The Chemistry of Powder and Explosives - Sciencemadness Dot Org

HEXAMETHYLENETRIPEROXIDEDIAMINE 451
Hexamethylenetriperoxidediamine (HMTD)
Hexamethylenetriperoxidediamine is the only organic peroxide
which has been considered seriously as an explosive. Its explosive
properties commend it, but it is too reactive chemically and too
unstable to be of practical use. It is most conveniently prepared
by treating hexamethylenetetramine with hydrogen peroxide in
the presence of citric acid which promotes the reaction by combining
with the ammonia which is liberated.
C6Hi2N4 + 3H2O2
CH2—0—0—CH2
> N—CH2—0—O—CH2—N + 2NH3
CHr-0—O—CH,
Hexamethylenetriperoxidediamine
Preparation of Hexamelftylenetriperexidediamine, Fourteen grams of
hexamethylenetetramine is dissolved in 45 grains of 30% hydrogen
peroxide solution which is stirred mechanically in a beaker standing in
a freezing mixture of cracked ice with water and a little salt. To the
solution 21 grams of powdered citric acid is added slowly in small
portions at a time while the stirring is continued and the temperature
of the mixture is kept at 0° or below. After all the citric acid has dissolved,
the mixture is stirred for 3 hours longer while its temperature
is kept at 0°. The cooling is then discontinued, the mixture is allowed
to stand for 2 hours at room temperature, and the white crystalline
product is filtered off, washed thoroughly with water, and rinsed with
alcohol in order that it may dry out more quickly at ordinary temperatures.
Hexamethylenetriperoxidcdiamine is almost insoluble in water
and in the common organic solvents at room temperature. It
detonates when struck a sharp blow, but, when ignited, burns
with a flash like nitrocellulose. Taylor and Rinkenbach fi3 found
its true density (20°/20°) to be 1.57, its apparent density after
being placed in a tube and tapped 0.66, and its density after
being compressed in a detonator capsule under a pressure of 2500
pounds per square inch only 0.91. They found that it required a
3-cm. drop of a 2-kilogram weight to make it explode, but that
fulminate required a drop of only 0.25 cm. In the sand test it
pulverized 2V& to 3 times as much sand as mercury fulminate,
and slightly more sand than lead azide. It is not dead-pressed
by a pressure of 11,000 pounds per square inch. It is considerably
113 Army Ordnance, 5, 463 (1924).