One-Pot Synthesis of Polymers Containing PC Bonds in the Main Chain.

Placement of phosphorus in the polymer main chain leads to organophosphorus polymers with potentially unique chemical and physical properties. Herein, it is demonstrated that the Abramov phosphonylation reaction can be extended to the synthesis of such polymers, by reacting di- or tricarbaldehydes with phosphinic acid (PA) in the presence of N,O-bis(trimethylsilyl)acetamide (BSA). This technique affords polymers with main chain PC bonds, wherein phosphorus (V), aromatic rings, and hydroxymethylene moieties are linked by bis(α-hydroxymethylene)phosphinic acid (BHMPA) units. The resulting polymers are water soluble, display resilience against acid- and base-catalyzed hydrolysis, and exhibit superior thermal stability with high char yield in air (≈83%) and nitrogen (≈76%) atmosphere.