Condensation polymerization of Cl3P=NSiMe3 at room temperature is one of the best methods for linear polydichlorophosphazene production. The living cationic nature of the polymerization mechanism of this material enables unique features such as the preparation of well-defined block, star, or organic-inorganic hybrid copolymers. Therefore, reproducible high yield synthesis of Cl3P=NSiMe3 from readily available and cheap chemicals under mild conditions is an important issue to be solved. In this study, PCl5 was reacted with hexamethyldisilazane at 0 Celcius degree in various solvents to investigate the formation efficiency of Cl3P=NSiMe3. It is found that the reaction carried out in toluene led to the direct preparation of polydichlorophosphazene in one pot from PCl5 and hexamethyldisilazane with high yield (~94%) and without isolation of any phosphazene intermediate. The resulting polydichlorophosphazene was then purified, and derivatized to hydrolytically stable polyaryloxyphosphazenes by a macromolecular nucleophilic substitution reaction. Considering the trending applications of polyorganophosphazenes, the phenolic reagents have been selected as covalently protected sulfonic or phosphonic acid derivatives to finally reach polyphosphazene-based polyelectrolytes. It is believed that the synthetic strategies developed here may simplify the requested bulk production of polyorganophosphazenes for organic electronics or biomaterial applications.

Easy synthesis of polydichlorophosphazene under mild conditions and its derivatization to hydrolytically stable polyphosphazene-based polyelectrolytes

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.