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Article

Novel Approach for the Synthesis of Chlorophosphazene Cycles with a Defined Size via Controlled Cyclization of Linear Oligodichlorophosphazenes [Cl(PCl2=N)n–PCl3]+[PCl6]

1
Faculty of Petrochemistry and Polymer Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, Russia
2
Taurida Academy, Department of Biochemistry, V. I. Vernadsky Crimean Federal University, Prospekt Akademika Vernadskogo 4, 295007 Simferopol, Russia
*
Author to whom correspondence should be addressed.
Academic Editor: Dario Pasini
Int. J. Mol. Sci. 2021, 22(11), 5958; https://doi.org/10.3390/ijms22115958
Received: 27 April 2021 / Revised: 13 May 2021 / Accepted: 19 May 2021 / Published: 31 May 2021
(This article belongs to the Section Macromolecules)
Despite a significant number of investigations in the field of phosphazene chemistry, the formation mechanism of this class of cyclic compounds is still poorly studied. At the same time, a thorough understanding of this process is necessary, both for the direct production of phosphazene rings of a given size and for the controlled cyclization reaction when it is secondary and undesirable. We synthesized a series of short linear phosphazene oligomers with the general formula Cl[PCl2=N]n–PCl3+PCl6 and studied their tendency to form cyclic structures under the influence of elevated temperatures or in the presence of nitrogen-containing agents, such as hexamethyldisilazane (HMDS) or ammonium chloride. It was established that linear oligophosphazenes are inert when heated in the absence of the mentioned cyclization agents, and the formation of cyclic products occurs only when these agents are involved in the process. The ability to obtain the desired size phosphazene cycle from corresponding linear chains is shown for the first time. Known obstacles, such as side interaction with the PCl6 counterion and a tendency of longer chains to undergo crosslinking elongation instead of cyclization are still relevant, and ways to overcome them are being discussed. View Full-Text
Keywords: phosphazenes; cyclization; controlled cycle size; living cationic polymerization; hexamethyldisilazane phosphazenes; cyclization; controlled cycle size; living cationic polymerization; hexamethyldisilazane
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MDPI and ACS Style

Gorlov, M.; Bredov, N.; Esin, A.; Sirotin, I.; Soldatov, M.; Oberemok, V.; Kireev, V.V. Novel Approach for the Synthesis of Chlorophosphazene Cycles with a Defined Size via Controlled Cyclization of Linear Oligodichlorophosphazenes [Cl(PCl2=N)n–PCl3]+[PCl6]. Int. J. Mol. Sci. 2021, 22, 5958. https://doi.org/10.3390/ijms22115958

AMA Style

Gorlov M, Bredov N, Esin A, Sirotin I, Soldatov M, Oberemok V, Kireev VV. Novel Approach for the Synthesis of Chlorophosphazene Cycles with a Defined Size via Controlled Cyclization of Linear Oligodichlorophosphazenes [Cl(PCl2=N)n–PCl3]+[PCl6]. International Journal of Molecular Sciences. 2021; 22(11):5958. https://doi.org/10.3390/ijms22115958

Chicago/Turabian Style

Gorlov, Mikhail, Nikolay Bredov, Andrey Esin, Igor Sirotin, Mikhail Soldatov, Volodymyr Oberemok, and Vyacheslav V. Kireev 2021. "Novel Approach for the Synthesis of Chlorophosphazene Cycles with a Defined Size via Controlled Cyclization of Linear Oligodichlorophosphazenes [Cl(PCl2=N)n–PCl3]+[PCl6]" International Journal of Molecular Sciences 22, no. 11: 5958. https://doi.org/10.3390/ijms22115958

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