1

United States Patent 0 "ice

3,313,739
Patented May 9, 1967

of the PETN is such that 100% will pass through a US.

3,318,739
Standard Sieve No. 200, and which as received, then dried
PROCESS FOR MAKING HEAT-STABILIZED
in vacuum at 50 C. for 4 hours, yielded 11+ ml. gas
PENTAERYTHRITOL TETRANITRATE
when subject to the 120 C. Vacuum Stability Test when
H. William Voigt, Jr., Stanhope, N.J., assignor to the
using a 2.3 g. sample for a 20 hour period. Dissolve the
United States of America as represented by the Secre
tary of the Army
coated PETN in 10 g. N-methyl-Z-pyrrolidone in a beaker
placed on a steam bath, the N-methyl-Z-pyrrolidone sol
No Drawing. Filed Nov. 4, 1966, Ser. No. 592,681
8 Claims. (Cl. 149-11)
vent being maintained at 60~80 C. Pour the resultant
solution slowly into a beaker containing about 50 ml. of
This invention relates to explosive compositions and 10 rapidly agitated ethanol held at about 20 C. until a
more particularly concerns methods for making heat
very ?ne, fuzzy-like suspension results. Filter the sus
stabilized PETN explosives.
pension on a Buchner ?lter using No. 54 ?lter paper. The
Pentaerythritol tetranitrate (PETN) has been used in
solid collected is washed twice with about 50 m1. por
such applications as boosters, squibs, initiators, blasting
tions of ethanol. The washed collected solid is then air

caps, sheet explosives, detonating cords, and the like. The

undesirable heat stability characteristics of PETN how
ever have prevented its general widespread use as a mili

tary explosive in this and many foreign countries.

dried in a steam oven at about 80 C. The dried PETN

produced was of extremely ?ne particle size (15 mi

crons). A 2.5 g. sample of this PETN produced 1.13

ml. gas in 20 hours and 1.59 ml. gas in 40 hours when

For example, commercial PETN yields an excess of 11
subjected to the 120 C. Vacuum Stability Test.
ml. of gas within a 17 hour period from only a 2.3 gram 20
EXAMPLE II
sample when subjected to the 120 C. Vacuum Stability

Test. Obviously, this instability of a high explosive such

as PETN would render it generally unsafe for military
applications in the ?eld. It would be most advantageous

The dry PETN is dissolved in N~methyl~2-pyrrolidone

in a manner described under Example I, except:

( 1) 0.08 g. of PVP having a molecular weight of about
for overall military purposes if methods could be devised 25 90,000, is co-dissolved with the PETN in the solvent, and
wherein this material could be rendered heat stable.
(2) 2-50 ml. portions of distilled water are used to
It is therefore an object of this invention to provide a
wash the collected solid in lieu of ethanol. (Ethanol may

heat stable PETN explosive.

be used satisfactorily however.)
Another object of the invention is to provide methods
A 2.5 g. sample of this PETN produced 1.29 ml. of gas
for preparing heat-stable PETN explosives.
30 in 20 hours and 1.63 ml. of gas in 40 hours when sub
Other objects and features of this invention will become
jected to the 120 C. Vacuum Stability Test.

apparent as the invetnion is more fully hereinafter dis

closed.
Brie?y, I have discovered processes for rendering PETN

EXAMPLE III
The dry PETN is coated, and dissolved in N-methyl-2

su?iciently heat stable by treating it with a solvent so as 35 pyrrolidone solvent in a manner described under Example
to reduce gassing of the PETN when subjected to ele
I with the following exception:
vated temperatures to such a degree that military stability
(1) 0.6 g. (6% by weight of the PETN) of a phenoxy
requirements for this explosive are readily met.
resin having the structure
More particularly, PETN may now be prepared such
that a 2.3 gram sample, when subjected to the 120 C. 40
Vacuum Stability Test for 20 hours will yield only about
1.20 ml. of gas and about 2.15 ml. of gas in a 40 hour

period.

The 120 C. Vacuum Stability Test measures the sta

bility of a material in ml. of gas liberated therefrom when 45
subjected to a pressure of about 5 mm. mercury at 120 C.

for a period of time. The test is described in Military

Speci?cation, MIL-P-387A, Ian. 9, 1957, and in Stand

ard Laboratory Procedures for Sensitivity, Brisance and
Stability of Explosives, Arthur J. Clear, Feltrnan Re

search Laboratories, Picatinny Arsenal, Dover, N.J., Janu

ary 1961, pages 25 to 30.

Military requirements specify that the maximum

amount of gas to be evolved in a 20 hour period from a

2.3 gram sample of PETN at 120 C. shall not exceed 55

we _

1.1 r In

OH:

H OH HlNg-ioo

and serving as a stabilizer and binder was co-dissolved

with the solvent.

(2) The solution was poured into about 50 ml. distilled

water maintained at 16 C. to form a suspension having
temperature of about 32 C.

(3) Wash the collected solid with 2-50 ml. portions of

distilled water.
Results of 120 C. Vacuum Stability Test on a 2.5 g.

sample showed 1.01 ml. and 1.84 ml. of gas evolved after
20 hours and 40 hours respectively.
EXAMPLE IV

The dry PETN, uncoated with any PVP, is dissolved

5 ml. In accordance with the objects and military re
in N-methyl-Z-pyrrolidone solvent in a manner described
quirements above-described, about 15 to 50 weight per
under Example I except:
cent of a commercial PETN, when dissolved in N-methyl
(1) PETN was dissolved in 20 g. solvent at a tempera
2-pyrrolidone to form a solution, and which was poured
into a suitable liquid to form a suspension, ?ltered, washed 60 ture of about 40 C.

( 2) Solution was poured into 100 ml. distilled water at

and dried, only 1.20 ml. of gas was evolved in a 20 hour
period at 120 C.
20 C., resultant suspension temperature being 30 C.
(3) Collected solids were washed with 2-50 ml. por
The following are illustrative examples of processes
tions distilled water.
of my invention:
For a 2.5 g. sample of PETN, the 120 C. Vacuum
EXAMPLE I
65
Stability Test revealed 1.28 and 2.11 ml. of gas evolution
Coat 10 g. of a standard commercial dry PETN (con
for a 20 hour and 40 hour period respectively.
forming to Mil. Spec. MILP~387A, Jan. 9, 1957) with
If in the preceding Example IV, acetone is substituted

about 0.2 weight percent polyvinyl pyrrolidone (PVP)

having a molecular weight of about 90,000 by dissolving 70
the proper quantity of PVP in water or ethanol and then
stirring the PETN thereinto and drying. The granulation

for N-methyl-2-pyrrolidone, about 35% PETN only may

be dissolved therein whereas about 50% PETN may be

readily dissolved in N-methyl-Z-pyrrolidone. Further, the

gas evolution characteristics of the acetone-dissolved

3,318,739

3
dissolved PETN.

My inventive process may be used advantageously in

N-methyl-Z-pyrolidone,

the stabilization of violent explosives such as mannitol

said polyvinyl pyrolidone having a molecular weight

of about 90,000.
5. The method of claim 3 wherein said dry, heat-un
stable pentaeirythritol tetranitrate and said N-methyl-Z

hexanitrate :

EXAMPLE V
8 g. dry heat-unstable PETN and 2 g. mannitol hexa

nitrate (100% passing through a US. Standard Sieve, No.

200 were each precoated with 0.2% PVP (molecular

weight about 90,000) and then dissolved simultaneously

4. The method of claim 1 wherein said dry, heat-un

stable pentaerythritol tetranitrate is co-dissolved with
about 0.8 weight percent of polyvinyl pyrrolidone in said

PETN is slightly inferior to the N-methy-l-Z-pyrrolidone

10

pyrolidone are present in an amount of about 10 g. each,

said elevated temperatures range between about 60 to

80 C., and

in 15 g. N-methyl-2-pyrrolidone maintained at 51 C. to
said liquid comprises about 50 ml. ethanol maintained
form a solution. The solution is poured into 75 ml. cold
at a temperature of about 20 C.
ethanol (0 C.) to form a suspension having -a tempera
6. The method of claim 3 wherein said coated heat
ture of about 180 C. The suspension is filtered and the
unstable pentaerythritol tetranitrate is co-dissolved with
collected solid washed with 6% ethanol in water at room 15 about 0.6 weight percent of a stabilizer having a structure

temperature. A very fine acicular product resulted having

a diameter of about 1 micron.

When subjected to a 95 C. Vacuum Stability Test, a

2.3 g. sample produced 5.58 ml. gas after 20 hours and
20
9.08 ml. of gas after 40 hours.
When the same quantities of untreated PETN-mannitol
7. A method for producing pentaerythritol tetranitrate
hexanitrate were subject to the 95 C. Vacuum Stability
mannitol hexanitrate heat stable at 120 C. comprising
Test, the explosive either exploded or produced 11+ ml.
the steps of
of gas within a period of 30 minutes.
coating a mixture of heat-unstable pentaerythritol tetra

From the foregoing description, it is apparent that I

have provided processes for obtaining heat-stabilized

nitrate and mannitol hexanitrate each with polyvinyl

PETN which permits its safe use in diverse applications,

dissolving said coated mixture in Nmethyl-2-pyrroli

both comercial and military. Further, other properties,

such as detonation rate, impact sensitivity, brisance, and
the like, are not deleteriously effected by my inventive
processes of providing heat-stabilized PETN.
Iclaim:
1. A method for producing pentaerythritol tetranitrate
heat stable at 120 C. comprising dissolving dry, heat-un

pyrrolidone,
done to form a solution,
30

group consisting of water and alcohols to form a sus

pension,
?ltering said suspension to collect a solid,
washing said solid and drying said washed solid to ob

tain heat-stable pentaerythritol tetranitrate-mannitol

hexanitrate.

stable pentaerythritol tetranitrate in N-methyl-Z-pyrroli

done maintained at elevated temperatures to form a solu

8. The method of claim 7 further characterized by said

heat-unstable PETN being present in an amount of about
8 grams,
said mannitol hexanitrate being present in an amount
of about 2 grams,

tion,

pouring said solution into a liquid selected from the

group consisting of water and alcohols to form a .sus

pension,
?ltering said suspension to collect a solid,
washing said solid and
drying said washed solid to obtaln .said heat-stable

pentaerythritol tetranitrate.
2. The method of claim 1 wherein said dry, heat-un
stable pentaerythritol tetranitrate is present in an amount
of about 10 grams,
said N-methyl-Z-pyrrolidone is present in an amount
ranging between about 10 to 20 grams maintained at
a temperature of about 40 C., and

said liquid comprises about 100 ml. of distilled water

maintained at about 20 C.
3. The method of claim 1 wherein said dry, heat-un

pouring said solution into a liquid selected from the

said polyvinyl pyrrolidone having am olecular weight

45

of about 90,000 and being present in an amount of

about 0.2 weight percent of said heat-unstable PETN
and mannitol hexanitrate, and
said N-methyl-2-pyrrolidone being present in an amount
of about 15 grams.

References Cited by the Examiner

UNITED STATES PATENTS
2,154,552
2,867,647
3,097,122

4/1939
l/1959
7/1963

Wyler __________ .__ 149--93 X

Gow et a1. ______ __ 149-93 X
Cox et -al _________ __ 14993 X

stable pentaerythritol tetranitrate is coated with about 55 L. DEWAYNE RUTLEDGE, Primary Examiner.

0.2 Weight percent of polyvinyl pyrrolidone having a

molecular weight of about 90,000.

S. I. LECHERT, JR., Assistant Examiner.