,a

. . .

UNITED STATES PATENT OFFICE.

HAROLD HIBBERT, OF WILIVINGTON, DELAWARE, AssIGNOR. To E. I. Du PonT DE
NEMOURS POWDER COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF
NEW TERSEY.
EXPOSIVE AND METHOD OF PRODUCING THE SAME AND IS INGREDIENTS.

1,008,333.
No Drawing.
Specification of Letters Patent. Patented Nov. 14, 1911.
Application filed January 31, 1911. Serial No. 605,801.
To all whom it may concern: The butylene glycol is represented in
Be it known that I, HAROLD HIBBERT, a formula in the following manner:
subject of the King of Great Britain, resid CH-CHO
ing at Wilmington, county of Newcastle,
and State of Delaware, have invented a new
and useful Improvement in Explosives and CHO
ch, 55

Methods of Producing the Same and Its In and when nitrated the formula is thus rep
gredients, of which the following is a full, resented:
clear, and exact description. CH-CHNo.
10 When glycerin is treated with the mixed 60
acids, nitric acid and sulfuric acid, for the
production of glycerin triaitrate, glycerin CaNO
trinitrate is produced, the formula of I produce the butylene glycol in the fol
which is: lowing manner, whereby a highly concen
5 trated solution of butylene glycol is directly 65
CHNO
chno, obtained in one operation from acetalde
CENO hyde, and the cost of evaporation, etc., is
thereby very much diminished: I take ethyl
This glycerin trinitrate has certain de alcohol (CHOH), which may be de-na
20 fects, among which it may be stated that the
tured without affecting the result. This
glycerin which is its base is expensive, and ethyl alcohol is first oxidized. Preferably I 70
the temperature of explosion of the explo accomplish this oxidation by the ordinary
sive mixture of the glycerin trinitrate is catalytic oxidation, such for instance, by
very high, which makes it in many cases not using
25 a good ingredient for smokeless powder.
ul. metallic platinum, copper or zinc
and heat. The resultant is acetaldehyde 75
I have discovered that if nitrated butylene. (CHO). This acetaldehyde is then con
glycol be formed, a product is obtained densed. I have used for this condensation
whose temperature of explosive ignition is an aqueous solution of an alkaline carbonate,
lower than that of glycerin trinitrate, which for instance, potassium carbonate; 450grams
30 enables it to be freely used as an ingredient
of acetaldehyde were cooled to a low tem 80
of Smokeless powder, safety explosives and perature say --5° to -10° C. preferably
dynamite. Further, I have discovered that -5° C. and 200 grams or thereabout of
such compound may be combined with ni powdered ice then added. A few drops of
trate derivatives, such, for instance, as ni a cooled solution
35 trated cellulose or nitrated starch, to form containing for example of potassium carbonate
19 grams of the car 85
a colloid of such mixture. It also may be bonate in 80 cubic centimeters of water were
mixed with glycerin trinitrate, and the re introduced into this mixture, the tempera
Sulting mixture has a lower freezing point ture not being allowed to rise above 10° C.
and is more stable than glycerin trinitrate. and preferably not above 5°C. After stand
40 While butylene glycol is known and is de ing some 10 or 15 minutes a further quan 90
scribed in text books, I believe myself to be tity of the carbonate solution was introduced
the first to have discovered nitrated buty to the mixture kept at a low temperature
lene glycol and its value for the purposes and again allowed to stand, contents, being
named. Further, the method of making kept as nearly as possible at a temperature
45 butylene glycol, as set out in the text books, of about 0°C. w 95
is so complicated as to render it very ex After the whole of the carbonate had been
pensive and difficult to carry out. My dis added, the reaction-product was kept in ice
covery, therefore, includes a simple method water for several hours to prevent any rise
for directly producing this butylene glycol of temperature and then for a further 20
50 as well as the nitrated butylene glycol.
hours at say -10° C. and at least below 15 OO
 s 1,008,333
C. If the pure acetaldolis required this may lene glycol mono nitrate and the butylene
be extracted with ether, but for the purpose. glycol dinitrate, although I have only shown
of obtaining butylene glycol this is unneces the formula of butylene glycol dinitrate.
SW. The condensation can be produced Having now fully described my invention, 50
by other alkaline carbonate or a borate, what I claim and desire to protect by Letters
phosphate, acetate or cyanid, of the metals Patent is:--
of the alkalies or of the alkaline earths, 1. The hereinbefore described method of
and where, in the claims, I mention an alka producing butylene glycol, which consists in
line salt, I mean to include as equivalents condensing acetaldehyde to acetaldol in the 55
O salts of metals of the alkalies or of the alka resence of ice in contact with the acetalde
line earths. The resultant of this condensa hyde, adding an alkaline salt, gradually ele
tion is acetaldol (CHO). This condensa vating the temperature during the condens
tion product is then directly reduced to buty ing operation from substantially below 15
lene glycol by means of a reducing agent, and C. to not above substantially 15° C., dilut 60
I have employed the following method: The ing the acetaldol solution with less than
aqueous solution of acetaldol, obtained by about 15 parts of water and adding an acid
condensing 450 grams of acetaldehyde with to render the resultant liquid approximately
potassium corbonate was diluted to less than neutral but preferably slightly acid, and
nine liters, say four liters, with water, the then, without isolating the acetaldol, reduc
20 solution rendered neutral but preferably ing the aqueous solution to butylene glycol
faintly acid by the addition of acid, say by means of a metal amalgam.
hydrochloric acid, and then 200 grams or a 2. The hereinbefore described method of
similar amount of aluminum amalgam producing butylene glycol, which consists in
added. It may be noted that the potassium condensing acetaldehyde to acetaldol in the 70
carbonate may be neutralized with acid be presence of ice in contact with the acetalde
fore the dilution with water. After stand hyde, adding potassium carbonate gradually
ing for some time so as to allow the reaction in the form of a strong aqueous Solution,
to proceed, say one or two days, the alumi gradually elevating the temperature during
num hydroxid was filtered off. After filter the condensing operation from substan 75
30 ing the solution, the butylene glycol was re tially below 15° C. to not above substan
covered by evaporating off the water under tially 15° C., diluting the acetaldol solution
reduced pressure. Other amalgams may be. with less than about 15 parts of water at a
used and, further, the aluminum or other temperature not above substantially 15°C.,
metal or an alloy or several metals may be adding an acid to render the resultant liq 80.
35 used and also without the use of mercury. uid approximately neutral but preferably
In this condition the butylene glycol exists slightly acid, and then, without isolating the
in a concentrated aqueous Solution and is acetaldol, reducing the aqueous solution to
isolated by simple distillation, preferably butylene glycol by means of aluminum
under vacuum. This butylene glycol may amalgam. 85
40 then be nitrated in any known way. In testimony of which invention, I have
When I speak of glycerin trinitrate, of hereunto set my hand, at Philadelphia, on
course I intend to include the glycerin mono this 23rd day of January, 1911.
and-dinitrates, although I have shown only HAROLD HIBBERT.
the formula of the glycerin trinitrate. In Witnesses:
45 like manner, when I use the term butylene M. M. HAMILTON,
glycol dinitrate I intend to include the buty A. J. MAGUIRE,