EP1299325A1

EP1299325A1 - Dispersant compositions comprising novel emulsifiers for water in oil emulsions

Info

Publication number: EP1299325A1
Application number: EP01957921A
Authority: EP
Inventors: Arend Jouke Kingma; Arno Lange; Hans Peter Rath
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-07-06
Filing date: 2001-07-05
Publication date: 2003-04-09
Anticipated expiration: 2021-07-05
Also published as: AU2001279714B2; BR0112162A; CA2414781A1; WO2002002485A1; ATE270260T1; TR200402500T4; DE10032829A1; EP1299325B1; JP2004502628A; ZA200300987B; US6913660B2; MXPA02012637A; CN1441755A; CN1178879C; US20030145925A1; AU7971401A; DE50102754D1; ES2223901T3

Abstract

In an explosive composition comprising an emulsifier in a water-in-oil emulsion, the emulsifier is a Mannich adduct (I) of (a) a mono- or polycyclic mono- to penta-hydroxy-aromatic compound (II), mono-, di- or tri-substituted by 6-400C alk(en)yl(aryl), (b) formaldehyde or its oligomer or polymer and (c) a nitrogen compound such as an amine with primary or secondary amine function(s) and ammonia. In an explosive composition comprising an emulsifier in a water-in-oil emulsion, the emulsifier is a Mannich adduct (I) of (a) a hydrocarbyl-substituted hydroxyaromatic compound of formula (II), (b) formaldehyde or its oligomer or polymer and (c) a nitrogen (N) compound selected from an amine with primary or secondary amine function(s) and ammonia. (R1>)nAr(OH)x (II) R1>a hydrocarbyl group, selected from linear or branched 6-400 carbon (C) alkyl, 6-400C alkenyl, 6-400C alkenyl-aryl or 6-400C alkyl-aryl; Ar : a mono- or polycyclic, optionally substituted aromatic ring; n : 1, 2 or 3; x : 1-5. An independent claim is also included for the production of the explosive composition by dissolving (I) in an organic liquid forming the oil phase, warming this solution if necessary and emulsifying an optionally warmed aqueous phase containing an inorganic oxidant.

Description

Explosive compositions comprising novel emulsifiers for water-in-oil emulsions

description

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. According to the prior art, emulsifiers of various types are used to produce such emulsions. For example, 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.

Today, 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. In addition, 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.

Surprisingly, this problem was solved by providing special emulsifiers based on Mannich adducts.

A first object of the invention relates to an explosive composition comprising a Mannich adduct in a water-in-oil emulsion as an emulsifier

a) a hydrocarbyl-substituted, hydroxyaromatic compound of the general formula I.

(R ⁱ ) _n Ar (0H) _x (I)

wherein

R ¹ for a hydrocarbyl group selected from a straight-chain or branched C ₆ -C ₄ oo-alkyl, C ₆ -C ₄ oo-alkenyl, C6-C4oo-alkyl-aryl or C6-C4oo-alkenyl-aryl -Rest, stands; 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;

b) formaldehyde, an oligomer or polymer thereof; and

c) a nitrogen compound selected from an amine and ammonia having at least one primary or secondary amino function.

Preferred compositions according to the invention are characterized in that Ar stands for a mononuclear aromatic radical and x stands for 1.

In the compositions according to the invention, nitrogen compounds of the general formula II are used in particular for adduct formation

H _NR 2R3 ₍ ii ₎ used where

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-,

C ₂ -C ₈ alkenyl aryl, hydroxy-C 1 -C 4 -alkyl, poly (oxyalkyl), polyalkylene polyamine or polyalkyleneimine; or together with the nitrogen atom to which they are attached represent a heterocyclic ring.

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).

For the preparation of the adduct are preferably used compounds of formula I wherein R ¹ _beta from a poly-C ^ -C derived -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 are obtained by reacting a poly (alkenyl) phenol with formaldehyde and a mono- or di- (hydroxyalkyl) amine.

If desired, 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.

The 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:

a) 0.5 to 20 wt .-% emulsifier as defined above;

b) 2 to 20% by weight of an oil-immiscible, water-immiscible organic liquid;

c) 2 to 30% by weight of water and / or at least one water-miscible organic liquid;

d) 40 to 90% by weight of an inorganic oxidizing agent;

e) 0 to 25% by weight of customary other explosive additives, such as density-adjusting agents, combustible inorganic or organic solids,

include.

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 (aromatic compound of the formula I, formaldehyde and nitrogen compound) are generally known compounds or can be prepared in a known manner by the person skilled in the art without undue effort.

Hydrocarbyl-substituted hydroxyaromatic compounds of the formula I:

In the compounds of the general formula I, 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. The 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. 20 -C-C ₂ o-alkyl substituents or -C-C ₂ o-alkoxy 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.

25 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.

30

The 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",

35 1988, Paris; or Kennedy et al, Polym. Bull. 1970, 8, 563. For this purpose, a hydroxyaromatic compound is reacted in a manner known per se with a polyalkene which has at least one C = C double bond to introduce the hydrocarbyl radical R ¹ (hydrocarbylated or alkylated).

40

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. In the hydrocarbylation, the hydroxyaromatic is reacted with 0.1 to 10, for example 0.1 to 5 molar equivalents of polyalkene.

If the hydroxyaromatic is used in excess, 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.

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. For example, 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, and iron halides, for example iron trichloride and iron tribromide. Preferred are adducts of boron trihalides, in particular boron trifluoride, with 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. For this purpose, the hydroxyaromatic is preferably dissolved in one of the reactants and / or a solvent, if appropriate with heating. In a preferred embodiment, 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. In a further preferred embodiment, 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.

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. After the addition has ended, 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.

In particularly preferred hydroxyaromatic compounds of the formula I, 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 α-olefinic double bonds of the type

polymer

as well as ß cal double bonds of the type

polymer which together are also referred to as vinylidene double bonds. Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds 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, 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.

Particularly suitable highly reactive polyisobutenes are, for example, the Glissopal® brands from BASF AG, in particular Glissopal 1000 (M _N = 1000), Glissopal V 33 (M _N = 550) and Glissopal 2300 (M _N = 2300) and their mixtures. 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. Of course, gaseous formaldehyde can also be used.

Nitrogen compound:

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:

a) H;

b) a Ci-Ciβ-alkyl radical; Examples of suitable alkyl radicals are 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;

c) a C ₂ -C ₈ alkenyl radical; examples of suitable 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;

d) a C ₄ -C ₈ cycloalkyl radical; Examples include cyclobutyl, cyclopentyl and cyclohexyl, and the analogues thereof substituted with 1 to 3 Cχ-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;

e) a CJ-Cis-alkyl-aryl radical; wherein the Ci-Ciβ-alkyl group is as defined above and the aryl group has the same meanings as the aryl group of R ¹ defined above;

f) a C ₂ -C ₈ alkenyl aryl radical; wherein the C ₂ -C ₈ alkenyl group is as defined above and the aryl group has the same meanings as the aryl group of R ¹ defined above;

g) a hydroxy-Ci-Ciβ-alkyl radical; where this corresponds to the one or more, preferably simple, in particular simple terminal, hydroxylated analogs of the above Ci-Ciβ-alkyl radicals; such as. 2-hydroxyethyl and 3-hydroxypropyl;

h) 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;

i) a polyalkylene polyamine radical of the formula

Z-NH-fCi-Cö-alkylene-NHJm-Cx-C _δ- alkylene,

wherein m is an integer from 0 to 5, Z is H or Ci-Cβ-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;

1) or together with the nitrogen atom to which they are attached for an optionally substituted 5 to 7-membered heterocyclic ring which is optionally substituted by one to three C 1 -C ₄ -alkyl radicals and which optionally carries a further ring heteroatom, such as 0 or N. ,

Examples of suitable compounds of the formula HNR ² R ³ are:

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 ;

secondary amines, such as dimethylamine, diethylamine, methylethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine, dihexylamine, dicyclopentylamine, dicyclohexylamine and diphenylamine ; and also secondary amines of the formula (CH ₃ -0-C ₂ H ₄ ) ₂ NH, (C ₂ H ₅ -0-C ₂ H ₄ ) ₂ NH, (CH ₃ -0-C ₃ H ₆ ) ₂ NH, ( C ₂ H ₅ -0-C ₃ H ₆ ) ₂ NH, (nC ₄ H ₉ -0-CH ₈ ) ₂ NH, (H0-C ₂ H ₄ ) ₂ NH, (HO-C ₃ H ₇ ) ₂ NH and (H0-C ₄ H ₈ ) ₂ NH;

- Heterocyclic amines, such as pyrrolidine, piperidine, morpholine and piperazine and their substituted derivatives, such as N-Ci-Cβ-alkylpiperazines and dimethylmorpholine.

Polyamines such as C 1 -C ₄ -alkylenediamines, di-Cχ-C ₄ -alkylene-triamines, tri-Cι-C ₄ -alkylene tetramines and higher analogues;

Polyethyleneimines, preferably oligoethyleneimines, consisting of 1 to 10, preferably 2 to 6 ethyleneimine units. Particular examples of 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.

As a rule, 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.

For example, the reactants aldehyde, amine and aromatic are used in an approximately equimolar ratio or in a ratio of approximately 2: 2: 1. As a rule, 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.

When Mannich adduct is formed, 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. As a rule, 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.

Explosive compositions:

The 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.

In the explosive compositions according to the invention, 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. 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.

In the 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.

As an inorganic oxidizing agent which is part of the discontinuous, aqueous phase, the compositions according to the invention contain in a proportion of about 40 to

15 95% by weight, e.g. about 50 to 90% by weight, based on the total weight of the composition, of at least one inorganic salt, dissolved in water and / or a water-miscible organic liquid, which in a proportion of about 2-30% by weight, based on the total weight of the composition

Hold 20 is. Suitable salts are alkali. Alkaline earth or ammonium nitrates, chlorates or perchlorates. Examples of 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

25 monium 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, ethylene diamine dichlorate and ethylene diamine diperchlorate. preferred

30 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. In small amounts, for example 0.1 to 5% by weight, based on the total weight of the composition, 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. Usually, 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. For this purpose, 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.

The present invention will now be explained in more detail with reference to the following exemplary embodiments.

Example 1: Preparation of a polyisobutene phenol by alkylation of phenol with a polyisobutene with M _N = 200

94 g of phenol were melted in a nitrogen atmosphere at 40 to 45 ° C in a 2 1 four-necked flask. 106 g of BF ₃ -diethyl ether adduct were added dropwise and the mixture was cooled to 10 ° C. 500 g of polyisobutene with M _N = 200 and an isopropenyl portion (α-olefinic end group) of 85%, dissolved in 150 ml of hexane, were added dropwise at 15 to 20 ° C. in the course of 90 minutes. The mixture was allowed to warm to room temperature within 1 hour and stirred overnight. The reaction was stopped by adding 200 ml of 25% ammonia solution. The organic phase was separated and then washed eight times with 500 ml of water, dried over Na ₂ S0 ₄ and the solvent and small amounts of phenol removed in vacuo. Yield: 330 g of oil (polyisobutene phenol).

According to iH-NMR, there is a mixture of 15 mol% 2, 4, 6-triisobutenylphenol, 65 mol% 2, 4-diisobutenylphenol and 20 mol% monoisobutenylphenols.

Example 2: Preparation of a polyisobutene phenol by alkylation of phenol with a polyisobutene with M _N = 550

404.3 g of phenol were melted in a 4 1 four-necked flask in a nitrogen atmosphere at 40 to 45 ° C. 191 g of BF ₃ -diethyl ether adduct were added dropwise and the mixture was cooled to 10 ° C. 1100 g of polyisobutene with M _N = 550 and a dimethylvinylidene content (β-olefinic end group) of 85%, dissolved in 1000 ml of hexane, were added dropwise at 5 to 10 ° C. in the course of 150 minutes. The mixture was allowed to warm to room temperature within 4 hours and stirred overnight. The reaction was stopped by adding 1200 ml of 25% ammonia solution. The organic phase was separated off and then washed eight times with 500 ml of water, dried over Na ₂ SO ₄ and the solvent and small amounts of phenol were removed in vacuo. Yield: 1236 g of oil (4-polyisobutene phenol).

NMR: 7.2 ppm (doublet, 2H), 6.7 ppm (doublet, 2H), 4.8 ppm (singlet, 1H), 1.75 ppm (singlet, 2H), 1.5-0, 5 ppm (singlets, 78H)

This corresponds to an Mw of 550 for the alkyl radical.

In the signal range of 7.1-6.75 ppm there are small signals which can represent 5-10% 2- or 2,4-substituted phenol.

Example 3: Preparation of a polyisobutene phenol by alkylation of phenol with a polyisobutene with M _H = 1000

203.1 g of phenol are melted under nitrogen at 40-45 ° C. in a 4-1 four-necked flask. 95.5 g of BF3-diethyl ether adduct are added dropwise and the mixture is cooled to 20-25 ° C. 998 g of polyisobutene with Mw - 1000 and an isopropenyl content of 85%, dissolved in 1800 ml of hexane, are added dropwise at 20-25 ° C. over 3 hours. Stir overnight. It is terminated with 500 ml of 25% ammonia solution. The organic phase is washed seven times with 500 ml of water, dried over Na ₂ Sθ ₄ and evaporated. Yield: 1060 g of oil ("PIB-phenol"), NMR: 7.2 ppm (doublet, 2H), 6.7 ppm (doublet, 2H), 4.8 ppm (singlet, broad 1H), 1.75 ppm (singlet, 2H), 1.5-0 , 5 ppm (singletts, 165H)

This corresponds to an Mw of 1150 for the alkyl radical.

In the signal range of 7.1-6.75 ppm there are small signals which can represent 5-10% 2,4-substituted phenol, which is in line with the small increase in molecular weight found.

Example 4: Preparation of various Mannich adducts of 4-polyisobutene phenols

a) 108 g of PIB phenol from Example 2 in 85 ml of toluene are placed in a 0.5-1 four-necked flask with a water separator.

35 g of diethanolamine and 10 g of paraformaldehyde are added, and water is refluxed for 2 hours under reflux. Now a further 17 g of diethanolamine and 5.2 g of paraformaldehyde are added and water is removed under reflux for 2 hours. The solution is filtered and evaporated. Yield: 130 g of 2,6-di (N, N-di-hydroxyethylaminomethyl) polyisobutenylphenol as an oil. According to NMR, the oil contains 10-15% 2- (N, N-di-hydroxyethylaminomethyl) -4-polyisobutenylphenol;

b) In a 0.5-1 four-necked flask with water separator

110 g of PIB phenol from Example 3 in 200 ml of toluene. 12 g of diethanolamine and 3.6 g of paraformaldehyde are added, and water is refluxed for 2 hours under reflux. The solution is filtered and evaporated. Yield: 115 g of 2- (N, N-di-hydroxyethylaminomethyl) -4-polyisobutenylphenol as an oil. According to NMR, the oil contains 20-30% 4-polyisobutenylphenol.

c) 107 g of PIB phenol from Example 3 in 200 ml of toluene are placed in a 0.5-1 four-necked flask with a water separator. 29 g of diethanolamine and 9 g of paraformaldehyde are added, and the water is removed under reflux for 2 h. The solution is filtered and evaporated. Yield: 118 g of oil. According to NMR 2- (, N-di-hydroxyethylaminomethy1) -4-polyisobutenylphenol and 2, 6-di (N, N-di-hydroxyethylaminomethyl) -4-polyisobutenylphenol as a 1: 1 mixture (mol: mol).

Example 5: Preparation of a liquid explosive emulsion

30 parts of an emulsifier prepared according to Example 4 are dissolved in 50 parts of mineral oil and heated to 70 ° C. 1100 parts of heated ammonium nitrate solution (80% in water, 80 ° C.) are added to this solution with vigorous stirring. The so obtained Emulsion is cooled to room temperature. The product obtained is transparent and shows no tendency to separate or crystallize even after 2 months of storage. A sample of the emulsion is overlaid with water and shows no cracking of the emulsion even after several weeks.

Claims

claims

1. Explosive composition comprising a Mannich adduct in a water-in-oil emulsion as an emulsifier

(R ⁱ ) _n Ar (0H) _x (I)

wherein

R ¹ for a hydrocarbyl group selected from a straight-chain or branched C ₆ -C ₄ oo-alkyl, C ₆ -C ₄ oo-alkenyl- C ₆ -C ₄ oo-alkenyl-aryl or C ₆ - C ₄ oo-alkyl-aryl radical;

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;

b) formaldehyde, an oligomer or polymer thereof; and

c) a nitrogen compound, selected from an amine and ammonia having at least one primary or secondary amino function.

2. Composition according to claim 1, characterized in that Ar stands for a mononuclear aromatic radical and x for 1.

3. Composition according to one of the preceding claims, characterized in that a nitrogen compound of the general formula II

HNR ² R ³ (II)

used where

R ² and R ³ independently of one another represent H, a Ci-Ciβ-alkyl-, C ₂ -Ci ₈ -alkenyl-, C ₄ -Ci8-cycloalkyl-, Ci-Cis-alkyl-aryl-, C ₂ -Ci ₈ - Alkenyl-aryl, hydroxy-C-Ciβ-alkyl, poly (oxyalkyl) -, polyalkylene polyamine or a polyalkyleneimine radical; or together with the nitrogen atom to which they are attached represent a heterocyclic ring.

4. Composition according to claim 1, characterized in that the emulsifier is contained in pure material form or as the mixture of substances obtained in the Mannich reaction.

5. Composition according to one of the preceding claims, characterized in that R ^{1 is derived} from a poly-C ₂ -Cg alkene.

6. The composition according to claim 5, characterized in that the poly-C ₂ -C ₆ alkene from monomers selected from ethylene,

Propylene, i-butylene, i-butylene, 2-butylene or mixtures thereof is built up.

7. The composition according to claim 6, characterized in that the poly-C ₂ -C ₆ alkene is a reactive poly-C ₂ -Cg alkene with high

Is part of terminal double bonds.

8. The composition according to claim 7, characterized in that the reactive polyalkene is a reactive polyisobutene.

9. The composition according to claim 8, characterized in that the reactive polyisobutene has at least one of the following properties:

a) proportion of vinylidene double bonds at least 70 mol%, based on the polyisobutene molecule;

b) uniform polyisobutene polymer structure, composed of at least 85% by weight of isobutene units;

c) number average molecular weight M _H in the range from about 200 to 10,000; and or

d) polydispersity in the range from 1.05 to 7.

10. Composition according to one of the preceding claims, characterized in that the Mannich adduct by reacting one molar equivalent of hydroxyaromatic compound of the formula I with 0.1 to 10 molar equivalents of formaldehyde, one

Oligomers or polymers thereof and 0.1 to 10 molar equivalents of the nitrogen compound.

11. Composition according to one of the preceding claims, characterized in that the Mannich adduct is obtained by reacting a poly (alkenyl) phenol with formaldehyde and a mono- or di- (hydroxyalkyl) amine.

12. Composition according to one of the preceding claims, characterized in that partially or completely oxalkylated in the Mannich adduct any free OH or NH groups present.

13. Composition according to one of the preceding claims, characterized in that it comprises a water-in-oil emulsion in which the emulsifier as defined in claim 1 in a proportion of about 1 to 20 wt .-%, based on the Total weight of the composition is included.

14. Composition according to one of the preceding claims, characterized in that it comprises:

a) 0.5 to 20 wt .-% emulsifier as defined in claim 1;

b) 2 to 20% by weight of an oil-immiscible, water-immiscible organic liquid;

d) 40 to 90% by weight of an inorganic oxidizing agent;

e) 0 to 25% by weight of customary further additives.

15. Use of a Mannich adduct as defined in claim 1 as an emulsifier for water-in-oil or oil-in-water emulsions for explosives.

16. A process for the preparation of an explosive composition according to any one of claims 1 to 14, characterized in that the Mannich adduct is dissolved in an organic liquid forming the oil phase, the organic solution is optionally heated and an optionally heated aqueous phase is emulsified therein, which comprises an inorganic oxidizing agent.