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Poly[3,3-bis(azidomethyl)oxetane]–2,4-dinitro-2,4-diazapentane

Thermal behavior and peculiarities of crystallization

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Abstract

Constructing phase diagrams for the mixtures of semicrystalline polymers and low molecular mass substances by DSC can meet with difficulties in the case of slow polymer crystallization. A problem of this kind is encountered for high-energy compositions poly[3,3-bis(azidomethyl)oxetane] (PBAMO)–2,4-dinitro-2,4-diazapentane (DNAP). In this study, the experimental phase diagram PBAMO–DNAP is constructed by an optical method, which makes it possible to visualize structural transformations. The kinetic studies by DSC and XRD reveal that 30–50 days of storing a homogenized PBAMO–DNAP mixture at room temperature are needed to attain stationary values of the crystallinity degree and heat of fusion. Even after that, the DSC method cannot deliver a solubility curve of DNAP in PBAMO, which is naturally generated by the optical method. This curve separates a domain of physical gels, effectively crosslinked by polymer crystallites and swollen with the plasticizer molecules, from a two-phase domain, in which the above gel reaches osmotic equilibrium with the pure plasticizer. It is also shown that the melting temperature of DNAP drops with growing the PBAMO content in the mixture, which is consistent with a decrease in the mean size of plasticizer crystals formed in polymer pores during the previous cooling.

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Acknowledgements

The study was carried out within the state assignment of the Ministry of Education and Science of Russia using the facilities of the shared equipment center “Upper Volga Regional Center for Physico-Chemical Research” and that of Ivanovo State University of Chemistry and Technology.

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Authors and Affiliations

  1. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaya ul. 1, Ivanovo, Russia, 153045

    Konstantin V. Pochivalov, Tatyana N. Lebedeva, Lyubov A. Antina, Anna N. Ilyasova, Mikhail Yu. Yurov & Andrey V. Basko

  2. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, Russia, 119991

    Yaroslav V. Kudryavtsev

  3. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, Russia, 119071

    Yaroslav V. Kudryavtsev

  4. Ivanovo State University of Chemistry and Technology, Sheremetevskii pr. 7, Ivanovo, Russia, 153000

    Alexander E. Zavadskii

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  1. Konstantin V. Pochivalov
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Correspondence to Yaroslav V. Kudryavtsev.

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Pochivalov, K.V., Kudryavtsev, Y.V., Lebedeva, T.N. et al. Poly[3,3-bis(azidomethyl)oxetane]–2,4-dinitro-2,4-diazapentane. J Therm Anal Calorim 131, 2225–2233 (2018). https://doi.org/10.1007/s10973-017-6758-6

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