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Home , Explosive, Nitrate, Nitrocellulose, Nitroglycerin

3,208,890 United States Patent Office Patented Sept. 28, 1965 2 3,208,890 From the table, it is thus evident that the two propyl GELATNIZED ene glycol dinitrates, and especially the 1,2-compound, Carl Torsten Edlund and Gustav Allan Wetterholm, Gyttorp, Sweden, assignors to Aktiebola are decidedly less soluble in than nitroglycol, where get, a company of Sweden by they are absorbed by the blood to a less degree. No Drawing. Filed Feb. 27, 1963, Ser. No. 261,521 Claims priority, application Sweden, Feb. 28, 1962, THE PRESENT INVENTION 2,232/62 The present invention relates to an explosive having an 5 Claims. (Cl. 149-47) improved physiological acceptance and a low sensitivity to impact, consisting of or containing propylene-glycol di The present invention generally relates to a novel ex 0. , and one or more inorganic -delivering plosive of the gelatinized type having improved physio salts. One important characterizing feature of the ex logical acceptance and a low sensitivity to impact. More plosive according to the invention is that the oxygen-de specifically the present invention pertains to an explosive livering inorganic or salts are present in a sufficient comprising an oxygen-delivering inorganic salt and an ex amount to substantially oxygen-balance the explosive. plosive oil consisting of propylene-glycol dinitrate or a 15 Because the according to the invention mixture of propylene-glycol dinitrate with no more than possess a combination of high insensitivity to impact with 50 percent of nitroglycerine. an excellent physiological acceptance, they represent a BACKGROUND valuable advance in the field of explosives. A further feature of the invention is that the explosive 1,2-propylene-glycol dinitrate and 1,3-propylene-glycol 20 contains 3-70% propylene-glycol dinitrate and 10-95% dinitrate (hereinafter simply referred to as "propylene oxygen-delivering inorganic salt. glycol dinitrate” unless one or the other of these individual The propylene-glycol dinitrate can either be the only compounds is especially intended) are known substances ingredient of the explosive oil, or it can be admixed having properties which render them suitable as explosives. with other liquid ingredients. If the explosive oil is a Both compounds have been suggested as ingredients in ex mixture of different substances, it may contain up to about plosive along with oxygen-delivering inorganic salts. 50 percent of nitroglycerine. It is natural that the ex Such explosives are as a rule highly insensitive to impact. plosive must not contain any substantial amounts of nitro Due to being considerably under-balanced with respect to glycol, because otherwise the two abovementioned essen oxygen, they have not, however, obtained any practicalim tial advantages of the explosive would be lost. If nitro portance up to the present. 30 glycol is present in the explosive oil serving as the basic It is known that propylene-glycol dinitrate-containing ingredient of an explosive, the content thereof should highly underbalanced explosives are highly insensitive to preferably not exceed about 2 percent. impact. It is also known that highly overbalanced as well as underbalanced explosives are generally insensitive GELATINIZING OF THE EXPLOSIVE OL to impact, but that the sensitivity to impact will increase on oxygen-balancing, so that mixtures of considerable sensi An explosive oil, consisting of propylene-glycol dini tivity will be obtained. It has now surprisingly been trate or at least mainly of this substance, does not form found that propylene-glycol dinitrate-containing explosives a gel with at usual . In can be produced which maintain their high insensitivity order to attain gelatinizing, increased temperatures to impact even after oxygen-balancing. 40 will be required. In this connection, it has been proved In comparison with explosives containing nitroglycol that, especially if subjected to alternating freezing and (the dinitrate of glycol) as an additive to nitro thawing, gels produced at high temperatures will gradu glycerine, our novel oxygen-balanced explosives present ally release their oil. It may be noted that amounts considerable advantages. The use of nitroglycol is, as as high as 14 percent of nitrocellulose have been sug known, connected with physiological drawbacks. When 45 gested to obtain an acceptable gel. According to a admixed with nitroglycerine, the nitroglycol will increase further embodiment of the invention, this amount can the vasodilatory effect on the blood veins of man which be decreased considerably if there is added to the ex is particularly manifested as headache and indisposition. plosive oil an agent capable of facilitating the gelatinizing Another reason why mixtures of nitroglycol with nitro (i.e., a gelatinizing aid) in an amount of 0.2-10 percent, glycerine are physiologically disadvantageous is ascribed 50 preferably 0.5-7 percent, based on the total weight of to the poisonous effect of the nitroglycol itself. In this the explosive oil. There is thus obtained the important connection, reference is made to the cases of Sudden col effect that the explosive oil will gelatinize at normal lapses which will frequently happen among workers of temperatures and, furthermore, the amount of gelatiniz explosive factories who come into contact with this Sub 55 ing agent (nitrocellulose) which is an expensive product, stance, usually a couple of days after leaving work. Pro can be decreased without any essential drawbacks re pylene-glycol dinitrate-containing explosives are decided Sulting. A fully acceptable gelatinizing of propylene ly more acceptable from a physiological viewpoint and do glycol dinitrate can be attained by less than 8 percent not possess the disadvantages above referred to. of nitrocellulose in the explosive oil. Usually, only 3-5 The better physiological acceptability of propylene percent is required to attain this result. glycol dinitrate may be explained by the fact that the sub 60 As gelatinizing aids may generally be mentioned hy stance has relatively little in the blood of man. drogen bond-forming substances. Such aids will be ef The solubility of the propylene-glycol dinitrates in water, fective in proportion to their ability to form such bonds. as compared with nitroglycerine and nitroglycol (the di As examples of such substances there may be mentioned: nitrate of ), is evident from the following .-Aliphatic monohydric primary, secondary table. The values set forth relate to the solubility at 65 and tertiary alcohols, containing from 1 to 10 carbon 20° C. , for example , , isopropylalcohol, Percent n-propylalcohol, the butyl alcohols, the amyl alcohols, Nitroglycerine ------0.18 n-decanol and nonyl carbinol, aliphatic polyhydric al Nitroglycol ------0.63 cohols such as ethylene-glycol, diethylene-glycol, the 1,3-propylene-glycol dinitrate ------0.24 70 propylene-glycols and ; 1,2-propylene-glycol dinitrate ------0.13 .-Aliphatic ketones such as , methyl 3,208,890 3. 4. ethyl-, methylisobutyl-ketone and up to the deca those skilled in the art without changing the essential nones as well as the bicyclic ketone ; characteristics and the basic concept of the invention. .-Esters of aliphatic alcohols with formic acid, Example I , and propionic acid, for example ethyl acetate and butyl acetate, polyhydric alcohols partially esterified A explosive was made up by mixing together With acetic acid or such as the partial esters the following ingredients: of ethylene-glycol, diethylene-glycol, the propylene 9. glycols and glycerol with acetic aaid and nitric acid, such 1,2-propylene-glycol dinitrate ------37.0 as mononitroglycerine, mononitroglycol and dinitro Nitrocellulose ------1.3 glycerine; O Methanol ------0.4 -With lower alkyls monosubstituted ethylene nitrate ------41.5 glycol and diethylene-glycol in which the lower alkyls nitrate ------18.75 may be methyl, ethyl, propyl and butyl, such as glycol Wood flour ------1.0 monomethylether and glycol-monoethylether. Chalk ------0.05 Other gelatinizing aids are mono- and di-nitrosubsti The oxygen-balance of the explosive was -4.0%. tuted derivatives of and toluene. If an ex The properties of the explosive were as following: plosive oil, containing propylene-glycol dinitrate, is free from nitroglycerine, the latter substance may be added as Volume weight ------1.53 a gelatinizing aid up to amounts of 8 percent, for ex Gap test (24 mm. ), mm. at 20° C. -- 120-130 20 Impact sensitivity test according to Kast, 2 kg. ample. fall weight, percent per cm. fall THE OXYGEN-DELIVERING INORGANIC SALT height ------0/60 As examples of suitable oxygen-delivering inorganic The mixture was prepared by first mixing together salt may especially be mentioned and/or per the propylene-glycol dinitrate and the nitrocellulose, of ammonium, alkali-metals and alkaline whereupon the methanol was added to the mixture ob earth metals, such as , nitrate, tained. Gelatinizing took place satisfactorily without and , ammonium per heating the mixture. Then the salt mixture was added and potassium . Other examples and finally the wood flour together with the chalk. are alkali metal and alkaline-earth metal chlorates, such as sodium chlorate and . 30 Example 2 As mentioned above, the addition of oxygen-delivering A was made up by mixing together salt should preferably be so adjusted that the explosive the following ingredients: will be about oxygen-balanced. In the following table, 9. there are set forth oxygen-balanced mixtures of different 1,2-propylene-glycol dinitrate ------37.0 oxygen-delivering salts and propylene-glycol dinitrate Nitrocellulose ------1.4 (PGDN). Ethyl diglycol ------0.4 TABLE ------41.3 Sodium nitrate ------18.85 Oxygen-balanced mixture 40 Cork flour ------1.0 Oxygen-delivering-salt Chalk ------0.05 Percent salt Percent The oxygen-balance of the explosive was -- 4.0%. The properties of the explosive were the following: Ammonium nitrate NH4NO3------Sodium nitrate NaNO3------Volume weight ------1.45 KNO3-- Gap test (25 mm. cartridge), mm. at 20° C. --- 140-180 Calcium nitrate Ca(NO3)2- Impact sensitivity test according to Kast, 2 kg. Barium nitrate BA(NO3)2- Potassium chlorate KClO3. fall weight, percent detonation per cm. fall Sodium chlorate NaClO3----- KClO4------weight ------0/06 NH ClO4------:66 50 Example 3 A plastic explosive was made up by mixing together the following ingredients: OTHER INGREDIENTS 9. The explosive according to the invention may contain 1,2-propylene-glycol dinitrate ------37.5 high brisant explosives such as trotyl, penty, hexogen Nitrocellulose ------1.3 etc. Furthermore, it may contain usual oxygen-con Methanol ------0.4 suming substances such as saw duct, flours of different Camphor ------0.4 kinds and metal powders, and usual fillers such as Ammonium nitrate ------41.1 kieselguhr. 60 Sodium nitrate ------18.75 TYPES OF EXPLOSIVE INVOLVED Wood flour ------O.S The gelatinized explosives according to the invention Chalk ------0.05 may be produced in different forms, namely, as powders The oxygen-balance of the explosive was -3.3%. or in plastic or semiplastic conditions. These explosives The properties of the explosive were the following: may also contain as an ingredient finely divided metals 65 Volume weight ------1.49 the content of which may be 8 percent or less. This Gap test (25 mm. cartridge), mm. at 20° C. -- 80-100 especially applies to powder explosives, but also the Impact sensitivity test according to Kast, 2 kg. plastic and semiplastic explosives may contain IoW fall weight, percent detonation per cm. fall amounts of finely divided metals. 70 weight ------0/60 EXAMPLES In the following table, there are listed further ex The following examples are illustrative of preferred amples for the composition of the explosive according to embodiments of the present invention. It should be the invention and an example of a composition, contain understood that these examples are not intended to limit ing ethylene-glycol dinitrate, given for purpose of com the invention and that obvious changes may be made by 75 parison. 3,208,890 6 TABLE set forth here are possible. For example, it would not involve invention to try closely related compounds in Powder Semiplastic explosive explosive view of the present broad disclosure or in trying amounts with nitro with nitro different than those disclosed. All such obvious modifi cellulose 5 cations would not avoid infringement under the well known "doctrine of equivalents.” What we claim is: 1,2-propylene-glycol dinitrate.------1. A plastic explosive consisting of the following in MethylethylketoneDinitrotoluene.------Trotyl------gredients in the following amounts: Nitrocellulose--- O G. Ammonium nitrate 1,2-propylene-glycol dinitrate ------37.0

Sulfur------Sodium nitrate.-- Nitrocellulose ------1.3 ------Methanol ------0.4 WoodKieselguhr fiour Ammonium nitrate ------41.5 Paraffin.-- Sodium nitrate ------18.75 Oxygen-balance, percent------Wood flour ------1.0 Properties: Chalk ------0.05 Volume weight------1.1 Detonation velocity, km.fs. --- 4.7 2. A plastic explosive consisting of the following in GF. st (25 mm. cartridge) mm. 20 gredients in the following amounts: Impact sensitivy test according to 0-10 G. Kast, by 2 kg. fall weight, percent 1,2-propylene-glycol dinitrate ------37.0 detonation per cm. fall height------060 Nitrocellulose ------1.4 Ethyl diglycol ------0.4 Plastic explosives 25 Ammonium nitrate ------41.3 Sodium nitrate ------18.85 With propylene-glycol With dinitrate ethylene Cork flour ------1.0 glycol Chalk ------0.05 dinitrate 3. An explosive composition having an improved physi 30 ological acceptance and a low sensitivity to impact com 1,2-propylene-glycol prising as its essential ingredients: dinitrate------(a) 10-95% by weight of an oxygen delivering inor 1,3-propylene-glycol ganic salt, Nitroglycerine------dinitrate------Ethylene-glycol 35 (b) 3-70% by weight of an explosive oil, said explo dinitrate------sive oil being selected from the group consisting of Dinitrotoluene Nitrocellulose the dinitrate of 1,2-propylene glycol, the dinitrate of Monoacetin 1,3-propylene glycol, and mixtures of one of these Ammonium nitrate.-- Sodium nitrate.------dinitrates with up to 50% by weight of nitroglycer Ammonium perchlorate. 40 1.ne, Wood flour------(c) 0.2-10% by weight of gelatinizing aid and a gela Chalk------tinizer for said explosive oil, Oxygen-balance, percent. (d) between 0 and 2% of nitroglycol, Properties: said oxygen-delivering inorganic salt being present in an Volume weight------1, 55 Detonatation welloc 45 amount to substantially the explosive. 3.2 4. An explosive composition according to claim 3 Gapity, test ES (25 - mm.------wherein said gelatinizer is nitrocellulose. cartridge) mm. at 5. An explosive composition according to claim 3 Impact--20 C------sensitivity 180-200 150-200 230 test according to wherein said oxygen-delivering inorganic salt is selected Kast, percent 50 from the group consisting of (a) nitrates of ammonium, detonation per cm. fall height.----- alkali metals and alkaline earth metals, (b) 0/60 0/60 0/60 0/60 10,30 of ammonium, alkali metals and alkaline earth metals and As is evident from the above examples, the novel ex (c) chlorates of alkali metals and alkaline earth metals. plosive according to the present invention has a very low sensitivity to impact. This is especially apparent 55 References Cited by the Examiner when comparing the fall heights of the explosives ac UNITED STATES PATENTS cording to the present invention (Examples 1 to 9) with 1,213,369 1/17 Hibbert ------149-104 what occurs to the nitroglycol-containing explosive ac 1,307,033 6/19 Barab ------149-104 cording to Example 10. While in the last mentioned 1,485,003 2/24 Woodbury ------149-47 X case, the percent of amounted to 10 percent 60 1,637,726 8/27 Bergeim ------149-47 X even for 300 mm. fall height, none of the nine compo 1,640,712 8/27 Moran ------149.95 sitions of explosives according to the present invention 1,879,064 9/32 Bryan ------149-104 gave any detonation even for a fall height as high as 2,481,795 9/49 Taylor et al. ------149-47 600 mm. 65 2,768,073 10/56 Davidson ------149-48 X Those skilled in the chemical arts, and particularly in the art to which this invention pertains, will readily ap CARLD. QUARFORTH, Primary Examiner. preciate that many modifications of the basic invention RUEBEN EPSTEIN, Examiner.