Synthesis of Aziridine Bonding Agent HX-752 and its Imide Derivatives

Document Type : Research Article


1 Department of Chemistry, Faculty of Basic Sciences, Imam Hossein University, Tehran, I.R. IRAN

2 University Complex of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, I.R. IRAN


One of the most important required additives in the production of composite solid propellants are bonding agents. These compounds are used in order to increase the adhesion between the polymer resin and the oxidizer and also to enhance the physical and mechanical properties and to improve the solids loading of propellants. In this research, in which the main goal was the synthesis of the bonding agent HX-752, the key intermediate, 2-methyl aziridine, was first synthesized from 1-amino-2-propanol with 51% yield by a new method.. The other intermediate, isophthalic chloride, was prepared from isophthalic acid using thionyl chloride as chlorinating agent. The desired product, 1,1'-isophthaloyl-bis(2-methylaziridine), HX-752, was finally synthesized by the reaction of isophthaloyl chloride with 2-methyl aziridine with 93% yield. In continuation of this work, MAPO (tris(2-metyl aziridine)phosphine oxide) was prepared from the reaction of 2-metylaziridine with phosphoryl chloride (POCl3) with 80% yield. Using piperidine and diethylamine, instead of 2-metylaziridine, the other fiveBonding agents similar to HX-752 and MAPO were also synthesized with appropriate yields. Characterization of the synthesized intermediates and products was performed by 1HNMR, 13CNMR, 31P-NMR spectroscopy and physical tests such as melting points for known compounds.


Main Subjects

[1] Chaturvedi S., Dave P. N., Solid Propellants: AP/HTPB Composite Propellants, Arab. J. Chem. 12 (8): 2061-2068 (2019).
[2] Hamilton R. S., Lund G. K., Hajik R. M., Solid Propellant Bonding Agents and Methods for Their Use, US Patent, 4,962,815, (2015).
[4] Hori K., Iwama A., Fukuda T., On the Adhesion between Hydroxy Terminated Polybutadiene Fuel-Binder and Ammonium Perchlorate. Performance of Bonding Agents, Propellants, Explos, Pyrotech, 10: 176-180 (1985).
[5] Hori K., Iwama A., Fukuda T., FTIR Spectroscopic Study on the Interaction Between Ammonium Perchlorate and Bonding Agents, Propellants, Propellants, Explos, Pyrotech, 15(3): 99-102 (1990).
[7] Deng J., Wang X., Li G., Luo Y., Effect of Bonding Agent on the Mechanical Properties of GAP High-Energy Propellant, Propellants Explos. Pyrotech, 42(4): 394–400 (2017).
[9] Shustov G.V., Krutius O.N., Voznesensky V.N., Chervin I.I., Eremeev A.V., Krostyanovsky R.G., Polyak F.D., Asymmetric Synthesis and Lactonization of 1-β-Hydroxyalkylaziridine-2-carboxylic Esters into 4-Oxa-1-azabicyclo[4.1.0]heptan-5-ones, Tetrahedron, 46: 6741-6752 (1990).
[10] Garner P., Dogan O., Pillai S., Auxiliary Mediated Synthesis of Aziridine-2-carboxylic Acid Derivatives, Tetrahedron Lett., 35: 1653-1656 (1994).
[11] Williams A.L., Johnston J.N., The Brønsted Acid-catalyzed Direct Aza-Darzens Synthesis of N-Alkyl cis-Aziridines, J. Am.Chem. Soc., 126: 1612-1613 (2004).
[15] Legters J., Thijs L., Zwanenburg B., A Convenient Synthesis of Optically Active 1H-Aziridine-2-carboxylic acids (Esters), Tetrahedron Lett., 30: 4881-4884 (1989).
[16] Serafin S. V., Zhang K., Aurelio L., Hughes A. B., Morton T. H., Decomposition of Protonated Threonine, Its Stereoisomers, and Its Homologues in the Gas Phase: Evidence for Internal Backside Displacement, Org. Lett., 6: 1561-1564 (2004).
[17] Campbell K.N., Mckenna J.F., The Action of Grignard Reagents on Oximes. I. the Action of Phenylmagnesium Bromide on Mixed Ketoximes, J. Org. Chem., 4: 198-205 (1939).
[18] Wenker H, The Preparation of Ethylene Imine from Monoethanolamine, J. Am. Chem. Soc., 57: 2328–2328 (1935).
[19] Roark D.N., Kusick B.C., Steuerle U., “Ullmann’s Encyclopedia of Industrial Chemistry”, Wiley-VCH Verlag GmbH & Co., Weinheim, (2005).
[20] Ueshima M., Shimasaki Y., Ariyoshi K., Yano H., Tsuneki H., New Vapor Phase Process for Synthesis of Ethylenimine by Catalytic Intramolecular Dehydration of Monoethanolamine, In Proc. of the 10th International Congress on Catalysis, 32: 2447-2450 (1992).
[21] Stogryn E.L., Brois S.J., A Related Reaction [2-(Aziridin- 1-yl)alkenyl]triphenylphosphonium Bromides Was Reperted, J. Am. Chem. Soc., 89(3): 605-609 (1967).
[22] Hoch J., Aziridine Synthesis, Compt. Rend. Acad. Sci., 31: 198, 1865 (1934).
[23] ابریشمی، فاطمه؛ سنتز 2-متیل آزیریدین با استفاده از نانوکاتالیزگرهای بر پایه SiO2 از طریق فرآیند آب زدایی درون مولکولی در فاز گازی، نشریهعلمی ـ پژوهشی مواد پرانرژی، (1) 9: صفحه 15 تا 25 (1393).
[26] Morimitso K. C., Composition And Method of Jeting , US Patent, 2014/0285594 (2014).