An Erratum to this paper has been published: https://doi.org/10.1134/S199079312435001X

The synthesis of new energy-intensive compounds, 7-allyl-7H-trifurazano[3,4-b:3',4'-f:3",4"-d]azepine (AzAll) and 7-allyl-7H-difurazano[3,4-b:3',4'-f]furoxano[3",4"-d]azepine (Az(O)All) is described for the first time. The main parameters of the crystal lattice are determined by X-ray diffraction analysis and experimental data on the heats of combustion and enthalpies of formation of these two compounds are obtained. A thermodynamic analysis of the effectiveness of these compounds as components of solid composite propellants and gas-generating fuels is carried out. It is shown that the compounds under consideration have no prospects for use in solid composite propellants, but they are very effective as potential dispersants of solid fuels for gas generator engines.

The paper presents the study of the calculated physicochemical properties of new high-energy 5/6/5 tricyclic structures, which are 1,2,3,4- or 1,2,4,5-tetrazines, fused with a pair of 1H-1,2,4-, 4H-1,2,4- or 1H-1,2,3-triazoles. Values of the enthalpy of formation in the gaseous phase have been determined by high-performance quantum-chemical calculations (within Gaussian 09 program package) using various methods for solving the stationary Schrödinger equation, including G4, G4MP2, ωB97XD/aug-cc-pVTZ, CBS-APNO, CBS-QB3, CBS-4M, B3LYP/6-311+G(2d,p), M062X/6-311+G(2d,p). The results of calculations obtained by the methods of atomization and isogyric reactions have been analysed. Various calculation methods have been compared in terms of accuracy and time consumption.

An Erratum to this paper has been published: https://doi.org/10.1134/S1990793124340013

To identify promising areas for the search for high-energy materials (HEMs), there is an urgent need for a comprehensive analysis of the energy potential of compounds of various classes. This paper studies the energy potential of some organic compounds containing the –N=N(O)–C(NO2)3 fragment in their structure as plasticizers of a polymeric binder in solid composite propellants. Nine trinitromethyl-ONN-azoxy-derivatives of furazan and one similar methane compound are studied, four of which are actually synthesized substances, the rest are still hypothetical structures. The ballistic efficiency of solid composite propellants of three different types (without metal, with aluminum, and with aluminum hydride (AH)) in which one of the studied compounds with a trinitromethyl-ONN-azoxy fragment acts as a plasticizer of the polymer binder is assessed. The values of its enthalpy of formation and density are determined by calculation. A comparative analysis of the ballistic efficiency of such propellants with similar compositions containing the most powerful of the currently considered energy-intensive components (nitroglycerin, tetranitromethane, or dinitrofurazan) as a plasticizer shows that practically all the studied representatives of the class of trinitromethyl-ONN-diazene oxides are significantly superior in terms of ballistic efficiency to the reference plasticizers.

The thermal stability of the propargyl derivatives of 7H-difurazanofuroxanoazepine and 7H-trifurazanoazepine in the isothermal and nonisothermal modes is studied. Formal kinetic regularities of the decomposition and temperature dependencies of the reaction rate constants are determined. The thermal stability of propargyl, cyanomethyl, allyl, and amine derivatives of azepines is compared.

The energy potential of hypothetical zwitterionic nitrohydrazine H3N ^+ N ^- NO2 as a component of solid composite propellants is estimated. Two-component formulations with a hydrocarbon or an active binder and three-component formulations with aluminum or aluminum hydride additives are considered. The highest calculated ballistic efficiency was obtained for formulations with an active binder and aluminum hydride. Their specific impulse exceeds 280 s, and with allowance for two-phase losses, the maximum effective impulse of the third stage rocket motor reaches 265.4 s, whereas for the optimized similar formulation based on ammonium dinitramide, this value is much lower (262.5 s).

The thermal stability of N-methyl derivatives of 7H-difurazanofuroxanoazepine and 7H-trifurazanoazepine in the nonisothermal and isothermal modes is studied. The formal-kinetic laws of the decomposition and temperature dependencies of the reaction rate constants are determined. The thermal stability of methyl, propargyl, cyanomethyl, allyl, and amine derivatives of azepines is compared.

Впервые синтезированы новые энергоемкие соединения 4,8-дицианометил-4H,8H-дифуразано[3,4-b:31,41-e]пиперазин (ДЦМФП) и 4,8-дитетразолометил-4H,8H-дифуразано[3,4-b:31,41-e]пиперазин (ДТМФП). Описан синтез этих соединений. Оба соединения исследованы как возможные диспергаторы твердых топлив для газогенерирующих двигателей, определены их плотности, энтальпии сгорания и образования, чувствительности к удару и трению (у ДЦМФП чувствительность очень низкая, на уровне тротила; у ДТМФП - на уровне октогена), оценена баллистическая эффективность твердых топлив на основе ДЦМФП и ДТМФП (у 7-амино-7Н-дифуразано[3,4-b:31,41-f]фуроксано[311,411-d]азепина, он же Az(O)NH2, первый выигрывает 4%, второй проигрывает ∼ 1,5%), проведено сравнение и с рядом других диспергаторов, разрабатываемых в течение последних нескольких лет. Методом дифференциального термического анализа (ДТА) в неизотермическом режиме проведено предварительное тестирование ДЦМФП и ДТМФП на термостойкость, показано, что эти компоненты весьма стабильны, так называемая температура начала интенсивного разложения составляет 312 и 270 ◦C соответственно.

Изучена термическая стабильность N-цианометильных производных 7 Н - дифуразанофуроксаноазепина и 7 Н - трифуразаноазепина в неизотермическом и изотермическом режимах. Определены формально-кинетические закономерности распада и температурные зависимости констант скорости реакций. Сопоставлена термическая стабильность цианометильных, аллильных и аминных производных азепинов.

The thermal stability of N-cyanomethyl derivatives of 7 H -difurasanofuroxanoazepine and 7 H -trifurazanoazepine in nonisothermal and isothermal modes is studied. The formal kinetic regularities of the decomposition and temperature dependences of the reaction rate constants are determined. The thermal stability of cyanomethyl, allyl, and amine derivatives of azepines is compared.

The ballistic characteristics of energy systems based on hydroxylammonium salts of nitroamine derivatives of some polynitrogen fused heterocycles are considered. The quantitative dependences of the energy parameters of such systems on the properties of the studied compound (the main filler), the proportion of aluminum, the presence of additional oxidizing agents in the composition, and the type of binder are established. All the considered compounds (I–V) outperform the classical energy components in the class of composite propellants (CPs) without condensed combustion products. The most effective component is dihydroxylammonium salt (E)-1,2-bis(3-nitroamino-[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-6-yl)diazene (V), which significantly exceeds many of the known components in terms of the value of the effective impulse in the third stage (Ief(3) = 279.7 s). However, when using a more realistic value of the enthalpy of the formation of compound V (according to our estimate) in the calculations, the indicator for the composition based on compound V dropped to 266.8 c, and the dihydroxylammonium salt of 1,4-bis(nitroamino)-3,6-dinitropyrazolo[4,3-c]pyrazole (I) with Ief(3) = 267.8 s performed the best.

The thermal stability of N-allyl derivatives 7H-difurazanofuroxanoazepine and 7H-trifurazanoazepine in the nonisothermal and isothermal modes is studied. The formal kinetic patterns of decay and the temperature dependences of the reaction rate constants are determined. The thermal stability of allyl and amine derivatives of azepines is compared.

Рассмотрены баллистические характеристики энергетических систем на основе гидроксиламмониевых солей нитроаминных производных некоторых полиазотистых конденсированных гетероциклов. Установлены количественные зависимости энергетических параметров таких систем от свойств изучаемого соединения (основного наполнителя), доли алюминия, наличия дополнительных окислителей в композиции и от типа связующего. Все рассмотренные соединения ( I – V ) превосходят классические энергетические компоненты в классе составов смесевых топлив без конденсированных продуктов сгорания. Наиболее эффективным компонентом оказалась дигидроксиламмониевая соль ( E )-1,2-бис-(3-нитроамино-[1,2,4]триазоло[4,3- b ][1,2,4,5]тетразин-6-ил)диазена ( V ), которая существенно превосходит по величине эффективного импульса на третьей ступени ( I ef (3) = 279.7 с) многие из известных компонентов. Однако при использовании в расчетах более реалистичного значения энтальпии образования V (по нашей оценке) этот показатель для состава на основе соединения V снизился до 266.8 с, а на первое место вышла дигидроксиламмониевая соль 1,4-бис(нитроамино)-3,6-динитропиразоло[4,3- c ]пиразола ( I ) с I ef (3) = 267.8 с.

The properties of azido-acetylenic derivatives of s -triazine containing various combinations of propynyloxy, propynylamino, N-methyl-propynylamino, and azido groups have been studied, and their enthalpy of formation in the condensed phase, density, and impact and friction sensitivities have been determined. Based on these data, the energy parameters of detonation, combustion, and adiabatic transformation for individual compounds and their compositions with the binder SKI-3 isoprene rubber have been calculated. The results of the integrated experimental and theoretical studies suggest a high heat of combustion of the investigated individual compounds and compositions based on them.

The energy and ballistic characteristics of model solid composite propellants (SCPs) based on some azido- and nitro-derivatives of N,N'-azoazoles are considered. The quantitative dependences of the energy parameters of the propellants on the properties of the compound under consideration (the main filler), the fractions of aluminum and additional oxidants in the composition, and the type of binder are established. The most effective component turns out to be 1,2-bis(3,5-dinitro-1H-1,2,4-triazol-1-yl)diazen (I) in a composition without aluminum with a mixture of an active and hydrocarbon binder in a ratio of 1.9 : 1. In the class of SCP compositions without condensed combustion products, compound I significantly exceeds many of the known components in terms of the effective impulse in the third stage (268.5 s).

The thermal stability of N-allyl derivatives 7 H - difurazanofuroxanoazepine and 7 H - trifurazanoazepine in the nonisothermal and isothermal modes is studied. The formal kinetic patterns of decay and the temperature dependences of the reaction rate constants are determined. The thermal stability of allyl and amine derivatives of azepines is compared.

Впервые синтезированы 7-цианометил-7 Н -дифуразано[3,4- b :3',4'- f ]фуроксано[3",4"- d ]азепин ( Az(O)CH 2 CN ) и 7-цианометил-7 Н -трифуразано[3,4- b :3',4'- d :3",4"- f ]азепин ( AzCH 2 CN ) как потенциальные диспергаторы твердых топлив для газогенераторных двигателей; определена их молекулярная структура, энтальпии сгорания и образования; оценена относительная дальность полета летательного аппарата при использовании Az(O)CH 2 CN и AzCH 2 CN в качестве диспергаторов топлива.