On the role of hydroxylamine in the amination reaction of Nitron-D with diethylenetriamine

Amination of Nitron-D with 7.754 molal aqueous solution of diethylenetriamine (DETA) was carried out in a reactor immersed in an oil bath with a temperature of 373 K at different synthesis times (0.25–6 hours) in the presence of hydroxylamine (HA) and in its absence (0.25–16 hours). The ion exchange capacities for amino and carboxyl groups were determined, and Fourier IR transmission spectra of the obtained samples were recorded. The dynamics of changes in the concentration of HA in the aminating solution (without nitron) and in the process of nitron amination over time were studied using liquid chromatography. It was found that the concentration of HA in the aminating solution (without nitron) rapidly decreases with time, decreasing to zero in 6 hours and in 2 hours, respectively, in the presence of nitron. A more rapid decrease in the concentration of HA in the solution in the presence of nitron is due to the transition of HA into the fiber volume with the formation of amidoxime fragments. The presence of amidoximes in the aminated fiber is confirmed by IR spectroscopy data for the absorption bands at 940 and 912 cm–1, related to the deformation vibration of NH2-groups bond and the stretching vibration of N–O, respectively.

1. Chemically active fibers for air and water purification FIBAN (in Russian). – URL: https://ifoch.by/research/fiban/ (date of access: 03 January 2025).

2. Gafurova D. A., Shakhidova D. N., Mukhamediyev M. G., Mukhamedov G. I. The mechanism of the catalytic effect of hydroxylamine on the reaction of polyacrylonitrile with nitrogen-containing bases. Zhurnal fizicheskoi khimii = Journal of Physical Chemistry, 2014, vol. 88, no. 11, pp. 1851–1854 (in Russian).

3. Nesterenok P. V., Kosandrovich E. G., Shachenkova L. N., Korshunova T. A. Catalytic method for synthesis of polyampholytes from (poly)acrylonitrile fiber. Vestsi Natsyyanal’nai akademii navuk Belarusi. Seryya khimichnykh navuk = Proceedings of the National Academy of Sciences of Belarus. Chemical series, 2014, no. 4, pp. 80–87 (in Russian).

4. Brikun I. K., Kozlovsky M. T., Nikitina L. V. Hydrazine and hydroxylamine and their application in analytical chemistry. Alma-Ata, 1967. 175 p. (in Russian).

5. Medyak G. V., Shunkevich A. A., Polikarpov A. P., Pansevich V. V., Akulich Z. I. Evaluation of factors affecting the sorption of sulfur dioxide by FIBAN fibrous anion exchangers. Vestsi Natsyyanal’nai akademii navuk Belarusi. Seryya khimichnykh navuk = Proceedings of the National Academy of Sciences of Belarus. Chemical Series, 2021, vol. 57, no. 1, pp. 101–108 (in Russian). https://doi.org/10.29235/1561-8331-2021-57-1-101-108

6. Gafurova D. A., Shahidova D. N. Physical and chemical features modification of “nitron” fiber by hydroxylamine. Vestnik Tverskogo gosudarstvennogo universiteta. Seriya: Khimiya = Bulletin of Tver State University. Series: Chemistry, 2016, no. 1, pp. 159–166 (in Russian).

7. Soldatov V., Pawlowski L., Shunkevich A, Wasag H. New materials and Technologies for Environmental Engineering. Part I. Syntheses and Structure of ion exchange fibers. Lublin, 2004. 127 p.

8. Kulinski D. A., Emets A. V., Kotetsky V. V., Wolf L. A. Modification of polyacrylonitrile and fibers based on it with hydroxylamine. Khimicheskie volokna = Chemical Fibers, 1976, no. 6, pp. 21–22 (in Russian).

9. Matusevich V. V., Polikarpov A. P., Grachek V. I., Lysenko G. N., Isakovich O. I., Medyak G. V., Shunkevich A. A., Akulich Z. I. Features of the new technology for producing fibrous anion exchange resin FIBAN AK-22 based on the use of hydroxylamine. Al’ternativnye istochniki syr’ya i topliva (AIST-2023): tezisy dokladov IX Mezhdunarodnoi nauchno-tekhnicheskoi konferentsii, 17–20 oktyabrya 2023 g., g. Minsk: v 2 ch [Alternative sources of raw materials and fuel (AIST-2023): abstracts of the reports IX International scientific and technical conference, Minsk, October 17–20, 2023: in 2 vol.]. Minsk, 2023, pp. 68–70 (in Russian).

10. Yavorsky I. A., Barinova A. P. IR spectroscopic study of thermal transformations of polyacrylonitrile in gaseous media. Khimicheskie volokna = Chemical Fibers, 1989, no. 2, pp. 21–25 (in Russian).

11. Bellamy L. J. The infra-red spectra of complex molecules. New York, 1975. 433 p. https://doi.org/10.1007/978-94-0116017-9

12. Reusch W. Infrared Spectroscopy. Virtual Textbook of Organic Chemistry. Michigan State University. Archived from the original on 21 June 2010. Retrieved 6 July 2009. Available at: https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/intro1.htm (Accessed 20 December 2024).

13. Nakanishi K. Infrared Spectra and STructure of Organic Molecules. Moscow, 1965. 216 p. (in Russian).

14. Yun Liu, Ruoven Yu., Uzen H. Reducing properties of amidooxime chelate non-spun fabric. Vysokomolekulyarnye soedineniya = High-molecular Compounds, 1993, vol. 35, no. 4, pp. 422–426 (in Russian).