Photoinduced bending of needle crystals caused by photochemical transformation can be used as an extremely sensitive method for studying the kinetics of the transformation. However, the determination of the absolute value of the quantum yield of the reaction requires an accurate value of the intensity of light penetrating the crystal, in contrast to reactions in solutions where only the value of the total absorbed irradiation dose is sufficient. To address this problem, this study utilizes the effect of photothermal bending of a crystal due to its heating by light, occurring simultaneously with the bending due to transformation and proportional to the same value of light intensity. The ratio of the amplitudes of the two effects is independent of the light intensity, which allows the quantum yield to be determined without knowledge of the intensity value. In addition, the method allows the light intensity and thermal conductivity of the crystal to be estimated. The method is applied to measure wavelength dependence of the quantum yield of nitro-to-nitrito photoisomerization in [Co(NH3)5NO2]Cl(NO3) crystals. A monotonically decreasing value of the quantum yield φ from 0.19 to 0.04 in the range of λ from 403 to 523 nm was obtained. This result indicates the qualitative differences in the transformation mechanism in crystals and in solutions, where φ = 0.03 independent of λ in the same wavelength range.
A [3 + 2] cycloaddition reaction using dialkyne and diazide comonomers, both bearing explosophoric groups, to synthesize energetic polymers containing furazan and 1,2,3-triazole ring as well as nitramine group in the polymer chain have been described. The developed solvent- and catalyst-free approach is methodologically simple and effective, the comonomers used are easily available, and the resulting polymer does not need any purification. All this makes it a promising tool for the synthesis of energetic polymers. The protocol was utilized to generate multigram quantities of the target polymer, which has been comprehensively investigated. The resulting polymer was fully characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers, thermochemical characteristics, and combustion features indicate the prospects of this polymer as a binder base for energetic materials. The polymer of this study surpasses the benchmark energetic polymer, nitrocellulose (NC), in a number of properties.
Polymers , Triazoles , Polymers/chemistry , Triazoles/chemistry , Plasticizers/chemistry , Aniline Compounds
A simple, mild and general method has been developed for the preparation of alkyl nitramines bearing a halogenoalkoxylic moiety. From these reactive halogen intermediates, a few azidoalkoxyl alkyl nitramines have been produced as energetic plasticizers. This simple protocol allows azidonitramino ether plasticizers to be obtained from available precursors in high yields, as it is safe and viable for large-scale operations. The resulting products have been fully characterized by spectral methods, and their impact sensitivity, thermal transformations and burning properties were determined, thus allowing complete comparison to the analogues including other combinations of structural units. Such characterization of these new plasticizers illustrates the extent to which the nature and position of the functional units can be used to tune the above properties of these nitramines. All azidonitramino ethers are liquid with excellent energetic performance and are promising candidates for new environmentally friendly energetic materials.
