EP0012827B1 - Gélatine explosive et préparation d'explosifs la contenant - Google Patents

Gélatine explosive et préparation d'explosifs la contenant Download PDF

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Publication number
EP0012827B1
EP0012827B1 EP79104425A EP79104425A EP0012827B1 EP 0012827 B1 EP0012827 B1 EP 0012827B1 EP 79104425 A EP79104425 A EP 79104425A EP 79104425 A EP79104425 A EP 79104425A EP 0012827 B1 EP0012827 B1 EP 0012827B1
Authority
EP
European Patent Office
Prior art keywords
explosives
nitrocellulose
explosive
elastomers
gelatinous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79104425A
Other languages
German (de)
English (en)
Other versions
EP0012827A2 (fr
EP0012827A3 (en
Inventor
Paul Dr. Lingens
Rolf Dr. Lafferenz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels Troisdorf AG
Dynamit Nobel AG
Original Assignee
Huels Troisdorf AG
Dynamit Nobel AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huels Troisdorf AG, Dynamit Nobel AG filed Critical Huels Troisdorf AG
Publication of EP0012827A2 publication Critical patent/EP0012827A2/fr
Publication of EP0012827A3 publication Critical patent/EP0012827A3/de
Application granted granted Critical
Publication of EP0012827B1 publication Critical patent/EP0012827B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • the present invention relates to gelatins from liquid explosives which are gelatinized with the aid of nitrocellulose. These gelatins can also optionally contain admixed powder for gelatinous explosives. Such mixtures are usually referred to as gelatinous or semi-gelatinous explosives.
  • liquid explosives especially nitric acid esters of glycerol and glycols and aromatic nitro compounds
  • the finished gelatins have a relatively soft consistency, so that processing and safety is guaranteed during the work processes.
  • This also applies to the gelatin components in gelatinous and semi-gelatinous nitrate explosives as well as in plastic, highly explosive explosives.
  • the soft consistency of these gelatins has the disadvantage that the liquid escapes or exhausts or exudes at a relatively low pressure load. This reduces the handling safety of the gelatins and the nitrate explosives produced with them.
  • the task was therefore to find explosive gelatins which, both by themselves and in admixture with admixture powder, do not exude the liquid explosive contained in them and which furthermore contain little or no nodules.
  • the gelatin should continue to have the same soft and elastic consistency as previously known explosive gelatins, which are gelatinized with the aid of nitrocellulose.
  • Explosive gelatins according to the invention and explosives which contain these gelatins sweat out the liquid explosive component to a considerably lesser extent than the previously known gelatins or gelatinous explosives which only thickened with nitrocellulose.
  • the addition of the elastomers preserves the known good properties of explosive gelatins and gelatinous explosives made therefrom. The elastic properties are not reduced, but even strengthened, and it is still possible to increase the nitrocellulose content of the known gelatins without impairing the desired consistency.
  • the addition of the elastomers according to the invention furthermore ensures good binding of the solid particles in the gelatinous and semi-gelatinous nitrate explosives and in plastic, highly explosive explosives. It is thus possible, when using these elastomers, to obtain explosive mixtures in addition to the nitrocellulose component which, because of their soft and elastic gelatin quality, are made safer and, consequently, can also be more securely patinated. A stringy consistency of the mixture, which occurred slightly with the previously known mixtures, is largely prevented according to the invention.
  • the gelatin according to the invention consequently improves the processability of the explosive mixtures containing it.
  • the explosive mixtures according to the invention tend to be less likely to segregate when subjected to pressure. Even at elevated storage temperatures, the exudation of nitric acid esters and nitro compounds is significantly reduced.
  • Another advantage of using the elastomers according to the invention in the gelatins is that the known nodule formation is reduced by the nitrocelluloses in gelatinous nitrate explosives.
  • the course of gelatinization or gel formation even allows that Advantageously, the entire admixture powder - ie the solid components such as nitrates and combustible substances - are premixed together with the elastomers and the nitrocellulose and then the liquid nitric acid esters, optionally together with the aromatic nitro compounds, can be added to this premix in the running mixer.
  • Elastomers that dissolve in gel-like form in liquid nitric acid esters and aromatic nitro compounds or that are swellable by them.
  • Elastomers with these solubility properties are particularly copolymers that contain polar and non-polar molecule or chain sections, such as.
  • Polyethylene in liquid nitric acid esters and aromatic nitro compounds practically insoluble, whereas polyvinyl acetate is soluble.
  • both the proportion of polar groups in the copolymer and the molecular weight are of essential importance.
  • the solubility of the elastomeric copolymer can be changed by varying the proportion of aromatic nitro compounds used when a mixture of nitric acid esters and nitro compounds is used.
  • elastomers those are particularly suitable which consist of copolymers of 50 to 80% vinyl acetate with 20 to 50% ethylene, in particular those with 60 to 75% vinyl acetate.
  • elastomers for example from the non-polar butadiene and the polar acrylonitrile, an acrylonitrile content of 25 to 60%, preferably 30 to 45%, has proven to be particularly suitable.
  • the Mooney viscosity which is characteristic of the elastomers used according to the invention and which is related to the molecular weight, is 5 to 75 Mooney, preferably 50 to 70 Mooney (100 ° C./time 4) based on DIN 53 523 and ASTM-D 1646-63 Minutes).
  • the ratio of the elastomeric copolymers to the nitrocelluloses is in the range between 1:10 and 10: 1, a ratio in the range 2: 1 to 1: 2 is particularly suitable.
  • This ratio depends on the type of explosive gelatin to be produced, the nitrate explosives or the plastic, highly explosive explosives.
  • the amount of nitrocellulose is of the same order of magnitude as that of the known gelatins.
  • This salary depends on on the composition of the explosive mixtures, as well as the moisture content and the nitrogen content of the nitrocellulose. It can fluctuate between 0.5 and 10% of the liquid explosives. In the case of explosive mixtures, it is generally between 2.5 and 5% of the liquid explosives.
  • Liquid explosives for the purposes of the present invention are to be understood primarily as nitric acid esters and aromatic nitro compounds and mixtures thereof.
  • the aromatic nitro compounds can also be solid compounds; according to the invention, they are then dissolved in the nitric acid esters.
  • Mainly glycerol trinitrate, glycol dinitrate and diglycol dinitrate or mixtures thereof come into consideration as nitric acid esters.
  • Aromatic nitro compounds are e.g. B. trinitroluene, dinitrotoluenes, dinitroxylenes, nitronaphthalenes or mixtures thereof.
  • admixing powder for gelatinous or semi-gelatinous explosives is understood to be a mixture of inorganic, oxygen-releasing, salts and combustible substances.
  • the admixture powder can optionally also contain inert substances or light metals. These are the same substances that are also present in the gelatinous or semi-gelatinous explosive mixtures known to date. Their share is of the same order of magnitude as the previously known gelatinous or semi-gelatinous explosives.
  • oxygen-releasing salts are preferably understood to mean ammonium nitrate and nitrates of the alkali and / or alkaline earth metals.
  • the combustible constituents contained in the admixture powder include Wood flours, vegetable flours, liquid or solid hydrocarbons, coke or hard coal flours and wax.
  • inert substances are substances such as understood surface-rich silica, surface-active agents, metal oxides, barium salts, alkaline earth carbonates, alkali chlorides or dyes.
  • the explosive mixtures containing the gelatin according to the invention can also contain, in addition to the liquid, thickened explosives mentioned, other solid explosives which are known to be used in explosive mixtures, such as e.g. Pentaerythritol tetranitrate, cyclotrimethylene trinitramine, cyclotetramethylene tetramine, trinitrophenylmethylnitramine.
  • solid explosives can also be present as the only solid component apart from the gelatinizing agents. The invention is illustrated by the following examples:
  • This example concerns the use of elastomers in explosive gelatins.
  • Nitroglycol or a mixture of nitroglycol and nitroglycerin with a technical mixture of dinitrotoluene and isomers (solidification point (EP) 15 ° C.) were introduced and then the elastomer with the nitrocellulose is added to this liquid mixture and gelatinized for 20 minutes in the known manner.
  • solidification point (EP) 15 ° C. solidification point
  • the gelatins produced with the copolymer had a slightly firmer consistency than the gelatin, which only contained nitrocellulose. All three gelatins could be processed to the same extent by adding ammonium nitrate to gelatinous explosives.
  • the gelatin without the addition of the copolymer clearly contained a larger number of larger gelatin nodules, while only a few and very small gelatin nodules were observed in the gelatins with the addition of copolymer.
  • test mixture 4 If the copolymer of vinyl acetate and ethylene in test mixture 2 was replaced by an elastomeric copolymer of acrylonitrile and butadiene (test mixture 4), explosive gelatins with the same favorable properties were also obtained.
  • the elastomeric copolymer consisted of 33% acrylonitrile and 67% butadiene. However, a temperature of 60 ° C during the mixing process was required to produce a homogeneous gelatin.
  • test mixture 5 has an inventive composition and the test mixture 6 is not according to the invention.
  • test mixtures (5 and 6) were prepared in two different ways; they are marked A and B in Table II.
  • Procedure A Here, the copolymer and nitrocellulose are first premixed homogeneously with all solid components in a mixing machine customary for explosives, and then the mixture of nitroglycol and liquid dinitrotoluenes is slowly added while the mixing machine is running. The mixture is then mixed for a further 15 minutes.
  • Procedure B According to this customary procedure, the mixture of nitroglycol and the liquid dinitrotoluenes is first gelatinized for 10 minutes after the addition of the thickener nitrocellulose and copolymer. The solid components are then added with the mixer running. The mixture is then mixed for a further 15 minutes.
  • This example relates to the use of elastomers together with nitrocellulose in plastic, high-explosive explosives, such as those used for. B. are listed in Table 111.
  • the test mixture 7 has a composition according to the invention, while the test mixtures 8 and 9 are not according to the invention. All three mixtures were prepared in the usual way (see Example 2, Comparative B).
  • the mixture 7 contains exactly as much nitrocellulose as the mixture 9, the addition of the copolymer gives it a soft, plastic consistency and is easy to deform.
  • the test mixtures 7 and 8 have approximately the same advantageous consistency. The liquation of the inventive composition 7 was only about 1/11 that of the test mixture. 8

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Medicinal Preparation (AREA)

Claims (3)

1. Gélatines explosives consituées de matières explosives liquides et de 0,5 à 10% de nitrocellulose, calculé sur les matières explosives liquides, éventuellement en mélange avec des poudres d'addition pour explosifs gélatineux, caractérisées en ce qu'elles contiennent des élastomères qui sont solubles ou gonflables dans les matières explosives liquides, les élastomères étant des copolymères comportant des fragments moléculaires polaires et non polaires et ayant une viscosité Mooney se situant entre 5 et 75 à 100 °C, le rapport pondéral entre les élastomères et la nitrocellulose se situant dans l'intervalle allant de 1 : 10 à 10 : 1.
2. Gélatines explosives suivant la revendication 1, caractérisées en ce que le rapport pondéral entre les élastomères et la nitrocellulose se situe dans l'intervalle allant de 2 : 1 à 1 : 2.
3. Procédé de préparation d'un mélange d'une poudre d'addition pour explosifs gélatineux avec des gélatines explosives suivant les revendications 1 et 2, caractérisé en ce qu'on mélange préalablement la poudre d'additon avec la nitrocellulose et les élastomères, puis on mélange les matières explosives liquides dans le mélange obtenu.
EP79104425A 1978-12-04 1979-11-09 Gélatine explosive et préparation d'explosifs la contenant Expired EP0012827B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782852335 DE2852335A1 (de) 1978-12-04 1978-12-04 Sprenggelatine und diese enthaltende sprengstoffe
DE2852335 1978-12-04

Publications (3)

Publication Number Publication Date
EP0012827A2 EP0012827A2 (fr) 1980-07-09
EP0012827A3 EP0012827A3 (en) 1981-09-30
EP0012827B1 true EP0012827B1 (fr) 1985-03-20

Family

ID=6056241

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79104425A Expired EP0012827B1 (fr) 1978-12-04 1979-11-09 Gélatine explosive et préparation d'explosifs la contenant

Country Status (4)

Country Link
EP (1) EP0012827B1 (fr)
DE (2) DE2852335A1 (fr)
ES (1) ES486538A0 (fr)
NO (1) NO148919C (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0731069A1 (fr) 1995-03-06 1996-09-11 SPRENGSTOFFWERK GNASCHWITZ GmbH Procédé de fabrication d'explosifs gélatineux et explosif fabriqué suivant le procédé

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE653682A (fr) * 1963-02-19
GB1190001A (en) * 1963-03-20 1970-04-29 Nitrochemie Gmbh Improvements in or relating to Solid Propellant Charges
DE1446929C1 (de) * 1963-06-12 1978-06-15 Wasagchemie Ag Treibmittel mit verbesserten Brenneigenschaften
US3943209A (en) * 1964-09-21 1976-03-09 The United States Of America As Represented By The Secretary Of The Army High volumetric energy smokeless solid rocket propellant
GB1277192A (en) * 1965-12-30 1972-06-07 Us Gov Sec Army Improvements in and relating to nitrocellulose base propellant compositions
US4029529A (en) * 1967-07-12 1977-06-14 The United States Of America As Represented By The Secretary Of The Navy Crosslinked carboxyl containing polymer and nitrocellulose as solid propellant binder
FR2231637A1 (en) * 1973-05-28 1974-12-27 Saint Louis Inst Plastic bonded explosive briquettes - obtd. using microencapsulated catalysts ruptured only during pressing for long mixing times

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0731069A1 (fr) 1995-03-06 1996-09-11 SPRENGSTOFFWERK GNASCHWITZ GmbH Procédé de fabrication d'explosifs gélatineux et explosif fabriqué suivant le procédé

Also Published As

Publication number Publication date
DE2967413D1 (en) 1985-04-25
ES8104977A1 (es) 1981-05-16
DE2852335A1 (de) 1980-06-26
ES486538A0 (es) 1981-05-16
NO793935L (no) 1980-06-05
NO148919C (no) 1984-01-11
NO148919B (no) 1983-10-03
EP0012827A2 (fr) 1980-07-09
EP0012827A3 (en) 1981-09-30

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