US3423256A

US3423256A - Explosives containing an impact-sensitive liquid nitrated polyol and trimethylolethane trinitrate and process of conitrating mixtures of polyols and trimethylol ethane

Info

Publication number: US3423256A
Application number: US696106A
Authority: US
Inventors: George L Griffith
Original assignee: Commercial Solvents Corp
Current assignee: BARCLAYS/AMERICAN/BUSINESS CREDIT Inc A CORP OF CT; Commercial Solvents Corp
Priority date: 1968-01-08
Filing date: 1968-01-08
Publication date: 1969-01-21
Anticipated expiration: 1986-01-21
Also published as: IL31366A0; DE1900785B2; DE1900785A1; DE1900785C3; GB1259634A; FR2000065A6

Description

United States Patent 24 Claims ABSTRACT OF THE DISCLOSURE An explosive sensitizer composition is provided including at least one impact-sensitive liquid nitrated polyol and trimethylolethane trinitrate. The trimethylolethane trinitrate decreases the impact-sensitivity of the composition as compared to the liquid nitrated polyol alone but does not decrease the detonator sensitivity. Examples of the preferred liquid nitrated polyols are nitroglycerine and ethylene glycol dinitrate.

There is also provided an explosive composition containing the above sensitizer composition, an inorganic oxidizer and a fuel.

There is further provided a process for preparing the above sensitizer by conitrating a mixture and preferably a solution of trimethylolethane and a polyol which forms an impact-sensitive nitrate ester, such as ethylene glycol and glycerol.

This application is a continuation-in-part of US. application Ser. No. 611,235 filed Jan. 24, 1967.

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 Powder 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 nitroglycerine, and Schonbein and Bottger 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 discoveries almost at once, and led to a proliferation of research and publications on the nitration of glycerine, starch and cellulose throughout the Western world. The nitration of cotton was effected by Schtinbein 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 other polyols, and from these experiments a series of polyol nitric acid esters were obtained, including pentaerythritol tetranitrate, 'dipentaerythritol hexanitrate, trimethylolethane trinitrate, the various nitro sugars, including nitroglycose, nitromannose, nitromal- 3,423,256 Patented Jan. 21, 1969 tose, nit-rosucrose, nitroarabinose and nitrolactose, nitromannite, trimethyleneglycol dinitrate, butyleneglycol dinitrate, propyleneglycol dinitrate and erythritol tetranitrate.

Nitroglycerine is probably the best known of the liquid nitroesters. It crystallizes in two forms, a stable form melting or freezing at 13.2-13.5 C., and a labile form melting at l.92.2 C. It is very sensitive to impact. A blow 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 wells.

Many other nitrated polyols have a similarly high sensitivity to impact, and no marked advantages from the standpoint of safety. Dinitroglycerine, for example, is hardly distinguishable from trinitroglycerine in this respect. Nitroglycide is even more sensitive than trinitroglycerine or dinitroglycerine, 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 nitroglycerine 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.

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 by combining an impactsensitive liquid nitrated polyol with trimethylolethane trinitrate. The trimethylolethane 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 polyols 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 starting materials, and preferably a solution of the trimethylolethane in a liquid polyol. Thus, the combinations of the invention can be prepared by conitration of (1) the polyol or polyols which are the starting material for the liquid nitrated polyol component, and (2) trimethylolethane, 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 trimethylolethane trinitrate.

The relative proportion of trimethylolethane trinitrate required is determined by the amount required to reduce sensitivity to impact, -while not 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 trimethylolethane trinitrate lies within the range from about 5 to about 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 conitrated polyol-trimethylolethane 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 an impact-sensitive liquid nitrate ester. The preferred polyols are glycerol and ethylene glycol, alone or in combination.

If the conitration reaction mixture comprises a solution of the trimethylolethane in a liquid polyol, the reaction can be carried out in the liquid phase in conventional equipment adapted to handle liquids, in the usual liquid nitration procedures. Trimethylolethane is soluble in liquid polyols such as ethylene glycol (up to 25% by weight of the solution at 25 C.) and glycerol (up to 20% by weight of the solution at 25 C.). The trimethylolethane is dissolved in the polyol, in this procedure, and the solution is conitrated in the usual way, as described below. :If the proportion of trimethylolethane trinitrate in the conitrated liquid polyol polynitrates of the invention exceeds the solubility of trimethylolethane in the polyol, then of course this procedure cannot be used.

The polyol and the trimethylolethane 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 concem tration, 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 trimethylolethane or solution thereof may or may not be soluble in the reaction mixture. If they are soluble, or are all liquids, the reaction mixture can be processed in liquid nitration equipment. If solids can be tolerated in the equipment used, i.e., if the equipment can handle slurries, whether any of the components is insoluble in the reaction mixture is unimportant. If the starting materials are soluble, the presence of the conitrate in a separate phase aids in driving the reaction to completion.

Satisfactory proportions of nitric acid in a mixture of nitric and sulfuric acids are withinthe 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 water. Preferred proportions of nitric acid are within the range from 33 to 43% and of sulfuric acid from 57 to 67% by weight.

The polyols can be mixed and then blended with the nitrating agent. This is the procedure used when a solution of trimethylolethane in the polyol is employed. However, if the trimethylolethane is used in an amount in excess of that soluble in the polyol, or if a solution of trimethylolethane in polyol is not used, it is usually preferable to add the polyol slowly to the nitrating agent, and then add the trimethylolethane.

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 nitric acid employed is normally that stoichiometrically required to nitrate the free hydroxyl groups of the polyols. A small excess, ranging from about J 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 45 -F., and consequently, 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 product can be washed with an aqueous alkali solution, so as to bring the pH to with-in the range from about 6 to about 8. 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 amrnonium 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 sufiicient 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 fullers earth.

Such compositions containing upwards of 15% of the mixture of nitrated polyl 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 trimethyloletllraine trinitrate together is less than 15% are granular so 1 s.

Compositions which are formulated as dry or dryappearing 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 trimethylolethane trinitrate blended or cointrated 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 50% of the total explosive sensitizer. Exemplary additional sensitizers include pentaerythritol tetranitrate, trinitrotoluene, pentryl, dipentaerythritol hexanitrate, mannitol hexanitrate, sorbitol hexanitrate, sucrose octanitrate, Pentolite (an equal parts by weight mixture of pentae-rythritol tetranitrate and trinitrotoluene), nitrostarch, Cyclonite (RDX, cyclotrimethylene trinitramine), Composition B (a mixture of up to 60% RDS, up to 40% TNT and 1 to 4% wax), Cyclotol (Composition B without the wax), dinitrotoluene, and tetryl.

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

Ammonium 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 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 upon the particular oxidizer used.

The inorganic oxidizer can be fine, 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 particular oxidizer and explosive sensitizers. For optimum effect, the oxidizer is used in an amount within the range from about 5 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 40% 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 upon the sensitivity and explosive effect desired, and these in turn are dependent upon the particular oxidize-r 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 30%.

Satisfactory metal fuels include aluminum, which can be in the form of powder, flake, a very finely-divided form known as atomized aluminum or granulated particles; ferrosilicon and ferrophosphorus. The metal fuel will usually comprise from about 0.5 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 carbonaceous fuels include powdered coal, petroleum oil, coke 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 0.3 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 trimethylolethane 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 liquidsare 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 then 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 solid material, which may or may not be inert, are also useful as the 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 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 a stirrer were placed 3 gallons of nitric acid and sulfuric acid containing 40% nitric acid and 60% sulfuric acid. To this mixture was added slowly, in small increments, 5 pounds of glycerol. During the addition, the temperature was kept at 38 F. After all of the glycerol had been added, 0.5 pound of trimethylolethane was added, while maintaining the temperature of the reaction mixture at 40 F. 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 reaction time was five hours.

At the conclusion of the reaction, the contents of the reactor was dumped into gallons of cold water, and the conitrate product which separated was removed by decantation. The conitrate 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 5% trimethylolethane trinitrate.

This reaction procedure was repeated, using diiferent proportions of glycerol and trimethylolethane, to give conitrates having weight ratios of nitroglycerine/trimethylolethane trinintrates 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.

*Nitroglyoerine.

In this test, the conitrates are shown to have a considerably reduced impact sensitivity, as compared to the nitroglycerine control.

Examples 6 to Examples 1 to 5 were repeated, substituting ethylene glycol for the glycerol. The conitrates were then subjected to impact sensitivity tests, exactly as in the previous examples, with the following results.

TABLE II Ratio of Impact Example Nitroglycol to Sensitivity No. Trimethylolethane (2 kg. wt.),

Trinitrate cm.

Control. 35 6 95: 5 45 75:25 45 50:50 50 25:75 55 *Ethylene glycol dinitrate.

The results show the considerably reduced impact sensitivity of the conitrates, as compared to ethylene glycol dinitrate.

Example 11 A dry stick dynamite powder was prepared, using the 25:75 conitrate of Example 4, formed by mixing the conitrate with the premixed solid ingredients noted in the table below. For comparison purposes, a control composition also was prepared using nitroglycerine.

Percent by Weight Cartridges 1% 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.

virtually relatively unimpaired detonator sensitivity and explosive power, as compared to nitroglycerine.

Example 13 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.

Percent by weight Ingredients Example 13 Control 25:75 conitrate of Exam le 9 Ethylene glycol dinitrate.

Ammonium nitrate, mill gra' Sodium nitrate Zinc oxide 0. 30 0.30 Aluminum (atomized, -90 mesh, +120 mesh). 5. 00 5.00

Cartridges 1% 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 ballistic pendulum values were determined.

TABLE V Test D sensitivity, 1% x 8. Ballistic pendulum value Impact sensitivity, 2 kg. weight Example 13 Control These results confirm the lower impact sensitivity 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.

Example 14 TABLE In 40 Table VI.

Test Example 11 Control TABLE VI D sensitivity, 1% x 8 Test Example 14 Control Ballistic pendulum value Impact sensitivity, 2 kg. weight cm 35 cm. D sensitivity 1% x 8 #1 cap #1 cap.

Ballistic pendulum value 9 7 9 6 Impact sensitivity, 2 kg. weight 3 These results confirm the lower sensitivity to impact of the conitrate over the control. The ballistic pendulum value of the D sensitivity show that the conitrate has virtually relatively unimpaired detonator sensitivity and explosive power, as compared to nitroglycerine.

Example 12 TABLE IV Test Example 12 Control "D sensitivity, 1% x 8 #1 cap #1 cap. Ballistic pendulum value .6. 9.5. Impact sensitivity, 2 kg. weight 80 cm 35 cm.

These results confirm the lower impact sensitivity of the conitrate over the control. The ballistic pendulum value and the D sensitivity show that the conitrate has These results confirm the lower impact sensitivity 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.

Example 15 A conitrate was prepared from glycerol and trimethylolethane containing 83 parts by weight of nitroglycerine and 17 parts by weight of trimethylolethane trinitrate. The nitrating procedure was as follows:

Into a 500 gallon reactor fitted with a cooling jacket for temperature control and a stirrer were placed 60 gallons of nitric acid and sulfuric acid containing 40% nitric acid and 60% sulfuric acid. To this mixture was added slowly, in small increments, a solution of 17 pounds of trimethylolethane in 83 pounds of glycerol. During the addition, the temperature of the solution and of the reaction mixture was kept at 40 F, The reaction was then allowed to continue at 40 F., with stirring throughout, until reaction was complete, as evidenced by a cessation in the evolution of heat. The total reaction time was five hours.

At the conclusion of the reaction, the contents of the reactor was dumped into 2000 gallons of cold water, and the conitrate product which separated was removed by decantation.

The conitrate was then washed with aqueous ammonia, and then with several cold water washings. The final product had a pH of 7.5, and contained 82.3% nitroglycerine and 17.7% trimethylolethane trinitrate.

This reaction procedure was repeated, using a lesser proportion of glycerol and trimethylolethane, to give cnitrates having weight ratios of nitroglycerine/trimethylolethane trinitrate ranging from 95:5 to 85:15.

Example 16 Example 15 was repeated, substituting ethylene glycol for the glycerol. The conitrates prepared had ratios of ethylene glycol dinitrateztrimethylol ethane trinitrate from 95:5 to 77:23.

Having regard to the foregoing disclosure, the following is claimed as the inventive and patentable embodiments thereof:

1. An explosive sensitizer composition consisting essentially of an amount within the range from about 95% to about 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 an amount within the range from about 5 to about 95% of trimethylolethane trinitrate, sufiicient to lessen the shock sensitivity of the nitrated polyol without significantly reducing the detonator sensitivity.

2. An explosive setnsitizer composition in accordance with claim 1, wherein nitrated polyol and trimethylolethane trinitrate are supported on a solid absorbent inert carrier.

3. An explosive composition in accordance with claim 1 including in addition an inorganic oxidizer salt.

4. An explosive composition in accordance with claim 1 including in addition a metal or carbonaceous 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 1 including at least two of said nitrated poly- 01s.

8. An explosive sensitizer composition in accordance with claim 7 wherein the two nitrated polyols are ethylene glycol dinitrate and nitroglycerine.

9. An explosive sensitizer composition in accordance with claim 1 in which the nitrated polyol and the trimethylolethane 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 ten carbon atoms and from about 5% to about 95% of trimethylolethane trinitrate, sufiicient to lessen the shock sensitivity of the nitrated polyol without significantly reducing the detonator sensitivity, the sensitizers together comprising from about 5 to about 45% by weight of the composition, an inorganic oxidizer salt in an amount within the range from about 5 to about 80%, and a metal or carbonaceous fuel in an amount within the range from about 0.5 to about 30%.

11. An explosive composition in accordance with claim 10 including 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. An 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 wherein the shock sensitive nitrated polyol is nitroglycerine.

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

17. An explosive composition in accordance with claim 10 wherein the inorganic oxidizer salt comprises a mixture of ammonium nitrate and an alkali or alkaline earth metal nitrate.

18. A process for preparing an explosive composition comprising an explosive sensitizer consisting essentially of an impact-sensitive liquid nitrated polyol and trimethylolethane trinitrate in an amount suflicient to lessen the impact sensitivity of the nitrated polyol without significantly reducing dctonator 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 trimethylolethane with concentrated aqueous nitric acid solution, and thereby forming a mixture of the liquid nitrated polyol and trimethylolethane trinitrate.

19. A process in accordance with claim 18, in which the polyol is selected from the group consisting of glycerol and ethylene glycol.

20. A process in acordance with claim 18 which comprises conitrating the polyol and trimethylolethane with aqueous nitric acid containing sulfuric acid in an amount sufficient to insolubilize the nitrated polyol and the trimethylolethane trinitrate in the reaction mixture.

21. A process in accordance with claim 21 which comprises absorbing the reaction product on a particulate absorbent for the explosive sensitizers.

22. A process in accordance with claim 18 in which the trimethylolethane is nitrated while in solution in the polyol.

23. A process in accordance with claim 22 in which the polyol is glycerol.

24. A process in accordance with claim 22 in which the polyol is ethylene glycol.

References Cited UNITED STATES PATENTS 2,709,130 5/ 1955 Rinkenbach 149-88 3,140,210 7/1964 Sampson 149-88 3,306,790 2/1967 Crescenzo et al. 14988 X 3,344,005 9/1967 Bronstein et al. 14988 X CARL D. QUARFORTH, Primary Examiner.

S. I. LECHERT, Assistant Examiner.

U.S. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,423, 256 January 21, 1969 George L. Griffith It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

"polyl should read polyol line 56, "cointrated Column 9, line 31, "setnsitizer should read line 41, the claim reference numeral "21" Column 4, line 43, should read coni trated sensitizer Column 10,

should read 18 Signed and sealed this 31st day of March 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr. Attesting Officer Commissioner of Patents