Thermal degradation of bis(azidomethyl)oxethane oligomer

Неделько, В. В.; Корсунский, Б. Л.; Шастин, А. В.; Larikova, T. S.; Бадамшина, Э. Р.; Лодыгина, В. П.; Ol’khova, O. M.; Zaverkina, M. A.

doi:10.1134/s1560090407010010

Cited by 3 publications

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“…Therefore, the IR intensity of the imines and azo compounds might be too weak to be observed. For the same reason, the absence of the sharp characteristic N–H stretching vibration in the region 3450 cm –1 to 3250 cm –1 due to primary or secondary amines, can not exclude their existence. ,, Nedel’ko et al observed cross-linking of chains upon the thermal degradation of an azide containing oligomer and the formation of azo compounds, secondary amines, and imines. Analogously, all before mentioned functional groups might be formed in this work upon degradation of the azido-group of the N 3 –SAM and subsequent reaction with the neighboring alkane chains.…”

Section: Resultsmentioning

confidence: 99%

An IR Spectroscopy Study of the Degradation of Surface Bound Azido-Groups in High Vacuum

et al. 2021

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Controlled surface functionalization with azides to perform on surface "click chemistry" is desired for a large range of fields such as material engineering and biosensors. In this work, the stability of an azido-containing self-assembled monolayer in high vacuum is investigated using in situ Fourier transform infrared spectroscopy. The intensity of the antisymmetric azide stretching vibration is found to decrease over time, suggesting the degradation of the azido-group in high vacuum. The degradation is further investigated at three different temperatures and at seven different nitrogen pressures ranging from 1 × 10 −6 mbar to 5 × 10 −3 mbar. The degradation is found to increase at higher temperatures and at lower nitrogen pressures. The latter supporting the theory that the degradation reaction involves the decomposition into molecular nitrogen. For the condition with the highest degradation detected, only 63% of azides is found to remain at the surface after 8 h in vacuum. The findings show a significant loss in control of the surface functionalization. The instability of azides in high vacuum should therefore always be considered when depositing or postprocessing azido-containing layers.

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Section: Resultsmentioning

confidence: 99%

An IR Spectroscopy Study of the Degradation of Surface Bound Azido-Groups in High Vacuum

et al. 2021

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“…The activation parameters obtained are close to these for ther molysis of many other organic azides. [17][18][19][20] The direct heating of small amounts (10-12 mg) of tetrazide 14 to the temperatures >100 °C (as well as heat ing at fast rates) leads to its explosive decomposition. This indicates the high thermal explosiveness of this compound.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, thermal stability, heats of formation, and explosive properties of cyano-substituted di-, tri-, and tetraazidopyridines

2009

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A method of synthesis of 2,6 diazido 3,5 dicyanopyridine, 2,4,6 triazido 3,5 dicyanopyri dine, and 2,3,4,5 tetraazido 6 cyanopyridine was developed. The heats of formation and ex plosive properties of compounds obtained were determined; kinetics and the composition of the gaseous thermolysis products were studied. The replacement of endocyclic nitrogen atoms by С-СN fragments in the aromatic ring of polyazides strongly reduces the explosive risk of these compounds with retention of the energetic properties of the molecules. For many years, nitrogen containing heterocyclic polyazides attract attention of researchers as potential priming explosives, molecular nitrogen generators, and as starting reagents for producing carbide-nitride nanoma terials. 1-6 However, the manufacture and the use of the majority of known polyazides does not have evident per spectives because of high sensitivity to mechanical im pacts and rather low thermal stability. The typical repre sentatives of such compounds are diazide 1, triazides 2, 3, 4, tetrazide 5, and pentazide 6 (see Refs 1, 2, 5, 6).Currently, two approaches are used for manufacture of high energy polyazides more suitable for practical use. In one of them, polyazides are synthesized on the base of polyatomic molecules with branched aromatic system, such as one in tetrazide 5. The latter, possessing rather high positive heat of formation, is less explosive than tri azide 2 (see Refs 3, 5). The second approach is based on the change in the aggregation state of high energy poly azides by introduction of aliphatic substituents to their aromatic rings. Liquid pentazide 6 (see Ref. 1) is an ex ample of such high energy and relatively safe azides.In the search for new high energy and relatively safe polyazides with low molecular weight and high melting point, we developed synthetic approaches, studied ther mal stability, and evaluated heats of formation and the sensitivity to mechanical impacts of tree novel nitrogen containing heterocyclic polyazides, viz., 2,6 diazido 3,5 dicyanopyridine, 2,4,6 triazido 3,5 dicyanopyridine, and 2,3,4,5 tetraazido 6 cyanopyridine. Some results of the present work were discussed in a preliminary report. 7 Results and DiscussionSynthesis of azides. Reactions of di and trichloropy ridines 7 and 8 with a fourfold molar excess of NaN 3 in aqueous acetone take 30 min at ~20 °C and result in for mation of diazide 9 and triazide 10 in 94% and 90% yields, respectively (Scheme 1). Reaction of tetrachloropyridine 11 with a sixfold molar excess of NaN 3 under the same conditions affords initially a complex mixture of mono (12), di (13) and triazides and only after 2 days it com pletes with formation of tetrazide 14 in 96% yield. The structure and the composition of novel azides is in com

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