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A Study on the Condensation of Nitramide (NH
2
 NO
2
) withFormaldehyde 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 uÈber die Kondensation von Nitramid (NH
2
NO
2
) mitFormaldehyd und Charakterisierung der entstehenden Produkte
Versuche zur Synthese von aliphatischen Polymethylennitroaminendurch die Reaktion zwischen NH
2
 NO
2
und Formaldehyd wurdenunternommen. Der Syntheseprozeû wurde ausgefuÈhrt in einem Zwei-komponentensystem Wasser 
a
Ethylacetat. Die LoÈslichkeit des erhal-tenen Produkts und seine Zersetzungsemp®ndlichkeit in verschiedenenLoÈsungsmitteln wurde untersucht. Die WaÈrmefestigkeit und dieTemperatur der Selbstzersetzung wurde bestimmt mittels DTA-TG.Trotz ihrer Eigenschaft als energetisches Material zeigt die Verbin-dung geringe Emp®ndlichkeit gegen machanische Ein¯uÈsse (Reibung).
EÂtude de la condensation du nitramide (NH
2
NO
2
) avec le form-aldeÂhyde et caracteÂrisation des produits formeÂs
On a entrepris des essais de syntheÁse de polymeÂthyleÁnenitroaminesaliphatiques par reÂaction entre NH
2
 NO
2
et du formaldeÂhyde. Le pro-cessus de syntheÁse s'est deÂrouleÂdans un systeÁme aÁdeux composantseau
a
ester aceÂtique. On a eÂtudieÂla solubiliteÂdu produit obtenu et sasensibiliteÂde deÂcomposition dans diffeÂrents solvants. La reÂsistance aÁlachaleur et la tempeÂrature de deÂcomposition spontaneÂe ont eÂteÂdeÂter-mineÂes par DTA-TG. MalgreÂses proprieÂteÂs de mateÂriau eÂnergeÂtique,le composeÂn'est que treÁs peu sensible aux in¯uences meÂcaniques(frottement).
Summary
Attempts have been made to synthesize aliphatic polymethylenenitroamines through reactions between NH
2
 NO
2
and CH
2
O. The process of synthesis has been achieved in a two-component system:water 
a
ethyl 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 self-decomposition have been determined through the DTA-TG method Despite being an energetic material, it shows little sensitiveness tomechanical stimuli (friction).
1. Introduction
The goal of this scienti®c work was to obtain aliphaticnitramines and study their characteristics:
NRCH
2
NRNO
2
NO
2
n
It is well known
(1)
, that such compounds are formed as by- products of RDX and HMX synthesis. Under such condi-tions, more aliphatic products are formed when there existsan 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 aliphaticnitramines will form. No attempts have been made with NH
2
 NO
2
due to the fact that it differs in its reactivityand other characteristics from organic amines. In Ref. 4 di-methylolnitraminewasobtained,throughareactionbetweennitrourethaneandformaldehyde,withtheassumptionthatthenitrourethane would hydrolyse and NH
2
 NO
2
would form:
OCOC
2
H
5
NHNO
2
hydrolysis
NH
2
NO
2
HCHO
O
2
NNCH
2
OHCH
2
OH
In an acid and dehydrating medium apart, from attachment,we can observe the condensation of primary nitramines withformaldehyde
(3)
:Inaccordancewiththismechanism,furtherpolycondensationof NH
2
 NO
2
into a product with a longer chain (polymethyl-enenitramine) seemed possible.In a water solution, NH
2
 NO
2
shows acid properties
(9)
. Itdecomposes 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 ioniccharacter with the participation of carbonium ion
CH
2
OHand 
À
 NHNO
2
. The methylolnitramine obtained during thisstep can further participate in the polycondensation process.With these assumptions in mind, the condensation processwas run under varied conditions and using different sub-strates with nitramino units.
2. Experimental Research
2.1 Polycondensation of CH 
2
O with NH 
2
 NO
2
The attempts of running polycondensation in a water solution, through mixing a water solution of nitramide withformaldehyde, did not give positive results. A stable productof condensation did not form.
#
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0721-3115/99/0612±0366 $17.50
X
50
a
0366 Propellants, Explosives, Pyrotechnics
24
, 366±370 (1999)
 
In further experiments formaldehyde (1.5g) in the form of a 36% water solution (formalin) and nitramide (3.4g) incrystalline form were used. The nitramide was solubilized inthe formalin solution and then the pH-value of the solutionwas lowered to approximately 1.6 through adding a KOHsolution, 30cm
3
of ethyl acetate were added to this solutionand mixed. After 120min, the product began to form on the phase boundary.The ®rst portion of the product (2.1g, with a breakdowntemperature of about 160
C) separated from the two-compo-nent solution after 24h. The second portion of the product(1.4g, with a breakdown temperature of approximately155
C) was obtained after the next 24h. The total yield of the product (assuming condensation to an aliphatic product)equals approximately 96% of the theoretical yield.
2.2 Synthesis of the Polycondensate Using Dinitrourea(DNU)
Keeping in mind the fact, that nitramide (NH
2
 NO
2
) formsduring the hydrolysis of dinitrourea (DNU)
(8)
, it was decided that this substance would be used in the synthesis of the polycondensate. DNU was obtained in accordance with Ref.8 from 30g of urea. After separating the post-reaction acids,DNU was added to 50cm
3
of the solution of formaldehydewithaconcentrationof19%.ThedissolutionoftheDNUwasconducted in such a way that the temperature of the solutiondidnotexceed30
C.ThepH-valueofthesolutionwasraised (pH
%
1.7) by dropping a KOH solution, and approximately120cm
3
ofethylacetatewereaddedwithstirring.Duringthis process partial separation of the precipitate of K 
2
SO
4
fromthe solution was observed. K 
2
SO
4
had formed from thesulphuric acid which remained in the crude sludge of DNU.After ®ltering off the K 
2
SO
4
, the solution was left to settlefor 48h. After this time, a deposit of the polycondensateseparated from the solution. The deposit was ®ltered off and it was thoroughly rinsed with water until the sulphate ions inthe ®ltrate were removed. 7g of the product were obtained withabreakdowntemperatureof158
C±162
C.Theyieldof the reaction is based on the following course of the process:
O
2
NNHCONHNO
2
+ H
2
O2NH
2
NO
2
+ CO
2
n
NH
2
NO
2
+
n
CH
2
OH(NNO
2
CH
2
)
n
OH
and equals approximately 50%.
2.3 Synthesis of the Polycondensate from Methylene Nitramine
1.46g of methylene dinitramine (obtained according toRef. 9) in 10cm
3
of water was mixed with 0.06g of formaldehyde (in the form of a 36% solution). 20cm
3
of ethyl acetate and ®ve drops of a 10% solution of KOH wereadded.Afterapproximately2htheproductstartedtoseparatefrom the solution. After 24h the product's yield based on analiphatic polymer equals approximately 90%. The break-down temperature of the product was approximately 158
C.
2.4 Identi®cation and Study of the Product of   Polycondensation
2.4.1 IdentificationAn initial study showed that all the products obtained through the three different methods possess similar charac-teristics. They do not easily dissolve in the main solvents.They partly (the lower homologues of the polymer) dissolvein acetone and acetonitrile. The products do not dissolve indiethyl ether, ethyl acetate and acetic acid. They decompose,especially when hot, in DMSO, formamide, a water solutionof KOH and even in hot water. The decomposition takes place gradually with the emission of gaseous products, untiltheentirepolymer hasdisappeared.Itwasfound(through thechromatographic method) that the main gaseous product was N
2
O.The elemental analysis of the product (for the ®rst method of synthesis):
C
À
16
X
45
7
H
À
3
X
36
7
N
À
36
X
04
7
If we assume a macromolecule of the polycondensateconsisting of 5 mers:
HOCH
2
NHNO
25
the theoretical values are:
C
À
15
X
46
7
H
À
3
X
09
7
N
À
36
X
08
7
2.4.2 Physical and Chemical Characteristics of the Polymer The thermal behaviour of the polymer was characterized  by DTA-TG analysis.The DTA and TG analysis showed a rapid decompositionofthepolymer,distinctiveforblastingmaterialsheatedtothe proper temperature of approximately 140
C (Fig. 1).The course of the TG shows a gradual mass decrement before the point of spontaneous decomposition, for the raw polymer starting from approximately 120
C. The polymer obtained in the second stage has a lower breakdown tem- perature (Fig. 2).The product's sensitivity to friction is smaller than that of HMX. As measured on the Peter's apparatus for HMX
À
3.92kg, for the product being studied 
À
6.32kg.The structure of the polymer HOCH
2
 ±[NNO
2
CH
2
]
n
 ±OH,according to data available in literature
(10)
, may decomposewith the release of formaldehyde and then N
2
O. Tests of theobtained product's behaviour in several environments wereconducted (Table1).The course of decomposition in time (the rate of emissionofgaseousproducts)canbethuscharacterizedas:veryfastinthe beginning and gradual decomposition towards the end.This can be explained by the lower stability of the low-molecule product being dissolved as opposed to that of a
Propellants, Explosives, Pyrotechnics
24
, 366±370 (1999) A Study on the Condensation of Nitramide with Formaldehyde 367
 
 polymer with larger macromolecules. The main gaseous product of decomposition is N
2
O (determined through thechromatographic method). The theoretical amount of gaseous products emitted, based on the earlier mentioned macromolecule (n
5), and emitted N
2
O equals approxi-mately 290cm
3
a
g (STP). The amount of gaseous productsemitted was different for decomposition in formamide and DMSO. The differences in the amounts of gaseous productsemitted may amongst others result from the difference insolubility of N
2
O (and perhaps CH
2
O) in various solvents.Hydroxymethylene nitramines should show better stabil-ity against acids than bases
(10,11)
, which has been con®rmed intheprocessofsynthesis,whereacidpropertiesofNH
2
 NO
2
,in the reaction in the phase boundary, did not prevent the
Figure 1.
DTA-TG curves of the polymer obtained in the ®rst stage (weight 17.48mg, heating rate 2
C
a
min).
Figure 2.
DTA-TG curves of the polymer obtained in the second stage (weight 48.6g, heating rate 2
C
a
min).
Table 1.
Results of the Measurement of the Product's Decomposition in Different EnvironmentsSolvent Temp.[
C]Time of full chemicaldecomposition[min]Polymer 
a
solvent[g
a
cm
3
]Amount of gaseous products(N
2
O)[g
a
cm
3
]Water 96 90 0.005 290 theoret.Formamide 21 137 0.037 246 exp.Dimethylsulfoxide 96 180 0.043 330 exp.
368 Z. Raszewski and M. Syczewski Propellants, Explosives, Pyrotechnics
24
, 366±370 (1999)
of 00

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