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Патент USA US2406572

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Patented Aua. 27, 1946
2,406,572
UNITED STATES PATENT OFFICE
2,406,572
EXPLOSIVE PERCHLORATES OF ALIPHATIC
NITROGENOUS CODIPOUNDS
Walter ‘W. Vogl, Omaha, Nelm, assignor to Ralph
E. Svoboda
No Drawing. Application June 13, 1941,
Serial No. 397,968
10 Claims.
1
(Cl. 52-1)
2
chlorides containing the perchlorates of the
metals may be used in the condition in which
they are produced in electrolysis, or after suit
chlorates with oxidizable materials, have been
proposed. Also perchlorates of aromatic amines,
able alteration in their concentration. If for
have been proposed for use in explosives, but 5 this process the dihydrochlorides or polyhydro
have not proven wholly satisfactory. The per
chlorides (as they are produced by ammonolysis
chloric acid esters of glycol and of lower alcohols
of alkylene-chlorides) are used as salts of the
were investigated as explosives, but were too
nitrogenous bases, and these salts are reacted
sensitive and were found to be too dangerous.
with the solution of sodium perchlorate, the
As the result of my researches, I propose the 10 resulting sodium chloride may be redissolved and
Perchlorates have heretofore been used in
explosives, e. g., mixtures of inorganic per
use, as explosive (alone'or with oxidizable sub
reused for electrolysis. The use of the per
chlorates covered by this invention as explosives,
nitrogenous compounds having two or more basic
is not limited to compounds which contain be
nitrogenous group and more than two carbon
sides the nitrogenous groups, only carbon and
atoms, or perchlorates of derivatives of such 15 hydrogen (like the alkylene-diamines, the di
compounds. Further my inventions cover proc
and poly-alkylene-polyamines), but includes
esses for the manufacture and the puri?cation
also substances containing other elements or
of such explosives. No explosive of this kind
groups like the alkyl-oxides or sul?des with basic
has been described or used in practice until now.
nitrogenous groups like diamino-diethyl-ether,
Many substances covered by this invention are 20 diamino-diethyl-sul?de. furthermore hydroxy
stances), of perchlorates of certain aliphatic
outstanding explosives of highest potency which
alkyl-alkylamines (with more than one amino
is in the order of magnitude of the energy of
group) amides of organic acids, carbamid and its
glycerine trinitrate. The other properties are
derivatives, etc. Another advantage of most of
much more favorable than those of the other
the explosives covered by this invention is the
explosives of highest energy and the velocity of 25 fact that they are very easy to purify even to
detonation is very great. They are not objec
the highest degree of purity. The raw materials
tionally sensitive to heat, mechanical impact,
for the explosives covered by this invention are
atmospheric conditions or electrical discharges.
available in the United States of America in
The lead-block test (modi?ed Trauzl-test)
practically unlimited quantities.
showed that the blasting of explosives covered by
The f_ollowing examples are given as illustra
this invention produces an enlargement of the
tion, without limiting the invention thereto:
borehole more than twice as large as that pro
Example 1.-To 200 kg. perchloric acid of
duced by the same amount of picric acid, am~
about 50% strength (sp. gr. 1.402), 46 kg. of
monium picrate and trinitrotoluene. Some of
commercial ethylene-diamine are added with in
the explosives covered by this invention have 35 tensive stirring; the temperature of the reaction
an excess of oxygen so that it is possible to in
should be kept below 60° C. The resulting solu
crease the heat developed by the explosion by
tion of ethylene-diamine-diperchlorate is then
addition of oxidizable substances like carbon,
concentrated (in vacuo or under atmospheric
metals, etc. Sometimes it is also possible to
pressure) until the formation of crystals starts,
increase the velocity of detonation by addition
i. e. until 90 kg. of water are evaporated. There
of another explosive with a de?ciency of oxygen,
after the concentrated solution is cooled with or
e. g. TNT. It is furthermore possible to manu
without stirring (depending on the size of
facture some of the explosives covered by this
crystals desired). The crystals are separated
invention in such a way that not all of the basic
from the mother liquor and if desired. rinsed
nitrogenous groups are linked to perchloric acid 45 with a saturated solution of pure ethylene-di
so that some of the basic groups are available
amine-diperchlorate in water or alcohol, and
for condensation or polymerization. Another
dried in vacuo. If an alcoholic solution is used
important advantage of this invention is that
for the rinsing, a rinsing with ethyl other may be
the processes for the manufacture of these ex
applied thereafter and the crystals dried in a
plosives are much easier and less dangerous than 50 current of air at 30° C. The ether may be re
the processes of making the explosives now in
covered by absorption. The above mentioned
use. Especially the process by double exchange
mother liquor is taken up in strong ethyl- or
reaction is very advantageous and economical
methyl-alcohol, either in its original concen
because the use of free perchloric acid is avoided.
tration or after concentrating it by evaporation
The liquors produced by the electrolysis of metal 55 or by increasing its concentration by the addi
2,406,572
4
tion of solid ethylene-diamine-perchlorate to be
puri?ed. The quantity of alcohol to be added to
the mother liquor has to be such that the re
sulting alcoholic solution of ethylene-diamine
diperchlorate contains at least 80 parts of alco
hol for 20v parts of water in the solution. To this
solution, ethyl-ether or benzene is added, to pre
cipitate the major part of the ethylene-diamine
diperchlorate, which is then separated from the
but the third basic nitrogenous group remains
free. The diethylene-triamine-diperch1orate is
then precipitated by adding to the actual solu
tion ten times its volume of a mixture of acetone
and ethyl ether 1:1. The precipitate is removed
and dried. To each 100 kg. of the dried diethyl
ene-triamine-diperchlorate 25 litres of 40%
formaldehyde solution are added and the mix
ture kept at 160° C. under re?ux for 40 hours.
Formaldehyde is given as an example of an al
liquid, rinsed with ether or benzene and dried.
A third fraction of ethylene-diamine~diperch1o
rate may be obtained from the residue of the
recovery of the organic solvents used in the
process.
dehyde. The water and the surplus of aldehyde
are thereafter removed by distillation in vacuo so
that the product of condensation and/or poly
merization remains as a mass which is plastic at
~
Example 2.—To 300 kg. of a watery solution, 15 ‘higher temperature. With this plastic mass,
20% of diethylene-triamine-triperchlorate may
having a temperature of about 90° 0., containing
100 kg.
bewell incorporated in order to increase the ve
of *7 propyleneidiamine-dihydrochloride, 7'
locity of detonation of the material. It will be
2&0 kg. of a I70% aqueous solution of sodium ‘per
observed that the triperchlorate has a higher ra
chlorate is added and thoroughly stirred. Then
ethylaleohol is added in small portions until the 20 tio of oxygen to carbon and hydrogen than does
the diperchlorate. If the mass has not the de
solution contains at least eight parts of Cz'HsO-H
gree of plasticity required, some water-soluble
foreach part of water in the solution, in order to
plasticizer (e. g. 9.5% glycerol) may be added
precipitate the NaCl as crystals. After removing
after 80% of the water has been removed by dis
the. crystals of'NaCl the solution is evaporated to
dryness. Any system of evaporation which is as tillation, and then the evaporation completed.
Example 6.——100 kg. of ferric perchlorate
suitable for salt solution and in which the tem
(FelClOQs) are dissolved in so litres of Water
perature of the parts in contact with the salt
and to this solution 38 kg. of commercial ethyl
does not exced 120° C. may be used. The vsolid
ene-diamine are added slowly with stirring.
residue is extracted with petroleum ether (or an
other solvent in which ‘the propylene-diamine
Then the mir'lture'is boiled and then ?ltered hot.
The iron hydroxide cake is rinsed ‘either with hot
diperclilorate is soluble but which does not dis
water or alcohol and the rinsingliquid added'to
solve the NaCl or "the NaClOt). After complete
the ?ltrate from which the ethylene-diamine-di
extraction, ‘the remaining petroleum ether solu
tion is ‘separated from any propylene-diamine
perchlorate is obtained ‘by one of the above proc
diperchlorate which may have crystallized, and "
water.
The propylene~diamine~diperchlorate is
and poly-ethylene~polyamine (a mixture which
results in the ammcnolysis of ethylene chloride)
thus transferred into a Watery solution from
which it is obtained in a manner similar to Ex
ample '1.
‘Example 3.--'To 100 ‘pounds of ‘a "70% solution
esses.
Example 7.—To a mixture of ethylene-diamine
the solution in petroleum ether is extracted with
so'much diluted perchloric acid is added that a
40
oi‘ barium perchlorate in 'water ‘are added '25
pounds of ethylene-diamine in 50% water solu
tion. After mixing, about 50 pounds of diluted
sulphuric acid (35 degrees‘Béx) are slowly ‘added
until no vmore precipitate is formed. The ‘precip
proportion of all the basic nitrogenous groups
present, equal to all the 4N3; groups can com
bine with perchloric acid and a further propor
tion of all the basic nitrogenous groups equal
to one-third of all the =NH groups can also com
blue with perchlo-ric acid. Then the solution is
kept at 100° C. under reflux and, with air bub
itatedrbar'iurn sulphate is separated and rinsed
bling through the liquid for’, 48 hours. ‘During
with water or dilutedalcohol. The rinsing water
or alcohol and the liquid containing the ethyl
ene~diamine-diperchlorate are concentrated.
this treatment, the air may cause oxidation of
some. of the bodies present, to aldehydes and/or
Example 4.-—'Ethylene-diam'ine carbonate ‘in
aldehyde given above. Then the water is evap
orated in vacuo. Should the resulting mass not
have the desired plasticity some of the plastic
explosive as described in Example 5, may be
aqueous solution is treated with a 50% solution
of perchloric acid, added in small portions until
allcarbonic acid is replaced by vperchloric acid.
ketones, which may react similarly to the form.
,
At ‘the end of the reaction it is advisable ‘to raise 55 added.
the temperature of the solution almost to the
These explosives are primarily intended for
boiling point. The end-point of the’ reaction is
the ?lling of bursting missiles, like bombs, shells
and torpedoes, but the easy regulation and the
determined by methyl orange as indicator; any
wide range of the velocity of detonation which is
excess of acid has to be thoroughly neutralized
either with ethy'lene-diamine base or with ethyl
possible with these explosives makes them also
very suitable for industrial blasting purposes
ene-diamine carbonate. To the neutral solution,
for each 100 kg. of ethylene-diamine carbonate
and the slowest burnincr product may be used .for
?re Works (signals, flares, etc.).
used, 10 kg. of strontium nitrate are added and
after this dissolves the whole batch is evaporat
I claim:
ed in “vacuo.
The remaining solids are powdered 65
and mixed with metallic magnesium in ?nest
powder inthe proportion of 30 parts of Mg for
I00 parts of the said solids.
Example 5.;To diethylene-triamine in satu
rated solution at 20° C. in ethyl alcohol (50 vol. 70
%), perchloric acid solution (e. g. @ 40%
1. .An explosive containing as its essential con
stituent a perchlorate of a basic nitrogenous
compound of an ethylenic hydrocarbon, said
compound‘ having more than two. basic nitrogea
nous groups and of which apart only of the basic
nitrogenous groups are combined with perchloric
acid.
7
.
2. An explosive containing as its essential con
strength, SD. 51‘. 1.293) is added until the pink
stituent a perchlorate of a propylene amine con
color of phenophthalein which was added as in
taining a plurality of basic nitrogen-hydrogen
dicator just disappears, i. e. until two of the basic
nitrogenous groups are neutralized by the acid 75 groups.
2,406,572
5
centage of perchloric acid radical than does said
3. An explosive containing as its essential con
stituent a perchlorate of a‘ polyalkylene poly
amine which contains, per molecule, at least
polyamine compound.
7. An explosive containing as its essential con
stituent, a dialkylene triamine perchlorate in
which only two of the basic nitrogenous groups
three basic nitrogenous groups, of which all but
one are linked to perchloric acid.
4. A novel explosive, containing as its essen
tial constituent a perchlorate of an alkylene
are united to perchloric acid and in which one
basic nitrogenous group is not united to per
chloric acid.
polyamine, such alkylene compound containing
8. A polyalkylene polyamine perchlorate, in
at least two carbon atoms in a straight chain,
and said amine containing -NH2 groups and a 10 which at least about two-thirds of the nitroge
nous groups contained therein are linked to per
=NH group, all but one of said nitrogenous
chloric acid and which compound also contains
groups, per molecule, being combined with per
a basic nitrogenous group which is not linked to
chloric acid and one of the said nitrogenous
perchloric acid.
groups being combined. with an aldehyde, such
product being a plastic.
15
9. An explosive containing diethylene tria
amine diperchlorate plasticized by condensation
5. An explosive containing as its essential com
with an aldehyde, and diethylene triamine tri
ponent a perchlorate of an aliphatic polyethyl
perchlorate.
ene polyarnine in which at least one but not over
10. An explosive containing as its essential
one-third of the total number of basic nitrogenous
groups contained therein remains free and all 20 constituent, a perchlorate of an alkylene amine,
which compound has at least three basic nitrog
other basic nitrogenous groups are linked to per
enous groups and the alkylene groups of which
chloric acid.
contain at least two carbon atoms, and in which
6. An explosive containing as its essential com
perchlorate at least two-thirds of the basic ni
ponent, a perchlorate of a polyalkylene poly
amine, in which all but one of the basic nitroge 25 trc-genous groups are combined with perchloric
acid, such compound also containing a basic ni
nous groups are linked to perchloric acid, and in
trogenous group which is not combined with per
which one of the basic nitrogenous groups is re
chloric acid.
acted with an aldehyde to form a resin, and
WALTER W. VOGL.
which explosive also contains an alkylene dia
mine perchlorate which contains a larger per 30
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