Abstract: | The reaction between diepoxides and difunctional acids of phosphorus was studied as a potential route to linear polyesters of phosphoric acid. The reaction between diepoxide and P? OH groups in H3PO4 and related acids leads to linear phosphates, but cyclic phosphates are also formed as side products. The formation of such unreactive groups terminates polyaddition. However, cyclization is practically eliminated when the epoxide ring is fused to another ring, such as in cyclohexene oxide. A commercially available diepoxide containing two cyclohexene oxide moieties, 3,4‐epoxycyclohexylmethyl‐3,4‐epoxycyclohexanecarboxylate (ERL), was, therefore, used for polyaddition studies. Indeed, in the polyaddition of ERL with ethylphosphoric acid, high molecular weight (number‐average molecular weight up to 104) linear polyphosphates were obtained. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3024–3033, 2001 |