US1307032A - Jacob barab - Google Patents

Description

10 liquid explosive UNITED STATES PATENT: oFFIoE.

. JAcoE ARAE, E :oovER, NEW JERSEY, ASSIGNOR r0 HERoULEs POWDER. ooMrANY, a or WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE.

m'rRoetYcoLs.

No Drawing.

" zenof the United States, residing at Dover,

county of Morris, and State of New Jersey,

have invented a new and useful Improve- 'nient in Nitroglycols, of which the following is a full, clear, and exact description.

In an application filed by me July 18, 1917, Serial No. 180,561, I set forth a new having substantially the percentage composition of propylene glycol dinitrate which is comparable in strength, quickness of action and capacity of absorption in a porous carrier, to nitroglycerin, but whlch' possesses certain valuable properties,

such as an extremely low freezing point, insensitiveness to friction and heat, and relative insensitiveness to shock, which are not pos- "sessed by nitroglycerin, and which render it safely available, in its liquid state, as an ex plosive, under conditions that would render the use of nitroglycerin very dangerous or even prohibitive. While propylene glycol dinitrate is sufliciently non-volatile at at- 2 5 mospheric temperatures to be satisfactory for practical use, it is clear that an explosive having the other qualities of nitrated propylene glycol, but possessed of a substantially lower volatility, would be of great practical advantage. My invention comprises an explosive of this character.

I have discovered that nitrated trimethylene glycol possesses all the valuable qualities of nitrated propylene glycol and .exhibits, in a pronounced degree, the other.

quality sought, namely comparatively low Volatility.

While trimethylene glycol has the same percentage composition as propylene glycol,

40 and While the percentage compositions of the nitrated products are the same, the two glycols are produced from entirely diiferent sources, and the two glycols, as well -as the two nitrated products, are expressed by differentformulae and have difierent physical and chemical characteristics. The formula for propylene glycol is;

error:

While that for trimethylene glycol is z men Specification of Letters Patent.

ered effective means of chlorinating the Patented June 1'7, 1919.

Application filed July 24, 191s. Serial No. 246,452.

The formula for nitrated propylene glycol 1s:

' omlvoa HNO;

. H8 I While that for nitrated" trimethylene glycolis:

'CHgNOa" omNoa It will be noted, from the above formulae,

that in propylene glycol the'OH radicals are adjacent, while-in trimethylene glycol the OH radicals are attached to the end carbons.

Comparing the formulae for the nitrated products, the same difference .exists with respect to the N0 radical.

The following differences in the physical properties of the two glycols may be emphasized. The boiling'point of propylene glycol is about 188 degrees (3., while the-boiling point of trimethylene glycol is about 2 06 degrees C. At 23 degrees (1., the specific gravity of propylene glycol is 1.0384, while the specific gravity of trimethylene glycol is 1.0672. Difierences of less importance are:

trimethylene glycol is a darker yellow, propylene glycol being almost or quite colorless. Both have a bitter sweet taste, but the bitterness of propylene glycol is relatively and actually slight.

The only practicable commercial way of producing propylene glycol is by the cracking of oil gas followedby a recently discov unsaturated derivatives (practically wholly propylene and ethylene) to chlorhydrins and making the glycols from the chlorhydrins. Trimethylene glycol,--however, is a by-proi and it has a eep yellow color and a faint.

ethereal odor. The most pronounced difi'er-- 10 ence is in their relative volatilities.

Taking nitrated propylene glycol asa standard for volatility, nitrated trimethylene glycol is only about 37% per cent. volatile.

difi'erent samplesof ten grams of 110 Thus,

duct in the manufacture of glycerin from (3., its color is a welght.

as compared with nitrated one-half of one per cent. occurred. During .the next ten days, the loss was about .fourfifths of one per cent. At .the end of the twenty-eight day period, the total loss was from 2.6 to 2.7 per cent. With corresponding samples of nitrated propylene glycol,

the loss approximated 7 per cent.

S1m1lar comparative volatility tests were made of samples of each of the explosives absorbed in one of the standard absorbents for nitroglycerin, namely: 14 percent. of wood pulp, 45 per cent. sodium nitrate and one .per cent. chalk, the remaining 40' per cent. being the liquid explosive. The test contlnued for. three days, at the end of which time the loss in weight of the nitrated propylene glycol-powder was about 1.52 er cent., while the nitrated trimethylene g ycol powder had lost about .59 per cent. in

Samples of the two liquid explosives, heated slowly in test tubes immersed in a paraflin bath, behaved quite differently.

While nitrated trimethylene glycol'began to boil at a lower temperature than'nitr'ated propylene glycol (148 C. as compared with 3'5 180 C.), the' latter completely evaporated during a rise of temperature through a further range of about 5 C., whereas the .former was raised in. temperature about 50- C. before it evaporated to dryness. Nitroglycerln started to boil, under the same conditlons, at about 145 C. and exploded at 218 C.

In other essential respects the two roducts have .similar' characteristics.- pon sub ect1on to extreme cold, nitrated propylene glycol becomes slightly viscous at -4=4 1s ver vlscous at .68 tremely stifi' at 7 7 C.- Nitrated trimethyl ene glycol becomes slightly viscous at .31 C., is very thick at 53 C. and solidifies at 57 C. These figures are approximate only, the slowness and gradualness of the passage of the liquid from fluidity to slight the theoretical advantage is with .'nitrated propylene glycol, but the freezing point, or,

even the temperature at whichviscosity is measurable, is so low that, for all practical purposes, the two exp osives are equally' valuable in "respect 0 qualities. .Y

Not only is nitrated trimethylene glycol, ropylene gl col, of low'volatility butt e spent ac1 s their non-freezing 'tion 1s required. A smaller proportion of satisfactory roduct. Y e I The speci 0 process of nitratin prolpylap lea-J weak ammonia solution. Y

G.,' and is ex.-

In regard to low freezingpoint,

from the former product are more or less unstable if allowed to stand without agita tion. 'The spent acids from nitrated trimethylene glycol are perfectly stable.

Trimethylene glycol may be nitrated by the known method most usually employed for nitrating glycerin, with the following. modifications: In view of the lower specific gravity of the glycol, more vigorous agitanitric acid will sufiice, about 166 pounds of nitric acid bein required-for100-pounds of trimethylene g ycol, while 205' pounds of I nitric acid are required for 100 pounds of i glycerin. v

Instead of washing alternately with water and sodium carbonate solution, the washing should be with pure water, although alternate washing with weak ammonia is permissible. The use ofsodium carbonate must be avoided. An extremely small quantity of sodium carbonate might not-beharmful', A

but-it wouldbe without utility, and close' adherence to the method in, vogue for purifying nitroglycerin would not" result In a ene glycol, as set forth in my .sai

tion, may be advantageously used in t e,ni- 95 tration of trimethylene glycol, but as this process is not herein claimed, it need not be I specifically set forth. No difficulty in stabilizing nitrated trimethylene glycol is encountered if the pro iluct is thoroughly washed. However, ni rated trimethylene glycol may be purified with fpure water, as

above stated, while the puri Like"nitrated propyleneglycol, nitrated trimethylene 1 col 1s non-hygroscoplc, endures the AbeI eat testat 71 C. for more than,an hour, decomposes above 140 degrees" 0., does not explode when a drop lsintro suddenly into a flame, remains hquidat atinospheric temperatures, is insemnt1vej,to

friction, is relatively insensitive to shock,

absorbents and is absorb'able in the ordinary to approximately the same dc When absorbed inan of t e usual absorbents employed in t e manufacture of dynamite, the new explosive, like nitrated propylene glycol, retains all its valuable qualities, and is non-exuding undergeneral. 120

conditions of use.

Notwithstanding, the insensltiveness to friction of the solid-explosive, it can be detO- nated satisfactorily, by. means of a 'weak-,

primer.

Another valuable quality of the'hquld exgulshing it from nitrogylcerin gelatins. A"?

cation of ni .trated propylene glycol requires the use of a need 1*10 1 25 plosive isthat itforms a colloid when mixed with nitrocellulose and the resultant gelatmu explosive has valuable propertles dlstmof nitrocellulose (showing 12.25 per cent. nitrogen) and 100 parts of nitrated trimethylene glycol.

While I'have herein described the product trimethylene glycol dinitrate and its process of manufacture, there may also be present in appreciable quantities,

in claiming the nitrated pure dinitrate.

It will also be understood that the nitrated product formlng the subject-matter of this patent may be added to nitroglycerin in different proportions for the purpose of producing what may be called either a modified nitrated trimethylene glycol or a modified nitroglycerin. For example, if nitrated trimethylene glycol be added to nitroglycerin, it will lower the latters freezing point" to a degree dependent upon the percentage of the addition and will render the nitroglycerin less sensitive to heat, friction and shock.

The new explosive may also be used in admixture with nitro-compounds, as, for example, trin-itrotoluol or trinitrotoluol oils. Having now fully described my invention, what I claim and desire to protect by Letters Patent is 1. The new explosive product which has substantially the percentage composition and molecular arrangement of trimethylene glycol dinitrate. v

2. The new explosive product having substantially the formula cmnoa (in,

1mma 3. The. new explosiveproduct which has the percentage composition of propylene glycol dinitrate but which difi'ers therefrom the mononitrate I glycol dinitrate whose in that the-NO radicals are attached to the end carbons and whose volatility is less than one-half that of propylene glycol dinitrate.

4. The new explosive product which has the percentage composition of propylene glycol dinitrate but which differs therefrom in that the N0 radicals are attached to the end carbons and which has ahigher specific gravity, a higher boiling point, and is substantially less volatile, than nitrated propylene glycol.

-5. The new explosive product trimethylene specific gravity at 27 degrees C. is approximatel 1.43. p

6. The new explosive product trimethylene glycol dinitrate having approximately the strength of trinitroglycerin and nitrated propylene glycol, which is non-freezing at l0 egrees remains liquid and stable within the highest range of atmospheric temperature, does not explode when va drop is suddenl introduced into a flame, to riction and relatively insensitive to shock, completely evaporates without explosion when slowly raised in temperature, and which is substantially less volatile than propylene glycol dinitrate.

7. An explosive comprising liquid trimethylene glycol dinitrate and an absorbent.

ene glycol dinitrate.

is insensitive In testimony of which invention, I have I hereunto set my hand, at Kenvil, N. J on this 17 day of July, 1908.

JACOB BARAB.