RU2415120C2 - Marked emulsion explosive compound (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to explosive compounds used in the industry of explosive works, including mining. Versions of marked emulsion explosive compounds contain a marking additive selected from nitro-derivative isomers of saturated hydrocarbons or nitro-derivatives of the aromatic family, which are dimethyldinitrobutane or para-mononitrotoluene.

EFFECT: invention enables detection of explosive compounds using equipment, while providing monitoring of handling and preventing their illegal use.

25 cl, 57 ex

Description

The invention relates to the field of explosive compositions used in industrial blasting, including mining.

Blasting operations with emulsion explosive compositions (EMU) is one of the rapidly developing scientific and technical areas. A large number of articles and patents are published annually on recipes and methods for their preparation, loading technology, safety and efficiency issues. However, for all the variety of EMUs, they have common features that make it possible to distinguish the following as the most significant.

1. The presence of two immiscible phases, one of which is aqueous or hydrophilic is represented by a solution of an inorganic salt-oxidizing agent or a mixture of several of them, the other is a hydrocarbon (hydrophobic, combustible phase), including a mixture (solution) of mineral or synthetic oils and surfactants ( Surfactant) with additives (if necessary) of fusible hydrocarbons as stabilizers obtained by mixing the indicated dispersion phases.

2. EMU sensitization by creating a mass of porosity emulsion due to solid particles - microspheres or chemical reaction of gas-forming reagents (gasification, gas saturation).

3. The presence in a number of compositions for increasing the explosion energy of a solid phase, which can be represented by ammonium nitrate granules or aluminum powders, ferrosilicon aluminum, ferrosilicon or military blasting explosives of the class of nitro derivatives of toluene, for example trotyl, nitramines, for example hexogen, nitroesters, for example pentaerythritol TEN), as well as gunpowder, including recovered from disposable ammunition.

Methods for the preparation of EMUs generally come down to mechanical dispersion of the hydrophilic oxidative phase in the hydrophobic combustible phase, resulting in a viscous mass - a dispersion, usually called a "matrix emulsion" into which sensitizers and, if necessary, a solid phase are introduced.

As one example, the composition of US Pat. US No. 6200398, which includes,% (by weight): 73.44 ÷ 76.78 ammonium nitrate; 0.236 zinc nitrate (modifications); 15.64 ÷ 18.48 water; 4.1 ÷ 7.0 oil or diesel fuel, or paraffin oil; 1,0 ÷ 1,233 surfactants - the products of the interaction of polyisobutylene with glyoxylic acid in the presence of methanesulfonic acid, which are condensed with alkanolamines from among ethanolamine, di-, triethanolamine, aminated paraffin, or dimethylaminopropylamine. The matrix emulsion was characterized by a viscosity of 1780 to 38000 cP and a microdrop size of 1.56 ÷ 1.93 μm.

Other emulsion formulations are also known, for example: US Pat. US No. 4820361, 4819178, 4931110, 5160387; US Pat. Australia No. 551923, 573677, 610692, 615597; European Pat. No. 0317221 B1, 0532179 A1; US Pat. RF №1819253, 1819254, 2123488, 2273627, and also - patent applications of the Russian Federation №2001115035, 2001109501, 2001108781, 2004113302, 2001114757 and others.

The general above-mentioned principles of EMU layout and schemes for their preparation are preserved, and the differences are reduced to the types of surfactants used, the presence of salt modifiers, methods for adjusting the pH of the oxidizing phase, hardware design, modes of production and sensitization of dispersion.

In connection with the increasing spread of emulsion explosives on the market and the increasing acts of terrorism, the problem of controlling the circulation of explosives and measures to counter their illegal use are becoming the focus of international organizations. So, since 1989, the Council of the International Civil Aviation Organization (ICAO) regularly reviews various aspects of this problem: handling explosives, measures to prevent their unauthorized use, marking BB for detection by technical means. To develop marking methods, a number of chemical compounds have been identified with properties that allow the detection and identification of explosives. Among these compounds, for a number of specific properties ensuring the fulfillment of a set of requirements for explosive compositions, nitro derivatives of isomers of saturated hydrocarbons, as well as aromatic nitro derivatives, in particular dimethyl dinitrobutane (DMDNB) and para-mononitrotoluene (p-MNT), turned out to be the most acceptable.

The presence of any of these compounds makes it possible to efficiently perform remote detection by the chromatographic method of explosives through analysis of an air sample.

To date, a number of patents are known that protect marking methods or marking additives (markers).

So for example, in US Pat. RU No. 2179961 was proposed to introduce solid additives into the products from explosives having the properties of semiconductors based on metal-oxide, which make it possible to fix the presence of explosives by the location method. The method involves preliminary coating of additives with insulating materials (for example, fluoroplastic), which complicates the technology. In addition, the presence of metallic impurities is not allowed in safety rules for the production of explosives.

US patents Nos. 4019053 and 5006299 provide for the marking of explosives with radioactive isotopes, which despite the attractiveness from the point of view of the possibility of effective detection requires the implementation of a series of measures to protect personnel in the production and use of such explosives.

RU patent No. 2134253 proposes the use of chemical compounds of the class of organometallic compounds — ferrocene and its derivatives, which have a high detection sensitivity in a gaseous medium using selective detectors based on the manifestation of molecular condensation nuclei (MoNak) as marking substances. However, despite the high reliability, this method has not found practical application due to the lack of commercially available selective detectors.

Patent application WO 2007091998 (A2) illustrates the possibility of using the method of ion mobility spectrometry to detect marking additives - p-MNT or DMDNB introduced for detection in individual explosives - trotyl, hexogen, ten.

At the same time, we did not find information on the labeling of industrial explosives, including emulsion formulations, which confirms the relevance, necessity and timeliness of solving this problem.

The technical task of the claimed invention is to modify EMU by the introduction of marking additives, providing the possibility of their detection by existing technical means.

The technical result is achieved in that the emulsion explosive composition contains a mixture of a dispersion of the oxidizing phase from an aqueous solution of an inorganic salt or a mixture of several of them, or the specified oxidizing phase containing a flame arrestor salt or salt inhibiting the reaction between EMU and sulfide-containing rock in a combustible phase from liquid hydrocarbons containing a surfactant, or in a combustible phase medium containing a surfactant and a dispersion stabilizer, with a sensitizer and a marker additive represented by p-MNT or DMDNB. Surfactant in this case is a compound of the class of esters of fatty acids or their anhydrides, or their amino derivatives, or a mixture of esters with acid anhydrides in any ratio. Sensitizers are microspheres made of glass or polymer, or aqueous solutions of blowing agents, such as sodium nitrite or its mixture with a solution of formaldehyde. Additionally, the composition may contain a solid phase from granules of ammonium nitrate, or energy additives from metal powders or their alloys, or blasting explosives of the class of nitro derivatives of toluene or nitramines, or nitroesters and gunpowders.

The basic ratio of the main components is the following, wt.%:

sensitizer 0.5 ÷ 10.0 marker additive 0.05 ÷ 3.0 dispersion - the rest is up to 100

When choosing markers are guided by the following factors:

- the marker additive must have a set of properties that ensure compatibility with EMU components, persistence (stability) during manufacture, technological processing, storage and use, migrate minimally from the mass of EMUs during the guaranteed storage period;

- securely fixed (detected) by the available technical means of detection in the vapor phase.

For a number of technical reasons, the already mentioned p-MNT and DMDB are recommended for use in the Russian Federation.

The method for producing labeled EMFs is basically typical: when heating and stirring, the oxidizing phase is prepared, the environment of the combustible phase, with dosing devices, they are fed into the device (apparatus) to obtain dispersion with vigorous stirring, which is then mixed with other components and processed into products or transported in mixing and charging machines to obtain EMU directly at the place of blasting.

The proposed solution can be implemented on the example of any EMU, justifying the introduction of an additive marker at one of the stages of production:

- at the stage of preparation of the combustible phase;

- into the apparatus for obtaining dispersion;

- into the dispersion stream at the outlet of the apparatus to obtain it (for example, into the discharge tray);

- into a dispersion mixer with a solid phase from ammonium nitrate granules, or with energy additives from metal powders or blasting explosives, or with sensitizers from solid porous particles, or from an aqueous solution of blowing agents.

Subsequent processing of the composition depends on the final type of product: it is packaged in shells, placed in a shipping container or loaded into a mixing and charging machine.

The possibility of implementing the invention is illustrated by examples (1 ÷ 57) of labeled EMU depending on changes in the concentration, type and method of administration of the marker additive. EMUs were packaged in polymeric shells, stored for 6 months, and the sample was tested for the possibility of detection using an ECHO-DEZ device, which has the following technical characteristics:

Lindane detection limit - 7.95 · 10 ^-13 , g / s; trinitrotoluene detection limit (TNT) with a syringe injector, g in the sample - 15.7 · 10 ^-12 ; TNT detection limit with concentration injector, g in the sample - 2.7 · 0 ^-12 ; lower limit of detection of TNT with concentration injector during selection 1 liter of air in the sample - 2.7 · 10 ^-15 g / cm ³ .

The preparation of EMUs corresponding to this application was carried out according to the usual scheme:

in two different containers prepared an aqueous solution of the oxidizing phase (temperature 75 ÷ 95 ° C) and a medium of a combustible phase in the form of a mixture (solution) of industrial oil and surfactant (temperature 60 ÷ 75 ° C), the contents of the tank with an aqueous solution of the oxidizing phase through a drain device with vigorous stirring, it was poured into the medium of the combustible phase, and after 3 minutes of additional mixing, a dispersion was obtained, which was converted into EMU by mixing with a sensitizer and an additive marker. The compositions of the oxidizing and combustible phases were changed depending on the need to obtain the required operational characteristics of the EMU determined by the field of application. All tested EMUs comprised 2 groups, one of which included a mixture of dispersion, sensitizer and marker additives, and the other a mixture of dispersion, sensitizer, marker additives and solid phase from ammonium nitrate granules or energy additives, or blasting explosives, or gunpowders. To increase the shelf life, dispersion stabilizers selected from paraffin or petrolatum, or bitumen, or polyisobutylene were introduced into some formulations.

The following is a description of examples that reflect the basic formulation relationships characterizing labeled EMU, and, in particular, such as:

- levels of mass fractions of sensitizers in the form of perlite sand (5.0 ÷ 10.0% - examples 3, 9 ÷ 13), or in the form of microspheres (0.5 ÷ 10.0% - examples 2, 4, 5, 14 ÷ 17, 19, 25, 26, 46 ÷ 49), or in the form of an aqueous solution of sodium nitrite with a concentration of 5.0 ÷ 15.0%, taken in the range from 0.5 to 2.5% (examples 1, 6, 7, 8, 20, 21, 27, 28, 30, 37, 38), or as a mixture of an aqueous solution of sodium nitrite with a concentration of 5.0 ÷ 15.0% with a formaldehyde solution with a concentration of 20.0 ÷ 30.0%, taken in the ratio 1: 3 in the range from 0.5 to 2.5% (examples 18, 22 ÷ 24, 31 ÷ 33, 50 ÷ 53),

- levels by mass fractions of marker additives (0.05 ÷ 3.0%) in the form of p-MNT or DMDNB - examples 1, 2, 3, 4, 5, 6, 9 ÷ 13, 21 ÷ 24, 31 ÷ 33 , 34 ÷ 36, 37, 38, 39, 40;

- levels by type and mass fractions of the components of the oxidative phase, including:

- by water - from 10 to 21% - examples 1, 2, 3, 4, 34 ÷ 36, 39, 40, 50 ÷ 53;

- for sodium nitrate and calcium nitrate 30 ÷ 18.0% - examples 3, 4, 5, 6, 21 ÷ 24, 29, 30, 34 ÷ 36, 39, 40, 46 ÷ 49, 50 ÷ 53;

- for salt flame arresters in the form of sodium chloride or potassium chloride 0.5 ÷ 7.0% - examples 10, 14 ÷ 18, 29, 30;

- for salts inhibiting the reaction with a sulfide-containing rock in the form of urotropine or urea 0.5 ÷ 1.5% - examples 19, 20, 21 ÷ 24, 29, 30, 50 ÷ 53, 54 ÷ 57;

- levels by types and mass fractions of the components of the combustible phase, including:

- industrial oil 5.0 ÷ 12.0% - examples 1, 9 ÷ 13, 14 ÷ 18, 21 ÷ 24, 25 ÷ 28, 31 ÷ 33, 41, 42 ÷ 45;

- surfactant 1.0 ÷ 4.0% - examples 1, 2, 3, 4, 5, 6, 9 ÷ 13, 14 ÷ 18, 19, 20, 21 ÷ 24, 25 ÷ 28, 29, 30, 31 ÷ 33, 34 ÷ 36, 37 ÷ 38, 39, 40, 41, 42 ÷ 45, 46 ÷ 49, 54 ÷ 57;

- for additives of dispersion stabilizers 0.2 ÷ 4.0% in the form of paraffin, or petrolatum, or bitumen, or polyisobutylene - examples 5, 6, 7, 8, 9 ÷ 13, 34 ÷ 36, 39, 40, 46 ÷ 49 , 50 ÷ 53;

- levels by type and mass fractions of the components of the solid phase, including:

- for ammonium nitrate in granules - from 10.0 to 80.0% - examples 37, 38, 39, 40, 41;

- for energy additives in the form of aluminum powder, or ferrosilicon aluminum, or ferrosilicon - from 2.0 to 12.0% - examples 31 ÷ 33, 34 ÷ 36;

- for gunpowder, or TNT, go to RDX, or PETN - 5.0 ÷ 50.0% - examples 42 ÷ 45, 46 ÷ 49, 50 ÷ 53;

- if possible, the use of ammonium nitrate granules in the form of a solid phase simultaneously (in a mixture) with gunpowder, or TNT, or RDX, or PETN - examples 54 ÷ 57.

Example 1

The dispersion having the composition,%: oxidative phase (90.45), including 21.0 water, 69.45 ammonium nitrate; combustible phase (9.0), including industrial oil 5.0; A surfactant of the class of fatty acid esters of the C ₁₂ -C ₁₆ fraction and the polyhydric alcohol pentaerythritol 4.0 was mixed with a 0.5% sensitizer in the form of an aqueous solution of sodium nitrite at a concentration of 10.0% and 0.05% of the marker additive p-MNT . EMUs weighing 300 g were placed in a polymer shell, the ends were sealed, stored for 6 months and tested for the presence of an additive marker; the device recorded its presence.

Example 2

Repeated experience approx. 1, but 0.5% polymer microspheres were used as a sensitizer, 0.05% DMDB as a marker marker additive, and a fatty acid ester of the C ₁₂ -C ₁₆ fraction and a polyhydric alcohol glycerol were used as a surfactant in the combustible phase. The preparation of the EMU sample for testing and the testing procedure was carried out similarly to example 1; the device detected a marker.

Examples 3.4

The dispersion having the composition,%: oxidative phase (78.0), including 10.0 water, 3.0 sodium nitrate (example 3) or 3.0 calcium nitrate (example 4), 65.0 ammonium nitrate ( examples 3, 4); combustible phase (9.0), including industrial oil 8.0 (examples 3, 4) and surfactants of the class of fatty acid esters of fraction C ₁₂ -C ₁₆ and polyhydric alcohol polyglycerol 1.9 (example 3) or a substance class of esters of fatty acids of fraction C ₁₂ -C ₁₆ and polyatomic alcohol - sorbitol 1.0 (example 4) were mixed with 10.0% of a sensitizer in the form of perlite sand (example 3) or glass microspheres (example 4) and with 3, 0% marker additive in the form of DMNB (examples 3 and 4). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 5, 6

The dispersion having the composition,%: oxidative phase (83.5), including 16.0 water, 18.0 sodium nitrate (example 5) or 18.0 calcium nitrate (example 6), 49.5 ammonium nitrate; combustible phase (13.0), including industrial oil 11.5 (examples 5, 6) and surfactant - a compound of the class of amino derivatives (amino esters) of fatty acids of the C ₁₂ -C ₁₆ fraction obtained by esterification of acids with an amino alcohol, for example triethanolamine 1, 0 (examples 5, 6) and 0.5 dispersion stabilizer in the form of paraffin (example 5) or in the form of petrolatum (example 6) were mixed with 0.5% of the sensitizer in the form of glass microspheres (example 5) or with 0.5% an aqueous solution of sodium nitrite with a concentration of 15.0% (example 6) and with a 3.0% marker additive in the form of p-MNT. EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 7, 8

The experiment of Example 6 was repeated, but 0.5% bitumen (Example 7) and 0.5% polyisobutylene (Example 8) were used as a dispersion stabilizer. EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 9, 10, 11, 12, 13

The dispersion having the composition,%: oxidative phase (83.45), including 16.0 water (examples 9 ÷ 13); 0.5 salt flame arrester in the form of sodium chloride (examples 9, 10), or potassium chloride 0.5 (examples 11 ÷ 13); 66.95 ammonium nitrate (examples 9 ÷ 13); combustible phase (11.5), including industrial oil 5.0 (examples 9 ÷ 13), a surfactant of the acid anhydride class in the form of alkenyl (polyisobutylene) succinic anhydride 2.5 (examples 9 ÷ 13) and a dispersion stabilizer in the form of paraffin 4.0 (examples 9 and 10), or petrolatum 4.0 (example 11); or bitumen 4.0 (example 12) or polyisobutylene 4.0 (example 13), mixed with 5% of the sensitizer in the form of perlite sand (examples 9 ÷ 13) and 0.05% of the marker additive in the form of DMNB (examples 9 ÷ 13 ) EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 14, 15, 16, 17, 18

The dispersion having the composition,%: oxidative phase (86.4), including 16.0 water (examples 14 ÷ 18); 7.0 salt flame arrester in the form of sodium chloride (examples 14, 18) or 7.0 salt flame arrester in the form of potassium chloride (examples 15, 16, 17); 63.4 ammonium nitrate (examples 14 ÷ 18); combustible phase (9.6), including industrial oil 5.0 (examples 14 ÷ 18), a surfactant of the class of amino derivatives of alkenyl- (polyisobutylene) succinic anhydride in the form of a condensation product of anhydride with alkanolamine, for example, triethanolamine 2.5, and a dispersion stabilizer in the form of paraffin 2.1 (example 14), or 2.1 petrolatum (example 15), or bitumen 2.1 (example 16), or polyisobutylene (examples 17 and 18) were mixed with 2.5% a sensitizer in the form of glass microspheres (examples 14–17) or with 2.5% aqueous solutions of sodium nitrite with a concentration of 15.0% and formaldehyde with a concentration of 30.0%, respectively cost by weight 1: 3 (Example 18) and with 1.5% marker additive in the form of p-MNT (Examples 14–18). EMU samples were prepared and tested according to example 1, the device recorded the presence of a marker.

Examples 19, 20

The dispersion having the composition,%: oxidative phase (89.0), including 16.0 water, 10.5 sodium nitrate (example 19) or 10.5 calcium nitrate (example 20), 62.0 ammonium nitrate ( examples 19, 20); 0.5 salt inhibitor of the reaction with sulfide-containing rocks in the form of urotropine (example 19) or 0.5 salt inhibitor in the form of urea (example 20), the combustible phase (9.0), including industrial oil 7.0 and A surfactant in the form of an amino derivative of alkenyl- (polyisobutylene) succinic anhydride obtained by condensation of an anhydride with a polyamine, for example, polyethylenepolyamine 2.0 was mixed with a 0.5% microsphere sensitizer (example 19) or with a 0.5% aqueous solution of sodium nitrite concentration 10.0% (Example 20) and with 1.5% marker additives in the form of DMDB (Example 19) or with 1.5% p-MNT (Example 20). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 21, 22, 23, 24

The dispersion having the composition,%: oxidative phase (85.45), including 16.0 water, 3.0 sodium nitrate (examples 21, 22) or 3.0 calcium nitrate (examples 23, 24), 61, 45 ammonium nitrate (examples 21 ÷ 24); 5.0 salt-inhibitor of the reaction with sulfide-containing rocks in the form of urotropine (examples 21, 22) or in the form of urea 5.0 (examples 23, 24); combustible phase (14.0), including industrial oil 12.0 (examples 21 ÷ 24); Surfactant in the form of a mixture of alkenyl- (polyisobutylene) succinic anhydride (0.1 part by weight) and its amino derivative (0.9 parts by weight) 1.0 (example 21), or as a mixture of alkenyl- (polyisobutylene) succinic anhydride (0.5 parts by weight) and its amino derivative (0.5 parts by weight) 1.0 (Example 22), or as a mixture of alkenyl- (polyisobutylene) succinic anhydride (0.9 parts by weight) and its an amino derivative (0.1 part by weight) 1.0 (examples 23, 24) and a dispersion stabilizer 1.0 in the form of paraffin (example 21), or in the form of petrolatum 1.0 (example 22), or in the form of bitumen 1, 0 (example 23), or in the form of polii Obutylene 1.0 (Example 24) was mixed with a 0.5% sensitizer in the form of an aqueous solution of sodium nitrite with a concentration of 5.0% (Example 21), or with 0.5 sensitizer in the form of an aqueous solution of sodium nitrite with a concentration of 10.0 mixed with 30.0% formaldehyde solution in a ratio of 1: 3 (examples 22, 23, 24) and with 0.05% marker additives in the form of p-MNT (example 21), or with 0.05% marker additives in the form DMDNB (examples 21, 23, 24). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 25, 26, 27, 28

The dispersion having the composition,%: oxidative phase (87.9), including 16.0 water, 11.0 sodium nitrate (examples 25, 26) or 11.0 calcium nitrate (examples 27, 28), 47, 4 ammonium nitrate (examples 25 ÷ 28); 3.5 salt flame arrester in the form of sodium chloride (examples 25, 26), or 3.5 salt flame arrester in the form of potassium chloride (examples 27, 28); combustible phase (10.1), including industrial oil 5.0 (examples 25 ÷ 28); Surfactant in the form of a mixture of alkenyl- (polyisobutylene) succinic anhydride and a fatty acid ester of the C ₁₂ -C ₁₆ fraction with a polyhydric alcohol-pentaerythritol (in a weight ratio of 0.95: 0.05) 2.0 (examples 25, 26) or as a mixture of an amino derivative of alkenyl- (polyisobutylene) succinic anhydride and a fatty acid ester of a C ₁₂ -C ₁₆ fraction with a polyhydric alcohol-glycerol (in a weight ratio of 0.5: 0.5) 2.0 (examples 27, 28 ) and a dispersion stabilizer in the form of paraffin 3.1 (example 25), or petrolatum 3.1 (example 26), or bitumen 3.1 (example 27), or polyisobutylene 3.1 (example 28) was mixed with 0.5% sensitizer in the form of microspheres (examples 25, 26), or with a 0.5% aqueous solution of sodium nitrite at a concentration of 5.0% (examples 27, 28) and with 1.5% marker additives in the form of p-MNT (examples 25, 26) or with a 1.5% marker additive in the form of DMDNB. EMU samples were prepared and tested according to example 1, the device recorded the presence of a marker.

Example 29, 30

The dispersion having the composition,%: oxidative phase (87.5), including 14.0 water, 3.0 sodium nitrate (example 29) or 3.0 calcium nitrate (example 30), 69.5 ammonium nitrate ( examples 29, 30); 0.5 salt flame arrester in the form of sodium chloride and 0.5 salt inhibitor of the reaction with sulfide-containing rocks in the form of urotropin (example 29), or 0.5 salt flame arrester in the form of potassium chloride and 0.5 salt inhibitor in the form of urea (example 30); combustible phase (9.0), including industrial oil 7.0 (examples 29, 30) and surfactant 2.0 (examples 29, 30) in the form of a mixture of the amino derivative of alkenyl- (polyisobutylene) succinic anhydride and fatty ester acids of fraction C ₁₂ -C ₁₆ with a polyhydric alcohol - polyglycerol in a weight ratio of 0.05: 0.95, or as a mixture of aminated alkenyl- (polyisobutylene) succinic anhydride and a fatty acid ester of fraction C ₁₂ -C ₁₆ with a polyatomic alcohol - sorbitol in a weight ratio of 0.95: 0.05 was mixed with 2.5% of the sensitizer in the form of microspheres (example 29) or with a 2.5% aqueous solution of n sodium yttrite with a concentration of 5.0% (example 30) and with 1.0% marker additive in the form of p-MNT (example 29) or DMDNB (example 30). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 31, 32, 33

The dispersion having the composition,%: oxidative phase (88.45), including 15.0 water, 73.45 ammonium nitrate; combustible phase (9.0), including industrial oil 5.0; A surfactant in the form of a mixture of aminated alkenyl- (polyisobutylene) succinic anhydride and a fatty acid amino fatty acid ester of fraction C ₁₂ -C ₁₆ with alkanolamine, for example triethanolamine, was mixed in a weight ratio of (0.95: 0.05) -4.0 with 0, 5% sensitizer in the form of an aqueous solution of sodium nitrite with a concentration of 5.0% in a mixture with an aqueous solution of formaldehyde (concentration of 20.0% (1: 3) and with 0.05% marker additives in the form of p-MNT and with 2.0 % solid phase in the form of an energy additive of metal powder - aluminum (example 31), or with 2.0% ferrosilicon (example 32), or 2.0% ferrosilicon (example 33) EMU samples were prepared and tested according to example 1, the device recorded the presence of a marker.

Examples 34, 35, 36

The dispersion having the composition,%: oxidative phase (77.25), including 10.0 water, 3.0 sodium nitrate (example 34) or calcium nitrate (examples 35 and 36), 64.25 ammonium nitrate (examples 34 ÷ 36); combustible phase (9.2), including industrial oil 8.0; Surfactant in the form of a mixture of aminated alkenyl- (polyisobutylene) succinic anhydride and a fatty acid amino fatty acid ester of fraction C ₁₂ -C ₁₆ with alkanolamine, for example triethanolamine, in a mass ratio (0.5: 0.5) -1.0 (example 34) or 0.75: 0.25 (example 35) or 0.05: 0.95 (example 36); dispersion stabilizer 0.2 in the form of paraffin (example 34) or 0.2 petrolatum (example 35) or 0.2 bitumen (example 36) was mixed with 1.5% of the sensitizer in the form of microspheres (examples 34 ÷ 36) and with 0, 05% of the marker additive in the form of DMDB (examples 34 ÷ 36) and with 12% of the solid phase in the form of an energy additive of powdered aluminum (example 34), or ferrosilicon (example 35), or ferrosilicon (example 36). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 37, 38

The dispersion having the composition,%: oxidative phase (71.5), including 18.0 water, 10.0 sodium nitrate (example 37) or calcium nitrate (example 38), 43.5 ammonium nitrate (examples 37, 38); combustible phase (13.0), including industrial oil 12.0 (examples 37, 38) and surfactant (1.0) in the form of a mixture of alkenyl- (polyisobutylene) succinic anhydride and amino acid fatty acid fraction C ₁₂ -C ₁₆ in a mass ratio (0.75: 0.25) -1.0 (examples 37.38) was mixed with 2.5% of the sensitizer in the form of an aqueous solution of sodium nitrite at a concentration of 5.0 (examples 37, 38) and with 3, 0% marker additives in the form of p-MNT (example 37) or with 3.0% marker additives in the form of DMDB (example 38) and with 10.0% of the solid phase in the form of granules of ammonium nitrate (examples 37, 38). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 39, 40

The dispersion having the composition,%: oxidative phase (35.0), including 10.0 water, 18.0 sodium nitrate (example 39), or calcium nitrate (example 40), 7.0 ammonium nitrate (examples 39 , 40); combustible phase (12.0), including industrial oil 9.8 (examples 39, 40) and surfactant (2.0) in the form of a mixture of the amino derivative of alkenyl- (polyisobutylene) succinic anhydride - a product of the condensation of anhydride with alkanolamine, for example with triethanolamine, and C ₁₂ -C ₁₆ fatty acid esters with a polyhydric alcohol - pentaerythritol in a mass ratio (0.95: 0.05) (Example 39), or in the form of a similar mixture in the ratio (0.05: 0.95) (example 40) and a dispersion stabilizer (0.2) in the form of petrolatum (example 39), or in the form of polyisobutylene (example 40) were mixed with 5.0% sensitizer in the form of microspheres (pr examples 39, 40) and with 3.0% marker addition in the form of DMDB (examples 39, 40) and 45.0% of the solid phase in the form of granules of ammonium nitrate (examples 39, 40). EMU samples prepared and tested according to example 1; the device detected a marker.

Example 41

The dispersion having the composition,%: oxidative phase (10.0), including 5.0 water, 5.0 ammonium nitrate; combustible phase (7.5), including industrial oil 5.0 and surfactant 2.5 in the form of a mixture of the amino derivative of alkenyl- (polyisobutylene) succinic anhydride and C ₁₂ -C ₁₆ fatty acid ester with polyhydric alcohol glycerol in the ratio (0.5: 0.5) was mixed with a 1.0% sensitizer in the form of an aqueous solution of sodium nitrite with a concentration of 10.0% and with 1.5% of the marker additive in the form of p-MNT and with 80.0% of the solid phase in the form of granules of ammonium nitrate. EMU sample prepared and tested according to example 1; the device detected a marker.

Examples 42, 43, 44, 45

The dispersion having the composition,%: oxidative phase (85.0), including 18.0 water, 67.0 ammonium nitrate; flammable phase (7.5), including industrial oil 5.0 and surfactant 2.5 in the form of a mixture of the amino derivative of alkenyl- (polyisobutylene) succinic anhydride and C ₁₂ -C ₁₆ fatty acid ester with polyhydric alcohol - polyglycerol the ratio (0.75: 0.25) (examples 42, 43), or in the form of a similar mixture, but in the ratio (0.25: 0.75) (examples 44, 45) was mixed with 1.0% of the sensitizer in the form microspheres (examples 42 ÷ 45) and with 1.5% marker additives in the form of DMDB (examples 42 ÷ 45) and with 5.0% solid phase in the form of gunpowder (example 42), or with 5.0% TNT (example 43), or with 5.0% RDX (example 44), or with 5.0% ten (example 45). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 46, 47, 48, 49

The dispersion having the composition,%: oxidative phase (59.8), including 15.0 water, 18.0 sodium nitrate (examples 46, 47), or 18.0 calcium nitrate (examples 48, 49), 26 8 ammonium nitrate (examples 46 ÷ 49); combustible phase (8.2), including industrial oil 6.0; Surfactant 2.0 in the form of a mixture of an amino derivative of alkenyl- (polyisobutylene) succinic anhydride and a C ₁₂ -C ₁₆ fatty acid ester with polyhydric alcohol sorbitol in the ratio (0.1: 0.9) (examples 46, 47), or in the form of a similar mixture in a ratio of 0.9: 0.1 (examples 48, 49) and a dispersion stabilizer (0.2) in the form of paraffin (example 46) or in the form of petrolatum (example 47), or in the form of bitumen (example 48 ), or in the form of polyisobutylene (example 49) was mixed with 0.5% of the sensitizer in the form of microspheres, with 1.5% of the marker additive in the form of p-MNT and with 30.0% of the solid phase in the form of gunpowder (example 46), or TNT (example 4 7), or RDX (example 48), or ten (example 49). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 50, 51, 52, 53

The dispersion having the composition,%: oxidative phase (35.0), including 10.0 water, 3.0 sodium nitrate (examples 50, 51), or 3.0 calcium nitrate (examples 52, 53), 0 , 5 salts of an inhibitor of the reaction with sulfide-containing rocks in the form of urotropine (examples 50, 51) or 0.5 salts of an inhibitor in the form of urea (examples 52, 53); combustible phase (13.0), including industrial oil 6.0 (examples 50 ÷ 53); Surfactant 3.0 in the form of alkenyl- (polyisobutylene) succinic anhydride (examples 50-53) and a dispersion stabilizer 4.0 in the form of paraffin (example 50), or in the form of petrolatum (example 51), or in the form of bitumen (example 52 ), or in the form of polyisobutylene (example 53) was mixed with a 0.5% sensitizer in the form of an aqueous solution of sodium nitrite with a concentration of 10.0% in a mixture (1: 3 by weight) with a 20% solution of formaldehyde (examples 50, 51) or with a 0.5% sensitizer - an aqueous solution of sodium nitrite with a concentration of 15.0% in a mixture (1: 3 by weight) with a 30% solution of formaldehyde (examples 52, 53), with a 1.5% marker additive in the formDMDNB (examples 50 ÷ 51) and with 50% of the solid phase in the form of gunpowder (example 50), or in the form of TNT (example 51), or in the form of hexogen (example 52), or in the form of ten (example 53). EMU samples prepared and tested according to example 1; the device detected a marker.

Examples 54, 55, 56, 57

The dispersion having the composition,%: oxidative phase (53.0), including 12.0 water, 39.5 ammonium nitrate and 1.5% salt-inhibitor of the reaction with sulfide-containing rocks in the form of urotropine (examples 54, 55) or urea (examples 56, 57); combustible phase (10.0), including industrial oil 6.0 and surfactant 4.0 in the form of aminated alkenyl- (polyisobutylene) succinic anhydride (examples 54 ÷ 57) were mixed with 1.0% sensitizer in the form microspheres and with 1.0% of the additive marker in the form of p-MNT (examples 54 ÷ 57) and with 20.0% of the solid phase in the form of granules of ammonium nitrate (examples 54 ÷ 57) and with 15.0% of the solid phase in the form gunpowder (example 54), either in the form of TNT (example 55), or in the form of hexogen (example 56), or in the form of ten (example 57). EMU samples prepared and tested according to example 1; the device detected a marker.

Claims (25)

1. Marked emulsion explosive composition, characterized in that it contains a mixture of a dispersion of the oxidizing phase from an aqueous solution of an inorganic salt or a mixture of several of them, or from an aqueous solution of an inorganic salt and a salt flame arrestor, or from an aqueous solution of a mixture of several inorganic salts and a salt flame arrestor or from an aqueous solution of an inorganic salt and a salt inhibiting the reaction with sulfide-containing rocks, or from an aqueous solution of a mixture of several inorganic salts and a salt inhibiting reaction with a sulfides by holding rocks in a medium of a combustible phase from liquid hydrocarbons, including a surfactant, or in a medium of a combustible phase from liquid hydrocarbons, including a surfactant and dispersion stabilizer, with a sensitizer and a marker additive in the form of para-mononitrotoluene or dimethyl dinitrobutane in the following ratio in the composition, wt.%:
sensitizer 0.5 ÷ 10.0 marker additive 0.05 ÷ 3.0 dispersion the rest is up to 100 2. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 0.5% sensitizer from an aqueous solution of sodium nitrite or microspheres; 0.05% marker additives in the form of para-mononitrotoluene and 99.45% dispersion, including: oxidative phase, including 21.0% water; 69.45% ammonium nitrate; a medium of a combustible phase from industrial oil 5.0% and surfactant 4.0%. 3. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 10.0% of the sensitizer in the form of perlite sand, 3.0% of the marker additive in the form of dimethyldinitrobutane and 87.0% of the dispersion,
including:
an oxidizing phase comprising 10.0% water; 3.0% sodium or calcium nitrate; 65.0% ammonium nitrate; a medium of a combustible phase from industrial oil 8.0% and a surfactant 1.0%. 4. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 0.5% sensitizer in the form of microspheres or an aqueous solution of sodium nitrite, 3.0% marker additives in the form of para-mononitrotoluene and 96.5% dispersion,
including:
an oxidizing phase comprising 16.0% water; 18.0% sodium or calcium nitrate; 49.5% ammonium nitrate; the environment of the combustible phase from industrial oil 11.5%; surfactant 1.0%, a dispersion stabilizer in the form of paraffin, or petrolatum, or bitumen, or polyisobutylene 0.5%. 5. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 5% sensitizer in the form of perlite sand; 0.05% marker additive in the form of dimethyldinitrobutane and 94.95% dispersion,
including:
an oxidizing phase comprising 16.0% water; 0.5% salt flame arrester in the form of sodium chloride or potassium chloride; 66.95% ammonium nitrate; medium of a combustible phase from industrial oil 5.0%; surfactant 2.5%; dispersion stabilizer in the form of paraffin or petrolatum, or bitumen, or polyisobutylene 4.0%. 6. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 2.5% sensitizer in the form of microspheres or an aqueous solution of sodium nitrite in a mixture with a solution of formaldehyde; 1.5% marker additives in the form of para-mononitrotoluene and 96.0% dispersion,
including:
an oxidizing phase comprising 16.0% water; 7.0% salt flame arrester in the form of sodium chloride or potassium chloride; 63.4% ammonium nitrate; medium of a combustible phase from industrial oil 5.0%; surfactant 2.5% and a dispersion stabilizer in the form of paraffin or petrolatum, or bitumen, or polyisobutylene 2.1%. 7. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 0.5% sensitizer in the form of microspheres or an aqueous solution of sodium nitrite; 1.5% marker additive in the form of dimethyldinitrobutane and 98.0% dispersion,
including:
an oxidizing phase comprising 16.0% water; 10.5% sodium or calcium nitrate; 62.0 ammonium nitrate; 0.5% salt inhibiting the reaction with sulfide-containing rocks in the form of urotropine or urea; a medium of a combustible phase from industrial oil 7.0% and a surfactant 2.0%. 8. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 0.5% sensitizer in the form of an aqueous solution of sodium nitrite; 0.05% marker additive in the form of para-mononitrotoluene and 99.45% dispersion,
including:
an oxidizing phase comprising 16.0% water; 3.0% sodium or calcium nitrate; 64.95% ammonium nitrate; 1.5% salt - an inhibitor of the reaction with sulfide-containing rocks in the form of urotropine or urea; the environment of the combustible phase from industrial oil 12.0%; surfactant 1.0% and a dispersion stabilizer in the form of paraffin, or petrolatum, or bitumen, or polyisobutylene 1.0%. 9. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 0.5% sensitizer from microspheres or a mixture of an aqueous solution of sodium nitrite with an aqueous solution of formaldehyde; 1.5% marker additive in the form of dimethyldnitrobutane and 98.0% dispersion,
including:
an oxidizing phase comprising 16.0% water; 11.0% sodium nitrate or calcium nitrate; 57.4% ammonium nitrate; 3.5% salt flame arrester in the form of sodium chloride or potassium chloride; medium of a combustible phase from industrial oil 5.0%; surfactant 2.0% and a dispersion stabilizer in the form of paraffin, or petrolatum, or bitumen, or polyisobutylene 3.1%. 10. Marked emulsion explosive composition according to claim 1, characterized in that it contains a mixture of 2.0% sensitizer in the form of microspheres; 1.5% marker additives in the form of para-mononitrotoluene and 96.5% dispersion,
including:
an oxidizing phase comprising 14.0% water; 3.0% sodium nitrate or calcium nitrate; 69.5% ammonium nitrate; 0.5% salt flame arrester in the form of sodium chloride or potassium chloride; 0.5% sulfide-containing reaction inhibitor salt is defined as urotropine or urea; a medium of a combustible phase from industrial oil 7.0% and a surfactant 2.0%. 11. Marked emulsion explosive composition according to claim 1, characterized in that as a sensitizer contains microspheres - from 0.5 to 10.0% or perlite sand - from 5 to 10%, or an aqueous solution of sodium nitrite concentration of 5 ÷ 15% , or its mixture 1: 3 with an aqueous solution of formaldehyde concentration of 20 ÷ 30%, taken in an amount of 0.5 ÷ 2.5% by weight of the composition. 12. The labeled emulsion explosive composition according to claim 1, characterized in that the combustible phase medium contains, as a surfactant, a compound selected from the class of fatty acid esters of fraction C ₁₂ -C ₁₆ with polyhydric alcohols from pentaerythritol, glycerol, polyglycerol , sorbitol, amino esters or amino derivatives of the class of said acids or acid anhydrides represented alkenyl- (polyisobutylene) succinic anhydride, or its mixtures with fatty acid esters of fraction C ₁₂ -C ₁₆ alcohol with a polyatomic and from among pentaerythritol, glycerol, polyglycerol, sorbitol, or with aminoester acid fraction C ₁₂ -C _16, or an amino derivative represented alkenyl- (polyisobutylene) succinic anhydride obtained by its condensation with an alkanolamine, preferably triethanolamine, or a polyamine, or mixtures thereof in any ratio alkenyl- (polyisobutylene) succinic anhydride with its amine derivatives or mixtures thereof in any ratio alkenyl- amino derivative (polyisobutylene) succinic anhydride with esters of acids of fraction c ₁₂ -C ₁₆ and polyhydric sleep comrade from among pentaerythritol, glycerol, polyglycerol, sorbitol or amines of these acids. 13. A labeled emulsion explosive composition, characterized in that it contains a dispersion mixture comprising an oxidizing phase from an aqueous solution of an inorganic salt, or a mixture of several of them, or from an aqueous solution of an inorganic salt and a flame arrestor salt, or from an aqueous solution of a mixture of several inorganic salts and salt flame arrester, or from an aqueous solution of an inorganic salt and an inhibitor of the reaction with sulfide-containing rocks, or from an aqueous solution of a mixture of several inorganic salts and an inhibitor of the reaction with sul containing rocks, in a combustible phase medium from liquid hydrocarbons containing a surfactant, or in a combustible phase from liquid hydrocarbons containing a surfactant and dispersion stabilizer, with a sensitizer and a marker additive in the form of para-mononitrotoluene or dimethyl dinitrobutane and additionally - with a solid phase selected from granules of ammonium nitrate or energy additives from powders of metals or their alloys, or blasting explosives, or gunpowders in the following ratio ponents, wt.%:
sensitizer 0.5 ÷ 5.0 marker additive 0.05 ÷ 3.0 solid phase 2.0 ÷ 80.0 dispersion the rest is up to 100 14. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 0.5% sensitizer in the form of an aqueous solution of sodium nitrite in a mixture with an aqueous solution of formaldehyde; 0.05% of the additive is a marker in the form of para-mononitrotoluene; 2.0% of the solid phase in the form of an energy additive from powders of metals or their alloys selected from aluminum or ferrosilicon, or ferrosilicon, and 97.45% of the dispersion,
including:
the oxidizing phase, including 15.0% water, 73.45% ammonium nitrate; a medium of a combustible phase from industrial oil 5.0%; surfactant 4.0%. 15. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 1.5% sensitizer in the form of microspheres, 0.05% of the additive is a marker in the form of dimethyldinitrobutane; 12.0% of the solid phase in the form of an energy additive from powders of metals or their alloys selected from aluminum or ferrosilicon or ferrosilicon aluminum, and 86.45% of the dispersion,
including:
an oxidizing phase comprising 10.0% water; 3.0% sodium nitrate or calcium nitrate; 64.25% ammonium nitrate; the environment of the combustible phase from industrial oil 8.0%; surfactant 1.0%; dispersion stabilizer in the form of paraffin or petrolatum, or bitumen 0.2%. 16. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 2.5% sensitizer in the form of an aqueous solution of sodium nitrite; 3.0% marker additive in the form of para-mononitrotoluene; 10.0% of the solid phase in the form of granules of ammonium nitrate and 84.5% dispersion,
including:
an oxidizing phase comprising 18.0% water; 10.0% sodium nitrate or calcium nitrate; 43.5% ammonium nitrate; the environment of the combustible phase from industrial oil 12.0%; surfactant 1.0%. 17. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 5.0% sensitizer in the form of microspheres; 3.0% dimethyl dinitrobutane marker additive; 45% of the solid phase in the form of granules of ammonium nitrate and 47.0% dispersion,
including:
an oxidizing phase comprising 10.0% water; 18.0% sodium nitrate or calcium nitrate; 7.0% ammonium nitrate; the environment of the combustible phase from industrial oil 9.8%; surfactant 2.0% and a dispersion stabilizer in the form of petrolatum or polyisobutylene 0.2%. 18. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 1.0% sensitizer in the form of an aqueous solution of sodium nitrite; 1.5% marker additive in the form of para-mononitrotoluene; 80.0% of the solid phase in the form of granules of ammonium nitrate and 17.5% dispersion,
including:
an oxidizing phase comprising 5.0% water; 5.0% ammonium nitrate; a medium of a combustible phase from industrial oil 5.0% and a surfactant 2.5%. 19. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 1.0% sensitizer in the form of microspheres; 1.5% marker additive in the form of dimethyldinitrobutane; 5.0% of the solid phase in the form of gunpowder or blasting explosive selected from TNT, or RDX, or PETN, and 92.5% of the dispersion,
including:
an oxidizing phase comprising 18.0% water; ammonium nitrate 67.0%; a medium of a combustible phase from industrial oil 5.0% and a surfactant 2.5%. 20. Marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 0.5% sensitizer in the form of microspheres; 1.5% marker additive in the form of para-mononitrotoluene; 30.0% of the solid phase in the form of gunpowder or blasting explosive selected from TNT, or RDX, or PETN, and 68.0% of the dispersion
including:
an oxidizing phase comprising 15.0% water; 18.0% sodium nitrate or calcium nitrate; 26.8% ammonium nitrate; a medium of a combustible phase from industrial oil 6.0%; surfactant 2.0% and a dispersion stabilizer in the form of paraffin, or petrolatum, or bitumen, or polyisobutylene 0.2%. 21. The marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 0.5% sensitizer in the form of an aqueous solution of sodium nitrite in a mixture with an aqueous solution of formaldehyde; 1.5% marker additive in the form of dimethyldinitrobutane; 50.0% of the solid phase in the form of a blasting explosive selected from TNT, or RDX, or PETN, or gunpowder, and 48% of the dispersion,
including:
an oxidizing phase comprising 10.0% water; 3.0% sodium nitrate or calcium nitrate; 21.5% ammonium nitrate; 0.5% salt inhibiting the reaction with sulfide-containing rocks in the form of urotropine or urea; a medium of a combustible phase from industrial oil 6.0%; surfactant 3.0% and a dispersion stabilizer in the form of paraffin, or petrolatum, or bitumen, or polyisobutylene 4.0%. 22. The marked emulsion explosive composition according to item 13, characterized in that it contains a mixture of 1.0% sensitizer in the form of microspheres, 1.0% marker additives in the form of para-mononitrotoluene; 20.0% of the solid phase in the form of granules of ammonium nitrate; 15.0% of the solid phase in the form of gunpowder or blasting explosive selected from TNT, or RDX, or PETN, and 63.0% of the dispersion,
including:
an oxidizing phase comprising 12.0% water; 39.5% ammonium nitrate; 1.5% salt inhibiting the reaction with sulfide-containing rock in the form of urotropine or urea; a medium of a combustible phase from industrial oil 6.0%; surfactant 4.0%. 23. The marked emulsion explosive composition according to item 13, characterized in that the solid phase from the granules of ammonium nitrate is introduced into the composition in an amount of from 10 to 80%, the energy additive from metal powders or their alloys is from 2 to 12%, and the powder or blasting explosive - trotyl or hexogen, or ten - from 5 to 50%. 24. Marked emulsion explosive composition according to item 13, characterized in that as a sensitizer contains microspheres - from 0.5 to 10.0%, or perlite sand - from 5 to 10%, or an aqueous solution of sodium nitrite concentration of 5 ÷ 15 %, or its mixture 1: 3 with an aqueous solution of formaldehyde concentration of 20 ÷ 30%, taken in an amount of 0.5 ÷ 2.5%. 25. The marked emulsion explosive composition according to claim 13, characterized in that the combustible phase medium contains, as a surfactant, a compound selected from the class of fatty acid esters of fraction C ₁₂ -C ₁₆ with polyhydric alcohols from the number pentaerythritol, glycerol, polyglycerol , sorbitol, or amino derivatives of the class of amino esters of these acids or acid anhydrides represented by alkenyl- (polyisobutylene) succinic anhydride, or mixtures thereof with fatty acid esters of fraction C ₁₂ -C ₁₆ with polyhydric alcohols from pentaerythritol, glycerin, polyglycerol, sorbitol, either with amino acid esters of the C ₁₂ -C ₁₆ fraction, or is an amino derivative of alkenyl- (polyisobutylene) succinic anhydride obtained by condensation with alkanolamine, preferably triethanolamine or polyamine, or mixtures thereof in any the ratios of alkenyl- (polyisobutylene) succinic anhydride with its amino derivatives, or mixtures in any ratios of the amino derivative of alkenyl- (polyisobutylene) succinic anhydride with esters of acids of fraction C ₁₂ -C ₁₆ and polyhydric alcohol in the number of pentaerythritol, glycerol, polyglycerol, sorbitol or amino esters of these acids.