Synthesis of polyarylaminophosphazenes

The synthesis of a series of Polybis(arylamino)phosphazenes is described. The polymers usually were prepared by treatment of polydichlorophosphazene in benzene–tetrahydrofuran with arylamines/triethylamine at reflux for 48–144 hr. The polymers, having viscosities of 0.3–1.4dl/g, are essentially free of active chlorine sites, as shown by elemental analysis and their longterm hydrolytic stability. Thermal analysis revealed glass transition temperatures between 53 and 105°C and decomposition temperatures between 243 and 266°C. Analysis by differential scanning calorimetry revealed no first‐order endothermic transitions. For comparison with the arylamino polymers, polydiethylaminophenylaminophosphazene, polybis(benzylamino)phosphazene, and polybis(β‐phenethylamino)phosphazene were prepared and are described.