Influence of reaction parameters on the living cationic polymerization of phosphoranimines to polyphosphazenes

摘要: A new approach to the synthesis of poly(dichlorophosphazene) and poly(organophosphazenes) has been developed via cationic condensation polymerization phosphoranimines. The effects solvent, temperature, concentration, initiator on Cl3PNSiMe3 PhCl2PNSiMe3 are described. ambient temperature is faster in toluene, benzene, dioxane than methylene chloride or chloroform. polymerizations were monitored by both NMR (31P 1H) GPC methods. initial rates slow, presumably because precipitation phosphazene short chain salts, RCl2PN−[PR(Cl)N]n−PCl3+PCl6- (where R = Cl Ph; n 0, 1, 2, ...). After chains redissolve (∼15−60 min), proceeds, with propagation following pseudo-first-order kinetics for monomers. reactions yielded polymers controlled molecular weights ...