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SYNOPSISThe reaction between bis ( 2,2,2-trifluoroethyl) phenylphosphonite and trimethylsilyl azide at temperatures from 70 to 120°C provides a mixture of bis (2,2,2-trifluoroethoxy)phenyl-N -( trimethylsilyl ) phosphoranimine and poly (phenyl-2,2,2-trifluoroethoxyphosphazene). The polymer is probably formed by phosphine azide intermediates because the phosphoranimine is thermally stable up to 200°C. The polyphosphazene is an amorphous stereorandom polymer with a glass transition temperature at -31°C.

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A b s t r a c t : Two new methods for the synthesis of polyphosphazenes are described. The first is based on the catalyzed polycondensation of phosphoranimines using various catalysts and initiators. Certain mechanistic aspects of this process with reactive intermediates are discussed. Linear polymers are formed quantitatively at temperatures around 100 OC in a few hours (the thermal process requires a few days at 200 OC). The second method is based on the direct reaction between phosphonites and phosphinites with silyl azides. This reaction proceeds by phosphine azide intermediates and provides new polyphosphazenes.