Studies on the mechanism of phosphazene ring-opening polymerization (ROP)


Abstract: In this study, the ring-opening polymerization (ROP) of cyclic trimer N_3P_3Cl_6 catalyzed by [Et_3Si(N_3 P_3Cl_6)][CHB_{11}H_5Br_6] (3) obtained from the reaction of N_3P_3Cl_6 (1) and Et_3Si(CHB_{11}H_5Br_6) (2) at room temperature was investigated. This provided a unique opportunity to explore the polymerization mechanism. The coordinatively unsaturated cation [N_3P_3Cl_5]^+ is responsible for the ROP of N_3P_3Cl_6, and is formed by the intramolecular elimination of Et_3SiCl from 3. The detection of Et_3SiCl by ^1H-NMR as the catalysis proceeded offers new evidence for the formation of [N_3P_3Cl_5]^+. The progress of the catalysis was followed using ^{31} P-NMR and revealed the build-up of a polymer. Cyclic phosphazenes with rings larger than that of N_3P_3Cl_6 [(Cl_2P=N)_n (n = 4-7)] were observed fairly early in the course of the ROP. The propagation of that polymerization at room temperature proceeded via a living cationic mechanism.

Keywords: ROP, polyphosphazenes, carboranes, spectroscopy

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