Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
  • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
  • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase

Definitions

• Explosive compositions comprising novel emulsifiers for water-in-oil emulsions
• the present invention relates to explosive compositions comprising special Mannich adducts in an aser-in-oil emulsion as an emulsifier, and to processes for producing these compositions.
• Liquid explosives usually comprise aqueous emulsions of an inorganic oxidizing agent, e.g. Ammonium nitrate, in a water-immiscible organic phase.
• an inorganic oxidizing agent e.g. Ammonium nitrate
• emulsifiers of various types are used to produce such emulsions.
• US Pat. No. 5,639,988 and US Pat. No. 5,460,670 describe the use of special hydrocarbyl polyamides as emulsifiers.
• US-A-4,356,044 and US-A-4,322,258 describe the use of sorbitan fatty acid esters, glycerol esters, substituted oxazolines, alkylamines and salts and derivatives thereof as emulsifiers for this purpose.
• US-A-3,447,978 suggests the use of various sorbitan fatty acid esters and various fatty acid glycerides as emulsifiers for liquid explosives. From US-A-4,141,767 is the use of
• Ci 4 -C 22 fatty acid amines or ammonium salts are known as emulsifiers for explosive compositions.
• WO 96/41781 describes emulsifier compositions which contain an alkylcarboxamide, alkenylcarboxamide, poly (alkyleneamine) or a (di) alkanolamine of a special structure as the main component.
• the emulsifier systems are suitable for the production of explosive emulsions.
• GB-A-2 187 182 describes explosive compositions comprising, as emulsifier, a poly [alk (en) yl] succinic acid or a derivative thereof.
• WO-A-88/03522 discloses nitrogenous emulsifiers for the production of explosive compositions which are derived from a carboxylic acylating agent, at least one polyamine and at least one acid or an acid-producing compound which are used to form a salt the polyamine is capable.
• amide derivatives of polyisobutylene succinic anhydride are predominantly used as emulsifiers for the production of water-in-oil emulsions for liquid explosives.
• These have the disadvantage that they are only accessible through complex synthesis.
• by-products are obtained in large amounts and in varying amounts during the synthesis, as a result of which the setting of a constant product quality, such as a constant viscosity of the emulsifier, is made more difficult.
• Corresponding disadvantages result from the manufacture of the explosive emulsion.
• the object of the present invention is therefore to provide improved emulsifiers for explosive emulsions which no longer have the disadvantages mentioned above.
• a first object of the invention relates to an explosive composition
• an explosive composition comprising a Mannich adduct in a water-in-oil emulsion as an emulsifier
• Ar represents a mono- or polynuclear, optionally substituted aromatic ring;
• n stands for an integer value 1, 2 or 3; and
• x represents an integer from 1 to 5;
• a nitrogen compound selected from an amine and ammonia having at least one primary or secondary amino function.
• compositions according to the invention are characterized in that Ar stands for a mononuclear aromatic radical and x stands for 1.
• compositions according to the invention nitrogen compounds of the general formula II are used in particular for adduct formation
• R 2 and R 3 independently of one another are H, a Ci-Cis-alkyl-, C 2 -Ci 8 -alkenyl-, C 4 -Ci 8 -cycloalkyl-, Ci-Cig-alkyl-aryl-,
• the invention also includes compositions in which the emulsifier (Mannich adduct) is pure, e.g. Isomerically pure form, or as the adduct mixture obtained in the Mannich reaction (e.g. mixture of mono- and diaminomethylated compounds).
• the emulsifier Mannich adduct
• the adduct mixture obtained in the Mannich reaction e.g. mixture of mono- and diaminomethylated compounds
• the poly-C 2 -C 6 -alkene is preferably composed of monomers selected from ethylene, propylene, 1-butylene, 2-butylene, i-butylene or mixtures thereof.
• the poly-C 2 -C 6 -alkene is preferably a reactive poly-C 2 -C 6 -alkene with a high proportion of terminal double bonds.
• the Mannich adducts used according to the invention are preferably obtained by reacting one molar equivalent of hydroxyaromatic compound of the formula I with 0.1 to 10 molar equivalents of formaldehyde, an oligomer or polymer thereof, and 0.1 to 10 molar equivalents of the nitrogen compound.
• Preferred mannich adducts are obtained by reacting a poly (alkenyl) phenol with formaldehyde and a mono- or di- (hydroxyalkyl) amine.
• any OH or NH groups present in the Mannich adduct can be partially or completely oxalkylated. This is achieved by means of customary oxalkylation processes which are familiar to the person skilled in the art.
• Explosive compositions according to the invention preferably contain a water-in-oil emulsion in which at least one emulsifier as defined above is present in a proportion of about 1 to 20% by weight, based on the total weight of the composition.
• compositions according to the invention are solid, pasty or, preferably, liquid and in particular pourable or pumpable at ambient temperature.
• Preferred explosive compositions are characterized in that they:
• customary other explosive additives such as density-adjusting agents, combustible inorganic or organic solids,
• Another object of the invention relates to the use of a Mannich adduct as defined above as an emulsifier for water-in-oil or oil-in-water emulsions for explosives, in particular liquid explosives.
• Another object of the invention relates to a method for producing an explosive composition according to the invention, which is characterized in that the Mannich adduct is dissolved in an organic liquid forming the oil phase, the organic solution is optionally heated and therein emulsifies an optionally heated aqueous phase which emits a includes inorganic oxidizer.
• the starting materials used to prepare the Mannich products used according to the invention are generally known compounds or can be prepared in a known manner by the person skilled in the art without undue effort.
• R 1 preferably represents straight-chain or branched alkyl, alkenyl, alkyl aryl or alkenyl aryl radicals, the alkyl or alkenyl part having a number average molecular weight M N of 200 or more, in particular 1000 or more.
• M N upper limit is approximately 10,000, preferably approximately 5000.
• the alkenyl group can contain one or more, such as 1 to 20, preferably isolated, double bonds.
• the aryl group of R 1 is preferably derived from mononuclear or 5 dinuclear condensed or uncondensed 4- to 7-membered, in particular 6-membered aromatic or heteroaromatic groups such as phenyl, pyridyl, naphthyl and biphenylyl.
• the hydroxyaromatic group -Ar (OH) x in compounds of the formula 10 I is derived from one or more hydroxylated, in particular one to five times, preferably one or two times, hydroxylated aromatic compounds which contain one or more, in particular 1 to 3, wear fused or uncondensed 4- to 7-membered, especially 6-membered aromatic or heteroaromatic rings.
• the hydroxylated aromatic compound can optionally be mono- or polysubstituted, in particular mono- or di-substituted.
• Compounds substituted in the ortho position to the hydroxy group are particularly suitable as substituted aromatics. Suitable substituents are e.g. B.
• substituents are C 1 -C 7 -alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and n heptyl.
• Non-limiting examples of such hydroxylated aromatic compounds are mononuclear aromatics, such as phenol, 2-ethylphenol, pyrocatechol, resorcinol, hydroquinone, o-, m- or p-creoles, dinuclear aromatics, such as alpha- or beta-naphthol, or trinuclear compounds such as anthranol.
• mononuclear aromatics such as phenol, 2-ethylphenol, pyrocatechol, resorcinol, hydroquinone, o-, m- or p-creoles, dinuclear aromatics, such as alpha- or beta-naphthol, or trinuclear compounds such as anthranol.
• hydroxyaromatic compounds of the general formula I used according to the invention can be prepared, for example, as described in: EP-B-0 628 022, US-A-5,300,701; Doctoral thesis D. Jamois, "Synthesis of oligoisobutenes telecheliques-phenol",
• the compounds of the general formula I can also be prepared analogously to the processes described in DE-A-199 48 114 and DE-A-199 48 111, to which express reference is hereby made.
• the hydroxyaromatic is reacted with 0.1 to 10, for example 0.1 to 5 molar equivalents of polyalkene.
• unreacted aromatic can be extracted by extraction with solvents, preferably polar solvents, such as water or Ci-C ß- alkanols or mixtures thereof, by stripping, ie by passing steam or, if appropriate, heating gases, e.g. , B. nitrogen, or removed by distillation.
• solvents preferably polar solvents, such as water or Ci-C ß- alkanols or mixtures thereof.
• the hydrocarbylation of the hydroxyaromatic is preferably carried out at a temperature of about 50 ° C to -40 ° C. Temperatures in the range from -10 to +30 ° C, in particular in the range from -5 to +25 ° C and particularly preferably from 0 to +20 ° C are particularly suitable for the hydrocarbylation.
• Suitable hydrocarbylation catalysts are known to the person skilled in the art.
• protonic acids such as sulfuric acid, phosphoric acid and organic sulfonic acids, for example trifluoromethanesulfonic acid
• Lewis acids such as aluminum trihalides, for example aluminum trichloride or aluminum tribromide
• boron trihalides for example boron trifluoride and boron trichloride
• tin halides for example tin tetretrachloride, titanium antitetrachloride, titaniumantogen halide, titaniumantogen halide, titaniumantogen halide, titaniumantogen halide, titaniumantogen halide, titaniumantogen halide, titaniumantogen halide, and iron halides, for example iron trichloride and iron tribromide.
• electron donors such as alcohols, in particular Ci-C ö alkanols or phenols, or ethers.
• Boron trifluoride etherate or boron trifluoride phenolate is particularly preferred.
• the hydrocarbylation is preferably carried out in a liquid medium.
• the hydroxyaromatic is preferably dissolved in one of the reactants and / or a solvent, if appropriate with heating.
• the hydrocarbylation is therefore carried out in such a way that the hydroxyaromatic is first melted with the addition of heat and then mixed with a suitable solvent and / or the alkylation catalyst, in particular the boron trihalide adduct. The liquid mixture is then brought to a suitable reaction temperature.
• the hydroxyaromatic is first melted and the polyalkene and optionally a suitable solvent are added. The liquid mixture obtained in this way can be brought to a suitable reaction temperature and the alkylation catalyst can then be added.
• Suitable solvents for carrying out this reaction are, for example, hydrocarbons, preferably pentane, hexane and heptane, in particular hexane, hydrocarbon mixtures, for example petroleum spirits with boiling ranges between 35 and 100 ° C., dialkethers, in particular diethyl ether and halogenated hydrocarbons, such as dichloromethane or Trichloromethane and mixtures of the aforementioned solvents.
• hydrocarbons preferably pentane, hexane and heptane, in particular hexane
• hydrocarbon mixtures for example petroleum spirits with boiling ranges between 35 and 100 ° C.
• dialkethers in particular diethyl ether
• halogenated hydrocarbons such as dichloromethane or Trichloromethane and mixtures of the aforementioned solvents.
• the reaction is preferably initiated by the addition of the catalyst or one of the two reactants.
• the component initiating the reaction is preferably added over a period of 5 to 300 minutes, the temperature of the reaction mixture advantageously not exceeding the temperature ranges specified above.
• the reaction mixture is preferably allowed to after-react at a temperature below 30 ° C. for 30 minutes to 24 hours, in particular 60 minutes to 16 hours.
• R 1 is derived from polyisobutenes.
• Particularly suitable polyisobutenes are so-called “highly reactive” polyisobutenes, which are distinguished by a high content of terminally arranged double bonds. Double bonds arranged at the terminal are ⁇ -olefinic double bonds of the type
• the highly reactive polyisobutenes can have a polydispersity in the range from 1.05 to 7, in particular from about 1.1 to 2.5, such as from less than 1, 9 or less than 1.5.
• Polydispersity is the quotient of the weight average molecular weight M w divided by the number average molecular weight M N.
• Glissopal 2300 2300
• Other number average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number average molecular weights or by extractive enrichment of polyisobutenes of certain molecular weight ranges.
• the organic phase is then separated off from the reaction mixture obtained in the hydrocarbylation described above, optionally washed with water, dried and excess hydroxyaromatic is optionally removed.
• the reaction product thus obtained which may contain a mixture of compounds of the formula I, is then used in the Mannich reaction.
• Formaldehyde component
• Suitable aldehydes are in particular formaldehyde, formalin solutions, formaldehyde oligomers, e.g. Trioxane, or polymers of formaldehyde, such as paraformaldehyde.
• Paraformaldehyde is preferably used.
• Formalin solution is particularly easy to use.
• gaseous formaldehyde can also be used.
• Amines suitable for carrying out the Mannich adduct formation according to the invention are, in particular, compounds of the formula II, ie HNR 2 R 3 .
• R 2 and R 3 can independently stand for:
• Ci-Ci ⁇ -alkyl radical examples include straight-chain or branched radicals having 1 to 18 carbon atoms, such as methyl, ethyl, i- or n-propyl, n-, i-, sec- or tert-butyl, n- or i pentyl; also n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl and n-octadecyl as well as the one or more branched analogues thereof; and corresponding radicals in which the carbon chain has one or more ether bridges;
• alkenyl radicals are the mono- or polysaturated, preferably mono- or di-unsaturated analogues of the abovementioned alkyl radicals having 2 to 18 carbon atoms, it being possible for the double bond to be in any position on the carbon chain;
• a C 4 -C 8 cycloalkyl radical examples include cyclobutyl, cyclopentyl and cyclohexyl, and the analogues thereof substituted with 1 to 3 C ⁇ -C 4 alkyl radicals; where the C 1 -C 4 alkyl radicals are selected, for example, from methyl, ethyl, i- or n-propyl, n-, i-, sec- or tert-butyl;
• Ci-Ci ⁇ -alkyl group is as defined above and the aryl group has the same meanings as the aryl group of R 1 defined above;
• a hydroxy-Ci-Ci ⁇ -alkyl radical where this corresponds to the one or more, preferably simple, in particular simple terminal, hydroxylated analogs of the above Ci-Ci ⁇ -alkyl radicals; such as. 2-hydroxyethyl and 3-hydroxypropyl;
• an optionally hydroxylated poly (oxyalkyl) radical which can be obtained by alkoxylation of the N atom with 2 to 10 C 1 -C 4 alkoxy groups, where individual carbon atoms can optionally carry further hydroxyl groups.
• Preferred alkoxy groups include methoxy, ethoxy and n-propoxy groups;
• m is an integer from 0 to 5
• Z is H or Ci-C ⁇ -alkyl and -CC 6 alkyl for radicals such as methyl, ethyl, i- or n-propyl, n-, i-, sec- or tert-butyl, n- or i-pentyl; also stands for n-hexyl; and Ci-C ß alkylene represents the corresponding bridged analogs of these radicals;
• k a polyalkyleneimine radical, built up from 1 to 10 C 1 -C 4 -alkyleneimine groups, in particular ethyleneimine groups;
• primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, cyclopentylamine and cyclohexylamine; and also primary amines of the formula CH 3 -OC 2 H 4 -NH 2 , C 2 H 5 -0-C 2 H4-NH 2 , CH 3 -0-C 3 H 6 -NH 2 , C 2 H 5 -0- C 3 H6-NH2, n-C4H 9 -0-C 4 H 8 -NH2, HO-C 2 H 4 -NH 2 , HO-C3H 7 -NH2 and HO-C 4 H 8 -NH 2 ;
• Heterocyclic amines such as pyrrolidine, piperidine, morpholine and piperazine and their substituted derivatives, such as N-Ci-C ⁇ -alkylpiperazines and dimethylmorpholine.
• Polyamines such as C 1 -C 4 -alkylenediamines, di-C ⁇ -C 4 -alkylene-triamines, tri-C ⁇ -C 4 -alkylene tetramines and higher analogues;
• Polyethyleneimines preferably oligoethyleneimines, consisting of 1 to 10, preferably 2 to 6 ethyleneimine units.
• suitable polyamines and polyimines are n-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, triethylenetetramine and polyethyleneimines, and their alkylation products, such as 3- (dimethylamino) -n-propyl- amine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine and N, N, N ', N'-tetramethyldiethylenetriamine.
• Ethylene diamine is also suitable. Production of the Mannich adducts:
• the Mannich adducts used according to the invention are prepared in a manner known per se, such as e.g. described in DE-A-2 209 579, US-A-3,649,229 or US-A-4,231,759, to which express reference is hereby made.
• the reaction can also be carried out analogously to the processes described in DE-A-199 48 114 and DE-A-199 48 111, to which reference is also expressly made here.
• the Mannich reaction is preferably carried out in such a way that the reactants aldehyde, amine and aromatic are combined in a temperature range between 10 and 50 ° C., optionally mixed for 10 to 300 minutes in this temperature range, and then within 5 to 180 minutes, preferably 10 to 120 minutes are brought to the temperature necessary for the removal of the water of reaction by distillation.
• the total reaction time for adduct formation is generally between 10 minutes and 24 hours.
• 0.1 to 10.0 mol, preferably 0.5 to 2.0 mol, of aldehyde and 0.1 to 10.0 mol, preferably 0.5 to 2.0 mol, of amine, based on 1 mol, are used hydrocarbyl-substituted aromatics of formula I.
• the reactants aldehyde, amine and aromatic are used in an approximately equimolar ratio or in a ratio of approximately 2: 2: 1.
• a largely uniform product image with a high proportion of amine-containing compounds can be achieved in this way.
• An approximately equimolar ratio of the reactants leads to the preferred formation of mono-aminomethylated compounds, and a ratio of the reactants of approximately 2: 2: 1 to the preferred formation of bisaminomethylated compounds.
• Suitable reaction temperatures for the Mannich reaction are preferably in the range from 10 to 200 ° C., in particular in the range from 20 to 180 ° C.
• water of reaction is formed. As a rule, this is removed from the reaction mixture.
• the water of reaction can be removed during the reaction, at the end of the reaction time or after the reaction has ended, for example by distillation.
• the water of reaction can advantageously be removed by heating the reaction mixture in the presence of entraining agents. For example, organic see solvents that form an azeotrope with water and / or have a boiling point above the boiling point of water.
• Particularly suitable entraining agents are benzene and alkyl aromatics, in particular toluene, xylenes and mixtures of alkyl aromatics with other (high-boiling) hydrocarbons.
• the water of reaction is removed at a temperature which corresponds approximately to the boiling point of the entrainer or the azeotrope of water and entrainer.
• Suitable temperatures for removing the water of reaction are therefore at normal pressure in the range from 75 to 200.degree. If the water of reaction is removed at reduced pressure, the temperatures have to be reduced in accordance with the reduced boiling temperatures.
• the Mannich adducts produced in this way have excellent emulsifier properties and are particularly suitable for producing explosive compositions according to the invention.
• the production of such explosives is described in more detail below.
• compositions according to the invention contain, in the solid, pasty or preferably liquid state, an oil-in-water or preferably a water-in-oil emulsion, produced using at least one of the emulsifiers described above.
• the oil phase-forming, water-immiscible organic liquid is present in a proportion of approximately 2-20% by weight, preferably approximately 3-12% by weight, in particular approximately 4-8% by weight, based on the total weight of the Composition included.
• the amount actually used varies depending on the organic liquid or liquids used.
• the organic liquid can be aliphatic, alicyclic, and / or aromatic and have a saturated or unsaturated character.
• the organic liquid used is preferably liquid in the preparation of the formulation.
• Preferred liquids include tall oil, mineral oils, waxes, paraffin oils, benzene, toluene, xylene, mixtures of liquid hydrocarbons, which are also known under the collective term crude oil distillates, such as, for.
• kerosene and diesel fuel As gasoline, kerosene and diesel fuel, and vegetable oils such as corn oil, cottonseed oil, peanut oil and soybean oil. Particularly preferred organic liquids are mineral oil, paraffin waxes, micro- crystalline waxes and mixtures thereof. Aliphatic and aromatic nitrogen-containing compounds can also be used.
• compositions according to the invention a proportion 5 of up to 15% by weight, e.g. about 1 to 12% by weight, further conventional solid or liquid flammable or oxidizable, inorganic or organic substances or mixtures thereof.
• examples include: aluminum particles, magnesium particles, carbon-containing materials, such as Carbon black, vegetable granules such as e.g. Wheat granules, and sulfur.
• compositions according to the invention contain in a proportion of about 40 to
• Suitable salts are alkali. Alkaline earth or ammonium nitrates, chlorates or perchlorates.
• suitable oxidizing agents are sodium nitrate, sodium chlorate, sodium perchlorate, calcium nitrate, calcium chlorate, calcium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium chlorate, amine
• the oxidizing agent is ammonium, sodium and / or calcium nitrate. About 10-65% by weight of the total oxidizing agent can be present in crystalline or particulate form.
• Water is generally used in a proportion of about 2-30% by weight, 35 based on the total weight of the composition. Water can also be used in combination with a water-miscible organic liquid in order to improve the solubility of the salts used, if necessary, or to change the crystallization temperature of the salts.
• Organic liquids which can be mixed with water are, for example, alcohols, such as methyl alcohol, glycols, such as ethylene glycol, amides, such as formamides, and analogous nitrogen-containing liquids.
• the emulsifier used for the dispersion of the aqueous phase is preferably about 0.5 to 20% by weight of a Mannich adduct according to the invention or a mixture of such adducts. If necessary, customary emulsifying additives can also be used. the.
• the compounds described in the prior art cited at the beginning, in particular the PIBSA derivatives or sorbitan fatty acid esters mentioned, can be mentioned as non-limiting examples.
• other customary emulsifiers known from the prior art such as, for. B. described in Ulimann's Encyclopedia of Industrial Chemistry, 5th edition, volume A9, pp. 313 to 318, can be used.
• Agents for adjusting the density of the composition can be used as further customary additives.
• the density of the compositions according to the invention is in the range from about 0.5 to about 1.5 g / ccm. Suitable means for density adjustment are, for example, glass beads, plastic beads, pearlite or foam-forming or gas-forming agents.
• the explosive compositions according to the invention are formulated in a conventional manner.
• the oxidizing agent is first dissolved in water or an aqueous solution at a temperature in the range of, for example, about 20-90 ° C.
• the aqueous solution is then added to a solution of the emulsifier and the water-immiscible organic liquid.
• the organic solution is also heated to a temperature similar to that of the aqueous solution.
• the resulting mixture is stirred to produce a uniform water-in-oil emulsion. Any other solid constituents that may be present are then stirred into the emulsion.

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• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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• Liquid Carbonaceous Fuels (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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