Note: Descriptions are shown in the official language in which they were submitted.
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TITLE: EMULSION COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to water-in-oil emulsion compositions and particularly
to explosive emulsions.
BACKGROUND OF THE INVENTION
Amine derivatives of succinic anhydride have been used as emulsifiers. U.S.
Patent 5,512,079 and 5,518,517 disclose amine derivatives of succinic
acylating
agents for use as emulsifiers in delayed release emulsion fertilizers.
Water-in-oil emulsions have been used for a variety of uses including
emulsion explosives. Water-in-oil explosive emulsions typically comprise a
continuous organic phase and a discontinuous oxidizer phase containing water
and
an oxygen-supplying source such as ammonium nitrate, the oxidizer phase being
dispersed throughout the continuous organic phase. Examples of such water-in-
oil
explosive emulsions are disclosed, inter alia, in U.S. Patents 5,047,175; and
4,828,633. The emulsifier is a salt derived from high molecular weight
carboxylic
acylating agent coupled to a low molecular weight carboxylic acylating agent.
Succinic acids and anhydrides are the preferred acylating agents. Other
examples of
such water-in-oil explosive emulsions are disclosed in U.S. Patents 3,447,978;
3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,218,272; 4,259,977;
4,357,184; 4,371,408; 4,391,659; 4,404,050; 4,409,044; 4,448,619; 4,453,989;
and
4,534,809; and U.K. Patent Application GB 2,050,340A.
U.5. Patent 4,710,248 discloses an emulsion explosive composition
comprising a discontinuous oxidizer-phase dispersed throughout a continuous
fuel
phase with a modifier comprising a hydrophilic moiety and a lipophilic moiety.
The
hydrophilic moiety comprises a carboxylic acid or a group capable of
hydrolyzing to
a carboxylic acid. The lipophilic moiety is a saturated or unsaturated
hydrocarbon
chain. The emulsion explosive composition pH is above 4.5.
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U.S. Patents 4,840,687 and 4,956,028 disclose explosive compositions
comprising a discontinuous oxidizer phase comprising at least one oxygen-
supplying component, a continuous organic phase comprising at least one water-
immiscible organic liquid, and an emulsifying amount of at least one nitrogen-
containing emulsifier derived from (A) at least one carboxylic acylating
agent, (B) at
least one polyamine, and (C) at least one acid or acid-producing compound
capable
of forming at least one salt with said polyamine. Examples of (A) include
polyisobutenyl succinic acid or anhydride. Examples of (B) include the
alkylene
polyamines. Examples of (C) include the phosphorus acids (e.g., O,S-
dialkylphosphorotrithioic acid). These explosive compositions can be water-in-
oil
emulsions or melt-in-oil emulsions.
U.S. Patent 4,863,534 discloses an explosive composition comprising a
discontinuous oxidizer phase comprising at least one oxygen-supplying
component,
a continuous organic phase comprising at least one carbonaceous fuel, and an
emulsifying amount of (A) at least one salt composition derived from (A)(1) at
least
one high-molecular weight hydrocarbyl-substituted carboxylic acid or
anhydride, or
ester or amide derivative of said acid or anhydride, the hydrocarbyl
substituent of
(A)(1) having an average of from about 20 to about 500 carbon atoms, and
(A)(2)
ammonia, at least one amine, at least one alkali or alkaline earth metal
compound;
and (B) at least one salt composition derived from B)(1) at least one low-
molecular
weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide
derivative of said acid or anhydride, the hydrocarbyl substituent of (B)(1)
having an
average of from about 8 to about 18 carbon atoms, and (B)(2) ammonia, at least
one
amine, at least one alkali or alkaline earth metal, and/or at least one alkali
or alkaline
earth metal compound.
U.S. Patent 4,822,433 discloses an explosive emulsion composition
comprising a discontinuous phase containing an oxygen-supplying component and
an organic medium forming a continuous phase wherein the oxygen-supplying
component and organic medium are capable of forming an emulsion which, in the
absence of a supplementary adjuvant, exhibits an electrical conductivity
measured at
60°C, not exceeding 60,000 picomhos/meter. The reference indicates that
the
conductivity may be achieved by the inclusion of a modifier which also
functions as
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an emulsifier. The modifier is comprised of a hydrophilic moiety and a
lipophilic
moiety. The lipophilic moiety can be derived from a poly[alk(en)yl] succinic
anhydride. Poly(isobutylene) succinic anhydride having a number average
molecular weight in the range of 400 to 5000 is specifically identified as
being
useful. The hydrophilic moiety is described as being polar in character,
having a
molecular weight not exceeding 450 and can be derived from polyols, amines,
amides, alkanol amines and heterocyclics. Example 14 of this reference
discloses
the use of a 1:l condensate of polyisobutenyl succinic anhydride (number
average
molecular weight = 1200) and dimethylethanol amine as the modifier/emulsifier.
U.S. Patent 4,919,178 discloses water in oil emulsion explosives in which
the emulsifier is the reaction product of two components. The first component
is the
reaction product certain carboxylic acids or anhydrides, including substituted
succinic acids and anhydrides with ammonia or an amine and an alkali metal or
an
alkaline earth metal. The second component is the salt of a phosphorous
containing
acid.
European Patent application EP 561,600 A discloses a water-in-oil emulsion
explosive in which the emulsifier is the reaction product of a substituted
succinic
acylating agent, having at least 1.3 succinic groups per equivalent weight of
substituents, with ammonia and/or an amine. The substituent is a polyalkene
having
number average molecular weight of greater than 500 and preferably 1300 -
1500.
U.5. Patent 4,919,179 discloses a water-in-oil emulsion explosive wherein
the emulsifier is a particular type of ester of polyisobutenyl succinic
anhydride.
U.S. Patent 4,844,756 discloses a water-in-oil emulsion explosive wherein
the emulsifier is a salt produced by reacting a hydrocarbyl substituted
carboxylic
acid or anhydride, including substituted succinic acids and anhydrides, with
ammonia, an amine, and/or an alkali or alkaline earth metal.
U.S. Patent 4,818,309 discloses a water-in-oil emulsion explosive wherein
the emulsifier is a polyalkenyl succinic acid or derivative thereof. The
succinic acid
may be used in the form of an anhydride, an ester, an amide or an imide. A
condensate with ethanolamine is preferred.
U.S. Patent 4,708,753 discloses a water-in-oil emulsion suitable for use in
explosive and functional fluids wherein the emulsifier is a reaction product
of a
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hydrocarbyl substituted carboxylic acid, including a succinic acid, with an
amine.
The substituent contains 20 - 500 carbon atoms, and the aqueous phase contains
a
water soluble, oil insoluble functional additive.
European Patent EP 102,827 A discloses a water-in-oil emulsion
composition useful as a well control fluid. The emulsifier is a polyamine
derivative,
especially an alkylene polyamine derivative, of a polyisobutenyl succinic
anhydride
or a borated or carboxylated derivative thereof.
U.S. Patent 4,445,576 discloses a water-in-oil emulsion composition useful
as a spacer fluid in well drilling. The emulsifier is an amine derivative,
especially a
polyamine derivative, of a polyalkenyl succinic anhydride.
U.S. Patent 4,999,062 describes an emulsion explosive composition
comprising a discontinuous phase comprising an oxygen-releasing salt, a
continuous
water-immiscible organic phase and an emulsifier component comprising a
condensation product of a primary amine and a poly[alk(en)yl]succinic acid or
anhydride and wherein the condensation product comprises at least 70% by
weight
succinimide product.
United States defensive publication T969,003 discloses water in oil emulsion
fertilizer compositions prepared by dissolving an invert emulsifier in an oil
such as
kerosene. A liquid (aqueous) fertilizer is emulsified with the oil to form an
invert
emulsifier.
Patent application WO 96/28436 describes gamma and delta lactones of
formulae (I) and (II)
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R*
R-CHZ
/ CHZ -Q
C
O
R-CHz (R)
used as emulsifiers in explosive compositions comprising a continuous organic
phase and a discontinuous aqueous phase containing an oxygen-supplying
compound. In the formulae, R is hydrocarbyl, R* is hydrogen, methyl or another
hydrocarbyl, and Q is an amide, ammonium salt or ester functionality.
Water-in-oil explosive emulsions are often blended with ammonium nitrate
prills or ANFO, a composition produced by adding a liquid oil such as light
oil and
the like to porous ammonium nitrate prills for the purpose of increasing the
explosive energy of such emulsions.
SUMMARY OF THE INVENTION
The present invention relates to an emulsion comprising
(A) a discontinuous phase;
(B) a continuous organic phase; and
(C) an emulsifying amount of at least one nitrogen and transition metal
containing composition derived from hydrocarbon substituted polycarboxylic
acids
or functional equivalent thereof, selected from the group consisting of
(C-1) amide and imide derivatives of transition metal salts,
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(C-2) transition metal complexes of non-acidic acylated nitrogen
compounds, and
(C-3) a mixture of acylated nitrogen compounds and transition metal
salts.
In one particular embodiment, the invention relates to explosive emulsions
wherein (A) is a discontinuous oxidizer phase comprising at least one oxygen-
supplying component and (B) is a continuous organic phase which comprises at
least
one carbonaceous fuel.
In another embodiment, the discontinuous phase (A) is a discontinuous
aqueous phase.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term "emulsion: as used in this specification and in the appended claims
is intended to cover not only water-in-oil emulsions but also melt-in-oil
emulsions.
The water-in-oil emulsions have a discontinuous aqueous phase, and explosive
emulsions contain oxidizing materials suspended in a continuous oil phase. The
melt-in-oil emulsions have a discontinuous oxidizer phase containing oxidizing
salts
which have a melting point low enough that they may be conveniently emulsified
into the continuous oil phase. The oxidizing salts may, and often do, contain
some
water of hydration and accordingly, an emulsion prepared without addition of
water
to form the discontinuous phase may actually contain some water. However, the
presence of water in a melt-in-oil emulsion is not required and the
discontinuous
phase often comprises a low melting mixture of oxidizing salts. Although there
is
not a sharp line between water in oil and melt-in-oil emulsions, the term
water in oil
is used when the salts are dissolved in additional water to form the
discontinuous
phase and the term melt-in-oil is used when the oxidizing salts are liquefied
without
the addition of water to form the discontinuous phase.
As used herein, the term "hydrocarbon" means a group which is purely
hydrocarbon, that is, a compound of hydrogen and carbon containing no hetero
atoms. The terms "hydrocarbyl" and "hydrocarbon based" mean that the group
being
described has predominantly hydrocarbon character within the context of this
invention. Hydrocarbyl and hydrocarbon based groups include groups that are
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purely hydrocarbon in nature, that is, they contain only carbon and hydrogen.
They
may also include groups containing non-hydrocarbon substituents or atoms which
do
not alter the predominantly hydrocarbon character of the group. Such
substituents
may include halo-, alkoxy-, nitro-, etc. These groups also may contain hetero
atoms.
Suitable hetero atoms will be apparent to those skilled in the art and
include, for
example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly
hydrocarbon in character within the context of this invention, these groups
may
contain atoms other than carbon present in a chain or ring otherwise composed
of
carbon atoms. Thus, the terms "hydrocarbyl" and "hydrocarbon based" are
broader
than the term "hydrocarbon" since all hydrocarbon groups are also
"hydrocarbyl" or
"hydrocarbon based" groups while hydrocarbyl groups or hydrocarbon based
groups
containing hetero atoms are not hydrocarbon groups as defined herein.
In general, no more than about three non-hydrocarbon substituents or hetero
atoms, and preferably no more than one, will be present for every 10 carbon
atoms
in hydrocarbyl or hydrocarbon based groups. Most preferably, these groups are
purely hydrocarbon in nature, that is they are essentially free of atoms other
than
carbon and hydrogen.
The Emulsions
The emulsifiers used in the present invention are particularly useful for
preparing oil continuous phase emulsions, that is, water-in-oil emulsions in
which
there are high levels of active components in the dispersed aqueous phase.
The water-in-oil emulsions have the bulk characteristics of the continuous oil
phase even though on a volume basis, the aqueous phase may be the predominant
phase. This characteristic is particularly useful in forming functional fluids
such as
metalworking fluids in which it is convenient to have the lubricity of an oil
phase,
while having the non-flammability of a material which is predominantly
aqueous.
This is especially true in the area of metal-cutting fluids where the
predominant oil
phase can provide lubrication, while the aqueous phase has a high heat
capacity, and
carries away the heat of the cutting operation better than the oil phase is
able to do.
The emulsions may be prepared by mixing the emulsifier with the oil phase
and then adding the oil phase to the aqueous phase, with stirring.
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Water-in-oil emulsions generally contain at least 2% by weight of the
continuous oil phase. More preferably, they contain between about 2% to about
10% by weight of the continuous oil phase, and most preferably, in the range
from
about 3.5 to about 8% by weight of the oil phase. The discontinuous aqueous
phase
comprises from about 5% to about 99% by weight, preferably at least about 90%
by
weight, more preferably from about 90% to about 98% by weight and most
preferably from about 92 to about 96.5% by weight based on the total weight of
the
emulsion. The emulsifiers are generally present at a level from about 4% often
from
about 5%, up to about 50%, often up to about 40% by weight, more preferably
from
about 12 to 20% by weight based upon the total weight of the organic phase.
(A) The Discontinuous Phase
The discontinuous phase of the emulsion rnay comprise a substantially
anhydrous component such as molten salts such as oxidizers. These include
melts of
non-aqueous oxidizing salts and may comprise eutectic mixtures.
More often the discontinuous phase is an aqueous phase comprising, for
example, oxygen supplying components in explosives, fertilizer components, and
the like.
B) The Continuous Organic Phase
The emulsion compositions of this invention comprise a continuous organic
phase which often comprises an oil or a wax.
In the water-in-oil emulsions of the present invention, the oil serves to
protect fertilizer components, which are in the aqueous phase, and control
their
release to the environment. In emulsion explosives, the oil prevents the
coalescence
of the discontinuous aqueous phase, but more importantly is the oxidizable
phase or
the fuel for the explosion. In metal working fluids, the oil provides
lubricating
properties. Many of the same types of oils may be used for these types of
compositions.
The oil that is useful in the emulsions of the present invention can include
oils from a variety of sources, including natural and synthetic oils and
mixtures
thereof. Hydrocarbon oils, for example, paraffinic, olefinic, naphthenic,
aromatic,
saturated or unsaturated hydrocarbons, may be used. In general, the oil is
water-
immiscible, emulsifiable and is either liquid at about 20°C or becomes
a liquid at a
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temperature of up to about 95°C, and preferably up to about
60°C. Oils from a
variety of sources, including natural and synthetic oils, may be used.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard
oil) as
well as solvent-refined or acid-refined mineral oils of the paraffinic,
naphthenic, or
mixed paraffin-naphthenic types. Oils derived from coal or shale are also
useful.
Synthetic oils include hydrocarbon oils such as polymerized and
interpolymerized
olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene
copolymers,
chlorinated polybutylenes, etc.); alkyl benzenes (e.g., dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.);
polyphenyls
(e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); and the like.
Another suitable class of synthetic oils that can be used comprises the esters
of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic
acid, malefic
acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid,
linoleic acid
dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a
variety
of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol,
ethylene glycol, diethylene glycol monoether, propylene glycol,
pentaerythritol,
etc.). Specific examples of these esters include dibutyl adipate, di(2-
ethylhexyl)-
sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,
diisodecyl
azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-
ethylhexyl
diester of linoleic acid dimer, the complex ester formed by reacting one mole
of
sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-
hexanoic acid, and the like.
Esters useful as synthetic oils also include those made by reacting CS to CZa
monocarboxylic acids mono alcohols or polyols. The mono alcohols include CI to
C~$ aliphatic alcohols. Polyols include neopentyl glycol, trimethylol propane,
pentaerythritol, dipentaerythritol, tripentaerythritol, and polyol ethers.
Silicon-based oils and silicate oils comprise another class of useful oils.
Also
useful are the liquid esters of phosphorous-containing acid, polymeric
tetrahydrofurans, and the like.
Unrefined, refined and rerefined oils and mixtures of thereof can be used.
Unrefined oils are those obtained directly from a natural or synthetic source
without
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further purification treatment. For example, a shale oil obtained directly
from a
retorting operation, a petroleum oil obtained directly from distillation or
ester oil
obtained directly from an esterification process and used without further
treatment
would be an unrefined oil. Refined oils are similar to the unrefined oils
except that
they have been further treated in one or more purification steps to improve
one or
more properties. Many such purification techniques are known to those of skill
in
the art such as solvent extraction, distillation, acid or base extraction,
filtration,
percolation, etc. Rerefined oils may be used as the oil phase. Such rerefined
oils are
also known as reclaimed or reprocessed oils and often are obtained by
processes
similar to those used to obtain ordinary refined oils. These rerefined oils
may be
additionally processed by techniques directed toward removal of spent
additives and
oil breakdown products.
Examples of useful oils include a white mineral oil available from Witco
Chemical Company under the trade designation KAYDOL; a white mineral oil
available from Shell under the trade designation ONDINA; and a mineral oil
available from Pennzoil under the trade designation N-750-HT. Diesel fuel oil
as
specified in ASTM D-975, Standard Specification for Diesel Fuel Oils, can be
used.
Also useful are waxes having melting points of at least about 25°C,
such as
petrolatum wax, microcrystalline wax, and paraffin wax; mineral waxes such as
ozoceite and montan wax; animal waxes such as spermacetic wax, and insect
waxes
such as beeswax and Chinese wax. Useful waxes include those identified by the
designation MOBILWAX 57, available from Mobil Oil Corporation, D02764, a
blended wax available from Astor Chemical Ltd., and VYBAR, available from
Petrolite Corporation. Preferred waxes are blends of microcrystalline waxes
and
paraffin.
In one embodiment, the oil comprises a combination of a wax and an oil.
The wax content can be at least about 25% and preferably is at least about 25%
up to
about 90% by weight of the organic phase, and the oil content can be at least
about
10% and preferably ranges from about 10% to about 75% by weight of the organic
phase.
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The Oxyen-Suppl in Component
In one embodiment, particulate-solid oxygen-supplying salts may be
incorporated into or blended with the inventive emulsions to increase the
explosive
energy of such emulsions. These salts can be ammonium nitrate, sodium nitrate,
calcium nitrate or mixtures of two or more thereof. Ammonium nitrate is
particularly useful. The oxygen-supplying component is preferably at least one
inorganic oxidizer salt such as ammonium, alkali or alkaline earth metal
nitrate,
chlorate or perchlorate. Examples include ammonium nitrate, sodium nitrate,
calcium nitrate, ammonium chlorate, sodium perchlorate and ammonium
perchlorate. Ammonium nitrate is preferred. Mixtures of ammonium nitrate and
sodium or calcium nitrate are also useful. In one embodiment, inorganic
oxidizer
salt comprises principally ammonium nitrate, although up to about 25% by
weight
of the oxidizer phase can comprise either another inorganic nitrate (e.g.,
alkali or
alkaline earth metal nitrate) or an inorganic perchlorate (e.g., ammonium
perchlorate
or an alkali or alkaline earth metal perchlorate) or a mixture thereof.
Ammonium nitrate particulate solids, (e.g., ammonium nitrate prills), which
are available in the form of preblended ammonium nitrate-fuel oil (ANFO)
mixtures,
can be used. Typically, ANFO contains about 94% by weight ammonium nitrate
and about 6% fuel oil (e.g., diesel fuel oil), although these proportions can
be varied.
The quantities of these particulate-solid oxygen-supplying salts or ANFO
that are used can comprise up to about 80% by weight of the total explosive
composition. In one embodiment of the invention, explosive compositions
comprising about 25% to about 35% by weight of the inventive emulsion and
about
65% to about 75% of particulate solid, oxygen-supplying salts or ANFO are
used.
In one embodiment, explosive compositions comprising about 45% to about 55% by
weight of the inventive emulsion and about 45% to about 55% of particulate
solid,
oxygen-supplying salts or ANFO are used. In one embodiment, explosive
compositions comprising about 70% to about 80% by weight of the inventive
emulsion and about 20% to about 30% of particulate solid, oxygen-supplying
salts
or ANFO are used. Ammonium nitrate prills are especially useful. These
particulate solids can be in the form of prills, crystals or flakes.
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In one embodiment, the oxygen-supplying component comprises from about
75% up to about 100% of the oxidizer phase.
The oxidizer phase may be a molten phase.
In this embodiment, the composition is a melt-in-fuel emulsion. In such
emulsions, the discontinuous oxidizer phase comprises a mixture of oxidizing
salts
which are melted and are used to form an emulsion much like that formed using
aqueous solutions of the oxidizing salts. The oxidizer melts may include
nonaqueous materials which decrease the melting point of the oxidizing salt
mixture.
Various eutectic combinations of oxidizing salts may be used. In addition to
the
salts, other ingredients may be added to the oxidizer melt such as perchlorate
adducts of amines, urea nitrate, urea perchlorate, nitroguanidine, guanidine
nitrate
and guanidine perchlorate. Occasionally, polyols such as ethylene glycol and
glycerol may be added to the molten inorganic oxidizer salts. When glycols are
used, in addition to lowering the melting point of the salt, they become part
of the
fuel for the explosive reaction. Melt-in-fuel emulsion explosives are the
subject of
numerous patents, and the method of forming suitable melts of oxidizer salts,
as well
as forming emulsions of such melts in a continuous oil phase are well known to
those skilled in the art.
(D) Sensitizers
There are several optional techniques for assuring that explosive emulsions
will properly detonate. In one embodiment of the invention, closed-cell, void-
containing materials are used as sensitizing components. The term "closed-
cell,
void-containing material" is used herein to mean any particulate material
which
comprises closed cell, hollow cavities. Each particle of the material can
contain one
or more closed cells, and the cells can contain a gas, such as air, or can be
evacuated
or partially evacuated. In one embodiment of the invention, sufficient closed
cell,
void containing material is used to yield a density in the resulting emulsion
of from
about 0.8 to about 1.35 g/cc, more preferably about 0.9 to about 1.3 g/cc,
more
preferably about 1.0 to about 1.1 g/cc. In general, the emulsions of the
subject
invention can contain up to about 15% by weight, preferably from about 0.25%
to
about 15% by weight of the closed cell void containing material. Preferred
closed
cell void containing materials are discrete glass spheres having a particle
size within
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the range of about 10 to about 175 microns. In general, the bulk density of
such
particles can be within the range of about 0.1 to about 0.4 ~I/cc. Useful
glass
microbubbles or mieroballoons which can be used are the microbubbles sold by
3M
Company and which have a particle size distribution in the range of from about
10 to
about 160 microns and a nominal size in the range of about 60 to 70 microns.
and
densities in the range of from about 0.1 to about 0.4 g/ce. ~Microballoons
identified
by the industry designation C15/250 which have a particle densit3~ of 0.15
gm/cc and
10% of such microballoons crush at a static pressure of 1724 kPa (250 psig)
can be used.
Also, microbaIloons identified by the designation 837/2000 which have a
particle density
of 0.37 gm/ec and 10% of such microballoons crush at a static pressure of
13789 kPa
(2000 psig) can be used. Other useful glass microballoons ate sold under the
trade
designation of ECCOSby Emerson & Gumming, Inc., and generally have a
patvcle size range from about 44 to about 175 microns and a bulk density of
about 0.15
to about 0.4 g/cc. Other suitable microballoons include the inorganic
microspheres sold
under the trade designation of Q-GEL by Philadelphia Quartz Comp~iny.
The closed cell, void containing material can be made of inert or reducing
materials. For example, phenol-formaldehyde microbubbles can be utilized
within
the scope of this invention. If the phenol-formaldehyde microbubbles are
utilised,
the microbubbles themselves are a fuel component for the explosive and their
fuel
value should be taken into consideration when designing a water-in-ail
emulsion
explosive composition. Another closed cell, void containing material which can
be
used within the scope of the subject invention is the SARAN~'rnicrospheres
sold by
Dow Chemical Company. The Saran microspheres have a diameter of about 30
microns and a particle density of about 0.032 g/cc. Because of the low bulk
density
of the saran microspheres, it is preferred that only from about 0.:?5 to about
1% by
weight thereof be used in the water-in-oil emulsions of the subject invention.
Many of the closed cell, void containing, materials are somewhat costly.
Accordingly, a lower cost means for generating gas bubbles is often preferred.
Chemical gassing in situ is frequently employed. Gas bubbles are generated in-
situ
by adding to the composition and distributing therein a gas-generating
material such
as, for example, an aqueous solution of sodium nitrite, often in combination
with
sodium thiocyanate or thiourea, to sensitise the explosive ernulsions. Within
13
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US001995
minutes of mixing the components, nitrogen bubbles begin to form and the
density
of the emulsion is thus lowered.
Chemical gassing results in emulsion densities generally corresponding to
the values obtained using closed cell void containing materials.
In order to obtain satisfactory.chemical gassing and re:fultant reduction of .
density of the emulsion, it has heretofore been necessary to reduce the pH of
the
emulsion. This is commonly accomplished by adding to the composition acidic
materials. The acid may be an organic acid or a mineral acid. t;ommonly used
are
acetic acid, often with a buffer such as sodium acetate, hydrochloric acid and
the
like.
There are several disadvantages associated with the need to reduce pH of the
emulsion in order to secure satisfactory chemical gassing. These include the
inherent danger of utilizing acids, costs associated with the additional
materials and
handling thereof and frequently, stability of the emulsion is redu~~ed. The
use of the
nitrogen and transition metal containing compositions as. emulsifiers obviates
the
need to reduce the pH of the emulsion in order to obtain satisfactory chemical
gassing and resultant reduction of density of the emulsion.
Other suitable sensitizing components which may be employed alone or in
addition to the foregoing include insoluble paWcuIate solid sell=explosives or
fuel
such as, for example, grained or flaked TNT, DNT, RDX and the like,
particulate
metal fuels such as alununum, aluminum alloys, silicon and ferro-silicon; and
water-soluble and/or hydrocarbon-soluble organic sensitizers such as, for
example,
amine nitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and the like.
The explosive emulsions of the present invention rnay tie formulated for a
wide range of applications. Any combination of sensitizing components may be
selected in order to provide an explosive composition of vif-tually any
desired
density, weight-strength or critical diameter. The quantity of solid self
explosives or
fuels and of water-soluble and/or hydrocarbon-soluble organic sensitizers may
comprise up to, about 50% by weight of the total explosive composition. The
volume of the occluded gas component may comprise up to about 50% of the
volume of the total explosive composition.
14
AMENDED SHEET
. . , n inn mnm ~ n . nC C..,r,.4 .,.. ~ 7S2Q U f 11 f 1
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
Supplemental Additives
Supplemental additives may be incorporated in the emulsions of the
invention in order to further improve sensitivity, density, strength, rheology
and cost
of the final explosive. Typical of materials found useful as optional
additives
include, for example, particulate non-metal fuels such as sulfur, gilsonite
and the
like; particulate inert materials such as sodium chloride, barium sulphate and
the
like; thickeners such as guar gum, polyacrylamide, carboxymethyl or ethyl
cellulose,
biopolymers, starches, elastomeric materials, and the like; crosslinkers for
the
thickeners such as potassium pyroantimonate and the like; buffers or pH
controllers
such as sodium borate, zinc nitrate and the like; crystals habit modifiers
such as
alkyl naphthalene sodium sulphonate and the like; liquid phase extenders such
as
formamide, ethylene glycol and the like; and bulking agents and additives of
common use in the explosives art. The quantities of supplemental additives
used
may comprise up to about 50% by weight of the total explosive composition.
(C) The Nitrogen and Transition Metal Containing Composition
The nitrogen and transition metal containing compositions serve as the
emulsifier for the emulsions of the present invention. The emulsifier
comprises from
about 5% to about 50% by weight of the total weight of the continuous organic
phase.
The emulsifier (C) comprises a nitrogen and transition metal containing
derivative of a
hydrocarbyl substituted, preferably hydrocarbon substituted polycarboxylic
acid,
preferably a succinic acid, or functional equivalent thereof, selected from
the group
consisting of
(C-1) amide and imide derivatives of transition metal salts,
(C-2) metal complexes of non-acidic acylated nitrogen compounds, and
(C-3) a mixture of acylated nitrogen compounds and transition metal salts.
The nitrogen and transition metal containing derivative of a polycarboxylic
acid is used in an emulsifying amount as explained in greater detail herein.
The emulsifier (C) is preferably oil-soluble. The hydrocarbyl substituent
contains from about 16 to about 750 carbon atoms, preferably from about 30 to
about
200 carbon atoms. Materials of this type are described by LeSuer in U.S.
Patents
3,163,603 and 3,306,908.
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
The emulsifier (C) may be prepared by the process which comprises reacting,
at a temperature within the range of from about 20°C to about
250°C, about two
equivalents of a polycarboxylic compound selected from the class consisting of
hydrocarbyl-substituted polycarboxylic acids and anhydrides wherein the
hydrocarbyl
substituent has at least about 16, preferably at least about 30, often at
least about SO
carbon atoms, up to about 750, preferably up to about 200, often up to about
100
carbon atoms, about one equivalent of a basic transition metal reactant
selected from
the class consisting of metals, oxides, hydroxides, carbonates and lower
alcoholates
and the successive combination of an alkali metal hydroxide and an inorganic
transition
metal salt selected from the class consisting of halides and nitrates, and
from one to
about five equivalents of an amine selected from the class consisting of
alkylene
polyamines and hydroxy alkyl-substituted alkylene polyamines, each as
described
herein. In the usual case from about one to about two equivalents of amine is
used.
In another embodiment, (C) is prepared by reacting one equivalent of a mono
transition metal salt of a hydrocarbyl substituted succinic acid, wherein the
hydrocarbyl
group is as defined hereinabove, with from about 1 to about 5 equivalents of
an amine
selected from the group consisting of alkylene polyamines and hydroxy alkyl
substituted alkylene polyamines having up to eight carbon atoms in the
alkylene group
and up to about 6 carbon atoms in the hydroxyalkyl group.
In another embodiment, (C) is prepared by reacting one equivalent of a
hydrocarbyl substituted succinic acid or anhydride wherein the hydrocarbyl
group is as
defined hereinabove, with from 1 to about 5 equivalents of an amine selected
from the
group consisting of alkylene polyamines and hydroxy alkyl substituted alkylene
polyamines having up to about 8 carbon atoms, preferably 2 or 3 carbon atoms,
in the
alkylene group and up to about 6 carbon atoms in the hydroxy alkyl group,
heating to
effect acylation, removing water to form an acylated amine then reacting the
acylated
polyamine with about one equivalent of a basic transition metal reactant
described
hereinabove and the successive combination of an alkali metal hydroxide and an
inorganic transition metal salt consisting of halides and nitrates.
In another embodiment, the emulsifier (C) is prepared by mixing together
individually prepared acylated nitrogen containing compounds, such as amides,
imides,
16
W~ O1/~73g1 CA 02380289 2002-O1-22 PCT/CTS00/19953
and the like with individually prepared transition metal salts. The transition
metal salts
may be mono- salts or full salts, preferably mono- salts.
The acylated nitrogen containing compounds are prepared by techniques well
known in the art. Such procedures are described in for example, LeSuer, U.S.
3,219,666 and numerous other U.S. patents. Procedures for preparing metal
salts of
hydrocarbyl group substituted polycarboxylic compounds are described in, for
example, U.S. Patent 3,271,310. The metal salts may be acidic salts and
neutral salts as
described in the 3,271,310 patent. The individually prepared components are
then
mixed together to form the emulsifier (C).
The Polycarboxylic Compound
Suitable carboxylic acids or anhydrides are hydrocarbyl substituted, aromatic,
cycloaliphatic and aliphatic, preferably oil-soluble acids. Polycarboxylic
acids are
defined herein as having 2 or more carboxyl groups. In one embodiment, the
carboxylic acylating agent is characterized by the presence within its
structure of from
about 0.8 to about 2 succinic groups per hydrocarbyl substituent. Preferably
the
hydrocarbyl substituent is aliphatic and contains at least 16 carbon atoms,
often from
about 30 carbon atoms, more preferably at least about 50 carbon atoms, up to
about
750, often to about 200, more preferably, up to about 100 carbon atoms.
Useful acids used to generate the emulsifier (C) may be illustrated by the
general formula
R-(COOH)n (11)
and the and functional equivalents thereof, such as the corresponding
anhydrides,
ester acids, or lactone acids thereof, wherein R is a hydrocarbyl group as
defined
hereinabove. R may be aliphatic, cycloaliphatic, or aromatic, including alkyl,
alkenyl, aralkyl and alkaryl, including mixtures of acids containing aliphatic
and
aromatic groups. Preferably R is an aliphatic group. The subscript 'n' is a
number
ranging from 2 to about 10, preferably 2 to about 4, more preferably 2 or 3,
especially 2. Preferred carboxylic acids include polyolefin substituted
succinic acids,
succinic anhydrides, ester acids or lactone acids. Mixtures of such acids are
also
useful. The substituted succinic acids have the formula
17
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
R4-CHCOOH
CH2COOH
wherein R4 is the same as R as defined above. Also contemplated are the
corresponding derivatives, the anhydrides, ester acids, or lactone acids of
this
succinic acid. R4 is preferably an olefin, preferably alpha-olefin polymer-
derived group
formed by polymerization of monomers such as ethylene, propylene, 1-butene,
isobutene, 1-pentene, 2-pentene, 1-hexene and 3-hexene. Such groups usually
contain
from about 16, often from about 30, frequently from about 50, up to about 750,
often
up to about 200, more often up to about 100 carbon atoms. R4 may also be
derived
from a high molecular weight substantially saturated petroleum fraction. The
hydrocarbon-substituted succinic acids and their derivatives constitute the
most
preferred class of carboxylic acids.
Included among the useful carboxylic reactants are hydrocarbyl substituted
cyclohexene dicarboxylic acids and anhydrides which may be obtained from the
reaction of e.g., malefic anhydride with an olefin while the reaction mass is
being
treated with chlorine.
Patents describing useful aliphatic polycarboxylic acids or anhydrides and
methods for preparing them include, among numerous others, U.S. Pat. Nos.
3,163,603
(LeSuer), 3,215,707 (Rense); 3,219,666 (Norman et al), 3,231,587 (Rense);
3,306,908
(I,eSuer); 3,912,764 (Palmer); 4,110,349 (Cohen); and 4,234,435 (Meinhardt et
al);
and U.K. 1,440,219 which are hereby incorporated by reference for their
disclosure of
useful carboxylic reactants.
As indicated in the above-mentioned patents, which are hereby incorporated by
reference for their disclosure of compounds useful as reactants for preparing
the
emulsifier (C) of this invention, the carboxylic acids (or various derivatives
thereof)
include those derived by the reaction of an alpha, beta-unsaturated carboxylic
acid
containing compound with a polyalkene or halogenated derivative thereof or a
suitable
olefin.
The polyalkenes from which the carboxylic acids reactants may be derived are
homopolymers and interpolymers, also referred to herein as copolymers, of
polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to
about 6
18
W0 ~1/~7381 CA 02380289 2002-O1-22 PCT/L1S00/19953
carbon atoms. The interpolymers are those in which two or more olefin monomers
are
interpolymerized according to well-known conventional procedures to form
polyalkenes having units within their structure derived from each of said two
or more
olefin monomers. Thus, "interpolymer(s)", or "copolymers" as used herein is
inclusive
of polymers derived from two different monomers, terpolymers, tetrapolymers,
and the
like. As will be apparent to those of ordinary skill in the art, the
polyalkenes from
which the substituent groups are derived are often conventionally referred to
as
"polyolefin(s)".
The olefin monomers from which the polyalkenes are derived are
polymerizable olefin monomers characterized by the presence of one or more
ethylenically unsaturated groups (i.e., >C=C<); that is, they are monolefinic
monomers
such as ethylene, propylene, 1-butene, isobutene, and 1-octene or polyolefmic
monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene.
These olefin monomers are usually polymerizable terminal olefins; that is,
olefins characterized by the presence in their structure of the group >C=CH2.
However, polymerizable internal olefin monomers (sometimes referred to in the
literature as medial olefins) characterized by the presence within their
structure of the
group
-C-C=C-C-
can also be used to form the polyalkenes. When internal olefin monomers are
employed, they normally will be employed with terminal olefins to produce
polyalkenes which are interpolymers. For purposes of this invention, when a
particular
polymerized olefin monomer can be classified as both a terminal olefin and an
internal
olefin, it will be deemed to be a terminal olefin. Thus, 1,3-pentadiene (i.e.,
piperylene)
is deemed to be a terminal olefin for purposes of this invention.
Polypropylene and polybutylene, particularly polyisobutylene, are preferred.
These typically have number average molecular weight ranging from about 300 to
about 5,000, more often from about 700 to about 2,000.
A preferred source of hydrocarbyl and hydrocarbon based groups R are
polybutenes obtained by polymerization of a C4 refinery stream having a butene
content of 35 to 75 weight percent and isobutylene content of 15 to 60 weight
percent in the presence of a Lewis acid catalyst such as aluminum trichloride
or
19
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
boron trifluoride. These polybutenes contain predominantly (greater than 80%
of
total repeating units) isobutylene repeating units of the configuration
CH3
I
-CHz
CH3
These polybutenes are typically monoolefinic, that is they contain but one
olefinic
bond per molecule.
The olefinic compound may be a polyolefin comprising a mixture of isomers
wherein from about 50 percent to about 65 percent are tri-substituted olefins
wherein
one substituent contains from 2 to about 500 carbon atoms, often from about 30
to
about 200 carbon atoms, more often from about 50 to about 100 carbon atoms,
usually aliphatic carbon atoms, and the other two substituents are lower
alkyl.
When the olefin is a tri-substituted olefin, it frequently comprises a mixture
of cis- and traps- 1-lower alkyl, 1-(aliphatic hydrocarbyl containing from 30
to about
100 carbon atoms), 2-lower alkyl ethene and l,l-di-lower alkyl, 2-(aliphatic
hydrocarbyl containing from 30 to about 100 carbon atoms) ethene.
In one embodiment, the monoolefinic groups are predominantly vinylidene
groups, i.e., groups of the formula
CHZ = (~
especially those of the formula
-CHZ -C= CH2
CH3
although the polybutenes may also comprise other olefinic configurations.
In one embodiment the polybutene is substantially monoolefinic, comprising
at least about 30 mole %, preferably at least about 50 mole % vinylidene
groups,
more often at least about 70 mole % vinylidene groups. Such materials and
methods
for preparing them are described in U.S. Patents 5,071,919; 5,137,978;
5,137,980;
5,286,823 and 5,408,018, and in published European patent application EP
646103-
A1, each of which is expressly incorporated herein by reference. They are
commercially available, for example under the tradenames ULTRAVIS~ (BP
Chemicals) and GLISSOPAL~ (BASF).
W~ ~1/~7381 CA 02380289 2002-O1-22 PCT/US00/19953
Specific characterization of olefin reactants (A) used in the processes of
this
invention can be accomplished by using techniques known to those skilled in
the art.
These techniques include general qualitative analysis by infrared and
determinations
of average molecular weight, e.g., M n, number average molecular weight, and M
W,
weight average molecular weight, etc. employing vapor phase osmometry (VPO)
and gel permeation chromatography (GPC). Structural details can be elucidated
employing proton and carbon 13 (C13) nuclear magnetic resonance (NMR)
techniques. NMR is useful for determining substitution characteristics about
olefinic bonds, and provides some details regarding the nature of the
substituents.
More specific details regarding substituents about the olefinic bonds can be
obtained
by cleaving the substituents from the olefin by, for example, ozonolysis, then
analyzing the cleaved products, also by NMR, GPC, VPO, and by infra-red
analysis
and other techniques known to the skilled person.
Numerous polycarboxylic acids are commercially available, many from more
than one source. The commercially available polycarboxylic acids can be used
in the
preparation of the compositions of this invention. While these commercially
available
polyacids, or derivatives thereof that contain the requisite hydrocarbyl
substituent may
be used by themselves, it is usually beneficial to employ them in combination
with
polyolefin substituted succinic acids, anhydrides or functional equivalents
thereof.
Those that do not contain the requisite hydrocarbyl substituent, must be used
together
with a substituted polycarboxylic acid, usually in amounts that do not exceed
about 20
mole % of the total acid functionality. Such commercially available
polycarboxylic
acids and anhydrides include, but are not limited to aliphatic acids such as
glutaric,
adipic, sebacic, azaleic, dodecanedioic, 5-norbornene dicarboxylic,
bicyclooctene
dicarboxylic, 2-OH-succinic, citric, tartaric, cyclopentane tetracarboxylic, 5
norbornene-2,3-dicarboxylic, cyclohexene-4,5-dicarboxylic and cyclohexane
dicarboxylic (1,2- 1,3-, and 1,4-). Also useful are aromatic acids and
anhydrides such
as phthalic, terephthalic, trimellitic anhydride, trimesic, pyromellitic, 2,3
naphthalenedicarboxylic, 1,8-naphthalic, benzophenone tetracarboxylic, and
1,1,3
trimethyl-3-phenylindane-4',5'-dicarboxylic.
21
CA 02380289 2002-O1-22 pCT~S00/19953
WO 01/07381
Polycarboxylic acids from vegetable- and animal-sourced carboxylic
compounds can be used. Dimer acids, made by the thermal coupling of
unsaturated
vegetable acids, are available from Emery, Westvaco, Unichema and other
companies.
The above-described classes of carboxylic acids derived from olefin polymers,
and their derivatives, are well known in the art, and methods for their
preparation as
well as representative examples of the types useful in the present invention
are
described in detail in the following U.S. patents:
3,172,892 3,316,771 3,522,179
3,216,936 3,373,111 3,542,678
3,219,666 3,381,022 3,542,680
3,271,310 3,341,542 3,579,450
3,272,746 3,344,170 3,632,510
3,278,550 3,448,048 3,632,511
3,281,428 3,454,607 3,639,242
3,306,908 3,515,669
Other useful acids are hydrocarbyl substituted aromatic polycarboxylic acids
such as substituted phthalic acid, mellitic acids, and the like.
Non-limiting examples of polycarboxylic compounds useful to prepare the
emulsifier (C) include those in the following examples. Parts in the following
examples
are, unless otherwise indicated, parts by weight. Temperatures are in degrees
Celsius
(°C). Filtrations employ a diatomaceous earth filter aid.
Example (C-1)-1
A mixture of 6400 parts (4 moles) of a polybutene comprising predominantly
isobutene units and having a number average molecular weight of about 1600 and
408
parts (4.16 moles) of malefic anhydride is heated at 225-240°C for 4
hours. It is then
cooled to 170°C and an additional 102 parts (1.04 moles) of malefic
anhydride is added,
followed by 70 parts (0.99 mole) of chlorine; the latter is added over 3 hours
at 170-
215°C. The mixture is heated for an additional 3 hours at 215°C
then vacuum stripped
at 220°C and filtered through diatomaceous earth. The product is the
desired
polybutenyl-substituted succinic anhydride having a saponification number of
61.8.
Example(C-1 )-2
A polybutenyl succinic anhydride is prepared by the reaction of a chlorinated
(4.3% Cl) polybutylene with malefic anhydride at 200°C. The polybutenyl
radical
22
W~ ~1/~~381 CA 02380289 2002-O1-22 pCT/C1S00/19953
contains an average of about 70 carbon atoms and contains primarily isobutene
units.
The resulting alkenyl succinic anhydride is found to have an acid number of
103.
Example (C-1)-3
A lactone acid is prepared by reacting 2 equivalents of a polyolefin ( M n
about
900) substituted succinic anhydride with 1.02 equivalents of water at a
temperature of
about 90°C in the presence of a catalytic amount of concentrated
sulfuric acid.
Following completion of the reaction, the sulfuric acid catalyst is
neutralized with
sodium carbonate and the reaction mixture is filtered.
Example (C-1)-4
An ester acid is prepared by reacting 2 equivalents of an alkyl substituted
succinic anhydride having an average of about 35 carbon atoms in the alkyl
group with
1 mole of ethanol.
Example (C-1)-5
A reactor is charged with 1000 parts of polybutene having a number average
molecular weight determined by vapor phase osmometry of about 950 and which
consists primarily of isobutene units, followed by the addition of 108 parts
of rnaleic
anhydride. The mixture is heated to 110°C followed by the sub-surface
addition of 100
parts CIZ over 6.5 hours at a temperature ranging from 110 to 188°C.
The exothermic
reaction is controlled as not to exceed 188°C. The batch is blown with
nitrogen then
stored.
Example (C-1)-6
A procedure similar to that of Example (C-1)-5 is repeated employing 1000
parts of polybutene having a molecular weight determined by vapor phase
osmometry
of about 1650 and consisting primarily of isobutene units and 106 parts
rnaleic
anhydride. Chlorine (90 parts) is added beginning at 130°C and added at
a nearly
continuous rate such that the maximum temperature of 188°C is reached
near the end
of chlorination. The residue is blown with nitrogen and collected.
Example (C-1)-7
A reactor is charged with 1000 parts of C1$_~ olefin mixture obtained from
Albamarle Corporation, Houston, Texas. The material is heated to 65°C
followed by
addition of 350 parts malefic anhydride. The temperature is increased to
213°C then
held at reflux until the total acid number is between 285-295. The reactor
contents are
23
W~ ~1/~7381 CA 02380289 2002-O1-22 PCT/US00/19953
stripped to remove volatile materials until analysis shows % malefic acid is
less than
0.30%
Example (C-1)-8
A reactor is charged with 1000 parts of a polybutene having a number average
molecular weight of about 1500 and 47.9 parts molten malefic anhydride. The
materials
are heated to 138°C followed by chlorination, allowing the temperature
to rise to
between 188-191°C, heating and chlorinating until the acid number is
between 43 and
49 (about 40-4-5 parts C12 are utilized). The materials are heated at 224-
227°C for
about 2.5 hours until the acid number stabilizes. The reaction product is
diluted with
438 parts mineral oil diluent and filtered with a diatomaceous earth filter
aid.
Amine Reactants
Suitable amine reactants, as defined herein, include monoamines and
polyamines. The amine reactants must contain at least one N-H group. Thus,
only
amines having primary and secondary amino groups are used in preparing the
emulsifiers of this invention. Polyamines may be used and are preferred,
provided that
they contain at least one primary or secondary amine group. The monoamines
generally contain from 1 to about 24 carbon atoms, preferably 1 to about 12,
and more
preferably 1 to about 6. Examples of monoamines useful in the present
invention
include primary amines, for example methylamine, ethylamine, propylamine,
butylamine, octylamine, and dodecylamine. Examples of secondary amines include
dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine,
ethylhexylamine, etc.
In another embodiment, the monoamine may be a hydroxyamine. Typically,
the hydroxyamines are primary or secondary alkanolamines or mixtures thereof.
Alkanol amines that can react to form amide can be represented, for example,
by the
formulae:
HZN -R'- OH, and
H
jN-R'-OH,
R4
wherein each R4 is independently a hydrocarbyl group of one to about 22 carbon
atoms
or hydroxyhydrocarbyl group of two to about 22 carbon atoms, preferably one to
about
24
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
four, and R' is a divalent hydrocarbyl group of about two to about 18 carbon
atoms,
preferably two to about four. The group -R'-OH in such formulae represents the
hydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group.
Typically, R' is an acyclic straight or branched alkylene group such as an
ethylene, 1,2-
propylene, 1,2-butylene, 1,2-octadecylene, etc. group. When two R4 groups are
present
in the same molecule they can be joined by a direct carbon-to-carbon bond or
through a
heteroatom (e.g., oxygen, nitrogen or sulfur) to form a S-, 6-, 7- or 8-
membered ring
structure. Examples of such heterocyclic amines include N-(hydroxyl lower
alkyl)-
morpholines, -thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and
the like.
Typically, however, each R4 is independently a methyl, ethyl, propyl, butyl,
pentyl or
hexyl group.
Examples of these alkanolamines include mono- and di- ethanolamine,
ethylethanolamine, etc.
The hydroxyamines can also be ether N-(hydroxyhydrocarbyl) amines. These
are hydroxy poly(hydrocarbyloxy) analogs of the above-described hydroxy amines
(these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N-
(hydroxyhydrocarbyl) amines can be conveniently prepared, for example, by
reaction
of epoxides with aforedescribed amines and can be represented by the formulae:
HZN - (R'O)X - H, and
H
jN-(R' O)x H,
Ra
wherein x is a number from about 2 to about 15 and R4 and R' are as described
above.
R4 may also be a hydroxypoly (hydrocarbyloxy) group.
Other useful amines include ether amines of the general formula
R60R' NHR~
wherein R6 is a hydrocarbyl group, preferably an aliphatic group, more
preferably an
alkyl group, containing from 1 to about 24 carbon atoms, R' is a divalent
hydrocarbyl
group, preferably an alkylene group, containing from two to about 18 carbon
atoms,
more preferably two to about 4 carbon atoms and R~ is H or hydrocarbyl,
preferably H
or aliphatic, more preferably H or alkyl, more preferably H. When R~ is not H,
then it
W~ X1/07381 CA 02380289 2002-O1-22 pCT/US00/19953
preferably is alkyl containing from one to about 24 carbon atoms. Especially
preferred
ether amines are those available under the name SURFAM produced and marketed
by
Sea Land Chemical Co., Westlake, Ohio.
The amine is preferably a polyamine. The polyamine may be aliphatic,
cycloaliphatic, heterocyclic or aromatic. Examples of the polyamines include
alkylene
polyamines, hydroxy containing polyamines, arylpolyamines, and heterocyclic
polyamines.
Alkylene polyamines are represented by the formula
HN-EAlkylene-N~Rs
Rs Rs
wherein n has an average value between about 1 and about 10, preferably about
2 to
about 7, more preferably about 2 to about 5, and the "Alkylene" group has from
1 to
about 10 carbon atoms, preferably about 2 to about 6, more preferably about 2
to about
4. RS is independently hydrogen or an aliphatic, amino-substituted aliphatic
or
hydroxy-substituted aliphatic group of up to about 30 carbon atoms. Preferably
Rs is H
or lower alkyl, most preferably, H.
Alkylene polyamines include methylene polyamines, ethylene polyamines,
butylene polyamines, propylene polyamines, pentylene polyamines, etc. Higher
homologs and related heterocyclic amines such as piperazines and N-amino alkyl-
substituted piperazines are also included. Specific examples of such
polyamines are
ethylene diamine, diethylene triamine, triethylene tetramine, tris-(2-
aminoethyl)amine,
propylene diamine, trimethylene diamine, tripropylene tetramine, tetraethylene
pentamine, hexaethylene heptamine, pentaethylenehexamine, aminoethyl
piperazine,
dimethyl aminopropylamine, etc.
Higher homologs obtained by condensing two or more of the above-noted
alkylene anunes are similarly useful as are mixtures of two or more of the
aforedescribed polyamines.
Ethylene polyamines, such as some of those mentioned above, are preferred.
They are described in detail under the heading "Diamines and Higher Amines" in
Kirk
Othmer's "Encyclopedia of Chemical Technology", 4th Edition, Vol. 8, pages 74-
108,
John Wiley and Sons, New York (1993) and in Meinhardt, et al, U.S. 4,234,435,
both of
which are hereby incorporated herein by reference for disclosure of useful
polyamines.
26
' CA 02380289 2002-O1-22
12-09-2001 US001995~
08/12/01 12:14 ~AX'44b 347 1110 LUBRIZOL PATENT i~-~ EPO-CHPT LI DD~
,f~uttiulc
Such polyamines are conveniently prepared by the reaction of ethylene
dichloride with
ammonia or by reaction of an ethylene imine with a sing opening reagent such
as
water, ammonia, etc. These reactions result in the production of a complex
mixture of
polyalkylene polyamines including cyclic condensation products such as the
, aforedesciibed piperazines. Ethylene polyamine mixtures are useful. . '
Other useful types of polyamine mixtures are those resulting from stripping of
the above-described polyamine mixtures to leave as residue wheat is often
termed
"polyamine bottoms". In general, alkylene polyarrtine bottoms can be
characterized as
having less than two, usually less than 1% (by weight) material broiling below
about
200°C. A typical sample of such ethylene polyarnine bottoms obtained
from the Dow
Chemical Company of Freeport, Texas, designated "E-100" has a specific gravity
at
15.6°C of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity
at 40°C of 121
mm2ls (centistokes). Gas chromatography analysis of such a sample contains
about
0.93'0 "Light Ends" (most probably diethylenetriamine), 0.72%
diethylenetetremine,
21.74% tetraethylenepentarnine and 76.61% pentaethylene hexamine and higher
(by
weight). These alkylene polyamine bottoms include cyclic condensation products
such
as piperxzine and higher analogs of diethylenetriamine, triethylenetetrF~mine
and the like.
Another useful polyarnine is a condensation product obtain~:d by reaction of
at
least one hydroxy compound with at least one polyamine reactant containing at
least
one primary or secondary amino group. The hydroxy compounds are preferably
polyhydric alcohols and amines. Preferably the hydroxy compounds are
polyhydric
amines. Polyhydric amines include any of the above-described tnonoarnines
reacted
with an alkylene oxide (e.g., ethylene oxide, propylene oxide, b4itylene
oxide, etc.)
having two to about 20 carbon atoms, preferably two to about four. Examples of
polyhydric amines include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino
methane, 2-amino-2-methyl-1,3-propanediol, N,N,N',N'-tetraki;~(2-
hydroxypropyl)
ethylenediamine, and N>N,N',N-tetralds(2-hydroxyethyl) ethylenedi;imine.
Polyamine reactants, which react with the polyhydric alcohol or amine to form
the condensation products or condensed amines, are described above. Preferred
polyamine reactants include triethylenetetramine (TETA),
tetraethylenepentamine
(TEPA), pentaethylenehexamine (PEHA), and mixtures of polyamines such as the
. above-described "amine bottoms".
27
AMENDED SHEET
. . , n .nn men t t o ~ (1R F-mPt .rtr . :125,5 t'' .U 11
W~ ~1/~7381 CA 02380289 2002-O1-22 PCT/US00/19953
The condensation reaction of the polyamine reactant with the hydroxy
compound is conducted at an elevated temperature, usually about 60°C to
about 265°C
in the presence of an acid catalyst.
The amine condensates and methods of making the same are described in
Steckel (US Patent 5,053,152) which is incorporated by reference for its
disclosure to
the condensates and methods of making amine condensates.
In another embodiment, the polyamines are hydroxy-containing polyamines.
Hydroxy-containing polyamine analogs of hydroxy monoamines, particularly
alkoxylated alkylenepolyamines can also be used. Such polyamines can be made
by
reacting the above-described alkylene amines with one or more of the above-
described
alkylene oxides. Similar alkylene oxide-alkanolamine reaction products can
also be
used such as the products made by reacting the aforedescribed primary,
secondary or
tertiary alkanolamines with ethylene, propylene or higher epoxides in a 1.1 to
1.2 molar
ratio. Reactant ratios and temperatures for carrying out such reactions are
known to
those skilled in the art.
Specific examples of alkoxylated alkylenepolyamines include N-(2-
hydroxyethyl) ethylenediamine, N,N-di-(2-hydroxyethyl)-ethylenediamine, 1-(2-
hydroxyethyl) piperazine, mono-(hydroxypropyl)-substituted
tetraethylenepentamine,
N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtained by
condensation of the above illustrated hydroxy-containing polyamines through
amino
groups or through hydroxy groups are likewise useful. Condensation through
amino
groups results in a higher amine accompanied by removal of ammonia while
condensation through the hydroxy groups results in products containing ether
linkages
accompanied by removal of water. Mixtures of two or more of any of the
aforesaid
polyamines are also useful.
In another embodiment, the polyamine may be a heterocyclic polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines, tetra- and
dihydropyridines, pyrroles, indoles, piperidines, imidazoles, di- and
tetrahydroimidazoles, piperazines, isoindoles, purines, N-
aminoalkylthiomorpholines,
N-aminoalkylmorpholines, N-aminoalkylpiperazines, N,N'-bisaminoalkyl
piperazines,
azepines, azocines, azonines, azecines and tetra-, di- and perhydro
derivatives of each
of the above and mixtures of two or more of these heterocyclic amines.
Preferred
28
V~~ ~1/~7381 CA 02380289 2002-O1-22 pCT/US00/19953
heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines
containing only nitrogen, or nitrogen with oxygen and/or sulfur in the hetero
ring,
especially the piperidines, piperazines, thiomorpholines, morpholines,
pyrrolidines, and
the like. Piperidine, aminoalkylsubstituted piperidines, piperazine,
aminoalkylsubstituted piperazines, morpholine, aminoalkylsubstituted
morpholines,
pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especially
preferred. Usually
the aminoalkyl substituents are substituted on a nitrogen atom forming part of
the
hetero ring. Specific examples of such heterocyclic amines include N-
aminopropylmorpholine, N-amino-ethylpiperazine, and N,N'-diaminoethyl-
piperazine.
Hydroxy alkyl substituted heterocyclic polyamines are also useful. Examples
include
N-hydroxyethylpiperazine and the like.
In another embodiment, the amine is a polyalkene-substituted amine. These
polyalkene-substituted amines are well known to those skilled in the art. They
are
disclosed in U.S. patents 3,275,554; 3,438,757; 3,454, 555; 3,565,804;
3,755,433; and
3,822,289. These patents are hereby incorporated by reference for their
disclosure of
polyalkene-substituted amines and methods of making the same.
Typically, polyalkene-substituted amines are prepared by reacting
halogenated-, preferably chlorinated-, olefins and olefin polymers
(polyalkenes) with
amines (mono- or polyamines). The amines may be any of the amines described
above. Examples of these compounds include poly(propylene)amine; N,N-dimethyl-
N-poly (ethylene/propylene)amine, (50:50 mole ratio of monomers); polybutene
amine; N,N-di(hydroxyethyl)-N-polybutene amine; N-(2-hydroxypropyl)-N-
polybutene amine; N-polybutene-aniline; N-polybutene-morpholine; N-
poly(butene)
ethylenediamine; N-poly(propylene)trimethylenedi-amine; N-
poly(butene)diethylene-
triamine; N',N'-poly(butene)tetraethylene-pentamine; N,N-dimethyl-N'-poly-
(propylene)-1,3-propylenediamine and the like.
The polyalkene substituted amine is characterized as containing from at least
about 8 carbon atoms, preferably at least about 30, more preferably at least
about 35 up
to about 300 carbon atoms, preferably 200, more preferably 100. In one
embodiment,
the polyalkene substituted amine is characterized by M n (number average
molecular
weight) value of at least about 500. Generally, the polyalkene substituted
amine is
29
CA 02380289 2002-O1-22
WO 01/07381 PCT/LJS00/19953
characterized by an n value of about 500 to about 5000, preferably about 800
to about
2500. In another embodiment n varies between about 500 to about 1200 or 1300.
The polyalkenes from which the polyalkene substituted amines are derived
include homopolymers and interpolymers of polymerizable olefin monomers of 2
to
about 16 carbon atoms; usually 2 to about 6, preferably 2 to about 4, more
preferably 4.
The olefins may be monoolefms such as ethylene, propylene, 1-butene,
isobutene, and
1-octene; or a polyolefinic monomer, preferably diolefinic monomer, such 1,3-
butadiene and isoprene. Preferably, the polymer is a homopolymer. An example
of a
preferred homopolymer is a polybutene, preferably a polybutene in which about
50%
of the polymer is derived from isobutylene. The polyalkenes are prepared by
conventional procedures.
The number of equivalents of acylating agent depends on the total number of
carboxylic functions present. In the determination of the number of
equivalents of
acylating agent, carboxyl functions which are not capable of reacting as a
carboxylic
acid acylating agent are excluded. In general, there is one equivalent of
acylating agent
for each carboxy group in the acylating agents. Conventional methods for
determining
the number of carboxyl functions (e.g., acid number, saponification number,
etc.) are
available and are well known to those skilled in the art.
An equivalent weight of monoamine is the molecular weight of the amine. The
equivalent weight of mixtures of monoamines can be determined by dividing the
atomic weight of nitrogen (14) by the %N contained in the mixture and
multiplying by
100. Equivalent weight of polyamines can be determined similarly.
Amounts of polyamines are often referred to in equivalents. One equivalent of
a polyamino compound or derivative thereof is its formula weight divided by
the
average number of nitrogen atoms therein which contain a basic N-H group. Thus
ethylene diamine contains 2 equivalents; N,N-dimethyl-propanediamine contains
one
equivalent.
In another embodiment, the polyamine may be a hydroxyamine provided that
the polyamine contains at least one condensable -N-H group. Typically, the
hydroxyamines are primary or secondary alkanol amines or mixtures thereof.
Such
amines can be represented by mono- and poly-N-hydroxyalkyl substituted
alkylene
polyamines wherein the alkylene polyamines are as described hereinabove;
especially
WD ~1/~~381 CA 02380289 2002-O1-22 PCT/US00/19953
those that contain two to three carbon atoms in the alkylene radicals and the
alkylene
polyamine contains up to seven amino groups.
Acylated amines useful in the preparation of the emulsifier (C) include, but
are
not limited by, those prepared by the processes described in the following
examples:
Example (C-2)-1
A reaction flask is charged with 698 parts of mineral oil and 108 parts of a
commercial polyethylene polyamine mixture having typical %N= 34. The materials
are stirred and heated to 135°C at which time 1000 parts of a
polybutene substituted
succinic anhydride prepared according to the procedure of Example (C-1)-1 are
added
over 1 hour. With N2 sparging, the temperature is increased to 160°C
and held there
for 4 hours while removing water and other volatile components. The product is
filtered using a diatomaceous earth filter aid yielding a filtrate typically
containing 2%
N and a total base number of 45.
Example (C-2)-2
A polybutene having a number average molecular weight = 1350 (1000 parts)
is reacted with 106 parts malefic anhydride with C12 blowing (total C12 about
90 parts).
To a reactor containing 1000 parts of the substituted succinic anhydride is
added 1050
parts mineral oil, the materials are heated, with mixing, to 120°C,
followed by addition
of 70 parts of the commercial amine mixture described in Example (C-2)-1. The
reaction mixture is heated to 155°C over 4 hours with N2 sparging to
remove volatiles
then filtered employing a diatomaceous earth filter aid. The filtrate
typically contains,
by analysis, 1.1%N and has a total base number = 20.
Example (C-2)-3
An acylated polyamine is prepared by reacting 1000 parts of polyisobutenyl
( M n 1000) substituted succinic anhydride with 85 parts of a commercial
ethylene
polyamine mixture having an average nitrogen content of about 34.5% in 820
parts
mineral oil diluent under conditions described in LeSuer US 3,172,892.
Example (C-2)-4
A composition is prepared by reacting a mixture of 275 parts mineral oil, 147
parts of a commercial ethyleneamine mixture having an average composition
corresponding to that of tetraethylenepentamine and 1000 parts of
polyisobutene ( M n
31
W~ ~1/~7381 CA 02380289 2002-O1-22 PCT/US00/19953
=1000) substituted succinic anhydride at 120-125°C for 2 hours and at
150°C for 2
hours then blown with nitrogen at 150°C for 5 hours to form an acylated
amine.
Example (C-2)-5
A solution of 698 parts mineral oil and 108 parts commercial ethylene
polyamine mixture containing an average of about 34% nitrogen is prepared and
heated
to 115°C. To the oil solution is added 1000 parts of the polybutenyl-
substituted
succinic anhydride of Example (C-1)-3 under NZ followed by heating to
150°C. The
reaction is continued at 143-150°C for 1 hour. The product is then
filtered.
Example (C-2)-6
The procedure of Example (C-2)-2 is repeated except the polybutenyl group on
the substituted succinic anhydride is derived from a polyisobutene having a
number
average molecular weight, measured by vapor phase osmometry, of about 1700.
Example (C-2)-7
To a mixture of 300 parts of the anhydride of Example (C-1)-2 in 160 parts
mineral oil are added, at 65-95°C, 25 parts of the ethylene polyamine
mixture of
Example (C-2)-4 followed by heating to 150°C with NZ blowing to dry the
material,
then diluted with 79 parts mineral oil.
Example (C-2)-8
A non-acidic nitrogen intermediate is prepared by reacting 2178 parts of the
polybutenyl succinic anhydride of example (C-1)-2 and 292 parts of triethylene
tetramine in 1555 parts mineral oil at 215°C for 12 hours, removing
aqueous distillate.
The Transition Metal Reactant
The metals of the metal salts useful in this invention are those metals
selected
from the class consisting of transition metals, preferably those from the
first transition
group of the Periodic Table of Elements. Preferred are copper and zinc; zinc
is
particularly preferred. Examples of metal compounds contemplated as reactants
in the
preparation of the emulsifier (C) are the transition metal oxides, hydroxides,
carbonates, methylates, propylates, pentylates, and phenoxides.
Amounts of metal reactant are often referred to in terms of equivalents. An
equivalent of metal is defined herein as the formula weight of the metal
divided by its
valence. Therefore, one equivalent of sodium is equal to its formula weight,
one
32
W~ ~1/~73g1 CA 02380289 2002-O1-22 pCT~S00/19953
equivalent of zinc is equal to one-half of its formula weight, one equivalent
of
aluminum is one-third of its formula weight. Similarly for ions, one
equivalent of
cupric ion is its formula weight divided by 2, one equivalent of cuprous ion
is its
formula weight.
The following examples illustrate process for preparing nitrogen and metal
containing derivatives (C) used as emulsifiers in the preparation of the
emulsions of
this invention. Unless indicated otherwise, all parts are parts by weight,
temperatures
are in degrees Celsius and pressures are atmospheric. All analytical values
are by
analysis. Filtrations employ a diatomaceous earth filter aid. These examples
are
intended to be illustrative only and are not intended to limit the scope of
the
invention.
Example C-1
To a mixture of 3264 parts of the anhydride of Example (C-1)-2, 2420 parts
mineral oil and 75 parts water are added, in three portions over 0.5 hours at
80-100°C,
122.1 parts zinc oxide. The materials are reacted for 3 hours at 90-
100°C then the
temperature is increased to 150°C and maintained at this temperature
until essentially
dry. The materials are cooled to 100°C then there is added, portionwise
over 0.5 hours,
245 parts of an ethylene polyamine mixture having an average composition
corresponding to tetraethylene pentamine and an average equivalent weight of
40.8.
The materials are heated to 150°C and are maintained at 150°C-
160°C for 5 hours
while N2 blowing to remove water. The materials are filtered. The filtrate
contains
1.63% Zn and 1.39% N.
Example C-2
To a mixture of 80 parts water, 36.5 parts zinc oxide and 650 parts mineral
oil
are added, as fast as possible without allowing the exothermic reaction to
exceed 93°C,
1000 parts of the anhydride of Example (C-1)-5. The materials are reacted for
1.5
hours at 87°C-93°C, then heated to 121°C. To this
material are added 36 parts of an
ethylene polyamine mixture containing about 34% N followed by heating to
148°C the
N2 blowing at 148-155°C to 0.3% maximum water content and filtration.
Mineral oil is
added to adjust % Zn to 1.55.
33
.,
12-09-2001 CA 02380289 2002-O1-22 US001995:
09/12/01 12:15 NAg~~44~ 347 1110 LUBRIZOL PATfiNT -~~1 EPU-CHPT II DMD -
1012/012
Example C- 3
A mixture of 35? parts cobaltous chloride hexahydrate, 2800 parts of the
product of Example (C-2)-7 and 250 parts xylene are heated under reflux while
removing water by azeotropic distillation. The residue is heated fof 2 hours,
mixed
with 560 parts mineral oil and filtered. The filtrate is heated to remove
xylene and the
residue is filtered yielding a 5096 in oil solution of,a metal complex
containing 1.2%
Co.
Example C- 4
The procedure of Example C-2 is repeated employing 1000 parts of an 80~9r. in
mineral oil solution of the anhydride of Example (C-1)-5, 64 palt:~ water,
29.2 parts
zinc oxide and 28.8 parts of ethylene polyamine mixture. After fi)~-~stion the
materials
are diluted with 132 parts additional mineral oil.
Example C-5 ,
An acylated nitrogen-containing compound is prepared by reacting 2076 pasts
of the anhydride of example (C-1)-1 and 292 parts triethylene tetrarnine in
1555 pans
mineral oil at 215°C while rennoving water, then the materials are
filtered. A mixture
of 485 parts of the f Itrate is reacted with 74 parts zinc dihydrogen
phosphate dihydrate
in 51 parts mineral oil at 160°C for 14.5 hours, mixed with 250 parts
by volume
xylene, then filtered. The filtrate is stripped to 130°C at 2 kPa (15
mm Hg), then
filtered again.
Exam-ple C-6
The procedure of Example 2 is repeated replacing the succinic anhydride of
Example (C-1)-5~with a stoichiometric equiv~ent amount of the anhydride of
example
(C-1 )-6
Example C-?
To 440 parts of the product of example (C-2)-8 are added at 1.40-150°C,
aver 6
hours, 324 parts of cupric benzoate. The mixture is heated at I40-150°C
for 3 hours,
f ltered, then stripped to 65°C at 4.6 kPa (35 mm Fig) and again
filtered.
Exarnnle C-8
The procedure of Example C-2 is repeated replacing zinc oxide with an
equivalent amount of zinc as zinc borate.
34
AMENDED SHEET
r _r ___~.inmnWftnl 1Q~nS2 rtllpT.nr.:r~3 r.uic
W~ ~1/~~381 CA 02380289 2002-O1-22 PCT/US00/19953
The Co-emulsifier
The co-emulsifier typically has hydrophilic-lipophilic balance (HI.,B) ranging
from about 1 to about 6. From about 1°70, often from about 5% to about
50% by weight
of co-emulsifier, based on total emulsifier content, may be used together with
the
emulsifier (C) used in this invention. Co-emulsifiers are used, for example,
to enhance
emulsion stability. Any water in oil emulsifier suitable for use in the
particular
application may be used as a co-emulsifier to prepare the emulsions of this
invention.
Any emulsifier which together with component (C) serves to establish the
requisite
water in oil emulsion and is stable to the conditions under which the emulsion
is
formed, may be used in the present invention. Such emulsifiers generally
consist of
lipophilic and hydrophilic portions.
The lipophilic portion of the co-emulsifier may be either monomeric or
polymeric in nature. Examples of suitable chain structures include those
described as
hydrocarbyl groups of the polycarboxylic acids used to prepared the
emulsifiers (C)
of this invention. These co-emulsifiers include the internal amine salts,
ester salts,
and the like which are well known in the art and which are mentioned in
several of
the patents referred to in the Background of the Invention of this patent
application.
The following example illustrates a representative co-emulsifier that may be
used to prepare the emulsions of this invention.
Co-emulsifier 1
A reactor is charged with 1151 parts mineral oil (Naphthenic pale 40N,
Diamond Shamrock) which is heated to 66°C. While maintaining this
temperature,
1000 parts of the product of Example (C-1)-6 are added and the materials are
mixed
thoroughly. Dimethylethanol amine (151 parts) is then added at such a rate
that the
batch temperature exotherms to 82°C. The batch is heated to 93°C
and is held at
temperature for 2 hours. The batch is heated to 160°C and is maintained
at
temperature until the total acid number is 13. The batch is then filtered.
Other suitable co-emulsifiers include salts of hydrocarbyl group substituted
succinic acylating agents, salts of partially esterifed hydrocarbyl group
substituted
poly-acids, sorbitan esters, such as sorbitan sesquioleate, sorbitan
monooleate,
sorbitan monopalmitate, the mono- and diglycerides of fat forming fatty acids,
soybean lecithin and derivatives of lanolin such as isopropyl esters of
lanolin fatty
V~~ ~1/~~3g1 CA 02380289 2002-O1-22 pCT~S00/19953
acids, mixtures of higher molecular weight fatty alcohols and wax esters,
ethoxylated fatty ethers such as polyoxyethylene(4) lauryl ether, and
oxazoline
emulsifiers such as substituted oxazolines such as 2-oleyl-4-4'-
bis(hydroxymethyl)-
2-oxazoline and suitable mixtures thereof.
Method of Making the Emulsions
A useful method for preparing the emulsions of this invention comprises
combining the organic components such as oil with the emulsifier to form a
premix
and combining the premix with the materials making up the discontinuous phase.
As noted hereinabove, the discontinuous phase may comprise a substantially
anhydrous molten oxidizer or may be an aqueous composition comprising water
and
one or more water soluble components such as oxidizing agents or fertilizer
components.
One useful method for making the explosive emulsions of the invention
comprises the steps of (1) mixing water, inorganic oxidizer salts (e.g.,
ammonium
nitrate) and, in certain cases, some of the supplemental water-soluble
compounds, in
a first premix, (2) mixing the carbonaceous fuel, the emulsifier of the
invention and
any other optional oil-soluble compounds, in a second premix and (3) adding
the
first premix to the second premix in a suitable mixing apparatus, to form a
water-in-
oil emulsion. The first premix is heated until all the salts are completely
dissolved
and the solution may be filtered if needed in order to remove any insoluble
residue.
The second premix is also heated to liquefy the ingredients. Any type of
apparatus
capable of either low or high shear mixing can be used to prepare these water-
in-oil
emulsions. Closed-cell, void containing materials, gas-generating materials,
solid
self explosive ingredients such as particulate TNT, particulate-solid oxygen-
supplying salts such as ammonium nitrate prills and ANFO, solid fuels such as
aluminum or sulfur, inert materials such as barites or sodium chloride,
undissolved
solid oxidizer salts and other optional materials, if employed, are added to
the
emulsion and simply blended until homogeneously dispersed throughout the
composition.
The water-in-oil explosive emulsions of the invention can also be prepared
by adding the second premix liquefied organic solution phase to the first
premix hot
aqueous solution phase with sufficient stirring to invert the phases. However,
this
36
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
method usually requires substantially more energy to obtain the desired
dispersion
than does the preferred reverse procedure. Alternatively, these water-in-oil
explosive emulsions are particularly adaptable to preparation by a continuous
mixing process where the two separately prepared liquid phases are pumped
through
a mixing device wherein they are combined and emulsified.
The emulsifiers of this invention can be added directly to the other
components of the emulsion. They can also be diluted with a substantially
inert,
normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene
or
xylene, to form an additive concentrate. These concentrates usually contain
from
about 10% to about 90% by weight of the emulsifier composition of this
invention
and may contain, in addition, one or more other additives known in the art or
described herein.
The following examples illustrate emulsions of this invention. Unless
otherwise indicated, all parts are parts by weight (pbw). Temperatures are in
degrees Celsius. Unless otherwise indicated, amounts of ingredients are as
prepared
or as available, without adjusting for oil or other diluent content.
Examples 1-2
An organic mixture is prepared by mixing at about 70°C, 19.34 parts
of the
product of Example C-2, 2.15 parts of the product of the Co-emulsifier 1
example,
and 45.71 parts Diesel fuel oil. A solution of 928.9 parts ammonium nitrate in
203.9
parts water is prepared. A base emulsion is prepared by adding the water
solution to
the organic solution over 1 minute in a food processor at 45% of full voltage.
After
addition is completed, the speed is increased to 65% of full voltage and is
maintained for 1.5 minutes.
Using this base emulsion, two sensitized explosive emulsions are prepared.
The first is prepared by combining 200 parts of the base emulsion with 2 parts
of a
15% aqueous solution of sodium nitrite. This is identified as Example 1. The
second
emulsion is prepared by combining 200 parts of the base emulsion with 2 parts
of an
aqueous solution containing 15 parts by weight sodium nitrite and 30 parts by
weight sodium thiocyanate. This emulsion is identified as Example 2.
37
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
Comparative Examples ,
Comparative emulsions are prepared. Each is prepared replacing the
emulsifiers of Examples 1 and 2 with equal weight (on a neat, diluent free
basis) of
prior art emulsifiers. The first, identified as Comp. 1, is prepared as in
Example 1
replacing the emulsifiers of that example with 1 part by weight (neat chemical
basis)
per 100 parts of emulsion of the product of Example (C-2)-3. The second is
prepared replacing the emulsifiers of Example 1 with 1 part by weight (neat
chemical basis) per 100 parts of emulsion of the product of the Co-emulsifier
1
example.
The emulsion densities (g/cm3) of the emulsions of the comparative
examples and the emulsion of Example 1 are measured over time. Emulsion
density
is measured by obtaining the weight of fixed volumes of the emulsion. The data
are
provided in the following table:
Emulsion Density
(g~cm3)
Emulsion:Comp 1 Comp 2 Example
1
Time (min.)
1 1.29 1.30 1.30
5 -- 1.30 1.23
1.29 1.30 1.11
30 1.29 1.30 1.10
1440 1.29 1.29 0.99
15 As is apparent from the foregoing data, the density of the emulsion of the
instant invention (Example 1) is reduced without the need to acidify the
emulsion.
The density of prior art emulsions (Comp 1 and Comp 2) remains essentially
unchanged.
In the preceding examples, the emulsifier of the instant invention contains
both a metal and nitrogen containing emulsifier and a co-emulsifier. In the
following
examples, the effects of pH and of relative amounts of co-emulsifier (the
product of
the Co-emulsifier 1 example) and of metal and nitrogen containing emulsifier
(Product of Example C-2) are examined. The active emulsifier is the total
weight of
emulsifier on a neat chemical basis.
38
WD ~l/~~3g1 CA 02380289 2002-O1-22 pCT~S00/19953
The emulsion compositions are as follows:
~h pH Low pH
Ammonium nitrate 77.408 77.304
Sodium acetate 0.038
Acetic acid 0.066
W ater 16.992 16.992
Active emulsifier 1.000 1.000
Diesel fuel 4.600 4.600
The aqueous phase of the high pH (5) emulsion is prepared from ammonium
nitrate and water. The aqueous phase of the low pH (2.5) emulsion is prepared
from
water, ammonium nitrate, sodium acetate and acetic acid. The aqueous phase is
prepared by mixing the components at 85°C. The organic phase of these
emulsions
is prepared by mixing the diesel fuel with the emulsifier at 70°C. It
should be noted
that the emulsifier also contributes about 1 part by weight of mineral oil
which also
serves as additional fuel. The metal and nitrogen containing emulsifier is
that of
Example C-2. The co emulsifier is the product of the Co-emulsifier 1 example.
In each example, the emulsifier and diesel fuel are mixed in a food processor
at 70°C and the aqueous solution is added over 1 minute while mixing at
45% full
voltage on the food processor. When the addition is completed, the voltage is
increased to 65%, increasing the speed of the processor and the emulsion is
mixed
for 1.5 minutes. The gassing reaction is carried out by rapidly stirring 2
parts of an
aqueous 15% sodium nitrite/30% sodium thiocyanate solution into 200 parts of
each
base emulsion. Each emulsion is transferred to a vessel of known volume and as
gassing progresses, the volume increases. Excess emulsion is scraped off the
top of
the vessel and the vessel is weighed at each time interval allowing
calculation of the
emulsion density.
Emulsion densities of several emulsions are given in the following table. The
percentage is the weight percent, based on the total weight of emulsifier in
the
emulsion, of metal and nitrogen containing emulsifier. Thus, 100% indicates
the
emulsifier is totally the product of Example C-2 and 0% indicates that the
emulsifier is 100% of the product of the Co-emulsifier 1 example.
39
W~ ~1/~7381 CA 02380289 2002-O1-22 pCT~S00/19953
~H Time (min) Densit~~/cm3
100% low 1 1.25
5 0.97
15 0.92
100% high 1 1.30
5 1.15
15 1.03
30 1.01
90% low 1 1.24
5 0.98
15 0.91
90% high 1 1.31
5 1.23
15 1.10
30 1.07
80% low 1 1.26
5 1.04
15 1.00
80% high 1 1.30
5 1.23
15 1.10
30 1.09
66% low 1 1.31
5 1.27
15 1.23
30 1.21
1080 1.11
0% low 1 1.31
low 5 1.31
15 1.31
0% high 1 1.31
5 1.31
15 1.31
CA 02380289 2002-O1-22
WO 01/07381 PCT/US00/19953
From the foregoing data it is apparent that emotions of the instant invention
are superior with respect to density reduction compared to emulsions of the
prior art
(0% N- and metal containing emulsifier).
It is known that some of the materials described above may interact in the
final formulation, so that the components of the final formulation may be
different
from those that are initially added. For instance, metal ions (of, e.g., a
detergent)
can migrate to other acidic sites of other molecules. The products formed
thereby,
including the products formed upon employing the composition of the present
invention in its intended use, may not susceptible of easy description.
Nevertheless,
all such modifications and reaction products are included within the scope of
the
present invention; the present invention encompasses the composition prepared
by
admixing the components described above.
Each of the documents referred to above is incorporated herein by reference.
Except in the examples, or where otherwise explicitly indicated, all numerical
quantities in this description specifying amounts of materials, reaction
conditions,
molecular weights, number of carbon atoms, and the like, are to be understood
as
modified by the word "about". Unless otherwise indicated, each chemical or
composition referred to herein should be interpreted as being a commercial
grade
material which may contain the isomers, by-products, derivatives, and other
such
materials which are normally understood to be present in the commercial grade.
However, the amount of each chemical component is presented exclusive of any
solvent or diluent oil which may be customarily present in the commercial
material,
unless otherwise indicated. It is to be understood that the upper and lower
amount,
range, and ratio limits set forth herein may be independently combined. As
used
herein, the expression "consisting essentially of" permits the inclusion of
substances
which do not materially affect the basic and novel characteristics of the
composition
under consideration.
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the specification.
Therefore, it is to
be understood that the invention disclosed herein is intended to cover such
modifications that fall within the scope of the appended claims.
41
