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

Authors : Selen BİLGE

Pages : 745-756

Doi:10.3906/zoo-1206-23

View : 16 | Download : 9

Publication Date : 0000-00-00

Article Type : Research Paper

Abstract :In this study, the ring-opening polymerization insert ignore into journalissuearticles values(ROP); of cyclic trimer N3P3Cl6 catalyzed by [Et3Siinsert ignore into journalissuearticles values(N3 P3Cl6);][CHB11H5Br6] insert ignore into journalissuearticles values(3); obtained from the reaction of N3P3Cl6 insert ignore into journalissuearticles values(1); and Et3Siinsert ignore into journalissuearticles values(CHB11H5Br6); insert ignore into journalissuearticles values(2); at room temperature was investigated. This provided a unique opportunity to explore the polymerization mechanism. The coordinatively unsaturated cation [N3P3Cl5]+ is responsible for the ROP of N3P3Cl6, and is formed by the intramolecular elimination of Et3SiCl from 3. The detection of Et3SiCl by 1H-NMR as the catalysis proceeded offers new evidence for the formation of [N3P3Cl5]+. 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 N3P3Cl6 [insert ignore into journalissuearticles values(Cl2P=N);n insert ignore into journalissuearticles values(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