SK4622001A3 - Emulsion explosive modifier - Google Patents

Abstract

A modifier of brisance (i.e. shattering effect) for water-in-oil emulsion explosives, composed of a macromolecular component consisting of a prepolymer or polymer with the construction units-[CH2-C(X)=CH-CH2]-in its macromolecule where X is -H or -CH3, and which is terminated by hydroxi- or isocyanate groups or polyisobutylene groupings. Its use in an emulsion explosive reduces its brisance while preserving its working ability and raising the physical consistency of this explosive.

Description

The invention relates to a water-in-oil emulsion explosive modifier consisting of a macromolecular component based on butadiene (liquid rubbers) and / or isobutylene.

BACKGROUND OF THE INVENTION

When we look at the water-in-oil emulsion explosives (code number W O) as a mixture of chemical components, it is an oxidation-reduction system, as with most mixed explosives. The fuel-oxidant mixture is supplemented with a suitable non-explosive sensitizer capable of participating by generating hot cores in initiating and developing a chemical reaction during detonation.

In most mixed explosives, the basic oxidant is ammonium nitrate, often in combination with other nitrates (eg sodium, potassium, calcium, Utne, etc.) or even perchlorates (sodium or ammonium). A wide, almost opaque palette of primarily carbonaceous compounds of mineral and / or synthetic origin is used as fuel (see, e.g., Xuguang: Emulsion Explosives. Metallurgical Ind. Press, Beijing, 1994). The most commonly used fuels are paraffin oils and waxes, mineral, petroleum or vegetable oils, microcrystalline waxes and some petroleum fractions. The choice of a particular fuel or fuel mixture is dictated by the requirements for the rheology of the resulting explosive and its physical and storage stability. In some cases, the fuel phase may also include metal powders (especially aluminum) and individual explosives (demilitarized trinitrotoluene and / or hexogen and demilitarized propulsive explosives).

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In conventional W / 0 emulsion explosives the rule is that both the oxidation and fuel components are present in the liquid state, the discontinuous oxidant phase in the form of microspheres of a supersaturated solution of oxidants and other water-soluble additives is dispersed in the continuous (oil) fuel phase. microgide (s) of the oxidant phase). The formation of a continuous and solid interface between the continuous and discontinuous phases is achieved by the addition of lipophilic-hydrophilic components to the oil phase, i.e. emulsifiers, of which sorbitan monooleate and / or sesquioleate are the most commonly used in the art.

Strengthening of the continuous phase film and thereby increasing the physical stability of the resulting emulsion (emulsion matrix) can be achieved by adding to the fuel phase some oligomers, polymers and / or copolymers (see, e.g., W. Xugitang: Emulsion Explosives. Metalliirgical Ind. Press, Beijing, 1994) . The use of isobutylene-butadiene-based oligomers, polymers and resins is also described in this regard (see, e.g., Can. Pcif. Appl. CA 2,107,966 from 1994 or .Jpn. Kokai Tokkyo Koho .IP 59,156,991 from 1984). here, in particular, the hydroxy-terminal liquid polybutadiene has a beneficial effect on increasing the stability of the emulsion. In the manufacture of such explosives, hydrophilic terminated polyisobutylenes sometimes appear as polymeric emulsifiers, the use of which significantly increases the life of the final product.

The extremely large interfacial interface surfaces in the emulsion explosive matrix ensure perfect contact of both phases, which is the most perfect of all mixed industrial explosives. This fact corresponds to the short reaction zone in the detonation wave: at a suitable sensitivity and initiation, explosives of this type can be considered to be largely equivalent to dynamites due to the high reactivity of the system, the high utilizable energy yield and the resulting rock disintegration effect.

Compared to dynamites (i.e. explosives containing nitroesters), emulsion explosives have a number of significant advantages such as insensitivity to mechanical stimuli, flame and sparks, high water resistance and minimal physiological activity not only of the emulsion composition itself, but also of explosion fumes. Emulsion explosives, however, can be phlegmatized, up to completely numb, by the dynamic shock, in particular a strong compression stress wave, caused by the detonation of a near charge in the rock mass. Another disadvantage is that only mine-safe explosives can be produced on the basis of emulsion explosives.

Categories. Both of these disadvantages are mainly related to the relatively high brisance (i.e.

the explosive effect).

The most widespread principle of designing mining-safe explosives containing nitroesters is to incorporate a cooling additive (the most recent sodium chloride) or a cooling ion exchange system (e.g., a mixture of ammonium chloride and sodium nitrate) into the explosive mixture. This leads to a decrease in the working ability and the chances of the resulting explosive compared to nitroester explosives without coolants. However, as is apparent from the exemplary part of the present invention, an analogous incorporation of sodium chloride in an amount of max. 10% by weight. into an emulsion explosive mixture, while reducing its working ability, but increasing brisance. The cooling effect of the additive can thereby be eliminated to some extent. The problem of emulsion explosives is a decisive factor in the construction of mining-safe explosives based on them. The data published so far show that a systematic study of the effect of the chemical nature of the components of the reduction-oxidation system of these explosives on their brisance has not been paid attention yet.

SUMMARY OF THE INVENTION

According to the present invention the water-in-oil emulsion explosive is treated by adding to the oil phase of a butadiene or isobutylene, prepolymer or polymer based macromolecular component with building units - [CH ₂ -C (X) = CHCH ₂ ] - in its macromolecule, where X is -H or -CH ₂ which is terminated by hydroxyl or isocyanate groups or polyisobutylene groups. The advantage is that the relatively small addition of said macromolecular components (0.50 to 1.80% by weight per weight of the resulting explosive) will significantly reduce brisance while maintaining the working ability of the emulsion explosive, but at the same time significantly increase its stability and modify the consistency of the resulting explosive. that, if the coolant is incorporated into its composition, it will provide a Category I mine safety explosive. A further advantage of the present invention is the availability of these macromolecular components which are industrially produced for the needs of the plastics and / or rubber industry, as well as for the production of special types of explosives.

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The use of butadiene or isobutylene-based macromolecular components within the meaning of the present invention has not been described in the literature to date and is documented by the following examples, which in no way exclude the possible variability of applications.

BRIEF DESCRIPTION OF THE DRAWINGS

The graph illustrates the graphical dependence of the relative working ability (RPS) of the emulsion explosives of Example 1 and Example 2 on their performance, represented by the product of the specific charge mass and the square of the detonation velocity, ie the expression p * D ² .

DETAILED DESCRIPTION OF THE INVENTION

Example I

A solution of ammonium nitrate (AN) and optionally sodium nitrate (SN) and / or calcium nitrate (CN) and / or sodium perchlorate (SP) in water having a temperature of 85-100 ° C, optionally containing other water-soluble components such as Sodium chloride (SN), glycol, and the like, is impregnated into an emulsifier, in which an intensively mixed (agitator at 1000 to 1500 rpm) oil phase 80-85 ° C warm, consisting of a mineral oil (having a specific weight) 910 kg.m'j pour point max. -5 ° C and flash point min. 66 ° C) and / or slack wax (throw (bend 39 ° C, flash time)

220-260 ° C and an oil content of about 1.5% by weight), sorbitan monooleate (M) and / or sorbitan sesquioleate (S), optionally also macromolecular components. After the inlet of the aqueous salt solution is complete, the mixture is stirred for an additional 5 minutes. The resulting explosive mixtures are then loaded into plastic casings prepared by charges of 32 mm diameter and weight of 400 g, which determine the specific charge mass (p), detonation velocity (D, initiation by detonator No. S) and relative working ability (KPS). . An overview of the composition of the individual mixtures prepared according to this procedure is given in the table of Example 1, which also includes the respective p, D and kPS values.

The following macromolecular components of the oil phase are used:

Liquid polybutadiene rubber (LBH) with hydroxyl end groups having an average molar mass of 2400-3100, a polydispersity index of approximately 1.1 and a hydroxyl content of approximately 0.7 mmol.g ^-1 , in which the number of structural units of its macromolecule - [CH ₂ -CH = CH-CH ₂ ] - is about 44 to 57.

liquid isocyanate prepolymer (LBD - terminated by isocyanatotolylene groups) with a basic polybutadiene chain of an average molar mass of 3200-3800, a polydispersity index of about 1.3 and a functionality of about 2.2, in which the number of structural building units of its macromolecule - [CH ₂ -CH = CHCH ₂ ] - is also about 44 to 57.

a solid polyisobutadiene (PIB) copolymer with 2 mol%. isoprene of an average molar mass of 200 000 of the general structural formula:

- [- (C (CH ₃ ) ₂ -CH ₂ -) _m - (- CH ₂ -C (CH ₃ ) = CH-CH ₂ -), -]> - wherein m »n.

In some LBD-containing emulsion mixtures, namely mixtures 1.1, 1.3 and 1.4 of the table, a crosslinking catalyst is used to obtain plastic, well-formable matrices capable of being filled with crystalline additives up to 50% by weight. without losing the coherence of the final mixture. The subject macromolecular additives also increase the lifetime of emulsion explosives containing them (min. 6 months) compared to emulsion explosives without their contents (lifetime 3 - 6 months).

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CN - calcium nitrate LBH - hydroxyterminated polybutadiene RPS - relative working ability

SP - Sodium perchlorate S - Sorbitan sesquioleate

NaCl - sodium chloride M - Sorbitan monooleate

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Example 2 (comparative)

It proceeds according to MS. U. S. Pat. 229745 (19S2): solution of ammonium nitrate (AN) and sodium (SN) 80-90 ^° C warm is presented to the emulsifier, to which is added a solution of oleic acid in mineral oil and then an aqueous solution of sodium hydroxide. The mixture is stirred until an emulsion is formed which is sensitized in the homogenizer by the addition of expanded perlite. An emulsion explosive of 62.9% by weight is thus obtained. AN, 13% by weight. SN, 12 wt.%. water, 2.5% sodium hydroxide, 2.8% wt. oil, 2.8 wt.%. oleic acid and 4 wt. of expanded perlite, which is declared as Emsit. Its average charge weight was 1.06 g.cm ^"3, the speed of detonation D = 4817 m s ^-1 and relative working ability RPS = 69.5%.

The graphical dependence of the relative working ability (RPS) of the emulsion explosives of Example 1 and Example 2 on their brisance, represented by the product of the specific charge mass and the square of the detonation velocity, is constructed by the expression p * D ² . It follows from this dependence that the macromolecular components of the oil phase in Example 1 significantly reduce the brisance of the respective emulsion explosives compared to explosives in which these components are not used (including Emsit of Example 2). This effect is significant in the production of mining-safe explosives. The graphical dependence also shows that in both groups of emulsion explosives the increasing solids content of higher molar mass in the detonation products corresponds to the decrease of RPS values and the increase of brisance (also for the content of mineral sensitizer).

The explosive mixture 1.7 of the table of Example 1, in the form of 32 mm diameter cartridges, when detonated at 1050 g, does not ignite a 9% methane airborne methane mixture and 1,200 g coal dust / air mixture at 300 g / m ³ dust. The determined limit charge (diameter · 32 mm) of this explosive is 1241 ± 72 g. The gaseous products of its detonation do not contain nitrogen oxides.

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Industrial usability

A water-in-oil emulsion matrix suitable for finalizing an emulsion explosive with suppressed fragmentation and retained sliding effect, for example explosives with increased mining safety.

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Claims (2)

A water-in-oil emulsion explosive modifier in which the discontinuous phase consists of an aqueous solution of inorganic nitrates and / or perchlorates, or other components of inorganic and organic nature, optionally comprising a cooling component from the group of inorganic chlorides, characterized in that it consists of prepolymer, or a polymer with building units - [CH 2 -C (X) = CH-CH ₂ ] - in its macromolecule, wherein X is -H or -CH% which is terminated by hydroxyl or isocyanate groups or polyisobutylene groups. An emulsion explosive modifier according to claim 1, characterized in that it constitutes 0.5 to 1.8% by weight. %, preferably from 0.6 to 1.57% by weight. explosives calculated on the weight of the final emulsion explosive. f r <ľ ¾ R r c r c rrrr, r < C. ^r : rf Ι.5ΟΕ + Ό7 1.70E + 07 1.90E + 07 2.10E + 07 2.30E + 07 2.50E + 07 2.70E + 07