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

• the present invention relates to explosive compositions comprising special in a water-in-oil emulsion as an emulsifier Mannich adducts and processes for the preparation of these compositions.
• Liquid explosives usually comprise aqueous emulsions of an inorganic oxidizing agent, such as ammonium nitrate, in a water-immiscible organic phase.
• emulsifiers of various types are used to produce such emulsions.
• US-A-5,639,988 and US-A-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 the use of C 14 -C 22 fatty acid amines or ammonium salts as emulsifiers for explosive compositions is known.
• 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 preparation 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 is capable of forming a salt with the polyamine is.
• Emulsifiers based on Mannich adducts derived from a polyamine are known from EP-A-320183.
• the object of the present invention is therefore to provide improved emulsifiers for explosive emulsions, which the no longer have the disadvantages mentioned above.
• compositions according to the invention are characterized in that that Ar represents a mononuclear aromatic residue, and x stands for 1.
• the invention also includes compositions in which the Emulsifier (Mannich adduct) in pure material, e.g. isomerically Form, or as the adduct mixture obtained in the Mannich reaction (e.g. mixture of mono- and diaminomethylated compounds) is included.
• Emulsifier Mannich adduct
• adduct mixture obtained in the Mannich reaction e.g. mixture of mono- and diaminomethylated compounds
• R 1 is derived from a poly-C 2 -C 6 -alkene.
• 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 is obtained by reacting a poly (alkenyl) phenol with formaldehyde and a mono- or di- (hydroxyalkyl) amine.
• Explosive compositions according to the invention preferably contain a water-in-oil emulsion in which at least one emulsifier as defined above in a proportion of approximately 1 to 20% by weight, based on the total weight of the composition is included.
• compositions of the invention are at ambient temperature solid, pasty or, preferably, liquid and in particular pourable or pumpable.
• 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 Preparation of an explosive composition according to the invention, which is characterized in that the Mannich adduct is in a the oil phase forming organic liquid dissolves the organic Solution heated if necessary and in it, if necessary warmed aqueous phase emulsified, which is an inorganic Includes oxidizing agents.
• 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, having.
• M N upper limit is approximately 10,000, preferably approximately 5000.
• the alkenyl group can have one or more, for example 1 to 20, preferably isolated, double bonds.
• the aryl group of R 1 is preferably derived from mononuclear or 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 I is derived from one or more hydroxylated, in particular one to five times, preferably one or two times, hydroxylated aromatic compounds which condensed one or more, in particular 1 to 3 or bear uncondensed 4- to 7-membered, in particular 6-membered aromatic or heteroaromatic rings.
• the hydroxylated aromatic compound can optionally be mono- or polysubstituted, in particular mono- or di-substituted.
• Compounds which are substituted in the ortho position to the hydroxyl group are particularly suitable as substituted aromatics. Suitable substituents are e.g. B.
• C 1 -C 20 alkyl substituents or C 1 -C 20 alkoxy substituents are particularly suitable substituents.
• Particularly suitable 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-cresol, binuclear 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-cresol
• binuclear aromatics such as alpha- or beta-naphthol
• trinuclear compounds such as anthranol.
• hydroxyaromatic compounds of 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; Dissertation D. Jamois, "Synthesis of oligoisobutenes telecheliques-phenol", 1988, Paris; or Kennedy et al, Polym. Bull. 1970, 8, 563.
• the compounds of general formula I can also in analogy to the processes described in DE-A-199 48 114 and DE-A-199 48 111 are produced, to which express reference is hereby made becomes.
• the hydroxyaromatic is 0.1 to 10, such as. 0.1 to 5 molar equivalents of polyalkene implemented.
• unreacted aromatic can be extracted by extraction with solvents, preferably polar solvents, such as water or C 1 -C 6 -alkanols or mixtures thereof, by stripping, ie by passing steam or, if appropriate, heating gases, e.g. As nitrogen, or removed by distillation.
• solvents preferably polar solvents, such as water or C 1 -C 6 -alkanols or mixtures thereof.
• the hydrocarbylation of the hydroxyaromatic is preferred in one Temperature from about 50 ° C to -40 ° C performed. Especially Temperatures in the range are suitable for the hydrocarbylation from -10 to +30 ° C, in particular in the range from -5 to +25 ° C and particularly preferably from 0 to +20 ° C.
• 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 tetrachaeze and titanium antantotechloride, titanium antioxidant, titanium halide, titanium tantalogenide; and iron halides, for example iron trichloride and iron tribromide.
• Adducts of boron trihalides, in particular boron trifluoride, with electron donors, such as alcohols, in particular C 1 -C 6 -alkanols or phenols, or ethers are preferred.
• electron donors such as alcohols, in particular C 1 -C 6 -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 carried out.
• the hydroxyaromatic is preferably in one the reactants and / or a solvent, optionally under Warm up, solved.
• the hydrocarbylation was carried out so that the hydroxyaromatic first melted with the application of heat and then with a suitable solvents and / or the alkylation catalyst, in particular the boron trihalide adduct. After that the liquid mixture is brought to a suitable reaction temperature brought.
• the hydroxyaromatic is first melted and with the polyalkene and optionally a suitable solvent. The the liquid mixture thus obtained can be brought up to a suitable reaction temperature brought and then with the alkylation catalyst be transferred.
• Suitable solvents for carrying out this reaction are for example hydrocarbons, preferably pentane, hexane and Heptane, especially hexane, hydrocarbon mixtures, e.g. Petroleum Benzine with boiling ranges between 35 and 100 ° C, dialkyl ether, especially diethyl ether and halogenated hydrocarbons, such as dichloromethane or trichloromethane and mixtures of the aforementioned solvents.
• hydrocarbons preferably pentane, hexane and Heptane, especially hexane
• hydrocarbon mixtures e.g. Petroleum Benzine with boiling ranges between 35 and 100 ° C
• dialkyl ether especially diethyl ether and halogenated hydrocarbons, such as dichloromethane or trichloromethane and mixtures of the aforementioned solvents.
• the reaction is preferably accomplished by the addition of the catalyst or one of the two reactants.
• the addition of the Reaction initiating component is preferably carried out via a Period of 5 to 300 minutes, the temperature of the reaction mixture advantageous the temperature ranges specified above does not exceed.
• the reaction mixture is left preferably 30 minutes to 24 hours, in particular 60 minutes to 16 hours, at a temperature below React after 30 ° C.
• 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 and ⁇ -olefinic double bonds of the type which together are also referred to as vinylidene double bonds.
• Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a vinylidene double bond content of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%.
• Polyisobutenes which have uniform polymer skeletons are particularly preferred. Uniform polymer structures have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight, of isobutene units. Such highly reactive polyisobutenes preferably have a number average molecular weight in the range mentioned above. In addition, 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, for example 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.
• Formaldehyde component
• Suitable aldehydes are in particular formaldehyde, formalin solutions, Formaldehyde oligomers, e.g. Trioxane, or polymers of formaldehyde, like paraformaldehyde. Paraformaldehyde is preferred used. Formalin solution is particularly easy to use. Of course, gaseous formaldehyde can also be used.
• Amines suitable for carrying out the Mannich adduct formation according to the invention are compounds of the formula II, ie HNR 2 R 3 .
• the production of the Mannich adducts used according to the invention takes place in a manner known per se, e.g. described in the DE-A-2 209 579, US-A-3,649,229 or US-A-4,231,759, followed by reference is hereby expressly made.
• the reaction can also in analogy to those in DE-A-199 48 114 and DE-A-199 48 111 described methods are carried out, whereupon likewise express reference is made.
• the Mannich reaction is preferably carried out so that the Reactants aldehyde, amine and aromatics in a temperature range between 10 and 50 ° C, if necessary 10 are mixed up to 300 minutes in this temperature range, and then within 5 to 180 minutes, preferably 10 to 120 minutes to remove the water of reaction by distillation necessary temperature are brought.
• the total response time adduct formation is generally between 10 minutes and 24 hours.
• 0.1 to 10.0 mol preferably 0.5 to 2.0, are used Mol of aldehyde, and 0.1 to 10.0 mol, preferably 0.5 to 2.0 mol Amine, based on 1 mol of hydrocarbyl-substituted aromatics Formula I a.
• This can usually be largely Uniform product image with a high proportion of amine-containing Reach connections.
• This leads to an approximately equimolar ratio the reactants for the preferred formation of mono-aminomethylated Compounds, a reactant ratio of about 2: 2: 1 for 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 during the formation of the Mannich adduct. Usually this is removed from the reaction mixture. The removal of the water of reaction can occur during the reaction, at the end of the reaction time or after the reaction has ended, for example by distillation, respectively.
• the water of reaction can advantageously be passed through Heating the reaction mixture in the presence of entraining agents remove.
• Organic for example, are suitable as entraining agents 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, especially with toluene, xylenes and mixtures of alkyl aromatics other (high-boiling) hydrocarbons. Usually will removing the water of reaction at a temperature which is approximately the boiling point of the entrainer or Azeotrope from water and entrainer corresponds.
• Suitable temperatures for removing the water of reaction are therefore at normal pressure in the range of 75 to 200 ° C. Becomes the water of reaction removed at reduced pressure, are the Temperatures corresponding to the reduced boiling temperatures reduce.
• the Mannich adducts produced in this way have excellent Emulsifier properties and are particularly suitable for Production of explosive compositions according to the invention.
• the production of such explosives is described in more detail below.
• compositions according to the invention contain in solid, pasty or preferably liquid state an oil-in-water or preferably a water-in-oil emulsion made at Use of at least one of the emulsifiers described above.
• the Organic phase-forming, water-immiscible liquid in a proportion of about 2-20% by weight, preferably about 3-12% by weight, in particular about 4-8% by weight, based on the total weight the composition included.
• the one actually used Quantity varies depending on the one or more used organic liquids.
• the organic liquid can be aliphatic, alicyclic, and / or aromatic and saturated or have unsaturated character. Is preferred the organic liquid used in the manufacture of the Liquid formulation.
• Preferred liquids include tall oil, mineral oils, waxes, paraffin oils, benzene, toluene, xylene, Mixtures of liquid hydrocarbons, which also under the Collective term crude oil distillates are known, such as. B.
• vegetable oils such as corn oil, Cottonseed oil, peanut oil and soybean oil.
• Particularly preferred organic liquids are mineral oil, paraffin waxes, microcrystalline waxes and mixtures thereof.
• Aliphatic and aromatic Nitrogen-containing compounds can also be used.
• compositions according to the invention in a proportion up to 15% by weight, e.g. about 1 to 12% by weight, other conventional ones solid or liquid flammable or oxidizable, inorganic or organic substances or mixtures thereof.
• examples include: aluminum particles, magnesium particles, carbonaceous materials such as Soot, vegetable granules, such as. Wheat granules, and sulfur.
• an inorganic oxidizing agent which is part of the discontinuous, is aqueous phase
• Compositions ranging from about 40 to 95% by weight, e.g. about 50 to 90 wt .-%, based on the total weight the composition at least one inorganic Salt dissolved in water and / or an organic miscible with water Liquid, which is in a proportion of about 2- 30 wt .-%, based on the total weight of the composition is.
• Suitable salts are alkali. Alkaline earth or ammonium nitrates, -chlorate or -perchlorate.
• Oxidizing agents are sodium nitrate, sodium chlorate, sodium perchlorate, Calcium nitrate, calcium chlorate, calcium perchlorate, potassium nitrate, Potassium chlorate, potassium perchlorate, ammonium chlorate, ammonium perchlorate, Lithium nitrate, lithium chlorate, lithium perchlorate, Magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, Aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, Zinc nitrate, zinc chlorate, zinc perchlorate, ethylenediamine dichlorate and ethylenediamine diperchlorate.
• preferred Oxidizing agent is ammonium, sodium and / or calcium nitrate. About 10-65% by weight of the total oxidizing agent can be crystalline or be contained in particulate form.
• Water is generally in a proportion of about 2-30 wt .-%, based on the total weight of the composition used. Water can also be used in combination with a water miscible organic liquid may be used to, if necessary To improve solubility of the salts used or to increase the crystallization temperature to change the salts. Miscible with water organic liquids are, for example, alcohols, such as Methyl alcohol, glycols such as ethylene glycol, amides such as formamides and analog nitrogen-containing liquids.
• emulsifier for the dispersion of the aqueous phase preferably about 0.5 to 20 wt .-% of an inventive Mannich adduct or a mixture of such adducts. Possibly usual emulsifying additives can be used. Non-limiting examples of this can be found in the introduction Compounds described in the prior art, in particular the aforementioned PIBSA derivatives or sorbitan fatty acid esters to be named. In small quantities, e.g. 0.1 to 5% by weight based on the total weight of the composition also other customary emulsifiers known from the prior art, such as B. described in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A9, pp. 313 to 318 become.
• means for adjusting the Density of the composition can be used.
• the density of the invention Compositions are in the range of 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 of the invention are more conventional Formulated wisely. Usually this is solved first Oxidizing agent in water or an aqueous solution at a Temperature in the range of about 20-90 ° C, for example. The aqueous solution then becomes a solution of the emulsifier and given water-immiscible organic liquid. The organic solution is also heated to a similarly high temperature as the aqueous solution warms up. The resulting mixture is used to create a uniform water-in-oil emulsion touched. Other solid components that may be present then stirred into the emulsion.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Colloid Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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