The enthalpies of combustion and enthalpies of formation of three trinitromethyl derivatives of 1,3,5-triazine are determined by the calorimetric method. The data obtained can be used for calculating the energy capabilities of related compounds by the method of replacing functional groups. As an example, the detonation characteristics of high-energy tris(trinitromethyl)-1,3,5-triazine are calculated.

The kinetics of the thermal decomposition of diazacyclic derivatives of 1,1-diamino-2,2-dinitroethylene (FOX-7) in a dilute solution of nitrobenzene and in the solid phase are studied by manometric and calorimetric methods. The activation energy data obtained for the solution are used for comparison with quantum chemical calculations and for establishing the relationship between the stability of compounds and the structure of the molecules. The decomposition of these derivatives in solution proceeds according to the same mechanism as the decomposition of FOX-7. Their activation energies decrease with the increasing C=C bond length and are in close agreement with the published data on quantum chemical calculations. By the nature of decomposition in the solid state, these compounds differ significantly from FOX-7. This difference is due to the fact that the condensed products of their decomposition are not solid but liquid compounds.

The kinetics of the thermal decomposition of 1,1-diamino-2,2-dinitroethylene (FOX-7) in solutions at temperatures of 180 to 240°C and a concentration of FOX-7 of ~1 wt % is studied by the gage and calorimetric methods. Chloro- and o-dichlorobenzene, nitrobenzene, and n-nitrotoluene are used as solvents. The dependence of the decomposition rate on the polarity of the solvent is shown, and the kinetic parameters of the reaction in the solution are determined. The data obtained are used to discuss the reaction mechanism and predict the rates of conversion of FOX-7 in the liquid and solid states.

An original synthesis of a new non-symmetric energetic ABB' type monomer, 2-azido-4-propargylamino-6- propargyloxy-s-triazine, with a total yield of 40% involves the sequential introduction of propargylamino, propargyloxy and azido groups into s-triazine. DFT investigation of azide- Cl alkyne cycloaddition mechanism at M06-2X/6-311++G(d,p) level of theory for this monomer predicts that the regioselectivity of polycycloaddition reaction should increase with the number of propargylamino groups in the monomer structure due to the stabilization of the transition state, leading to 1,5-triazole regioisomer.

The kinetics of the thermal decomposition of 1,1-diamino-2,2-dinitroethylene (FOX-7) in the solid state is investigated by the manometric and calorimetric methods. The conditions are found under which the solid-phase reaction and the accompanying fast side processes of substance sublimation and vapor decomposition are separated in time, and the contribution of secondary reactions to the initial rate of solid-phase decomposition is small. The rate constant of the noncatalytic stage of decomposition of the substance in the solid phase is determined under these conditions.

Efficient methods for the synthesis of novel azidopropargylamino-substituted 1,3,5-triazines were developed. 4,6-Diazido-N-(prop-2-yn-1-yl)-1,3,5-triazin-2-amine was obtained by the method of sequential nucleophilic substitution of chlorine atoms in cyanuric chloride by amino and azido groups or by the method of selective substitution of the azido group in triazidotriazine with propargylamine. 6-Azido-N-2,N-4-dimethyl-N-2,N-4-di(prop-2-yn-1-yl)-1,3,5-triazine-2,4-diamine was obtained by nitrosation of the corresponding 6-hydrazinyl-N-2,N-4-dimethyl-N-2,N-4-di(prop-2-yn-1-yl)-1,3,5-triazine-2,4-diamine. Monomers with a lower melting point were obtained by N-methylation of azidopropargylamino-substituted 1,3,5-triazines.

The decomposition rate of 1,1-diamino-2,2-dinitroethylene (FOX-7) at 200°C in a wide range of changes in the conditions of the experiment and methods of sample preparation is measured. The nature of the first stage of decomposition is established and the reason the reaction stopped at this stage is found.

The standard enthalpies of formation were measured experimentally for the compounds 4,6-diazido-N-(2,2,2-trinitroethyl)-1,3,5-triazine-2-amine, 6-azido-N2,N4-bis(2,2,2-trinitroethyl)-1,3,5-triazine-2,4-diamine, 6-azido-N2,N4-dinitro-N2,N4-bis(2,2,2-trinitroethyl)-1,3,5-triazine-2,4-diamine, and N2,N4,N6-trinitro-N2,N4,N6-tris(2,2,2-trinitroethyl)-1,3,5-triazine-2,4,6-triamine: 690.1 ± 5.9, 326.2 ± 13.6, 630.1 ± 6.1, and 415.9 ± 9.3 kJ/mol, respectively. Based on these values, the energy equivalent of replacing the hydrogen atom and the azide group with trinitroethylamine and trinitroethylnitramine groups in triazine and azido-substituted derivatives of triazine has been determined. Calculations have shown that 6-azido-N2,N4-dinitro-N2,N4-bis(2,2,2-trinitroethyl)-1,3,5-triazine-2,4-diamine, and N2,N4,N6-trinitro-N2,N4,N6-tris(2,2,2-trinitroethyl)-1,3,5-triazine-2,4,6-triamine with an oxygen saturation coefficient greater than 1.0 can be used as the basis for designing low-aluminum compositions with a specific impulse of 257–260 s.

The kinetics of thermal decomposition of 2,4-bis(dimethylamino)-6-trinitromethyl-1,3,5-triazine has been studied in melt and in a dilute solution of dinonyl phthalate by manometric and gravimetric methods. The reaction has proven to be self-accelerated. The additives of N-phenylmorpholine significantly have accelerated the decomposition. A conclusion has been drawn that the dimethylamine substituents in the molecule of the initial substance are directly involved in a rate-limiting step of the reaction. Compared to the reaction in the melt, the reaction in a dilute solution has been much slower (which is not typical of the thermal decomposition of nitro compounds). This result is explained by the fact that some of the rate-limiting steps of the process are bimolecular. This is confirmed by the values of the activation parameters for the initial steps of thermal decomposition.

To predict the thermal stability of high-energy triazine derivatives and the compatibility of trini-tromethyl substituents with dialkylamino groups in particular, thermal conversions of 2,4-bis( N, N -dimethyl-amino)-6-trinitromethyl-1,3,5-triazine ( I ) have been investigated in a temperature range of 170–623 K via differential thermal analysis, mass spectrometry, and single-crystal and powder X-ray diffraction. Compound I is characterized by a strong anisotropy of temperature expansion, and at 365 K it undergoes α- I → β- I polymorphic transformation that is preceded by an abrupt drop in density. A polymorphic transformation occurs with the destruction of crystals and is accompanied by the partial mechanochemical decomposition of I . The melting of I at about 396 K results in abrupt acceleration of its decomposition. The thermal effects of the polymorphic transformation, melting, and decomposition of I have been measured. The activation parameters of decomposition of I in melt have been estimated based on the data of differential scanning calorimetry. The composition of the gaseous products being formed has been determined, and mechanism of decomposition of I has been proposed, according to which the dimethylamino group is oxidized by the nitro group at the limiting stage of the process.

Nowadays, hyperbranched polymers (HBP) are obtained by different polycondensation and polyaddition reactions [1]. Almost interest is the reaction of 1,3-dipolar cycloaddition of azides to alkynes (1,3-DCA) [2, 3]. There is a series of papers dedicated to the preparation of triazine-triazole HBPs [4, 5, 6]. These polymers were obtained by the reaction of azido-acetylene AB2 monomers polyaddition: 2-azido-4,6-bis (propyne-2-yloxy) -1,3,5-triazine (ABPOT) and 2,4-diazido-6- (propine-2-yloxy) -1,3,5-triazine (DAPOT) (Fig. 1).

An alternative procedure for synthesizing 2,4,6-tris(2,2,2-trinitroethylamino)-1,3,5-triazine was developed. Nitration of this compound gave hitherto unknown 2,4,6-tris(2,2,2-trinitroethylnitramino)-1,3,5-triazine, which is of interest as potential component of solid rocket fuel compositions.

Methods were developed for the synthesis of 6-azido-2,4-bis(2,2,2-trinitroethylamino)- 1,3,5-triazine and its N-nitro derivatives (6-azido-2,4-bis(2,2,2-trinitroethyl)nitramino-1,3,5-triazine and 6-azido-2-(2,2,2-trinitroethylamino)-4-(2,2,2-trinitroethyl)nitramino-1,3,5-triazine) containing combinations of azido, trinitroethyl, and nitramine groups. These compounds are of interest as components of energetic composites. The molecular and crystal structures of 6-azido-2,4-bis(2,2,2-trinitroethylamino)-1,3,5-triazine and 6-azido-2,4-bis(2,2,2-trinitroethyl) nitramino-1,3,5-triazine were studied by X-ray diffraction and NMR spectroscopy.