Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure

Condensation of hexakis-2-(formylphenoxy)cyclotriphosphazene with malonic acid yielded hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene (2-CEPP), whose structure was confirmed by <sup>31</sup>P, <sup>1</sup>H, <sup>13</sup>C NMR spectroscopy and MALDI-TOF ma...

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Main Authors: Pavel Yudaev, Anastasia Konstantinova, Vladimir Volkov, Evgeniy Chistyakov
Format: Article
Language:English
Published: MDPI AG 2023-09-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/28/18/6571
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author Pavel Yudaev
Anastasia Konstantinova
Vladimir Volkov
Evgeniy Chistyakov
author_facet Pavel Yudaev
Anastasia Konstantinova
Vladimir Volkov
Evgeniy Chistyakov
author_sort Pavel Yudaev
collection DOAJ
description Condensation of hexakis-2-(formylphenoxy)cyclotriphosphazene with malonic acid yielded hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene (2-CEPP), whose structure was confirmed by <sup>31</sup>P, <sup>1</sup>H, <sup>13</sup>C NMR spectroscopy and MALDI-TOF mass spectrometry. A quantum-chemical calculation for the 2-CEPP molecule using the ab initio methods in the 6-311G<sup>**</sup> basis set and the DFT-PBE0/6-311g** method was performed with geometry optimization of all parameters by the standard gradient method. The acid strength of 2-CEPP was theoretically estimated. Using the small-angle X-ray scattering method, it was found that 2-CEPP is an amorphous substance, which, when heated, can transform into a crystalline state. However, when heated at 370 °C, 2-CEPP undergoes decarboxylation and polymerization to form an insoluble heat-resistant product. The occurrence of decarboxylation and polymerization reactions in the formed styrene fragments was confirmed by thermal (differential-scanning calorimetry) and spectral (solid-state <sup>13</sup>C NMR spectroscopy) analysis.
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spelling doaj.art-04f91e8533174d8781ae1db8d93209852023-11-19T12:09:19ZengMDPI AGMolecules1420-30492023-09-012818657110.3390/molecules28186571Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling StructurePavel Yudaev0Anastasia Konstantinova1Vladimir Volkov2Evgeniy Chistyakov3Mendeleev University of Chemical Technology of Russia, Miusskaya sq., 9, 125047 Moscow, RussiaMendeleev University of Chemical Technology of Russia, Miusskaya sq., 9, 125047 Moscow, RussiaShubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, Leninsky Prospect, 59, 119333 Moscow, RussiaMendeleev University of Chemical Technology of Russia, Miusskaya sq., 9, 125047 Moscow, RussiaCondensation of hexakis-2-(formylphenoxy)cyclotriphosphazene with malonic acid yielded hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene (2-CEPP), whose structure was confirmed by <sup>31</sup>P, <sup>1</sup>H, <sup>13</sup>C NMR spectroscopy and MALDI-TOF mass spectrometry. A quantum-chemical calculation for the 2-CEPP molecule using the ab initio methods in the 6-311G<sup>**</sup> basis set and the DFT-PBE0/6-311g** method was performed with geometry optimization of all parameters by the standard gradient method. The acid strength of 2-CEPP was theoretically estimated. Using the small-angle X-ray scattering method, it was found that 2-CEPP is an amorphous substance, which, when heated, can transform into a crystalline state. However, when heated at 370 °C, 2-CEPP undergoes decarboxylation and polymerization to form an insoluble heat-resistant product. The occurrence of decarboxylation and polymerization reactions in the formed styrene fragments was confirmed by thermal (differential-scanning calorimetry) and spectral (solid-state <sup>13</sup>C NMR spectroscopy) analysis.https://www.mdpi.com/1420-3049/28/18/6571phosphazenemodeling structurenanoparticlequantum-chemical calculationthermal crystallizationheat-resistant polymer
spellingShingle Pavel Yudaev
Anastasia Konstantinova
Vladimir Volkov
Evgeniy Chistyakov
Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
Molecules
phosphazene
modeling structure
nanoparticle
quantum-chemical calculation
thermal crystallization
heat-resistant polymer
title Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
title_full Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
title_fullStr Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
title_full_unstemmed Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
title_short Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
title_sort hexakis 2 β carboxyethenylphenoxy cyclotriphosphazene synthesis properties modeling structure
topic phosphazene
modeling structure
nanoparticle
quantum-chemical calculation
thermal crystallization
heat-resistant polymer
url https://www.mdpi.com/1420-3049/28/18/6571
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AT vladimirvolkov hexakis2bcarboxyethenylphenoxycyclotriphosphazenesynthesispropertiesmodelingstructure
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