Aldehyde Nitramide

366

Propellants, Explosives, Pyrotechnics 24, 366±370 (1999)

A Study on the Condensation of Nitramide (NH2NO2) with Formaldehyde and the Characteristics of the Products Formed
Z. Raszewski and M. Syczewski Division of High Energetic Materials, Department of Chemistry, Warsaw University of Technology (Politechnika) ul. Noakowskiego 3, 00-664 Warszawa (Poland)

Eine Studie uber dieKondensation von Nitramid (NH2NO2) mit È Formaldehyd und Charakterisierung der entstehenden Produkte Versuche zur Synthese von aliphatischen Polymethylennitroaminen durch die Reaktion zwischen NH2NO2 und Formaldehyd wurden unternommen. Der Syntheseprozeû wurde ausgefuhrt in einem ZweiÈ È komponentensystem WasseraEthylacetat. Die Loslichkeit des erhaltenen Produkts und seine Zersetzungsemp®ndlichkeit inverschiedenen È È Losungsmitteln wurde untersucht. Die Warmefestigkeit und die Temperatur der Selbstzersetzung wurde bestimmt mittels DTA-TG. Trotz ihrer Eigenschaft als energetisches Material zeigt die Verbindung geringe Emp®ndlichkeit gegen machanische Ein¯usse (Reibung). È

 Etude de la condensation du nitramide (NH2NO2) avec le form   aldehyde et caracterisation des produits formes Á ÂÁ On a entrepris des essais de synthese de polymethylenenitroamines   aliphatiques par reaction entre NH2NO2 et du formaldehyde. Le proÁ   Á Á cessus de synthese s'est deroule dans un systeme a deux composants     eauaester acetique. On a etudie la solubilite du produit obtenu et sa     Á sensibilite de decomposition dans differents solvants. La resistance a la    Â  chaleur etla temperature de decomposition spontanee ont ete deter  Â    minees par DTA-TG. Malgre ses proprietes de materiau energetique,  Á  le compose n'est que tres peu sensible aux in¯uences mecaniques (frottement).

Summary
O C
Attempts have been made to synthesize aliphatic polymethylene nitroamines through reactions between NH2NO2 and CH2O. The process of synthesis has been achieved in atwo-component system: wateraethyl acetate. The solubility of the obtained product, as well as, its susceptibility to chemical decomposition in different solvents have been studied The product's heat resistance and its temperature of selfdecomposition have been determined through the DTA-TG method Despite being an energetic material, it shows little sensitiveness to mechanical stimuli (friction).NHNO2 OC2H5

hydrolysis

NH2NO2

HCHO

CH2OH O2N N CH2OH

In an acid and dehydrating medium apart, from attachment, we can observe the condensation of primary nitramines with formaldehyde(3):

1. Introduction The goal of this scienti®c work was to obtain aliphatic nitramines and study their characteristics:
R N CH2 NO2 N nR NO2

It is well known(1), that such compounds areformed as byproducts of RDX and HMX synthesis. Under such conditions, more aliphatic products are formed when there exists an excess of amine groups in the system. Chapman and his co-authors(2), by conducting a series of reactions between organic nitramines and formaldehyde, have ascertained that under certain conditions aliphatic nitramines will form. No attempts have been made with NH2NO2 due tothe fact that it differs in its reactivity and other characteristics from organic amines. In Ref. 4 dimethylol nitramine was obtained, through a reaction between nitrourethane and formaldehyde, with the assumption that the nitrourethane would hydrolyse and NH2NO2 would form:
# WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

In accordance with this mechanism, further polycondensation of NH2NO2into a product with a longer chain (polymethylenenitramine) seemed possible. In a water solution, NH2NO2 shows acid properties(9). It decomposes in reactions with bases(9). Due to this fact the process could only be run under a speci®c low pH-value (maximum value 1.6). In the ®rst stage, the process may have a typically ionic character with the participation of carbonium ion ‡CH2OH and ÀNHNO2. The...