok","family":"Kang","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry The University of Arizona  Tucson AZ 85721 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