SUBMISSION

Phosphazene superbase interactions with phosphonitrilic chloride trimer

Nicholas Aleksandr Johnson

Yuan Xue

Claire Tessier

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Presented at
ACS Fall 2022

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Abstract

Polyphosphazenes are a versatile class of macromolecules however they suffer from low commercial viability due to issues regarding their synthesis. Polyphosphazenes are classically synthesized via high-temperature ring-opening polymerization (ROP) of phosphonitrilic chloride trimer, [PCl2N]3. While polyphosphzenes have been studied for decades, the mechanism is still not fully understood and the search for new initiators to the polymerization is ongoing. We have begun to study the use of phosphazene superbases as potential initiators for the ROP of [PCl2N]3. Phosphazene superbases have been shown to be effective initiators in many ring-opening polymerizations due to the strong Brønsted basicity and the low nucleophilicity they exhibit. Through our initial studies, the phosphazene superbase acted as a nucleophile when reacted with [PCl2N]3. This reaction produced a tadpole-like structure. A similar structure has been implicated as the product of the initiating step of the ROP of [PCl2N]3. Further studies and characterization of this tadpole structure could give useful information into the initiating steps of the ROP of [PCl2N]3. The results of this study were characterized via X-ray crystallography and multi-nuclear NMR.

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