Polyesters of phosphoric acid: Synthesis and kinetics of hydrolysis

Abstract

Three major methods have been elaborated in our laboratory for preparation of polymers with poly(alkylene phosphates) backbones: ring‐opening polymerization, poly‐condensation and transesterification, and polyaddition. The second method is based on the reaction of the commercially available compounds, namely dialkyl (or diaryl)‐H‐phosphonates and glycols. Reaction of the aliphatic H‐phosphonates with aliphatic glycols is a reversible process, whereas polycondensation of diphenyl H‐phosphonates with aliphatic and cycloaliphatic diols is practically irreversible. This latter method has recently been developed and is described in this paper. Poly H‐phosphonates with M̄n up to 40–103 were prepared. Polymers are easily oxidized and quantitatively converted into the relatively stable poly(alkylene phosphates). Some physical properties of these polymers and kinetics of their hydrolysis is discussed.