United States Patent 1 O

,.

IC

1
.

3,311,513

Patented Mar. 28, 1967

2
-

NITRAMINE, NITROCELLULOSE EXPLOSIVE -'

WITH ESTER PLASTICIZER

. .

Charles Donald Forrest, Westville, N.J., assignorto? E.- I.

du Pont de Nemours and Company, Wilmington, Del.,
. a corporation of Delaware

No Drawing. Filed Mar. 5, 1965, Ser. No. 437,555

8 Claims.

3,311,513

(6]. 1492)

Lions containing these high loadings of PJETN show in

creasing brittleness with increasing PETN content, even
at ambient temperatures, but particuiarly when exposed
to subzero temperatures. Hence today tend to crack,
craze and split when subjected to ?exural stresses at low

temperatures. Additionally, when the known PETN-con

taining compositions are formulated so that they do
possess optimum physical characteristics, including ?exi
bility, the detonation velocity of such compositions gen

This invention is concerned with improved detcnating 10 erally does not exceed about 7000 meters per second,
explosive compositions that combine desirable. explosive
which is lower than desired for some applications of this
properties with such physical-mechanical characteristics
type of charge. In some instances, the requirement that
as ?exibility, high resistance'to compressive and tensile
ultra?ne crystals of PETN be used in the compositions
forces and good lowlten'iperature properties, and with
of US. Patent 2,992,087 in order to achieve propagation
improved shaped explosive articles obtainable therefrom. 15 reliability and uniformity of explosiveproperties can be
It has long been a goal in the art of explosives to pro
a disadvantage. A further limitation is imposed by the
vide detonating explosive compositions that not only
need to use one speci?c class of plasticizer esters, if
possess-high sensitivity to detonation by standard ex
the explosive compositions are to perform reliably, par
plosive initiators, coupled with low sensitivity to initiation
ticularly after exposure to elevated temperatures.
by impact, but also meet the requirements of a high 20
This invention provides improvments in detonating ex
degree of dimensional stability under stress, coupled
plosive compositions comprising crystalline organic high
with good ?exibility. However, only in recent years has
explosives in a binder composition ofnitrocellulose and
any real success been achieved in this ?eld, particularly
selected plasticizers. More particularly, the invention
in terms of ability to maintain these desired explosive
provides improvements in the subject type of explosive
and physical characteristics over a wide range ofen 25 compositions whereby highly desirable physical and ex
vironmental conditions.
plosive properties, including properties not achievable
One recently developed type of ?exible, yet dimen
heretofore, are obtained, The invention additionally
sionally stable, detonating explosive composition is de
provides new and improved methods for preparing said
scribed in U.S. Patent 2,992,087. Compositions de
explosive compositions.
,
scribed therein include at least about 44% by weight of 30
The improved de'tonating explosive compositions of
the crystalline explosive, pentaerythritol tetranitrate
this invention, which are readily worked into self~sup
(PETN), of speci?ed very ?ne particle size, in admixture
porting and dimensionally stable, yet ?exible articles, e.g.,
with a binder composition of about 6.5 to 14% by weight
sheets, cords, tapes and the like, comprise uniform blends
of soluble nitrocellulose of average degree of polymeriza
of:
'
tion about 2000 to 3000 and about 15 to 35% of selected

(1) about from 65 to 85%, preferably about from 68

trialkyl esters of Z-acetoxy-1,2,3-propanetricarboxylic

to 80% by Weight of crystalline explosive nitramine hav

acid.
As is demonstrated in US. Patent 2,992,087, the

ing an average particle size below about 200 microns,

andv preferably below about 100 microns and selected
PETN-containing compositions described therein have
from the group consisting of -cyclotrimethylenetrinitra
many advantages from the point of View of physical 40 mine and cyclotetramethylenetetranitramine;
characteristics. They are readily formulated, and the
(2) about from 0.5 to 15%, and preferably about
rheological properties of the ?nished compositions are
from 2 to 8% by weight of soluble nitrocellulose hav
such as to permit easy forming, e.g., by rolling or ex
ing an average degree of polymerization of about from

trusion, into shaped articles'of various con?gurations.

2000 to 3000; and

The shaped products themselves are characteristic bv

a high degree of ?exibility and good dimensional stability

(3) about from 10 to 34.5%, and preferably abou

from 12 to 30% by weight of ester selected from phos
phateand carboxylate esters having the formulas:

understress, even after subjection to serve environmental

conditions such as prolonged exposure to high tem

peratures and to Water, including exposure at high hy

drostatic pressures. The compositions of US. Patent
2,992,087 also have, and maintain, a desirable combina

tion of explosive properties.

Even though these compositions will prop-agate a
detonation reliably, even in sheets as thin as 1/16 inch

and thinner and are very insensitive to initiation by im

pact, the PETN-co-ntainin-g compositions of US. Patent

2,992,087 have been found to have several disadvantages.
High loadings or concentrations of crystalline high ex
plosive are desirable for certain applications of this type
of charge.

However, when an attempt is made to em

ploy PETN loadings above about 65% by Weight of the

total composition, blending of the charge components
and shaping or forming of the ?nished products both
become increasingly difficult operations. Also, when
fabricated, for example, into cords or sheets, the composi

in which each R (i.e., each R can be the same or different

60 from the other Rs) represents an aliphatically satu

rated organic radical of about 1 to 8 carbon atoms

free of functional substituents, i.e., inert in the system;

][ is a hydrocarbon nucleus of about 1 to 8 carbon
atoms; and each of m, n, p, and q is a cardinal number of .

0 to l, the sum of n, p, and q being 2 to 3.

3,311,513

and from microscopic measurement values for particles

generally smaller than the standard 325-mesh sieve aper
tures of 43-44 microns.) In general, however, superior

The crystalline high explosive component of the

compositions of this invention is chosen from the organic

explosive nitramines, cyclotrimethylenetrinitramine and

plosive products prepared therefrom. The subject nitra

initiation sensitiveness is achieved when the average par

ticle size is below about 100 microns, and preferably
about from 1 to 75 microns. Thus, nitramine crystals of
these relatively smaller particle sizes are generally pre
ferred in the instant compositions.

mines, which are known by several alternative designa

tions. have the structural formulas:

10 the instant invention will be one of high-viscosity, soluble

cyclotetramethylenetetranitramine.

As is shown more

fully hereinafter, these crystalline explosive nitramines

have been found to be unique in their ability to impart
certain highly desirable characteristics to shaped ex

The nitrocellulose used in the explosive compositions of

types. To meet the requirement of high viscosity, the
average degree of polymerization, or average number

N07

of anhydroglucose units in the nitrocellulose molecules,

will be in the range of about from 2000 to 3000.

To

provide the necessary solubility, by which in the nitro

sellulose art is meant solubility in a mixture of ethyl
ether and ethyl alcohol, the nitrocellulose also will have
a nitrogen content generally above 7% and usually above

Cyclotrimethylenetrinitramlne
Alternative common names: RDX, hexagen, cyclonite
Chemical name: Hexahydro-l,3,5-trinitro-s-triazene '

30

about 9%, but below 13%. Provided that these two re

quirements are met, any of the industrial grades of nitro
cellulose, which ordinarily have a nitrogen content in
the range of about 10 to 12.3%, as well as the pyro
cottons, which generally have a nitrogen content of
12% or higher, can be used. High-viscosity, soluble
grades of nitrocellulose having a nitrogen content of
about 12.2 to 12.6%, such as are ordinarily used in the
formulation of dynamites, constitute a readily available
and especially suitable form of the nitrocellulose in the

instant compositions.
Shaped explosive products having desired physical and
explosive characteristics are obtained when the concen
tration of nitrocellulose is at least about 0.5% of the

Cycl0tetramethylenetetrauitramine
Alternative common names: HMX, octogen, homocyclo
nite
Chemical name: Octobydro-1,3,5,7 - tetranitro - l,3,5,7

tetrazocine
These nitrarnines can be used individually in the explo
sive compositions of this invention, but they also are

suitably employed in combination. For example, the

mixed nitramine products that are obtainable by subject
ing hexamethylenetetrarnine, or the precursors, formalde
hyde and ammonium nitrate, to nitrolysis processes can

total charge weight. On the other hand, nitrocellulose

concentrations above about 15% of the total composition
make increasingly dif?cult the incorporation of this com
ponent into the compositions, and do not materially im
prove either the explosive or the physical character
istics of the products over those achieved at lower con

centration levels. A particularly preferred range of con

40 centration for the nitrocellulose, especially when the ex

plosive nitramine loading is in range of about 68 to 80%,

is about from 2 to 8% of the total composition.
The nitrocellulose plasticizer chosen for the composi
tions of this invention is of primary importance, in that
such plasticizer not only affects the physical and explo
sive characteristics of the product in the as-made state
but also, and more signi?cantly, in?uences the retention

of these properties over a wide range of environmental

be used in lieu of the substantially pure individual
conditions. Numerous plasticizers for nitrocellulose are
nitramines.
As indicated hereinbefore, the concentration or load 50 known. However, for satisfactory performance of the
instant explosive compositions over a temperature range
ing of explosive nitramine will generally be about from
of 40 to +1600 F., it has been found that plasticizers
65 to 85% of the total weight of the explosive composi
of both the phosphate ester and carboxylate ester types
tion. Concentrations of explosive nitramine appreciably
are uniquely suitable. These plasticizers can be described
below this range, in addition to imparting lower densities
and lower explosive strengths per unit weight of charge, 55 by the general formulas:
make the charges increasingly insensitive to initiation.
Also, even when suitably initiated, such low-concentra

tion charges often fail to propagate a detonation, or the

detonation may proceed at low velocity.

On the other hand, explosive nitramine loadings above 60
about 85% make the compositions increasingly difficult
to mix and shape and, at thesame time, tend to impart
less than optimum physcial characteristics to the ?nished
products. An optimum balance of explosive character
istics and physical properties has been found to be present
in which each R represents an aliphatically saturated or
in shaped explosive products when the explosive nit-ramine
ganic radical of about 1 to 8 carbon atoms free of func
concentration is about from 68 to 80% of the charge
tional substituents, preferably, a saturated hydrocarbon
weight. Accordingly, this latter concentration range is
radical; ]~[ is a hydrocarbon nucleus of about 1 to 8

especially preferred in the instant explosive compositions.

carbon atoms; and each of m, n, p and q is a cardinal

Shaped explosive products of satisfactory sensitivity 70 number of 0 to 1, inclusive, the sum of n, p and q being
to initiation are obtained when the explosive nitramine
component is in the form of crystals having an average

particle size below about 200 microns. (Average par

ticle size, as used herein, means weight average particle
size, as calculated from standard sieve analysis values

2 to 3. (By free of functional substituents, it is meant

that the molecules of the organic monohydroxy com
pound or compounds from which the phosphate and car
=boxylate esters are derived shall be free of reactive groups
other than the OH function.)

'

3,311,513

Within the ester groups represented by the foregoing

formulas, optimum properties are generally achieved in
the ?nished explosive products when R is a saturated ali
phatic acyclic or cyclic radical containing about from

ever, it has been found that the ?nished explosive products

have improved uniformity and, more particularly, are

consistently obtained free of voids, air bubbles, and similar
inhomogeneities, when a uniform blend of a portion of

4 to 8 carbon atoms. As previously indicated, the in

dividual Rs can be like or different. Likewise, it is

the crystalline explosive nitramine and the plasticizer ester

is ?rst formed; this is blended with the nitrocellulose until
substantially no lumps or inhomogeneities (uncolloided
nitrocellulose) are present therein; and ?nally the remain
ing part of the crystalline explosive nitramine is incorpo

preferred that the hydrocarbon nucleus, ]--[, repre

sent either a saturated hydrocarbon nucleus, particular

ly an acyclic saturated hydrocarbon nucleus, or a ben

zenoid nucleus containing up to about 8 carbon atoms. 10 rated, in one or more portions, and blending is continued
Compatability with nitrocellulose tends to decrease when
until the mass is uniformly mixed and preferably is in
such organic nuclei, and/or the organic portions of the
the form of small unconsolidated granules.

hydroxy compounds from which the ester plasticizers are

In following the said improved method of preparing the

prepared, contain more than about 8 carbon atoms.

A representative but not exhaustive group of speci?c ,
ester plasticizers that can be used effectively, either alone

or in combination, in thepresent explosive compositions

explosive compositions, the quantity of crystalline explo

sive nitramine incorporated in the first blending operation
will generally be about from 50 to 90% by weight of the
total nitramine to be used in the formula, and preferably

includes:

about from 65 to 85% of the total nitramine.

triethyl phosphate
tributyl phosphate
tris(2-ethylhexyl) phosphate
tris(tetrahydrofurfuryl) phosphate
bis(Z-ethylhexyl) adipate
diisoctyl adipate

maining 10 to 50% of explosive nitramine subsequently

20 added to the mass free of uncolloided nitrocellulose is
incorporated in one or more portions, and mixing is con

tinued until a granular but non-consolidated product is

obtained. To facilitate blending, the mixing operations

ordinarily are carried out at elevated temperatures, gen

bis(Z-ethylbutyl) azelate
bis(Z-ethylhexyl) sebacate

di-n-butyl phthalate
diisobutyl phthalate
bis(Z-ethylhexyl) phthalate
vtriethyl 2-acetoxy-1,2,3~propanetricarboxylate
tri-n-butyl 2-acetoxy-l,2,3-propanetricarboxylate
tris(2-ethy1hexyl) Z-acetoxy-l,2,3-propanetricarboxylate
Among these esters, tributyl phosphate, dibutyl pht-halate,
bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) sebacate, and

especially, tributyl Z-acetoxy-1,2,3-propanetricarboxylate,

are particularly effective and are preferred.

The re

>

In selecting any particular plasticizer from the above

group for any particular composition of this invention, or
a plasticizer mixture therefor, several criteria should be
observed. The plasticizer should both have a negligible,

i.e., a low, rate of evaporation in the composition, and be

liquid over the temperature range of use, e.g., 40 to

+16O F. The plasticizer in addition to having a low

solubility in and solvent power for water, should be sub
stantially a non-solvent for the particular nitramine se
lected. Conversely, the plasticizer should be at least par

erally in the range of about from 100 to 150 F., and pref
erably about from 120 to 140 F.
The explosive nitramine can be incorporated into the
compositions in a substantially dry state. However, to
minimize dusting of the crystalline explosive and also to
30 reduce its impact sensitivity and associated hazards dur

ing the manufacturing operation, it is advantageous to

have the nitramine in a wetted state during its incorpora
tion. The wetting agent can be a liquid which has sub
stantially no solvent power either for the explosive nitra

mine or for the remaining composition components.

Water is particularly suitable in this capacity, not only be

cause it meets the nonsolvent criterion, but also because

it is relatively easily removed following incorporation of

the nitramine.
A modi?cation of the foregoing wetting method for

minimizing dusting and impact sensitiveness in the explo

sive nitramine also has been found to be effective, particu
larly in cases where the crystalline nitramine consists of

moderately ?ne to very ?ne particles, i.e., is below about

100 microns in average particle size. This modi?cation,
which also avoids any need for introduction and subse

quent removal of a foreign liquid wetting agent during

processing, involves the use of the explosive nitramine in
tially miscible with the grade of nitrocellulose employed,
the form of crystals having a preformed coating of one of
and preferably completely miscible therewith. Finally, in
the particular composition in which it is used, the plastic 50 the aforementioned plasticizer esters. To be effective,
especially with respect to reducing impact sensitivity, the
izer should maintain relatively constant properties with
coating on the explosive crystals will generally constitute
time and over the temperature range to which it is to be
at least about 5% by weight thereof, and can range up to
exposed. Some helpful guides for selection within the
about 25% of the total weight of nitramine and ester.
aforementioned unique group can be obtained from Chap
ter 15 of The Technology of Solvents and Plasticizers by 55 The advantages of using ester-coated crystalline nitramine
in terms of safety during manufacture of the instant explo
A. K. Doolittle, New York, John Wiley and Sons, Inc.
sive compositions can be seen from the following tabu
(19574).
'
lated drop-test data. In each case, the particular explo
The concentration of ester plasticizer in the explosive
compositions will generally be about 10 to 34.5% by 60 sive nitramine is taken from the same lot of very ?ne ma
terial ( all below 44 microns), and the coating agent is the
weight, and preferably about from 12 to 36%. When
tri-n-butyl ester of 2-acetoxy-1,2,3-propanetricarboxylic
the nitrocellulose concentration is in the preferred range
acid, used in the speci?ed concentration. The drop tests,
of about from 2 to 8%, and especially when the nitro
cellulose constitutes 4% by weight or less of the total

a standard method of measuring sensitiveness to initiation

of detonation by impact, are conducted with a modi?ca
explosive composition, optimum product ?exibility at low 65 tion of the apparatus described in U.S. Bureau of Mines

temperatures, including subzero temperatures, usually has

been found to be achieved by employing an ester plastic
' izer-to-nitrocellulose ratio of at least about 4/1.
' The explosive compositions of this invention can be

Bulletin 346 (1931). In the tests, the maximum height

from which the impacting weight (5 kg.) falls on the test
specimen is 56 inches, and the test samples are placed in
.a small metal cup rather than directly on the anvil. Im

prepared by several methods, including the procedure of 70 pact sensitivity is reported as the minimum distance of
the aforementioned U.S.P. 2,992,087, wherein water

wetted crystalline high explosive is blended with the plas

weight drop (in inches) that causes detonation in 50% of

the samples (20 trials in each case). (Samples that con~
sistently fail to detonate when the weight is dropped from

ticizer ester, generally at an elevated temperature, and

then the blend, preferably after being freed of excess
the maximum height of 56 inches are reported to have a
water, is intimately mixed with the nitrocellulose. How 75 sensitivity of 56+ inches.)

3,311,513

sheets and cords make optimum use of the outstanding

Cyclotrimethylenetrinitramine

properties of the products of this invention.

Impact sensitivity (inches)

The following examples provide speci?c illustrations of

the explosive compositions of this invention, their explo

0 __________________________________ __ 12-14
5 _________________________________ __
54

sive and physical characteristics, and their advantages. In

the examples, parts and percentages reported are by

Wt. percent of Ester:

10 __________________________________ __
20 __________________________________ __

weight.

56+
56+

EXAMPLES 1 TO 6

CyclotetramethyIenetetranitramine
Wt. percent of Ester:

10

heating, and means for measuring temperature within the

0 ____________________________________ __ 6-8
5 ____________________________________ __
1O ____________________________________ __

The compositions of following Table I are produced in

a mixer provided with an agitator, a water jacket for

Impact sensitivity (inches)

mixer charge. In each case, the crystalline explosive

nitramine, cyclotrimethylenetrinitramine (referred to as

43
53

RDX in the table), is premixed at about 130 F. with

approximately 15 to 20% of water, and a portion of the
While other materials such as Waxes and oils have been
wet nitramine ranging from about 15 to 25% of the total
used effectively to desensitize the subject explosive nitra
is removed from the mixer. The portion of heated, wet
mines per se, the presence of substantial quantities of such
nitramine remaining in the mixer thereafter is blended for
20
additives in the explosive compositions of this invention
several minutes with the tributyl ester of 2-acetoxy-l,2,3
has a deleterious effect on the properties of the ?nished

propanetricarboxylic acid (designated ester in the table)

explosive products, especially on their physical-mechan

until a uniform mixture is obtained. Free water in the

mixture then is decanted, and a small amount (0.2-0.5 %
of the total composition) of an inert pigment or dye, e.g.,

ical characteristics at elevated temperatures (>l00 F.)

Accordingly, it is preferred in the present compositions to
con?ne the desensitizing agents for the explosive nitra
mine to the aforedescribed nonsolvent wetting liquids and

lead chromate, is added, if desired, to impart a distinctive

color to the ?nal composition. Three portions of high

esters. The latter materials are especially advantageous

in that they simiultaneously serve the dual functions of

viscosity, soluble nitrocellulose (NC in the table) having

nitrocellulose plasticizer and explosive nitramine desensi

lymerization around 3000 then are incorporated at inter

vals of a few minutes, the portions constituting about one

a nitrogen content of about 12.3% and a degree of po

tizer.

Depending on the particular mixing procedure em

half, one-fourth, and one-fourth of the total nitrocellulose,

respectively. Heating, at the speci?ed temperature, and

ploy, all or a portion of the explosive nitramine used in

the instant compositions can be in the form of crystals
provided with a coating of the aforementioned esters.
The proportion of ester incorporated in the form of such
coating can constitute as little as about one~sixth of the

agitation are maintained during and after this addition

until all lumps or inhomogeneities are gone, signifying the
absence of uncolloided nitrocellulose, and until the mix

Accordingly,

ture is substantially water-free. The remaining portion

of the wet crystalline cyclotrirnethylenetrinitramine then

Where necessary, supplemental portions of uncombined

is incorporated, and the mixture is maintained at about

total ester to as much as 100% thereof.

130 F. with agitation for several additional minutes, un

The nitrocellulose used in the explosive compositions 40 til the mass is converted into small, substantially dry non

ester are used.

can be wetted with alcohol, with water, or with combina

tions of the two. However, it has also been found suit
able and advantageous in certain cases to incorporate sub

stantially dry nitrocellulose.

consolidated granules.

tough yet ?exible sheet explosive products characterized

by a high degree of uniformity in thickness, composition,

(Warning: Dry nitrocel

_ lulose is sensitive to ignition by static charges.

Finally the granular mass is re

moved from the mixer and passed to an extruder to form

Accord 45 and consistency.

ingly, personnel and manufacturing equipment and fa

cilities should be appropriately protected when the form
of nitrocellulose is used.) Employing dried nitrocellulose
is of particular merit when ester-coated crystalline nitra

In Table I, the formulas of Examples 1 to 4, inclusive,

contain very ?ne crystals of cyclotrimethylenetrinitrarnine
(average particle size, 7-10 microns), whereas the for
50 mula of Example 5 contains crystals of somewhat larger
mine is also employed, as the need for removal of any
size (average particle size, 70-80 microns), and that of
foreign wetting agents during processing is thereby entire
Example 6 contains relatively coarse crystals (average
ly avoided.
particle size, 170-180 microns).

The generally granular explosive products obtained by

blending the components in the aforedescribed manner are

readily converted into compact, self-supporting yet ?ex~

55

ible articles such as sheets, tapes, cords, blocks and other

rectilinear and curvilinear shaped articles, including those

of relatively complex con?guration, e.g., having V-grooves
or cavities therein as well as those, such as sheets or
blocks, of relatively plain con?guration. The shaping can 60

be accomplished by pressure molding, rolling extrusion,

and similar forming operations, and can be conducted at
ambient or elevated temperatures, depending on the par

TABLE I

Example _____________________ __ 1

2 l 3 y 4 y 5

Percent RDX ________________ __

68

70

72

75

70

70

Percent Ester- __

26

25

24

20

25

25

Percent NO __________________ _.

ticular composition and type of forming involved. The 65

shaped articles can thus be obtained in a variety of shapes
and thicknesses or diameters. In addition, they are easily
cut or sliced to give special con?gurations not obtained

Explosive characteristics of the foregoing formulas are

assessed by determining the densities of the sheet prod
by the usual forming procedures. Of the aforementioned
shaped explosive products, sheets that are about from 70 ucts (at the same thickness and at equivalent weight load
ings per unit of area) and by measuring the velocity of
0.05 to 0.50 inch in thickness and have a loading of about
from 1.3 to 14.0 grams per square inch of surface area
and cords that are about from 0.125 to 0.75 inch in diam

detonation of the sheets when suitably initiated by an ex

plosive initiator. These values are reported in Table II,

in which the example designations refer to those of
_ eter and have a loading of about from 0.3 to 1.2 grams
per inch of length are especially suitable, in that such 75 Table I.

3,311,513
TABLE II
Example ____________________________ __

Density, g./cc _______________________ __

1. 52

1. 52-

1. 53

1. 58

1. 51

Detonattioi
' ia orTest:
________________________ __

(B)

( l)

(b

(a >

( l)

7, 460

7, 170

Velocity of Detonation, meters/

'

sec.d __________________________ _.

>

7, 250

1. 53
(0)

7, 460

7, 250

6, 670

a Blasting cap with base charge of12 grains of PETN.

bBlasting cap with base charge of 9 grains of PETN.
a 8-gram pellet of waxed cyclotrimethylenetrinitramine.

mid iheets 0.160 inch in thickness are used except for Example 6, where the sheet is 0.320 inch
0

Sheet explosive products having similar explosive and

portions to that part of the cyclotetramethylenetetranitra~

physical characteristics are obtained when one of the '

mine-ester mixture remaining in the mixer, and mixing
esters, tributyl phosphate, dibutyl phthalate, bis(2-ethyl 20 is continued at the same temperature until the mass is

hexyl) adipate, or bis(2-ethylhexyl) sebacate, is sub

substantially free of uncolloided nitrocellulose. The por

tion of the cyclotetramethylenetetranitramine-ester mix
ture previously reserved is incorporated into the mix
ture, and the resulting mass is agitated until small, non
consolidated granules are obtained. During the last few
minutes of mixing, the mixer is maintained under vacuum

stituted on an equivalent weight basis for the tributyl

Z-acetoxy-1,2,3-propanetricarboxylate in the formulas of

the above tables. These formulas also can be shaped
. into tough yet resilient and ?exible sheet products by cold

or hot rolling procedures, or alternatively, they can be

converted into tapes, cords, and similar con?gurations, for

example, by extrusion through suitable dies.

EXAMPLE 7

Following the general procedure of Examples 1 to 6,

to allow entrapped air to escape from the mass.

The

product then passes to an extruder that is ?tted with dies

of various sizes to prepare cord products ranging from
30 0.125 to 0.25 inch in diameter.

a composition of 70% cyclotetramethylenetetranitramine

TABLE III

having an average particle size in the 1215 micron range,

22% of tributyl Z-acetoxy-1,2,3-propanetricarboxylate,

Example _____________________________ __

compositions of Examples 1 to 6 is prepared by ?rst

adding all the tributyl ester to the ?ne-particle cyclotetra

Percent HMX 1_

80.0

85.0

85.0

Percent Ester- __

17. 5

13. 5

14. 5

methylenetetranitramine and allowing the mixture to stand

Percent NC"...

2. 5

1. 5

0. 5

and 8% of the high-viscosity, soluble nitrocellulose of the 35

10

for a period su?icient for the ester to coat and soak

1 Substantially all particles smaller than 50 microns; aver
age particle size less than 8 microns.

into the nitramine crystals. At a temperature of approxi

mately 140 F., the nitrocellulose, in water-wet state, then

is incorporated into the coated crystals in approximately
three equal portions. Mixing is continued at the speci?ed
temperature until the nitrocellulose is thoroughly blended

Explosive characteristics of the foregoing compositions

are assessed by determining the densities of the cord
products (at the same diameter and at equivalent weight
loadings per unit of length) and by measuring the detona
tion velocities of the cords when initiated by a lO-gram
PETN primer. These values are reported in Table IV,
in which the example designations refer to those of
Table III.

in and the mixture is substantially dry. The mass then

is removed from the mixer and extruded through dies
to form explosive cords of various diameters. One cord
product so obtained has a diameter of 0.460 inch and a

density of 1.58 g./cc. When initiated with the aid of an

18-gram pellet of waxed cyclotrimethylenetrinitramine,

a 44-inch length of this cord detonates completely at a
velocity of 7350 meters per second.

TABLE IV

Finished cyclotetramethylenetetranitramine~containing
Example _____________________________ __
explosive products of substantially the same physical and
explosive properties are obtained when the foregoing 55
Density, g./cc ________________________ __
procedure for preparing the subject formula is modi?ed
Velocity of Detonation, meters/sec;
by withholding from the blending process a portion of
0.125-in. cord _____________________ __
0.187-iu. cord _ _
the ester-coated cyclotetramethylenetetranitramine, e.g.,
0.250in. cord _____________________ __

about from 10 to 25% thereof, until after the nitrocel- ..

lulose is added and thoroughly blended in. The more 60

granular product so obtained is, however, somewhat easier
to handle and fabricate into void-free shaped articles such
as cords, tapes, and sheets.
EXAMPLES 8 to 10

65

Following the general procedure of the foregoing ex

amples, the compositions of following Table III are

10

1. 64

1. 67

1. 69

7, 350
7, 640
7, 975

7, 620
7, 875
8, 195

8, 020
8, 100
8, 250

EXAMPLES 11 to 15

Following Table V reports explosive and physical char

acteristics of several explosive compositions of this inven

tion, together with characteristics of explosive composi

tions of the type disclosed in U.S.P. 2,992,087. The crys

talline high explosives used in the compositions of Table
V are of comparable very ?ne particle size, i.e., substan
amount of cyclotetramethylenetetranitramine (HMX in
Table III) with the speci?ed proportion of tributyl 70 tially all of the particles are smaller than 44-50 microns.
Z-acetoxy-1,2,3-propanetricarboxylate (ester in Table
The average particle size of the PETN is about 7 to 10
III) and setting aside a portion of approximately 30%
microns, and that of the cyclotrimethylenetrinitramine

prepared by thoroughly blending and coating the speci?ed

of the resulting mixture for later use.

Then, at a tem

perature of about 140 F., the total quantity of nitrocel~.

lulose (NC) speci?ed is added in dry form in several

(RDX) and cyclotetramethylenetetranitramine (HMX)

is 8 microns or less. The ester in the compositions of

Table V is tributyl Z-acetoxy-l,2,3-propanetricarboxylate.

s, a 1 1, 5 1 e

1q

ll

4..

TABLE V

Flexibilityh at

Density,

VOD,e

g./cc.

meters/sec.

Compositions of This Invention

Ambient

Temp.

Low Temp.

11. 63/29/8% RDX/Ester/NC _____________ __

1. 48

12. 68/26/6% HMX/Ester/NO _____________ _.

1. 52

Googa%~40 F. and

13. 70/22/8% I'lMX/Ester/NCuh

1.58

Good, at 37 F.

14. 72/23/5% RDX/Ester/NO ______ _-

1. 55

Gool,a%40
F. and
5
.

15. 80/l7.5/2.5% HMX/Ester/NC __________ _.

1. 64

Good, at ~40 F.

Do.

'

Compositions of U.S.P. 2,992,087 (for Com

parison):

A. 63/29/8% PETN/ESter/NO ________ __

1.43-1.46

6, 700-6, 900 _____do ..... __ Gooioag 40 F. and

B. 67/27/6% PETN/Ester/NC...

1. 47

6, SOD-7,000

P001, at ;-20 F.

C. 71/24/5% PEIN/Ester/NC___
__
D. 80/17.5/2.5% PE'lN/Ester/NC ____ __

1. 48
1.53

7, 000

(0)

a Poor, at l0 F.
Poor, at 40 F.

n Velocity of detonation.

b Flexibility at ambient temperature (about 70-75 F.) is determined by manual twisting and bending of the
sheet or cord product in the as-made state. Low-temperature ?exibilities are determined after at least several
hours storage of the sheet or cord at the indicated subzero temperature or temperatures. The low-temperature
test results reported are based on a quick folding of the chilled specimen around a 54-inch wood dowel so that it

is bent back on itself essentially 180, followed by immediate visual inspection of the sample for erazing, cracks
and similar ?aws. .In the table, good indicates absence of brittleness and ?aws; iair" means moderate

brittleness; and poor indicates signi?cant brittleness and cracking-craziug ?aws.

e Cord product is too fragile to permit detonation velocity determinations on 10-15 inch lengths generally
used for this test.

(a) about from 68 to 80% by weight of crystalline

explosive nitramine having an average particle size

As can be seen from the data of Table V, the composi

tions of this invention containing the crystalline explosive

below about 100 microns and selected from the group

nitramines, cyclotrimethylenetrinitramine and cyclotetra

mcthylenetctranitramine, are generally superior to similar
explosives containing PETN in density and in velocity of 30
detonation at each level of high explosive loading exem
pli?ed. The compositions of this invention, particularly
those containing high explosive loadings on the order of

consisting of cyclotrimethylenetrinitramine and cy

clotetramethylenctetranitramine;
(b) about from 2 to 8% by weight of soluble nitro
cellulose having an average degree of polymeriza
tion of about from 2000 to 3000; and

(0) about from 12 to 30% by weight of

of Z-acetoxy-1,2,3-propanetricarboxylic
tion, markedly superior to the comparable PETN-con 35
5. A detonating explosive composition
taining compositions in their ability to withstand exposure
wherein the crystalline explosive nitramine
to normal and low (Subzero) temperature Without becom
68 to 80% of the total composition weight are, in addi

tributyl ester
acid.
of claim 4
has an aver

age particle size of about from 1 to 75 microns.

6. In a method for preparing improved detonating ex

ing so brittle as to be in?exible and subject to cracking

and crazing. The compositions of the instant invention

thus make it possible to employ these high explosive load 4'0 plosive compositions comprising uniform blends of:
(a) about from 65 to 85% by weight of crystalline
ings and to enjoy the attendant advantages of high density
explosive nitraminc having an average particle size
and high velocity of detonation without sacri?ce in the
below about 200 microns and selected from the group
physical-mechanical characteristics of the compositions at
consisting of cyclotrimethylcnetrinitramine and cy
normal and low temperatures.
15
clotctramcthylenctetranitraminc;
What is claimed is:
(b) about from 0.5 to 15 % by weight of soluble nitro
1. Improved detonating explosive compositions com
cellulose having an average degree of polymerization
prising uniform blends of z
of about from 2000 to 3000; and
(a) about from 65 to 85% by weight of crystalline
(c) about from 10 to 34.5% by weight of ester selected
explosive nitramine having an average particle size
from phosphate and carboxylate esters having the
below about 200 microns and selected from the group 50
formulas:
consisting of cyclotrimethylenetrinitramine and cy

clotetramethylenetetranitramine;
(b) about from 0.5 to 15% by weight of soluble nitro
cellulose having an average degree of polymerization
of about from 2000 to 3000; and

O
55

RO-i|0R and ]-l(cooa>n

(I)R

(c) about from 10 to 34.5% by weight of ester selected

from phosphate and carboxylatc esters having the

(Og'C}I3)rn

(00011)
(c 0 o R) q

formulas:

in which each R represents an aliphatically saturated

E!)

i
(0o-oiii)m

60

of about 1 to 8 carbon atoms; and each of m, n, p,

and q is a cardinal number of 0 to l, the sum of
n, p, and q being 2 to 3,

RO1|OR and ]- (o0oR)..

OR

(O 0 0 R)

(C O OR>q

65

in which each R represents an aliphatically saturated

organic radical of about 1 to 8 carbon atoms free of
functional substituents; ][ is a hydrocarbon nucleus

prising a uniform blend of:

the steps comprising intimately blending about from 50

to 90% of the total weight of said crystalline explo
sive nitramine with said ester and said nitrocellulose
until a ?rst substantially homogeneous mass is

of about 1 to 8 carbon atoms; and each of m, n, p,

and q is a cardinal number of 0 to l, the sum of 70
n, p, and q being 2 to 3.

2. A sheet explosive of the composition of claim 1.

3. A detonating cord of the composition of claim 1.
4. An improved detonating explosive composition com

organic radical of about 1 to 8 carbon atoms free of

functional substituents; ][ is a hydrocarbon nucleus

formed, then intimately blending the remaining por

tion of said nitramine with said ?rst mass until a

uniform product is obtained.

7. A method according to claim 6 wherein the crystal
line explosive nitramine has an average particle size below
about 100 microns; the ester is tributyl 2-acetoxy-l,2,3
5 propanetricarboxylate; and the crystalline explosive nitra

3,311,513

13

14

mine introduced in said blending operations is precoated

References Cited by the Applicant

UNITED STATES PATENTS

with about from 5 to 25% of said ester, based on the '

total weight of nitramine and ester.

8. Crystals of explosive nitramine having an average

2,992,087

particle size below about 100 microns and selected from

2,999,743

cyclotetramethylenetetranitramine, said crystals being

3,093,521
3,138,501
3,147,162

the group consisting of cyclotrimethylenetrinitramine and 5

coated with about from 5 to 25% of tributyl 2-acetoxy
1,2,3-propanetricarboxylate, based on the total Weight of

nitramine and carboxylate.

References Cited by the Examiner
UNITED STATES PATENTS
3,227,588
3,235,420

1/1966
2/1'9166

Jones et .al. ______ __ 149-92 X

Murphy ________ __ 149-92 X

7/1961 Fassnachet et al.

9/ 1961 Breza et al.
6/ 1963 Breza.
6/ 1964 Wright.
9/ 1964 Paul.

10

CARL D. QUARFORTH, Primary Examiner.

L. DEWAYN-E R'UTLEDGE, Examiner.

15- S. ]. LECHERT, Assistant Examiner.