[0001] The invention relates to emulsion explosive compositions having a discontinuous phase
comprising an oxygen- releasing salt and a continuous liquid organic phase and in
particular to emulsion explosives compositions containing an oil-soluble polymer having
associative groups.
[0002] Emulsion explosive compositions have been widely accepted in the explosives industry
because of their excellent explosive properties and ease of handling. The emulsion
explosive compositions now in common use in the industry are of the water-in-oil type
first disclosed by Bluhm in US Patent No. 3 447 978 and comprise as components:
(a) a discontinuous aqueous phase comprising discrete droplets of an aqueous solution
of inorganic oxygen- releasing salts;
(b) a continuous water-immiscible organic phase throughout which the droplets are
dispersed; and
(c) an emulsifier which forms an emulsion of the droplets of oxidizer salt solution
throughout the continuous organic phase.
[0003] For some applications, water content of the oxidizer phase of the emulsion may be
eliminated or reduced to a low level, for example, to less than 4% by weight of the
total emulsion composition. Such compositions are conveniently referred to as melt-in-oil
or melt-in-fuel emulsion explosives and have been described, for example, in US Patent
4 248 644.
[0004] The term "emulsion explosive" is used herein to embrace compositions of both the
water-in-oil and the melt-in-oil types.
[0005] Emulsion explosives may be handled in bulk and are easily loaded into boreholes for
large-scale blasting operations. A particular problem however arises where boreholes
contain water, for example, after rain. In such cases, and in particular where boreholes
become completely or partially filled with water, the explosive performance of emulsion
explosives is severely reduced. This is a particular problem when using blends of
emulsion explosive and a solid adjuvant such as ammonium nitrate prills or ANFO.
[0006] Indeed, in many cases it is difficult to detonate an emulsion explosive charge which
has been loaded into a borehole containing water.
[0007] Due to these problems it has generally been the practice to drain water from a borehole
before loading the explosive. This is both time consuming and labour intensive.
[0008] If emulsion explosives are carefully loaded into the bottom of a borehole via a hose,
it is sometimes possible to displace water from the bore-hole. However, this again
is a time consuming procedure and unsatisfactory for deep boreholes.
[0009] We have now developed an emulsion explosive composition which is highly elastic and
which may be loaded into wet boreholes without using such procedures.
[0010] Further advantages of the composition of the present invention will become evident
on considering the physical properties of the emulsion explosive composition.
[0011] Accordingly we provide an emulsion explosive composition comprising a discontinuous
phase comprising at least one oxygen-releasing salt; a continuous organic phase; an
emulsifying agent; and at least one polymer soluble in the organic phase and wherein
the polymer comprises associative functional groups.
[0012] Generally the associative functional groups are polar groups capable of entering
into specific association with other associative groups.
[0013] Examples of associative functional group may be selected from a group of : ionmeric
functional groups; functional groups which are capable of protolytic reactions; and
groups capable forming hydrogen bonds.
[0014] Examples of functional groups capable of association through hydrogen bond formation
may be selected from the group consisting of hydroxyl, carboxyl and carboxamide functional
groups.
[0015] Examples of ionomeric functional groups include those selected from the groups of
salts of sulphonic and carboxylic acids such as metal and ammonium ion salts thereof,
and quaternary ammonium salts.
[0016] Examples of groups capable of undergoing protolytic reaction include acid groups
such as carboxylic, sulphonic and phosphoric acid groups and basic groups such as
nitrogen-containing basic groups.
[0017] Examples of nitrogen-containing basic groups may be chosen from the groups of formula
I

where R¹ and R² may be aryl, aralkyl, alkyl cycloalkyl or hydrogen and R¹ and R²
may together form a 5 or 6 membered heteocyclic ring by a linking group of 4 or 5
members; and nitrogen containing heteroaromatic group such as pyridyl, picolinyl,
quinolinyl, isoquinolinyl and quinoxalinyl groups and the salts thereof. Preferred
acid and basic groups include the carboxylic acid group, sulphonic acid group and
pyridyl group.
[0018] Examples of the group of formula I wherein R¹ and R² form a heterocycle include pyrazolinyl,
pyrrolidinyl, peperazinyl and morpholinyl.
[0019] The said polymer may comprise more than one type of functional group. For example
said polymer may comprise a plurality of different monomers capable of undergoing
dipole-dipole interaction or protolytic reaction with one another.
[0020] Polymers suitable for use in preparation of compositions of the invention may be
prepared by conventional polymerization techniques. Suitable polymers may be prepared
by addition polymerization reactions using at least one main monoethylenically unsaturated
monomer and at least one associative monomer comprising a functional group chosen
from associative functional groups as hereinbefore described, and groups capable of
conversion to said associative functional groups.
[0021] Examples of main monoethylenically unsaturated monomers (hereinafter referred to
as main monomer) may be selected from the group consisting of: alkenes, preferably
comprising from 2 to 6 carbon atoms such as ethylene and propylene; higher alkyl acrylates
and methacrylates, in which the alkyl group contains from 4 to 18 carbon atoms, for
example 2-ethyl hexylacrylate, stearyl methacrylate and lauryl 30 methacrylate; styrenes;
alkyl styrenes in which the alkyl group contains from 1 to 12 carbon atoms, for example
tertiarybutyl styrene; and vinyl esters of fatty acids, such as vinyl stearate.
[0022] Particularly preferred main monomers are lauryl methacrylate, styrene and tert-butylstyrene.
[0023] Examples of associative monomers may be chosen from the groups consisting of:
vinyl substituted nitrogen containing heteroaromatic compounds such as vinyl pyridines,
vinylpicolines, vinyl quinolines, vinylisoquinolines and vinyl quinoxalines, hydroxy(C₁
to C₆)alkyl acrylates and methacrylates, such as hydroxyethyl acrylate and hydroxy
propyl methacrylate; acrylic acid, methacrylic acid and their metal or amine salts;
acrylamide; methacrylamide; acids selected from the group of styrene sulfonic acid,
vinyl sulfonic acid, 2-acrylamides, propane sulfonic acid, acrylic acid, methacrylic
acid; and the metal salts of these acids; halide salts of quaternary ammonium compounds
selected from the group consisting of dimethylammonium methacrylate, diethylammonium
ethyl-methacrylate; diethylammonium ethyl-methacrylate; and precursors of these monomers.
Particularly preferred associative monomers are methacrylic acid and metal and amine
salts thereof, and vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine.
[0024] Where the associative monomer comprises an associative group precursor, the precursor
will be capable of conversion to an associative group following polymerization.
[0025] For example, dienes such as norbornene and butadiene may be used in the preparations
of polymers, and the monmeric units derived therefrom may be converted to sulfonic
acids and thence to salts of sulfonic acids by procedures known to those in the art.
[0026] Emulsion polymerization is a particularly convenient technique for preparation of
copolymers for use in the present composition However, the method of preparation is
not narrowly critical and the skilled artisan will be well acquainted with a wide
variety of techniques for preparation of suitable polymers.
[0027] The polymers can conveniently be obtained by aqueous emulsion copolymerisation of
the constituent monomers employing if necessary a minor proportion of a water-miscible
organic co-solvent, such as acetone, in order to enhance the solubility of the monomer
mixture in the aqueous continuous phase (the main monomers described above will inherently
have very low solubilites in water and a measurable degree of solubility in the continuous
phase is necessary if the polymerisation is to proceed at an acceptable rate). The
polymerisation is generally carried out at a temperature in the range 0 - 70°C, preferably
10 - 60°C, in an inert gas atmosphere and in the presence of a water-soluble free
radical initiator system, such as ammonium persulphate or potassium persulphate in
combination with sodium dithionite optimally, sodium sulphite, sodium thiosulphate
or ascorbic acid. There may be added to the polymerisation mixture water-soluble surfactants
such as sodium dodecylbenzenesulphonate, sodium dioctylsulphosuccinate, sodium lauryl
sulphate or salts of sulphated nonylphenol-ethylene oxide condensates. The amount
of initiator (or initiator combination) used may typically lie in the range 0.05%
to 1%, and the amount of surfactant in the range 1% to 15%, based on the weight of
the monomer mixture. The polymerisation may be effected by a "one-shot" procedure,
in which all the monmer required is introduced into the reaction mixture at once,
or by a "seed and feed" procedure in which a small proportion of the total monomer
mixture is polymerised initially to form a "seed" polymer dispersion and the remainder
of the monomer is then added gradually. Chain transfer agents, such as n-octyl mercaptan,
dodecyl mercaptan or chloroform, may also be added during the course of the polymerisation,
especially in the later stages when more than 75% of the monomer has beeen polymerised,
in order to regulate the formation of the polymer.
[0028] Typically, the polymers are prepared using 0.001 to 30% associative monomer by weight
of total monomer and preferably 0.01 to 20% w/w.
[0029] Typically, the total amount of said polymer will comprise in the range of 0.001 to
10% by weight of the emulsion composition. However, we have found that particularly
good results are obtained by using in the range of 0.01 to 2% of the total emulsion
composition. Generally, the amount of polymer will be in the range of 0.001 to 20%
w/w based on the organic phase and preferably in the range 0.1 to 10%. However, higher
or lower quantities may be used if desired, the amount of polymer being determined
without undue experimentation based on the required properties of the emulsion.
[0030] As hereinbefore stated the polymer is soluble in the organic phase. Generally, the
polymer will be soluble in the organic phase at the polymer/organic phase weight ratio
to be usd in the emulsion explosive.
[0031] Hence the polymer will generally be soluble in the organic phase at a concentration
of at least 0.001% w/w and preferably at least 0.1% w/w.
[0032] One polymer particularly useful for the preparation of composition of the invention
is a polymer of styrene, lauryl methacrylate and methacrylic acid.
[0033] An example of such a polymer may be derived by emulsion polymerization from a mixture
of 10-80% w/w styrene, 10-80% w/w lauryl methacrylate and 0.1-10% w/w methacrylic
acid. A particularly preferred composition comprises 50-60% lauryl methacrylate, 40-50%
styrene and 1-4% methacrylic acid.
[0034] As hereinbefore discussed, the emulsion explosive compositions of the present invention
have advantages over conventional explosives, making them more suitable for loading
in wet boreholes.
[0035] Without wishing to be bound by theory, we believe that the better wet borehole performance
of the emulsions of the invention may be due to their elastic and cohesive nature.
Unlike conventional emulsion explosives which tend to break up when loaded into water,
the emulsions of the present invention pass easily through water. The cohesive properties
and resilience also make the emulsion explosive composition particularly useful in
packaged products.
[0036] Emulsion explosives of the invention typically have an elastic modulus in the range
100-1000 Pa at 20°C. Typically, the viscosity is in the range 120,000 to 800,000 cp
at 20°C.
[0037] The advantages of the emulsion explosive compositions are particularly apparent when
the polymer has an average weight molecular weight of at least 1 x 10⁵. Preferably
the polymer has an average molecular weight in the range 5 X 10⁵ to 1 X 10⁷, more
preferably 1 x 10⁶ to 1 x 10⁷. This is particularly surprising as it was expected
that the bulk of high molecular weight polymer molecules may disrupt the stability
of an emulsion explosive.
[0038] For example, in the case of water-in-oil emulsion explosives. it is generally believed
that droplets of oxidizer solution in an emulsion explosive are separated by bilayers
of oil phase which are 5 to 20 nm thick, hence bulky polymer molecules of molecular
weight 1 x 10⁶ and higher that are typically 100 to 200 nm in diameter were not expected
to be compatible with an emulsion explosive.
[0039] Suitable oxygen-releasing salts for use in the discontinuous phase component of the
composition of the present invention include the alkali and alkaline earth metal nitrates,
chlorates and perchlorates, ammonium nitrate, ammonium chlorate, ammonium perchlorate
and mixtures thereof. The preferred oxygen-releasing salts include ammonium nitrate,
sodium nitrate and calcium nitrate. More preferably, the oxygen-releasing salt comprises
ammonium nitrate or a mixture of ammonium nitrate and sodium or calcium nitrates.
[0040] Typically, the oxygen-releasing salt component of the compositions of the present
invention comprises from 45 to 95% and preferably from 60 to 90% by weight of the
total composition. In compositions wherein the oxygen-releasing salt comprises a mixture
of ammonium nitrate and sodium nitrate, the preferred composition range for such a
blend is from 5 to 80 parts of sodium nitrate for every 100 parts of ammonium nitrate.
Therefore, in the preferred compositions of the present invention, the oxygen-releasing
salt component comprises from 45 to 90% by weight (of the total composition) ammonium
nitrate from 0 to 40% by weight (of the total composition) sodium or calcium nitrates.
[0041] The discontinuous phase may be entirely devoid of water, in the case of a melt-in-oil
emulsion or may contain water in the case of a water-in-oil emulsion. In the latter
case, the amount of water employed in the compositions of the present invention is
typically in the range of from 1 to 30% by weight of the total composition. Preferably
the amount employed is from 5 to 25%, and more preferably from 6 to 20%, by weight
of the total composition.
[0042] The organic phase component of the composition of the present invention comprises
the continuous "oil" phase of the emulsion explosive and is a fuel. Preferably the
organic phase is water-immiscible. Suitable organic fuels include aliphatic, alicyclic
and aromatic compounds and mixtures thereof which are in the liquid state at the formulation
temperature. Suitable organic fuels may be chosen from fuel oil, diesel oil, distillate,
kerosene, naphtha, waxes, (eg. microcrystalline wax), paraffin oils, benzene, toluene,
xylenes, asphaltic materials, polymeric oils such as the low molecular weight polymers
of olefins, animal oils, fish oils, and other mineral, hydrocarbon or fatty oils,
and mixtures thereof. Preferred organic fuels are liquid hydrocarbons generally referred
to as petroleum distillates such as gasoline, kerosene, fuel oils and paraffin oils.
[0043] Typically, the organic fuel or continuous phase of the emulsion explosive composition
of the present invention comprises from 2 to 15% by weight and preferably 3 to 10%
by weight of the total composition.
[0044] The emulsifying agent component of the composition of the present invention may be
chosen from the wide range of emulsifying agents known in the art for the preparation
of emulsion explosive compositions. Examples of such emulsifying agents include alcohol
alkoxylates, phenol alkoxylates, poly(oxyalkylene) glycols, poly(oxyalkylene) fatty
acid esters, amine alkoxylates, fatty acid esters of sorbitol and glycerol, fatty
acid salts, sorbitan esters, poly(oxyalkylene) sorbitan esters, fatty amine alkoxylates,
poly(oxyalkylene) glycol esters, fatty acid amides, fatty acid amide alkoxylates,
fatty amines, quaternary amines, alkyloxazolines, alkenyloxazolines, imidazolines,
alkylsulfonates, alkanoylsulfonates, allkylsulfosuccinates, alkylphosphates, alkenylphosphates,
phosphate esters, lecithin, copolymers of poly(oxyalkylene) glycols and poly(12-hydroxystearic
acid) polyalkylene succinic acid and derivatives thereof, and mixtures thereof. Among
the preferred emulsifying agents are the 2-alkyl- and 2-alkenyl-4,4ʹ-bis (hydroxymethyl)
oxazoline, the fatty acid esters of sorbitol, lecithin, copolymers of poly(oxyalkylene)
glycols and poly(12-hydroxystearic acid), and mixtures thereof, and particularly sorbitan
mono-oleate, sorbitan sesquioleate, 2-oleyl- 4,4ʹ-bis (hydroxymethyl) oxazoline, mixture
of sorbitan sesquioleate, lecithin and a copolymer of poly(oxyalkylene glycol and
poly (12-hydroxystearic acid), polyisobutylene succinic acid and derivatives thereof,
and mixtures thereof.
[0045] Typically, the emulsifying agent component of the composition of the present invention
comprises up to 5% by weight of the total composition. Higher proportions of the emulsifying
agent may be used and may serve as a supplemental fuel for the composition but in
general it is not necessary to add more than 5% by weight of emulsifying agent to
achieve the desired effect. One of the advantages of the compositions of the present
invention is that stable emulsions can be formed using relatively low levels of emulsifying
agent, and for reasons of economy it is preferable to keep to amount of emulsifying
agent in the range from 0.1 to 2.0% by weight of the total composition.
[0046] If desired, other optional fuel materials, hereinafter referred to as secondary fuels,
may be incorporated into the compositions of the present invention in addition to
the water-immiscible organic fuel phase. Examples of such scondary fuels include finely-
divided solids, and water-miscible organic liquids which can be used to partially
replace water as a solvent for the oxygen-releasing salts or to extend the aqueous
solvent for the oxygen-releasing salts. Examples of solid secondary fuels include
finely divided materials such as: sulfur; aluminum; and carbonaceous materials such
as gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic
acid, sugars such as glucose or dextrose and other vegetable products such as starch,
nut meal, grain meal and wood pulp. Examples of water-miscible organic liquids include
alcohols such as methanol, glycols such as ethylene glycol, amides such as formamide
and amines such as methylamine.
[0047] Typically, the optional secondary fuel component of the compositions of the present
invention comprise from 0 to 30% by weight of the total composition.
[0048] It lies within the invention that there may also be incorporated into the emulsion
explosive compositions hereinbefore described other substances or mixtures of substances
which are oxygen-releasing salts or which are themselves suitable as explosive materials.
As a typical example of such a modified emulsion explosive composition, reference
is made to compositions wherein there is added to and mixed with an emulsion explosive
composition as hereinbefore described up to 90% w/w of a solid oxidizing salt such
as ammonium nitrate or an explosive composition comprising a mixture of a solid oxidizing
salt such as ammonium nitrate and fuel oil and commonly referred to by those skilled
in the art as "Anfo". The compositions of "Anfo" are well known and have been described
at length in the literature relating to explosives.
[0049] Mixtures of solid ammonium nitrate or "Anfo" and the emulsion explosive of the invention
are suited to use in wet bore holes and water containing bore holes. Mixtures of "Anfo"
(or solid ammonium nitrate) and conventional emulsion explosive generally give poor
performance when loaded into bore holes containing water. The mixture tends to break
up on impact with water and this tends to result in the dissolution of the ammonium
nitrate. In contrast, mixtures of "Anfo" with the emulsion explosive of the present
invention may be used in bore holes containing water without significant loss of performance.
[0050] Accordingly there is provided an explosive composition comprising a emulsion as hereinbefore
described and up to 90% w/w of a composition comprising an ammonium nitrate fuel oil
mixture.
[0051] Typically, the proportion of ammonium nitrate or "Anfo" in such compositions will
be in the range 20-80% w/w.
[0052] It also lies within the invention to have as a futher explosive component of the
composition well known explosive materials comprising one or more of, for example,
trinitrotoluene, nitroglycerine or pentaerythritol tetranitrate.
[0053] Accordingly there is provided an explosive composition comprising as a first component
an emulsion explosive composition as hereinbefore described and as a second component
an amount of material which is an oxidizing salt or which is in its own right an explosive
material.
[0054] Generally it is not necessary to use thickening agents in the discontinuous phase
of the present composition as the amount of polymer may be varied according to the
properties desired. However, if desired, the discontinuous phase of the compositions
of the present invention may comprise thickening agents which optionally may be cross-linked.
The thickening agents, when used in the compositions of the present invention, are
suitably polymeric materials, especially gum materials typified by the galactomannan
gums such as locust bean gum or guar gum or derivatives thereof such as hydroxypropyl
guar gum. Other useful but less preferred gums are the so-called biopolymeric gums
such as the heteropolysaccharides prepared by the microbial transformation of carbohydrate
material, for example the treatment of glucose with a plant pathogen of the genus
Xanthomonas typified by
Xanthomonas campestris.
[0055] Typically, where used, the optional thickneing agent component of the compositions
of the present invention comprises from 0 to 2% by weight of the total composition.
[0056] As indicated above, when used in the compositions of the present invention, the thickening
agent optionally may be cross-linked. It is convenient for this purpose to use conventional
cross-linking agents such as zinc chromate or dichromate either as a separate entity
or as a component of a conventional redox system such as a mixture of potassium dichromate
and potassium antimony tartrate.
[0057] Typically, the optional cross-linking agent component of the compositions of the
present invention comprises from 0 to 0.5% and preferably from 0 to 0.1% by weight
of the total composition.
[0058] The emulsion explosive compositions of the present invention may additionally comprise
a discontinuous gaseous component.
[0059] The methods of incorporating a gaseous component and the enhanced sensitivity of
emulsion explosive compositions comprising such gaseous components have been previously
reported. Typically, where used the said gaseous component will be present in an amount
required to reduce the density of the composition to with in the rane 0.8 to 1.4 gm/cc.
[0060] The gaseous component may, for example, be incorporated into the composition of the
present invention as fine gas bubbles dispersed through the composition, as hollow
particles which are often referred to as microballoons or microspheres, as porous
particles, or as mixtures thereof.
[0061] A discontinuous phase of fine gas bubbles may be incorporated into the compositions
of the present invention by mechanical agitation, injection or bubbling the gas through
the composition, or by chemical generation of the gas in situ.
[0062] Suitable chemicals for the in situ generation of gas bubbles include peroxides, such
as hydrogen peroxide, peroxide nitrates, such as sodidum nitrite, nitrosoamines, such
as N, Nʹ-dinitrosopentamethylene tetramine, alkali metal borohydrides, such as sodium
borohydride, and carbonates, such as sodium carbonate. Catalytic agents such as thiocyanate
or thiourea may be used to accelerate the decomposition of a nitrite gassing agent.
Suitable small hollow particles include small hollow microspheres of glass or resinous
materials, such as phenol-formaldehyde and urea-formaldehyde. Suitable porous materials
include expanded minerals, such as perlite.
[0063] Where used, the gaseous agent is preferably added during cooling, after preparation
of the emulsion, and typically comprises 0.05 to 50% by volume of the total emulsion
explosive composition at ambient temperature and pressure. More preferably, where
used, the gaseous component is present in the range 10 to 30% by volume of the emulsion
explosive composition and preferably the bubble size of the occluded gas is below
200 µm. More preferably,at least 50% of the gas component will be in the form of bubbles
or microspheres of 20 to 90 µm internal diameter.
[0064] The pH of the emulsion explosive compositions of the present invention is not narrowly
critical. However, in general the pH is between 0 and 8, preferably between 0.5 and
6.
[0065] The emulsion explosive composition of the present invention may be prepared by a
number of methods.
[0066] The polymer may be mixed with the oil phase before preparation of the emulsion. Alternatively,
it may be more convenient to prepare the emulsion composition of the invention by
mixing of a composition comprising at least one polymer with an emulsion explosive
composition comprising: a discontinuous phase comprising at least one oxygen releasing
salt; a continuous organic phase; and an emulsifying agent.
[0067] If desired, the polymer may be added using both methods, that is adding the polymer
to the oil phase before preparation of the emulsion and also to the emulsion once
prepared.
[0068] When a composition comprising the polymer is added to the prepared emulsion, the
polymer may, for example, be in the form of a solid such as a powder, a solution in
a suitable solvent such as a hydrocarbon solvent or as an aqueous dispersion.
[0069] Aqueous dispersions of polymer may be prepared by methods well known to those skilled
in the art. For example, such a dispersion may be formed by mixing a fine powder of
polymer with an aqueous composition in the presence of a surfactant.
[0070] In a particularly preferred embodiment of the process of the invention we therefore
provide a process comprising mixing an aqueous dispersion of said polymer with an
explosive composition comprising (a) an emulsion explosive comprising a discontinuous
aqueous phase comprising an oxygen releasing salt, a continuous organic phase and
an emulsifying agent and optionally (b) solid ammonium nitrate or a mixture of solid
ammonium nitrate and fuel oil. Generally, the composition is mixed for a period following
additive of the polymer so as to facilitate dispersion within the emulsion explosive.
[0071] One preferred method of preparing suitable polymers involves an emulsion polymerization
technique which produces a latex of the product (i.e., an aqueous dispersion of small
polymer particles). We have found it to be particularly convenient in many instances
to use such composition in preparation of the emulsion explosive composition of present
invention.
[0072] In an embodiment of the invention there is thus provided a process for the preparation
of an emulsion explosive composition, the process comprising:
dissolving said oxygen-releasing salt in water at a temperature above the fudge point
of the salt solution, preferably at a temperature in the range of 25 to 110°C, to
give an aqueous salt solution;
optionally mixing said polymer with said water immiscible organic phase;
combining said salt solution, said water-immiscible organic phase, said water-in-oil
emulsifying agent.
Mixing until the emulsion is uniform and if said polymer has not been added, adding
a said polymer.
[0073] The invention is now demonstrated by but in no way limited to the following examples
in which all proportions are on a weight basis unless otherwise specified.
Example 1
[0074] A high molecular weight (average molecular weight in excess of 1 x 10⁶) copolymer
of tert-butyl styrene and 4-vinyl pyridine (97:3 by weight) was prepared by emulsion
polymerization.
Emulsion Polymerization Method - (preparation of polymer latex)
[0075] The surfactant AEROSOL OT (AEROSOL is a trade mark) (available from American Cyanamid),
(0.3 g) and initiator ammonium persulfate, (0.10 g) were dissolved in acetone (10.0
g) and water (50.0 g) the monomers (tert-butyl styrene, and 4-vinylpyridine; 20 g)
were added, and the mixture emulsified by stirring. The mixture was flushed with nitrogen
for ten minutes, sealed, and the temperature raised to 50°C and maintained at that
temperature for 24 hours, with gentle stirring. The resulting product was a latex
of polymer. The polymer was found to have an average molular weight of approx. 1.19
x 10⁶ g mol⁻¹.
Powder To prepare the polymer as a powder a small amount of latex (10 g) was added dropwise
to a large excess of methanol (100 g), and the polymer isolated by filtration. The
polymer was dried in air and ground to a fine powder.
Examples 2 and 3 and Comparative Example A
[0076] These examples demonstrate the effect on the viscosity of an emulsion explosive composition
of the addition of a polymer powder prepared according to Example 1.
Example 2
[0077] A diesel solution for use as the organic phase was prepared by dissolving copolymer
powder prepared according to Example 1 in diesel oil at a temperasture of 80°C to
give a concentration of 1% w/w of diesel solution.
[0078] An emulsion composition was then prepared using the following components

The method used was as follows:
The ammonium nitrate and calcium nitrate were dissolved in the water at a temperature
of about 80°C to give the oxidizer phase. The oxidizer phase was combined with a mixture
of the diesel solution and emulsifier and the resulting mixture was stirred rapidly
to form an emulsion.
Example 3
[0079] The procedure of Example 2 was repeated except that the diesel solution was prepared
using 2% w/w of copolymer prepared according to Example 1.
Comparative Example A
[0080] The procedure of Example 2 was repeated except that copolymer was not used in the
organic phase.
[0081] The viscosities of the emulsions of Examples 2, 3 and Comparative Example A were
measured at room temperature (20°C) with a BROOKFIELD instrument using spindle #7
on speed 5 rpm and the results are shown in the Table 1 below.

Example 4 and Comparative Example B
[0082] This example demonstrates a method of preparation of an emulsion of the invention
by addition of a polymer powder to a preformed emulsion.
[0083] An emulsion having the following components was prepared according to Example 2,
the organic phase not containing dissolved polymer.

[0084] * The emulsifier was a 1:1 molar condensate of poly(isobutylene) succinic anhydride
and ethanolamine and had an average molecular weight in the range of 800 to 1200.
[0085] A sample of the composition was set aside for comparison (Comparative Example B).
NITROPRIL is a trade mark.
Example 4
[0086] To a sample of the prepared emulsion (200 g) at 80°C was added polymer powder (0.24
g, 2% w/w on diesel) prepared according to Example 1. The composition was heated at
80° for four hours with occasional stirring, then allowed to cool. The composition
was stored at room temperature overnight.

Examples 5 to 7 and Comparative Examples C and D
[0087] The following examples demonstrate the highly viscoelastic nature of the explosives
of the invention.
Comparative Example C
[0088] An emulsion composition having the following components was prepared according to
Example 2, the organic phase being free of polymer.

[0089] * The emulsifier was a 1:1 molor condensate of poly(isobutylene)succinic anhydride
and ethanolamine and had an average molecular weight in the range 800 to1200.
[0090] A sample of emulsion was set aside for comparison and the bulk of the emulsion was
used in preparation of the following compositions.
Examples 5 to 7
[0091] To three samples of emulsion prepared above were added polymer latexes prepared according
to the procedure of example 1 using the monomer compositions shown in Table 3 below
(numbers in brackets show the proportion of each monomer based on the total monomer
composition). The average molecular weight of polymers used in Examples 6 and 7 was
measured and found to be 1.23 x 16⁶ g mol⁻¹ for example 6 and 0.82 x 10⁶ g mol⁻¹ for
example 7.
[0092] In each case the appropriate latex was added to the emulsion to give a polymer concentration
of approx. 6% w/w on the organic phase and the latex was thoroughly mixed with the
emulsion.
Comparative Example D
[0093] An emulsion explosive composition was prepared using the above procedure except that
the polymer added in Examples 5 to 7 was omitted.
[0094] The viscosity of the emulsion compositions was measured at room temperature using
a BROOKFIELD instrument spindle #7 at speed 5.
[0095] The yield stress and elastic modulus of the compositions was measured using a BOHLIN
Rheometer.

[0096] *
Elongation is a comparative measure of viscoelasticity of the emulsion compositions and was
determined using the following method:-
A spatula having a 1 cm width blade was inserted into a bulk sample of emulsion at
an angle of about 45° to the surface to a depth of about 1 cm. The spatula was raised
vertically from the emulsion at a rate of about 1 cm S⁻¹ until the thread of emulsion
between the spatula and bulk sample broke or became less than 1 mm in thickness. The
height of the spatula above the bulk emulsion was measured at this stage.
Compositions of the invention typically have an elongation in the range 2 to 30 cm
(preferably 4 to 20 cm).
Examples 8 to 10 and Comparative Example E
[0097] These examples demonstrate the advantage of using explosives of the present invention
when loading into wet boreholes.
Comparative Example E
[0098] An emulsion explosive prepared according to Comparative Example C (7.5 kg) was mixed
with "ANFO" (ammonium nitrate fuel oil mixture) (7.5 kg). The mixture was gassed using
an
in-situ nitrite gassing agent.
Example 8
[0099] An emulsion explosive prepared according to Comparative Example C was (7.5 kg) was
throughly mixed with polymer latex (37.5 g latex containing 9.38 g of *polymer) to
give a polymer concentration of 0.13% w/w on total emulsion. This emulsion mixture
was combined and mixed with 7.5 kg of "ANFO" and the composition was gassed using
an
in-situ nitrite gassing agent.
Example 9
[0100] An emulsion/ANFO mix was prepared according to Example 8 except that 75 g of latex
containing 18.75 g *polymer was added.
[0101] * The polymer latex used in Examples 8 and 9 was prepared according to the procedure
of Example 1 using the monomers styrene (47%), lauryl methacrylate (50%) and methacrylic
acid (3%) [percentages based on w/w of total monomer]
Example 10
[0102] An emulsion/ANFO mix was prepared according to Example 8 except that the quantity
of Latex was adjusted to provide a polymer concentration of 0.5% w/w on total emulsion
prior to addition of ANFO.
[0103] The performance of the explosives prepared in Examples 8, 9 and Comparative Example
E on loading into wet boreholes was tested using the following procedure:-
[0104] The explosive sample was dropped 3 metres into water 2 metres deep. The explosive
was allowed to settle and was then removed from the water. After 2 hours the total
detonation energy of the explosive was tested.
[0105] Results of the tests are shown in Table 4.

[0106] The above results clearly show the 25 superiority in performance of the compositions
of the present invention over corresponding compositions devoid of polymer.