US3617409A - Nitrocellulose-nitroglycerine explosive with ethylene oxide - Google Patents

Nitrocellulose-nitroglycerine explosive with ethylene oxide Download PDF

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Publication number
US3617409A
US3617409A US850652A US3617409DA US3617409A US 3617409 A US3617409 A US 3617409A US 850652 A US850652 A US 850652A US 3617409D A US3617409D A US 3617409DA US 3617409 A US3617409 A US 3617409A
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parts
composition
long chain
inclusive
explosive
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Expired - Lifetime
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US850652A
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English (en)
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Gwyn Harries
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Orica Ltd
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ICI Australia Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
    • C06B31/56—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitrocellulose present as less than 10% by weight of the total composition

Definitions

  • This invention relates to new gelatin-type dynamite compositions and, more particularly, to compositions comprising a reduced amount of explosive nitric ester.
  • Dynamites produced for industrial uses must be manufactured to provide a variety of specific characteristics, such as plasticity, density and explosive strength.
  • Gelatin compositions are produced by gelatinizing a liquid explosive nitric ester with nitrocellulose of suitable characteristics and incorporating therein a number of solid materials.
  • the solids most frequently incorporated are oxidizing salts, combustible carbonaceous materials, stabilizers and thickeners.
  • Nitroglycerine and ethylene glycol dinitrate and mixtures thereof are the most commonly used liquid explosive nitric esters. Nitroglycerine may also be modified by additives such as nitrobenzene or nitrotoluene.
  • the completed blend is of a plastic consistency and is packaged in paper shells usually by an extrusion process.
  • a very important type of gelatin dynamites are the so-called ammonia gelatins where a portion of the liquid explosive nitric ester is replaced by ammonium nitrate.
  • Ammonium nitrate is a high-strength explosive compound and, within limits, can be substituted for nitroglycerine without substantially altering the explosive characteristics of the composition. Such replacement is economically desirable, since the liquid nitric ester is more expensive than the ammonium nitrate.
  • sodium nitrate may be used to prepare the so-called sodium nitrate gelatins.
  • Gelatin dynamites are prepared in two categories, the true gelatin, which is a relatively smooth soft solid and the semigelatin which is more crumbly.
  • the true gelatins usually contain more liquid nitric ester than the semigelatins.
  • true gelatins are preferred to semigelatins for use in the field.
  • hitherto there has been a definite limiting point in the amount of solids which may be introduced without loss of the plasticity essential to extrusion and field use. This point is frequently reached before the desired explosive characteristics can be obtained or before the desired degree of replacement of the liquid explosive by ammonium nitrate has been attained.
  • the alternative has been hitherto, to either use true gelatins with unnecessary high contents of nitric esters or to use semigelatins with somewhat lower nitric ester content, but less desirable flow properties, water proofness and storage properties.
  • the function of the added plasticity-promoting agent is to increase the plasticity of gelatinous explosives containing nitroglycerin or other liquid explosive nitric ester. This is particularly important in the case of gelatin dynamites containing relatively large amounts of solid inorganic nitrates for example, ammonium nitrate, sodium nitrate or both. In such explosives it is necessary to have sufficient nitroglycerin present to allow ready extrusion through an orifice into the paper shells to b e filled and to maintain plasticity for use in the field. The presence of the plasticity-promoting agents effects equivalent ease of extrusion with markedly lowered content of liquid explosive.
  • a gelatinized explosive composition comprising, (1) at least one liquid explosive nitric ester; (2) nitrocellulose; (3) at least one inorganic oxidizing agent; (4) at least one carbonaceous combustible material; (5) as a plasticity-promoting agent, at least one condensation product of from 2 to 12 inclusive moles, preferably from 2 to 5 inclusive moles, of ethylene oxide with a compound selected from the group consisting of alkyl phenols, long chain alcohols, long chain carboxylic acids, long chain amines, amides of long chain carboxylic acids and alkylolamides of long chain carboxylic acids; and (6) optionally water.
  • long chain we mean a chain having at least eight carbon atoms and preferably more than 12 carbon atoms.
  • Suitable plasticity-promoting agents are the compounds prepared by condensation of an ethylene-oxide-reactive compound selected from the group consisting of alkyl phenols, long chain alcohols, long chain carboxylic acids, long chain amines, amides of long chain carboxylic acids and alkylolamides of long chain carboxylic acids with ethylene oxide.
  • alkyl phenols there may be mentioned octyl phenol, dioctyl phenol, nonyl phenol, dinonyl phenol, dodecyl phenol, didodecyl phenol, tributyl phenol and similarly substituted cresols, for example diisobutyl cresol and derivatives thereof.
  • derivatives we mean alkyl phenols bearing substituents which do not effect the phenolic and alkylic nature of the compound for example the benzyl ether or the sulfate of an octyl or nonyl phenol or alkali metal salts thereof.
  • Suitable long chain alcohols which may be reacted with ethylene oxide are the saturated or unsaturated longchain alcohols.
  • the saturated or unsaturated longchain alcohols For example capryl alcohol, lauryl alcohol. cetyl alcohol, tridecyl alcohol, stearyl alcohol or oleyl alcohol or mixtures of these may be used.
  • Long chain carboxylic acids which may be reacted with ethylene oxide either by themselves or in the form of their amides or alkylolamides are the saturated or unsaturated long chain carboxylic acids.
  • caprylic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, linolenic acid and ricinoleic acid or mixture or derivatives thereof may be used or their corresponding amides and alkylolamides.
  • Suitable long chain amines which may be reacted with ethylene oxide are for example, caprylamine and stearylamine.
  • Useful molar ratios of ethylene oxide to ethylene-oxidereactive compound range from 2:1 to l2zl; preferred ratios range from 2:1 to 5:1. At ratios greater than 12:1 little further benefit is achieved.
  • the amount of the plasticity-promoting agent used varies with the type of plasticity-promoting agent and the composition to which it is added. Amounts from 0.1 to 5 percent w/w of the total compositions are useful; we prefer that the amount be in the range from 0.2 to 2 percent w/w ofthe total composition.
  • liquid explosive nitric ester for example, nitroglycerine
  • nitroglycerine a liquid explosive nitric ester
  • the nitrocellulose used in our compositions should be of the type conventionally used in explosives and should be present in quantity sufficient to form a thickened viscous fluid when the liquid nitric ester is partially gelatinized by solution of the nitrocellulose therein.
  • amounts ranging from 0.4 to 1 percent w/w of the composition are satisfactory and amounts as little as 0.2 percent may be used for example when the amounts of liquid explosive nitric ester present is low, for example, 8.0 percent w/w.
  • the oxygen-releasing salt be chosen from the nitrates of ammonium or the alkali metals and of these we prefer ammonium nitrate and sodium nitrate.
  • the particle size and shape of the oxygen-releasing salt is not critical and is well known from the art ofinorganic nitrate manufacture; powders and ground prilled particles are satisfactory.
  • the amount of oxygen-releasing salt in our compositions should be such that it constitutes more than percent w/w of the composition. Thus, for example, satisfactory compositions may be obtained when the total amount of oxygen-releasing salt, or mixtures of such salts, is in the range from to 80 percent w/w, preferably from to percent w/w, of the total composition.
  • Carbonaceous combustible materials should preferably be used in finely divided from and amongst suitable products, there may be mentioned asphalt, naphthalene, sugar, urea, hexamethylenetetramine, cellulosic materials such as sawdust or woodmeal, or cereal products, for example, flours, dextrins or starches. They should be present in amount in the range from 4 to 12 percent w/w, preferably from 5 to 9 percent w/w, of the total composition.
  • compositions according to our invention further reagents such as water, in amounts in the range from zero to 1.5 parts; conventional thickener-s, for example, guar gum, in amounts in the range from zero to two pans; conventional fillers for example, calcium carbonate, china clay, barium sulfate and ammonium phosphates in amounts in the range from zero to 10 parts; or modifiers for the liquid explosive nitric ester for example, nitrotoluene in amounts in the range from zero to nine parts, all per 100 parts by weight of the final mixture.
  • reagents such as water, in amounts in the range from zero to 1.5 parts
  • conventional thickener-s for example, guar gum, in amounts in the range from zero to two pans
  • conventional fillers for example, calcium carbonate, china clay, barium sulfate and ammonium phosphates in amounts in the range from zero to 10 parts
  • modifiers for the liquid explosive nitric ester for example, nitrotoluene in amounts in the range from
  • an explosive composition of matter comprising 1) from 8.0 to 18.5 inclusive parts of at least one liquid explosive nitric ester; (2) from 0.2 to one inclusive part of nitrocellulose; (3) from 60 to inclusive parts, preferably from 70 to 75 inclusive parts of at least one inorganic oxidizing agent selected from the group consisting of the nitrates of ammonium and the alkali metals; (4) from four to 12 inclusive parts, preferably from five to nine inclusive parts, of at least one carbonaceous combustible material; (5) as a plasticitypromoting agent from 0.2 part to two parts inclusive ofat least one condensation product of from 2 to 12 inclusive moles, preferably of from 2 to 5 inclusive moles, of ethylene oxide with a compound selected from the group consisting of alkyl phenols and derivatives thereof, alkyl cresols and derivatives thereof, long chain alcohols, long chain carboxylic acids, long chain amines, amides of long chain carboxylic acids and alkylolamides of long chain carboxylic acids and (6)
  • compositions according to this invention are plastic masses, ranging in plasticity from soft and slightly sticky to stiff and dry which are extrudable in a deformable, solid and cohesive form. They are advantageous in that they have a lower liquid explosive content, which does not have an undesirable effect on the extrudability or on the explosive properties, and consequently there is a resultant cost saving for comparative uses. A further cost saving results in the field since our compositions have a relatively high density enabling a large weight of explosive to be packed in a given volume so minimizing the amount of drilling required for a given quantity of explosive.
  • BSS sieve 4 passes No.18 BSS sieve 20-35% retained No.36 BSS sieve Coarse ammonium passed No.6 BSS sieve nitrate 99% retained No.36 BSS sieve 2.
  • Cartridge count is a measure of density after extrusion 6.
  • A.D.C. is a contraction of the well-known Ardeer Douand the value shown is the number of cartridges each 8 inches ble Cartridge Test and is a measure of the sensitivity to long and 1 inch in diameter which weigh 50 pounds detonation of the explosive. The higher the value, the more 3.
  • Ballistic mortar B.G. is a term indicating the power sensitive to detonation is the explosive. of the explosive compared to a blasting gelatin containing 91.2 5 V.O.D. is the velocity of detonation expressed in meters percent w/w nitroglycerine. per second when determined by the Dautriche method.
  • Water resistance hrs. is the period of time expressed in S" stiff hours, that a cartridge may be immersed in water and after this treatment be sensitive to detonation.
  • Pressure exudation is the percentage of absorbable vs: very iff material forced out of an explosive when the explosive is sub- N normal jected to a pressure of 75 lbs./sq. in. for 4 minutes. SLst. slightly sticky TABLE II Example Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Ground ammonium nitrate pri1ls(1) 73.5 74. 0 72. 9 72. 9 Ground high density ammonium nitrate prills (1) 72. 4
  • Fine ammonium nitrate (1) Coarse ammonium nitrate (1).
  • the said condensation product comprises from 2 to 5 inclusive F th f 55 moles of ethylene oxide in the molecule.
  • a composition ofmatter according to claim 1 which compansfn i par S g. u 9 g g prises in addition an amount of water no greater than that at me ammonium m ta parts 9 mm mate an which the plastic or semiplastic property of the compound is parts of wheat flour was prepared using the apparatus and retained method of the previous examples. Attempts to extrude the composition into a deformable solid and cohesive form were exPloswe' composmorl of matter comprlsmg l from 8.0 to 18.5 inclusive parts of nitroglycerin; (2) from 0.2 to one 1 unsuccessful.
  • An explosive composition of matter co prising (1) parts of at least one inorganic oxidizing agent selected from nitroglycerine; (2) nitrocellulose; (3) at least one inorganic the group H iStiHg f h ni rates f mm ni m n he aloxidizing agent selected from the group consisting of the Kali metals; from four l0 12 inclusive Parts of at least one nitrates of ammonium and the alkali metals; (4) at least one r nac Com i le i l and 8S 3 p i i ycarbonaceous combustible material and (5) as a plasticitypromoting agent from 0.2 part to two inclusive parts of at least promoting agent at least one condensation product of from 2 one condensation product of from 2 to 12 inclusive moles of to l2 inclusive moles of ethylene oxide with a compound ethylene oxide with a compound selected from the group conselected from the group consisting
  • composition of matter according to claim 4 comprising in addition water present in amount up to 1.5 parts by weight per parts by weight of the composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Medicinal Preparation (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
US850652A 1968-09-06 1969-08-15 Nitrocellulose-nitroglycerine explosive with ethylene oxide Expired - Lifetime US3617409A (en)

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AU43045/68A AU416157B2 (en]) 1968-09-06 1968-09-06

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US (1) US3617409A (en])
AU (1) AU416157B2 (en])
DE (1) DE1942400A1 (en])
FR (1) FR2017548A1 (en])
GB (1) GB1213078A (en])
ZA (1) ZA696035B (en])

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595430A (en) * 1984-05-07 1986-06-17 Atlas Powder Company Desensitized dynamites

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002070437A1 (en) * 2001-03-02 2002-09-12 Rocktek Ltd Composite propellant and cartridge incorporating same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3305415A (en) * 1965-03-15 1967-02-21 James E Webb Process for preparing sterile solid propellants
US3429755A (en) * 1967-12-14 1969-02-25 Aerojet General Co Nitrocellulose-base propellant containing ethylene cyanohydrin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3305415A (en) * 1965-03-15 1967-02-21 James E Webb Process for preparing sterile solid propellants
US3429755A (en) * 1967-12-14 1969-02-25 Aerojet General Co Nitrocellulose-base propellant containing ethylene cyanohydrin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595430A (en) * 1984-05-07 1986-06-17 Atlas Powder Company Desensitized dynamites

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Publication number Publication date
ZA696035B (en) 1971-04-28
AU416157B2 (en]) 1971-08-23
AU4304568A (en]) 1971-02-25
DE1942400A1 (de) 1970-03-12
FR2017548A1 (en]) 1970-05-22
GB1213078A (en) 1970-11-18

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