Examining the Properties of (Co)Polymer Networks Prepared by the Phosphane‐Ene Reaction

Abstract Polymer networks have emerged as materials with widespread application, including their use in drug delivery, catalysis, and flexible electronics. They have traditionally been derived from organic building blocks using well‐developed reaction types. Advances in main group synthetic chemistry have opened the door for the production of new polymer networks, including those containing phosphorus atoms that offer the traits of Lewis basic phosphorus centers. Here, the radical‐catalyzed phosphane‐ene reaction is used to prepare (co)polymer networks from i BuPH 2 , trivinyltriptycene ( TVT ), and 1,3,5‐triallyl‐1,3,5‐triazine‐2,4,6‐trione ( TTT ), which are the first of their type to include TVT . Networks rich in TVT exhibited greater thermal stability and reduced network mobility compared to those rich in TTT . Despite the rigidity, 3D, and internal free volume associated with the triptycene units present in TVT ‐rich networks, their swellability is similar to networks rich in TTT indicating that the presence of phosphines may be a dominating factor in the respective structure‐property relationships.