IL29373A - Explosives containing an impact-sensitive liquid nitrated - Google Patents

Description

β»ΛΊ » ΤΊ3 lK'VlB ytBJ O^'-JBH Τ*>* 'ΤΒΠ »n an *ΤΒ i W>'na*Tm ΠΒ*Λ^ EXPLOSIVES CONTAINING AN IMPACT-SENSITIVE LIQUID NITRATED POLYOL AND TRIMETHYLOLETHANETRINITRATE SPECIFICATION : This invention relates to explosive compositions based on a combination of an impact-sensitive liquid nitrated polyol and trimethylolethane trinitrate as explosive sensitizers, and more particularly to explosive compositions comprising an impact-sensitive liquid nitrated, polyol and trimethylolethane trinitrate produced by conitration of the respective polyols, and also to explosive compositions comprising such a nitrated polyol, trimethylolethane trinitrate, and an inorganic oxidizer, such as an inorganic nitrate, and to a process for forming the same. .

Tenney L. Davis,- The Chemistry of Powde and Explosives (1941) points out that the history of modern explosives commenced with the joint discoveries of nitroglycerine and nitrocellulose. These two materials were prepared independently, but at about the same time. Sobrero first prepared nitro-glycerine,- and Schtfnbein and Bdttger independently each nitrated cotton. Prior to that, Braconnot had prepared a nitric ester from starch which he called xyloidine. The possibilities of the use of these materials in artillery occurred to the discoverers almost at once, and led to a pro-liferation of research and publications on the nitration of glycerine, starch and cellulose throughout the Western world. The nitratio of cotton was effected by Schdnbein by the use of a mixture of nitric acid and sulfuric acid in the proportion of 1:3 by volume (British patent No. 11,407/1846). Mixed acids were nearly always- used thereafter in the nitration of these raw materials .

The development of nitroglycerine led to experiments in the nitration of othe polyols, and from these experiments a series of polyol nitric acid esters were obtained, including pentaerythr itol tetranitrate, dipentaeryth itol hexanitrate, tr itnethylolethane trinitrace, the various nitro sugars, including nitroglycose, nitromannose, nitromaltose, nitro- sucrose, nitroarabinose, and nitrolactose, ni'tromannite , tri- methyleneglycol dinitrate, butyleneglycol dinitrate, propylene- glycol dinitrate and erythritol tetranitrate.

Nitroglyce ine is probably the best known of the liquid nitroesters. It crystallizes in two forms, a stable form melting or freezing at 15.2-15 · 5°C . , and a labile form melting at 1.9-2.2°C. It is very sensitive to impact. A blo of a steel hammer, or the impact of iron striking against stone, or of porcelain against porcelain, can detonate it.

It is, however, a very powerful explosive, and has consequently found wide use in dynamites as well as in propellants, ballistite and cordite. Despite its sensitivity, it is still used, as a liquid to a limited extent, such as in the blasting of oil Many other nitrated polyols have a similarly high sensitivity · to impact, and no marked advantages from the standpoint of safety. Dinitroglyce ine , for example, is hardly distinguishable from t initroglyce ine in this respect. Nitroglycide is even more sensitive than tr initroglyce ine or dinitroglyce ine, nitroglycol slightly less so, and the nitro- sugars are in the same category as nitroglycol.

In order to make nitroglycerine both safe and more convenient to use, Nobel developed dynamite, a mixture of n troglyceri e and a nonexplosive porous absorbent, .the. straight dynamites, dynamites with an active base such as an inorganic nitrate with a carbonaceous fuel , and the blasting gelatins or gelatin dynamites, which included nitrocellulose as well. These, however, : still presented a possible danger resulting from exudation of the nitroglycerine.

Patent No. 2,703,130 discloses combinations of triniethy- lolethane trinitrate and 2,2-dimethyl-l ,3-propanediol dinitrate.

These- mixtures avoid the impact sensitivity problems presented b nitroglycerin, ethylene glycol dinitrate, and similar nitric acid polyol esters, because neither of these nitric acid esters is impact-sensitive. However, these polynitrates do not have the desirable properties of nitroglycerin or ethylene glycol dinitrate, either, and therefore have not really resolved the problem.

In accordance with the invention, explosive compositions which have excellent detonator sensitivity but which are relatively insensitive to impact and which have a reduced tendency to ignite . and detonate upon exposure to an open flame, are prepared b combining an impact-sensitive liquid nitrated noliiol with .trii cthy-' lolethane trinitrate. The trimethylol ethane trinitrate is miscible therewith in all proportions, and the mixture can. thus be readily prepared by careful and safe blending procedures. ' One or more liquid nitrated p lyols can be used in these combinations.

The combinations of the invention can be prepared by simple mixing or blending of the components, but from the standpoint of safety in handling, it is in general preferred to prepare the mixture in situ by conitration of a mixture of the polyol '-storting materials. component, and (2) tr imethylolethane, using nitric acid as. a nitrating agent, preferably in admixture with sulfuric acid.

The conitrates as well as the blends of the invention are liquids, being based on the liquid nitrated polyol and the liquid t imeth lolethane trinitrate.

The relative proportion of t imethylolethane tri- . nitrate required is determined by the amount required to reduce sensitivity to impact, while. ot significantly reducing detonator sensitivity. The maximum amount is established as that which can be tolerated without rendering the composition nondetonable. . In general, the. amount of t imethylolethane trinitrate lies within the range from abou t 5 to about 95 , and the proportion of · nitrated polyol is within the range from about 95 to about.5^, based on the total explosive sensitizer of the composition.

A coniirated polyol - tr imethylolethane mixture is prepared by nitrating the polyols together by action of a concentrated nitric acid. The conitration is. applicable to any aliphatic polyol, or combination of two or more aliphatic polyols' having at least two up to about six alcoholic hydroxyl groups;, and from two to. about ten carbon atoms, that upon nitration yields a impact-sensitive liquid nitrate ester . The preferred polyols are glycerol- and ethylene glycol, alone or in combinatio The polyol and the t imethylolethane are used in. the proportions required to . give the desired final conitrate, which proportions ,. as indicated above, are determined by the sensitivity desired in the composition.

The usual nitrating agent is nitric acid. However, fuming nitric acid, can also be used. The reaction proceeds well in a concentrated nitric acid solution containing at least 10$, and preferably about 12 .75$, nitrogen, or more.

The conitrate is soluble in nitric acid at this \ concentration, and thus it is necessary to isolate the, product by precipitation. Dilution of the reaction solution with water, with sulfuric acid, or with spent acid from some previous nitration, will result in separation of the. liquid ester. This can be removed, and washed.

In the preferred process, a sufficient amount of sulfuric acid is blended with the concentrated nitric acid to form a reaction mixture in which the conitrate is insoluble. The polyol and tr imethylolethane may or may not be soluble in the reaction mixture, but this is unimportant. If the starting materials are soluble, the insolubility of the conitrate aids in driving the reaction to completion.

Satisfactory, proportions of nitric acid in a mixture of nitric and sulfuric acids are within the range from about 95 to about 25$ by weight, and of sulfuric acid, within the range from about 5 to about 75$ by weight. The reaction mixture can also include up to 10$ water . Preferred proportions of nitric acid are within the range from 55 to 43 and of sulfuric acid. from 57 to 67$ by weight.

The polyols can be mixed and then blended with the nitrating agent. However, it is usually preferable to. add the polyol slowly' to the nitrating agent. The polyols are best conitrated together, but if desired, a proportion of one of the polyols can be nitrated first separately, and then the other added, and the conitration continued until completion. The reaction mixture is preferably stirred or otherwise agitated throughout the reaction.

The amount of. itric acid employed is normally, that rStoichiometrically required to nitrate the free hydroxyl groups of the polyols. A small excess, ranging from about 5 to 25$, can be used to ensure completion of the nitration.

The nitration is carried out at a temperature at which the esterification proceeds but below the temperature of decomposition of the conitrate reaction product. Since the reaction will proceed at a satisfactory speed, even at room temperature, the maximum temperature normally used is- about 75°F. Excellent yields are obtained if the reaction is' . conducted at from. about 25 to about 5°F., and consequently, y these temperatures are preferred.

The reaction is exothermic, and cooling may be required to maintain the temperature within this range.

The conitrate is separated from the reaction mixture upon completion of the esterification, and washed several times with cold water to remove excess acid. If desired, the Any alkaline substance can be used. for this purpose, but. it is usually preferable to employ an organic or inorganic base, such as sodium hydroxide, potassium hydroxide, calcium .hydroxide,, or a quaternary ammonium hydroxide, such as trimethyl phenyl ammonium hydroxide, or an organic amine, such as triethanolamine or tributylamine. A volatile base such as an organic amine or ammonia can be used, to avoid contamination of the product by residual solid alkali.

The conitrates of the invention are useful as sensitizing explosives in any type of explosive formulation. In such formulations, the conitrates , just as the simple blends, display the desirable properties of the nitrated polyols, with excellent detonator sensitivity, plus the additional feature of being less sensitive to impact.

The compositions of the invention are liquid unless, solid ingredients are added thereto in a sufficient amount to absorb or adsorb the liquid. Solid carbonaceous fuels can be added to the composition, and in addition or alternatively, there can be added inorganic oxidizers. Inert sorbents- -for the liquid nitrated polyol and trimethylolethane trinitrate can also, be added, such as kieselguhr, diatomaceous earth, charcoal, siliceous earth, and fuller's earth.

Such compositions containing upwards of 15 of the mixture of nitrated polyol and trimethylolethane trinitrate will be of a soft consistency, extrudable using a screw type or cylinder type extruder, while compositions in which the proportion of nitrated polyol and trimethylolethane trinitrate to ether is less than 15$ are ranular solids. : Compositions which are formulated as dry or dry-appearing solids will be found to have a cohesiveness which reduces .dusting, due to the presence of the liquid nitrated polyol and trimethylolethane trinitrate. Such compositions can be formulated as granules which will retain their shape, and are essentially nonfriable.

The nitrated polyol and t imethylolethane trinitrate blended or conitrated compositions are useful explosive sensitizers for explosive compositions. They can serve as . the only explosive sensitizers, and such compositions are preferred. However, if desired, additional explosive, sensitizers, either liquids or solids, can be added, in an amount up to approximately 5C$ of the total explosive sensitizer Exemplary additional sensitizers include pentaerythritol tetranitrate, trinitrotoluene, pentryl, dipentaerythr itol hexanitrate, mannitol hexanitrate, sorbitol hexanitrate, sucrose octanitrate, Pentolite (an equal parts by weight mixture of pentaerythritol tetranitrate and trinitrotoluene), nitro- : starch, Cyclonite (RDX, cyclotrimethylene tr initramine)..

Composition B (a mixture of up to 6C$ RDX, up to 0$ TNT and 1 to wax), Cyclotol (Composition B without the wax) di-nitrotoluene, and tetryl.

In formulating explosive compositions, these explosive sensitizers are preferably used with an inorganic oxidize salt, to compensate for the oxygen deficiency of the nitrated polyol and the t imethylolethane trinitrate. Preferably, the oxidizer employed is an inorganic nitrate.

Amnionium nitrate and nitrates of the alkali and alkaline earth metals, such, as sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate, and barium nitrate are exemplary inorganic nitrates. Ammonium, nitrate and mixtures of ammonium nitrate and another nitrate in minor proportion are preferred. Excellent results are obtained with mixtures of ammonium nitrate and sodium nitrate, and such mixtures 'are frequently preferred over ammonium nitrate alone.

As the inorganic oxidizer, there can also be used a chlorate or a perchlorate of an alkali or alkaline earth metal, such as sodium chlorate, potassium chlorate,, barium chlorate, sodium perchlorate, potassium perchlorate, barium perchlorate and calcium perchlorate. Mixtures of nitrates, chlorates , and perchlorates ; of nitrates and chlorates; of nitrates and perchlorates ;, and of chlorates and perchlorates , can be used. . .

When mixtures of ammonium oxidizer and the other oxidizer are used, the relative proportion of ammonium oxidizer is important for good explosive shock and, power. The ammonium oxidizer is employed in a proportion within the range from about 50 to 95$ by weight of the total oxidizer, and the other oxidizer. or oxidizers in the proportion of from about 5 to about 50$ of the total oxidizer. For optimum power, the proportions are from 80. to 90$ ammonium oxidizer, and from 10 to 20$ other oxidizer or oxidizers. The proportions of oxidizers selected within these ranges will depend upon the sensitivity and explosive effect desired, and these, in turn, are dependent The inorganic oxidizer can be f ne, coarse, or a blend, of fine and coarse materials. Mill and prill inorganic oxidizers are quite satisfactory. For best results, the inorganic oxidizers should be fine-grained.

The relative proportions of oxidizer and explosive sensitizers will depend upon the sensitivity and explosive power desired, and these, in turn, are dependent upon the particula oxidizer and explosive sensitizers. For op imum effect, the oxidizer is used in an amount within the range from about to about 80%, and the explosive sensitizer in an amount within the range from about 5 "'to' about .40 by . . weight of the explosive composition. From about 10 to about 0$. explosive sensitizer, and from about 50 to about 80% inorganic oxidizer give the best results. The proportions of oxidizers selected within these ranges will depend upo the sensitivity and explosive effect desired, and these in turn are dependent upon the particular oxidizer used. \ In addition to these materials , the explosive compositions of the invention can include a fuel, which. can . be either a metal fuel or a carbonaceous fuel, in an amount of from about 0.5 to about J0 .

Satisfactory metal fuels include aluminum, which can be in the form of powder flak , a very finely-divided form known ;as atomized aluminum or granulated particles; ferrosilicon and ferrophosphorus . The metal fuel will usually comprise from, about 0. to about 25$ of the composition.

A carbonaceous fuel can also be included, either as the only fuel or in; combination with a metal fuel. Satisfactory, dust, charcoal, bagasse, dextrine, starch, wood meal, wheat- flour, bran pecan meal, and similar nut. shell meals. The carbonaceous fuel will usually be used in an amount within the range from 0.5 to about 30 .

Mixtures of metal and. carbonaceous fuels can also be used, if desired.

Stabilizers can be included in an amount within the range from about O.J to about 2 of the composition. Zinc oxide, ethyl centralite, diphenylamine, carbazole, calcium carbonate, aluminum oxide and sodium carbonate are useful stabilizers.

The explosive compositions are readily prepared by simple mixing or blending of the ingredients. The trimethylol •ethane trinitrate and nitrated polyol if not in the form of the conitrate are easily blended, and form a homogeneous liquid composition, since they are completely miscible one with the other in all proportions. These liquids are usually absorbed by or adsorbed on the solid ingredients which form the remainder of the explosive composition. In most cases, the solid materials including the inorganic oxidizer and explosive sensitizers, fuels and antacid, if any, would be mixed first, to form a homogeneous solid blend, and the the nitrated polyol - trimethylolethane trinitrate. mixture and any other liquid ingredients, such as oil and fuel, if used, would then be added, with stirring until a homogeneous mixture is . formed. · ■ The nitrated polyol - trimethylolethane trinitrate combinations of the invention when absorbed or adsorbed on a as Che sensitizing explosive in detonating fuse. For this purpose, the combination would be used as the core within the tube of protective material, such as a waterproofed textile.

The following Examples in the opinion of the inventors represent preferred embodiments of this invention.

Examples 1 to 5 A group of conitrates was prepared from glycerol and trimethylolethane in which the proportions of the conitrates ranged from 95 parts by weight of nitroglycerine and 5 parts by weight of· trimethylolethane trinitrate to 5 parts by weight of nitroglycerine and 95 parts by weight of trimethylolethane trinitrate. The nitrating procedure for the 95:5 product was as follows: Into a 20 gallon reactor fitted with a cooling jacket for temperature control and stirrer were placed 5 gallons of nitric acid and sulfuric acid containing Oo nitric acid and β0% sulfuric acid. To this mixture was added slowly, in small increments, .5 pounds of glycerol;-. During the addition, the temperature was kept at 58°F. After all of. the glycerol . had been added, 0.5 pound of trimethylolethane was added, while maintaining the temperatur of the . reaction mixture at ½0°Ρ. The reaction was then allowed to continue at this temperature, with stirring throughout,, until reaction was complete, as evidenced by a cessation in the evolution of heat. The total reactio time was five hours. · · At the conclusion of ..the reaction, the contents of the reactor was - dumped into 100 gallons of cold water, and the co- The c.onitrate was then washed with aqueous, ammonia, and then with several cold water washings. The final product had a pH of 7 .5 , and contained 95$ nitroglycerine and $ trimethylol- ethane trinitrate.

This reaction procedure was repeated, using different . proportions of glycerol and trimethylolethane, to give conitrates having weight' ratios of nitroglycerine/trimethylol- ethane trinitrate ranging from 95 : 5 to 5 : 95.

The resulting conitrates were tested for impact sensitivity by dropping a.2 kilogram weight on 0.1 gram samples of the material, starting at a height of 100 cm., and decreasing the height in 5 cm. increments until no detonation occurred. The maximum height at which no detonation occurred was then noted. The following results were obtained.

'. TASLE I Ratio of Nitroglycerine Example to Trimethylolethane No . Trinitrate Impact Sensitivity ' '■· ■ 2 kg. wt. · ontrol Nitroglycerine . ^ 15 cm. - 1 ·· . ■■ . 95 : 5 ; "' · 20 2 75 : 25 ' . 20 ' 3 50 : 50 " ■ . · 25 : 75 0 '.. - 5 : 95 · 70 In this test, the. conitrates are shown to have a considerably. reduced impact sensitivity, as compared to the jo by Weight Ingredients Example 11 :■-.· .- Control : 75 Conitrate of Example 4- 18.00 Nitroglycerine 18 .00 Ammonium nitrate, mill, grained 53 .70 53 .70.

Sodium nitrate 23.00 23.00 Zinc oxide . 0.30 0.30 Wheat flour 5.00 5.00 100.00^ 100.00^ Cartridges 1- 1/4 inch in diameter by 8 inches long were filled with the above compositions. These cartridges were subjected to "D" sensitivity' test , and the impact sensitivity in the 2 kg. weight test and the ballistic pendulum values were also determined.

TABLEJ.II Test Example 11 Cont ol >iDn sensitivity 1-1/4" x 8" #1 cap . #1 cap- Ballistic Pendulum value 9.7 9.5 ' Impact Sensitivity 4 cm. 35 cm. 2 kg. weight These results confirm the lower sensitivity to impact of the conitrate ove the control. The ballistic pendulum value and the "D" sensitivity show that the conitrate has. virtually relatively unimpaired detonator sensitivity and explosive power, as compared to nitroglyce ine.

Example 2 A dry stick dynamite powder was prepared, exactly as in Example 11, using a 5^95 blend of tr imethylolethane trinitrate and nitroglycerine. Cartridges 1-1/4 inch in diameter by 8 , inches long were filled with this composition, and the cartridges were subjected to the "D" sensitivity test, and the impact sensitivity and ballistic pendulum values were determined, ·.··;■*; as in Example 11. The results are given in Table IV.

• ■ . - TABLE IV . ·■ . ·.-"·.. .10 ■ Test Exam le 12. Control "D" sensitivity #1 cap #1 cap : . ■ L-iA" x 8" Ballistic Pendulum Value 9.6 9.5 Impact Sensitivity . 80 cm. 3 cm. .' ·· 2 kg. weight . . These results confirm the lower impact sensitivity of the conitrate over the control. The ballistic pendulum value ; ' and the "P" sensitivity show that the conitrate has virtuall relatively unimpaired detonator sensitivity and explosive · power, as compared to nitroglyce ine.

A dry stick powder was prepared, using the 25=75 . conitrate of Example 9, formed by mixing the conitrate with, the premixed solid ingredients noted in the Table below. by Weight Ing edients Example 13 Cont ol ' 25 : 75 Conitrate of Example 9 18 .00 - Ethylene glycol dinitrate - 18 .00 Ammonium nitrate, mil grained 53.70 53.70 Sodium nitrate 23 .00 . 23 .00 • Zinc oxide O.3O 0.30 Aluminum, (atomized, -90 mesh, 5.00 5 .00 ' . +120 mesh) 100.00% 100.00^ Cartridges 1- 1/4 inch in diameter by 8 inches long were filled with the above compositions. These cartridges were subjected to the "D" sensitivity test, and the impact sensitivity in the 2 kg. weight test, and the ballisti " endulum values were determined TABLE V.

Test , ■ Example 13 Control "D" sensitivity #1 cap . #1 cap 1-1/4" x 8" Ballistic Pendulum Value . 9 .9 . 7 $ .6 Impact Sensitivity : 40 cm. 25 cm. 2 kg. weight . .'.·'·"··. w mpac sens v y of the conitrate over the control. The ballistic pendulu value and the "D" sensitivity show that the conitrate has virtually relatively unimpaired detonator sensitivity and explosive power, as compared to ethylene glycol dinitrate.

Example 1 A dry stick dynamite powder was prepared, exactly as in Example 13, using a 5:95 blend of trimethylolethane tri¬ nitrate and ethylene glycol dinitrate. Cartridges 1-1/4 inches in diameter by 8 inches long were. filled with this composition and the cartridges were subjected to the "D" sensitivity test and the impact sensitivity in est and the ballistic pendulum values were Example The results are given in Table VI.

: TABLE VI Test Example 1 : Control ..

"D" sensitivity 1-1/4" x 8" #1 cap \ #1 cap '.

Ballistic Pendulum Value 9.7 9.6 '...'· Impact sensitivit 2 kg. weight 35 cm 25 cm These results confirm the lower impac . sensitivit of the conitrate over the control. The ballistic pendulum . value and the "D" sensitivity show that the conitrate has : virtually relatively unimpaired detonator sensitivity and explosive power, as compared to ethylene glycol dinitrate.

Claims (19)

Having regard to the foregoing disclosure, the. following is claimed as the inventive and patentable embodi-. ments thereof :

1. An explosive sensitizer composition consisting essentially of an amount within the range from about 95 to about 5 of an impact-sensitive liquid nitrated polyol derived from an aliphatic polyol having from two to about six alcoholic hydroxyl groups and from two to about ten carbon atoms and a amount within the range from about 5 to about 95 of tri- ''..;'··. methylolethane trinitrate, sufficient to lessen the shock sensitivity of the nitrated polyol without significantly reducing, the detonator sensitivity.

2. An explosive sensitizer composition in acqord-ance with claim 1, wherein nitrated polyol and t imethylol-ethane trinitrate are supported on an absorbent inert carrier. j5.

3. An explosive composition in accordance with ; claim 1 comprising in addition an inorganic oxidizer.

4.. An explosive composition in accordance with . .claim 1 comprising in addition a fuel.

5. An explosive sensitizer composition in accordance with claim 1 wherein the nitrated polyol is nitroglycerine,

6. An explosive sensitizer composition in accordance with claim 1, wherein the nitrated polyol is ethylene glycol dinitrate.

7. , An explosive sensitizer composition in accordance with claim, l.compr ising at least two nitrated polyols .

8. An explosive sensitizer, composition in accordance with claim 7 wherein the two nitrated polyols are ethylene glycol dinitrate and nitroglyce ine. ; Q

9. A explosive sensitizer composition in accord-; ance with claim 1 in which the nitrated polyol and the tr i-methylolethane trinitrate are in the form of a conitrated , ! mixture .

10. An explosive composition comprising an explosive sensitizer consisting essentially of from about 95$ to ' about 5$ of a shock-sensitive liquid nitrated polyol derived from an aliphatic polyol having from two to about six alcoholic hydroxyl groups and from two to about te carbon atoms and from about 5$ to about 9 $ of trimethylole thane: trinitrate, sufficient to lessen the shock sensitivity of the nitrated polyol without significantly reducing the detonator sensitivit the sensitizers together comprising from about 5 to about $ by weight of the composition, an inorganic oxidizer in an amount withi the range from about 5 to about 80$, and a fuel in an amount within the range from about 0.5 to about 50$.

11. An explosive composition in accordance with claim 10 comprising an inert particulate absorbent for the explosive sensitizers.

12. An explosive composition in accordance with claim 10 wherein the fuel is a carbonaceous fuel.

13. A explosive composition in accordance with claim 10 wherein the shock sensitive nitrated polyol is ethylene glycol dinitrate. * ·

14. An explosive composition in accordance with claim 10 wherein the fuel is aluminum. .

15. An explosive composition in accordance with claim 10 wherei the shock sensitive nitrated polyol is nit oglycerine.

16. An explosive composition in accordance with claim 10 wherei the inorganic oxidizer comprises ammonium nitrate.

17. A explosive composition in accordance with claim 10 wherei the, inorganic oxidizer comprises a mixture of ammonium nitrate and a metal nitrate.

18. A process for preparing an explosive composition comprising an explosive sensitizer consisting essentially of an impact-sensitive liquid nitrated polypi and tiimethylol-! ethane trinitrate in an amount sufficient to lessen the impac sensitivity of the nitrated polyol without significantly reducing detonato sensitivity, which comprises conitrating a mixture of a polyol having from two to about six alcoholic hydroxyl groups and from two to about ten carbon atoms and ; t rimethylolethane with concentrated aqueous nitric acid solution, and thereby forming a mixture of the liquid nitrated polyol and trimethylole hane trinitrate. '

19. '. A process in accordance with claim l8, in which the polyol is selected from the group consisting of .1 : glycerol' and ethylene glycol.