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Chemical design and characterization of cellulosic derivatives containing high-nitrogen functional groups:Towards the next generation of energetic biopolymers

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Defence Technology（防务技术） 2022年第4期18卷 537-546页

作者： Ahmed Fouzi Tarchoun Djalal Trache Thomas M.Klapotke Amir Abdelaziz Mehdi Derradji Slimane Bekhouche Energetic Materials Laboratory Teaching and Research Unit of Energetic ProcessesEcole Militaire PolytechniqueBP 17Bordj El-Bahri16046AlgiersAlgeria Energetic Propulsion Laboratory Teaching and Research Unit of Energetic ProcessesEcole Militaire PolytechniqueBP 17Bordj El-Bahri16046AlgiersAlgeria Department of Chemistry Ludwig Maximilian University Butenandtstrasse 5-13(D)D-81377MunichGermany Process Engineering Laboratory Teaching and Research Unit of Energetic ProcessesEcole Militaire PolytechniqueBP 17Bordj El-Bahri16046AlgiersAlgeria

In this research,a promising class of insensitive and high-energy dense biopolymers,which contain nitrogen-rich 1H-tetrazol-1-yl acetate and nitrate ester functional groups,was successfully synthesized through tetrazole derivatization and nitration of cellulose and its micro-sized derivative(TNCN and TCMCN).Their molecular structures,physicochemical properties,thermal behaviors,mechanical sensitivities and detonation performances were studied and compared to those of the corresponding nitrocellulose and nitrated micro-sized cellulose(NCN and CMCN).The developed energetic TNCN and TCMCN exhibited insensitive character with excellent features such as density of 1.710 g/cm3and 1.726 g/cm3,nitrogen content of 20.95%and 22.59%,and detonation velocity of 7552 m/s and 7786 m/s,respectively,and thereby demonstrate their potential applications as new generation of energetic biopolymers to substitute the common NCN.Furthermore,thermal results showed that the designed nitrated and chemical modified cellulosic biopolymers displayed good thermal stability with multistep decomposition mechanism.These results enrich future prospects for the design of promising insensitive and high-energy dense cellulose-rich materials and commence a new chapter in this field.

关键词： Cellulose Surface functionalization Tetrazole nitrate ester Nitrogen-rich polymer Energetic properties

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Nitroxy-and azidomethyl azofurazans as advanced energetic materials

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Defence Technology（防务技术） 2022年第8期18卷 1369-1381页

作者： Aleksei B.Sheremetev Svetlana F.Mel'nikova Elizaveta S.Kokareva Ruslan E.Nekrutenko Kirill V.Strizhenko Kyrill Yu Suponitsky Thanh Dat Pham Alla N.Pivkina Valery P.Sinditskii Zelinsky Institute of Organic Chemistry Russian Academy of Sciences47 Leninsky ProspMoscow119991Russia Saint Petersburg State Institute of Technology 26 Moskovskii PrSt Petersburg190013Russia Mendeleev University of Chemical Technology Moscow125047Russia N.N.Semenov Federal Research Center for Chemical Physics Russian Academy of Sciences4 Kosygina Str119991MoscowRussia

Progress in the rocket industry is only possible on the basis of new, higher performance and more environmentally friendly materials compared to up-to-date propellant ingredients for liquid, solid, gelled and hybrid propellant systems. In this work, synthetic methods have been developed for the preparation of new energetic azofurazans bearing nitroxymethyl or azidomethyl groups. All prepared compounds were fully characterized by multinuclear NMR and IR spectroscopies, as well as elemental analyses. An analysis of the structural features based on the X-ray single-crystal diffraction made it possible to discuss their influence on the densities of the azofurazans of this study. Thermal decomposition and combustion of nitroxymethyl and azidomethyl azofurazans were studied using a number of complementary experimental techniques, namely thermogravimetry, differential scanning calorimetry, manometry, microthermocouple measurements in the combustion wave. The structural and physical characteristics of these new energetic analogues illustrate the extent to which the nature of the explosophoric groups can be used to tune the performace of the azofurazan framework. These azofurazans possess positive calculated enthalpy of formation and are promising candidates for new environmentally friendly energetic materials.

关键词： Azofurazan Azide nitrate ester X-ray Combustion

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