Note: Descriptions are shown in the official language in which they were submitted.
-1_
2606B
Title: WATER-IN-OIL EMULSIONS
technical Field
This invention relates to water-in-oil emulsions which are useful
as explosives. These emulsions contain at least one emulsifier derived from at
least one substituted succinic acylating agent. The substituted succinic
acylating
agent consists of substituent groups and succinic groups wherein the
substituent
groups are derived from a polyalkene (e.g., polybutene), said acylating agents
being characterised by the presence within their structure of an average of at
least 1.3 succinic groups for each equivalent weight of substituent groups.
l3a~ound of the In ey ration
Hydrocarbyl-substituted carboxylic acylating agents having at least
about 30 aliphatic carbon atoms in the substituent are known. Examples of such
acylating agents include the polyisobutenyl-substituted succinic acids and
anhydrides. The use of such carboxylic acylating agents as additives in
normally
liquid fuels and lubricants is disclosed in U.S. Patents 3,288,714 and
3,346,354.
These acylating agents are also useful as intermediates for preparing
additives
for use in normally liquid fuels and lubricants as described in U.S. Patents
2,892,786; 3,087,936; 3,163,603; 3,172,892; 3,189,544; 3,215,707; 3,219,666;
3,231,587; 3,235,503; 3,272,746; 3,306,907; 3,306,908; 3,331,776; 3,341,542;
3,346,354; 3,374,174; 3,379,515; 3,381,022; 3,413,104; 3,450,715; 3,454,607;
3,455,728; 3,476,686; 3,513,095; 3,523,768; 3,630,904; 3,632,511; 3,697,428;
3,755,169; 3,804,763; 3,836,470; 3,862,981; 3,936,480; 3,948,909; 3,950,341;
and
4,471,091; and French Patent 2,223,415.
~~<v.~~
_2_
U.S. Patent 4,234,435 discloses carboxylic acid acylating agents
derived from polyalkenes s~ich as polybutenes, and a dibasic carboxylic
reactant
such as malefic or fumaric acid or certain derivatives thereof. These
acylating
agents are characterized in that the polyalkenes from which they are derived
have an Rein value of about 1300 to about 5000 and an Iviw/Mn value of about
1.5
to about 4. The acylating agents are further characterized by the presence
within their structure of at least 1.3 groups derived from the dibasic
carboxylic
reactant for each equivalent weight of the groups derived from the polyalkene.
The acylating agents can be reacted with an amine to produce derivatives
useful
per se as lubricant additives or as intermediates to be subjected to post-
treatment with various other chemical compounds and compositions, such as
epoxides, to produce still other derivatives useful as lubricant additives.
Water-in-oil explosive emulsions typically comprise a continuous
organic phase (e. g., a carbonaceous fuel) and a discontinuous aqueous phase
containing an oxygen-supplying component (e.g., ammonium nitrate). 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.S. Patent 4,216,040 discloses water-in-oil emulsion blasting
agents having a discontinuous aqueous phase, a continuous oil or water-hnmis-
cable liquid organic phase, and an organic cationic emulsifier having a
lipophilic
portion and a hydrophilic portion, the lipophilic portion being an unsaturated
hydrocarbon chain.
U.S. Patents 4,708,753 and 4,844,756 disclose water-in-oil emulsions
which comprise (A) a continuous oil phase; (B) a discontinuous aqueous phase;
(C)
a minor emulsifying amount of at least one salt derived from (C)(I) at least
one
hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide
derivative of said acid or anhydride, the hydrocarbyl substituent of (C)(I)
having
an average of from about 20 to about 500 carbon atoms, and (C)(II) ammonia or
61 d'~ ~ ~. J~ l~ ;1
R3 A. SiC
-3-
at least one amine; and (D) a functional amount of at least one water-soluble,
oil-insoluble functional additive dissolved in said aqueous phase. The '756
patent
discloses that component (C)(IID can also be an alkali or alkaline-earth
metal.
These emulsions are useful as explosive emulsions when the functional additive
(D) is an oxygen-supplying component (e.g., ammonium nitrate).
U.S. 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.
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 dd]uvant, 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 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 1:1 condensate of polyisobutenyl succinic
anhydride (number average molecular weight g 1200) and dinnethylethanol amine
as the modifier/emulsifier.
~~~.4(~~
-4-
U.S. Patent 4,828,633 discloses salt compositions which comprise
(A) at least one salt moiety derived from (A)(I) at least one high-molecular
weight polycarboxylic acylating agent, said acylating agent (A)(I) having at
least
one hydrocarbyl substituent having an average of from about 20 to about 500
carbon atoms, and (A)(ll) ammonia, at least one amine, at least one alkali or
alkaline earth metal, and/or at least one alkali or alkaline earth metal
compound;
(B) at least one salt moiety derived from (B)(1) at least one low-molecular
weight
polycarboxylic acylating agent, said acylating agent (8)(I) optionally having
at
least one hydrocarbyl substituent having an average of up to about 18 carbon
atoms, and (B)(II) ammonia, at least one amine, at least one alkali or
alkaline
earth metal, and/or at least one alkali or alkaline earth metal compound; said
components (A) and (B) being coupled together by (C) at least one compound
having (l) two or more primary amino groups, (1i) two or more secondary amino
groups, (iii) at least one primary amino group and at least one secondary
amino
group, (iv) at least two hydroxyl groups or (v) at least one primary or
secondary
amino group and at least one hydroxyl group. These salt compositions are
useful
as emulsifiers in water-in-oil explosive emulsions.
U.S. Patents 4,840,687 and 4,956,028 disclose explosive composi-
tions comprising a discontinuous oxidiser 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
-5-
component, a continuous organic phase comprising at least 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)(1D 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, 4,919,178 discloses emulsifiers which comprise the
reaction product of component (I) with component (II). Component (I) comprises
the reaction product of certain carboxylic acids or anhydrides, or ester or
amide
derivatives thereof, with ammonia, at least one amine, at least one alkali
and/or
at least one alkaline-earth metal. Component (II) comprises certain
phosphorous-
containing acidsg or metal salts of said phosphorous-containing acids, the
metals
being selected from the group consisting of magnesium, calcium, strontium,
chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc,
cadmium, aluminum, tin, lead, and mixtures of two or more thereof. These
emulsifiers are useful in water-in-oil explosive emulsions.
U.S. Patent 4,956,028 discloses an explosive composition which
comprises 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 aeylating 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. These explosive
compositions can be water-in-oil emulsions or melt-in-oil emulsions.
-s-
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 corxiponent
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 7096 by weight succinimide product.
Water-in-oil explosive emulsions are often blended with ammonium
nitrate grills or ANFO for the purpose increasing the explosive energy of such
emulsions. Among the commercially available ammonium nitrate grills that are
used are those that are made using one or more crystal habit modifiers to
control
crystal growth and one or more surfactants to reduce caking. A problem with
using these treated grills is that they tend to destabilize the emulsions. It
would
be advantageous to provide explosive emulsions that remain stable when blended
with such treated ammonium nitrate grills.
Summanr of the Invg~ntig_n
This invention is directed to water-in-oil emulsions which are useful
as explosives. These emulsions comprise a discontinuous aqueous phase
comprising at least one oxygen-supplying component, a continuous organic phase
comprising at least one carbonaceous fuel, and a minor emulsifying amount of
at least one emulsifier. The emulsifier is the product made by the reaction of
component (A) with component (~): component (A) being at least one substituted
succinic acylating agent, said substituted succinic acylating agent consisting
of
substituent groups and succinic groups wherein the substituent groups are
derived
from a polyalkene, said acylating agents being characterized by the presence
within their structure of an average of at least 1.3 succinic groups for each
equivalent weight of substituent groups; and component (B) being ammonia
and/or
at least one amine. In one embodiment, these emulsions are stably blended with
ammonium nitrate grills that have been made using one or more crystal habit
modifiers to control crystal growth and one or more surfactants to reduce
caking.
_?-
~ecr_._rinr_ion of the Preferred Embodiment
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
compositions derived from such emulsions wherein at temperatures below that
at which the emulsion is formed the discontinuous phase is solid or in the
form
of droplets of super-cooled liquid. This term also covers compositions derived
from or formulated as such water-in-oil emulsions that are in the form of
gelatinous or semi-gelatinous compositions.
The term "hydrocarbyl" is used herein to include:
(1) hydrocarbyl groups, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic- and alicyclic-
substituted aromatic groups and the like as well as cyclic groups wherein the
ring
is completed through another portion of the molecule (that is, any two
indicated
groups may together foran an alicyclic group);
(2) substituted hydrocasbyl groups, that is, those groups
containing non-hydrocarbon groups which, in the context of this invention, do
not
alter the predominantly hydrocarbyl nature of the hydrocarbyl group; those
skilled in the art will be aware of such groups, examples of which include
ether,
oxo, halo (e. g., chloro and fluoro), alkoxyl, mercapto, alkylmercapto, vitro,
nitroso, sulfoxy, etc.;
(3) hetero groups, that is, groups which, while having predomi-
nantly hydrocarbyl character within the context of this invention, contain
other
than carbon in a ring or chain otherwise composed of carbon atoms. Suitable
heteroatoms will be apparent to those of skill in the art and include, for
example, sulfur, oxygen, nitrogen and such substituents as pyridyl, furanyl,
thio-
phenyl, imidazolyl, etc.
In general, no more than about three nonhydrocarbon groups or
heteroatoms and preferably no more than one, will be present for each ten
carbon atoms in a hydrocarbyl group. Typically, there will be no such groups
or
heteroatoms in a hydrocarbyl group and it will, therefore, be purely
hydrocarbyl.
_8_
The hydrocarbyl groups are preferably free from acetylenic
unsaturation; ethylenic unsaturation, when present wild generally be such that
there is no more than one ethylenic linkage present for every ten carbon-
to-carbon bonds. The hydrocarbyd groups are often completely saturated and
therefore contain no ethydenic unsaturation.
The term "dower" as used herein in conjunction with terms such as
adkyl, alkenyl, alkoxy, and the like, is intended to describe such groups
which
contain a total of up to 7 carbon atoms.
The inventive water-in-oil emulsions, which are useful as
explosives, comprise a discontinuous aqueous phase comprising at least one
oxygen-supplying component, a continuous organic phase comprising at deast one
carbonaceous fuel, and a minor emulsifying amount of at least one emulsifier.
In one embodiment, these emulsions are stably blended with ammonium nitrate
pridls that have been treated with surfactants and crystad growth modifiers.
The continuous organic phase is preferably present at a level of at
least about 296 by weight, more preferably in the range of about 296 to about
1596 by weight, more preferably in the range of about 3.596 to about
10°!0, more
preferably about 596 to about 8% by weight based on the total weight of the
water-dn-oil emulsion. The discontinuous aqueous phase is preferably present
at
a level of at least about 8596 by weight, more preferably at a level in the
range
of about 8596 to about 9896 by weight, more preferably about 9296 to about
9596
by weight based on the total weight of the emulsion. The emulsifier is
preferably present at a level in the range of about 5% to about 9596, more
preferably about 596 to about 5096, more preferably about 596 to about 2096,
more
preferably about 1096 to about 2096 by weight based on the total weight of the
organic phase. The oxygen-supplying component is preferably present at a level
in the range of about 7096 to about 9596 by weight, more preferably about
?59'0
to about 9296 by weight, more preferably about 7896 to about 9096 by weight
based on the total weight of the aqueous phase. The water is preferably
present
at a level in the range of about 596 to about 3096 by weight, more preferably
about 896 to about 2596 by weight, more preferably about 1096 to about 2296 by
weight based on the weight of the aqueous phase.
The Carbonaceous F~gl
The carbonaceous fuel that is useful in the emulsions of the
invention can include most hydrocarbons, for example, paraffinic, olefinic,
naph
thenic, aromatic, saturated or unsaturated hydrocarbons, and is typically in
the
form of an oil or a wax or a mixture thereof. In general, the carbonaceous
fuel
is a water-immiscible, emulsifiable hydrocarbon that is either liquid or
liquefiable at a temperature of up to about 95°C, and preferably
between about
40°C and about ?5°C. Oils from a variety of sources, including
natural and
synthetic oils and mixtures thereof can be used as the carbonaceous fuel.
hlatoral 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 and halo-substituted
hydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,
polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated
polybutylenes, etc.); alkyl benzenes de.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
CA 02091405 2002-09-18
-10-
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 from C5 to
C12 monocarboxylic acids and polyols and polyal ethers such as neopentyl
glycol;
trimethylol propane, pentaerythrItol, dipentaerythrltol, tripentaerythritol,
etc:
Silicon-based oils such as the palyalkyl-, polyaryl-, polyalkoxy-, or
polyaryloxy-siloxane oils and silicate oils comprise another class of useful
oils.
These include tetraethyl-silicate, tetraisopropylsilicate, tetra-(2-
ethylhexyl)-sili-
cate, tetra-(4-methyl-hexyl)-silicate, tetra(p-tent-butylphenyl)-silicate,
hexyl-
(4-methyl-2-pentoxy)-di-siloxane,poly(methyl)-siloxanes,poly-(methylphenyl)-si-
loxanes, etc. Other useful synthetic oils include liquid esters of phosphorus-
con-
taining acid (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of
decane
phosphonic acid, etc.), polymeric tetrahydrofurans, and the like.
Unrefined, refined and rerefined oils (and mixtures of each with
each other) of the type disclosed hereinabove can be used. Unrefined oils are
those obtained directly from a natural or synthetic source without 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 are obtained by
processes
similar to those used to obtain refined oils applied to refined oils which
have
been already used in service. Such rerefined oils are also known as reclaimed
or
reprocessed oils and often are additionally processed by techniques dfrected
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-mark KAYD(JL; a white mineral
CA 02091405 2002-09-18
oil available from Shell under the trade-mark ONDINA; and a mineral oil
available from Pennzoil under the trade designation N-750-HT. Diesel fuel
(e.g., Grade No. 2-D as specified in ASTM D-975) can be used as the oil.
'Che carbonaceous fuel can be any wax having melting point of at least
about 25 °C, such as petroleum wax, microerystalline wax, and paraffin
wax,
mineral waxes such as ozocerite and montan wax, animal waxes such as
spermacetic wax, and insect waxes such as beeswax, and Chinese wax. Useful
waxes include waxes identified by the trade-mark MOBILWAX 57 which is
available from Mobil Oil Corporation; D02764 urhich is a blended wax available
from Astor Chemical Ltd., and the trade-mark VYBAR which is available from
Petrolite Corporation. Preferred waxes are blends of microcyrstalline waxes
and
paraffin.
In one embodiment, the carbonaceous fuel includes a combination
of a wax and an oil. The wax content can be at least: about 25% and preferably
in the range of about 25% 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.
The Ox~u~plyin~Component
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 amnoonium nitrate, sodium nitrate,
calcium nitrate, ammonium chlorate, sodium perchlorate and ammonium
perchlorate. Ammoniumnitrate is preferred. Mixtures ofammonium 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.
-12-
The Emulsifier
The terms "substituent" and "acylating agent" or "substituted
succinic acylating agent" are to be given their normal meanings, For example,
a substituent is an atom or group of atoms that has replaced another atom or
group in a molecule as a result of a reaction. The term acylating agent or
substituted succinic acylating agent refers to the compound per se and does
not
include unreacted reactants used to form the acylating agent or substituted
succinic acylating agent.
The substituted succinic acylating agent (A) utilized in the prepara
tion of the emulsifier can be characterized by the presence within its
structure
of two groups or moieties. The first group or moiety is referred to
hereinafter,
for convenience, as the "substituent group(s)'° and is derived from a
polyalkene.
The polyalkene from which the substituted groups are derived is characterized
by an Mn (number average molecular weight) value of at least about 500, more
preferably at least about 1000, more preferably at least about 1300, more
preferably at least about 1500. Advantageously, the polyalkene has an Mn in
the
range of about 500 to about 10,000, more preferably about 1000 to about 7000,
more preferably about 1300 to about 5000, more preferably about 1500 to about
5000, mare preferably about 1500 to about 3000, more preferably about 1500 to
about 2400, more preferably about 1500 to about 2000, more preferably about
1600 to about 1900. The polyalkene preferably has an Mw/Mn value of at least
about 1.5, preferably from about 1.5 to about 5, more preferably about 2 to
about 5, more preferably about 2.8 to about 5, more preferably about 2.8 to
about 4.5, more preferably about 3.3 to about 3.9. The abbreviation Mw is the
conventional symbol representing the weight average molecular weight.
Gel permeation chromatography (GPC) is a method which provides
both weight average and number average molecular weights as well as the entire
molecular weight distribution of the polymers. For purpose of this invention a
series of fractionated polymers of isobutene, polyisobutene, is used as the
calibration standard in the GPC. The techniques for determining Mn and Mw
CA 02091405 2003-05-02
'13-
values of polymers are well known and are described in numerous books and
articles. For example, methods for the determination of Mn acrd molecular
weight distribution of polymers is described in W.W. Yaa, J.J. Kirkland and
D.D.
81y, "Modern Size Exclusion Liquid Chromatographs", J.Wiley & Sons, Inc.,
1979.
Polyalkenes having the Mn and Mw values discussed above are
known in the art and can be prepared according to conventional procedures. Fvr
example, some of these polyalkenes are described a~ exemplified in U.S. Patent
4,234,435. Several such polyalkenes, especially polybutenes, are commercially
available.
1 o The second group or moiety in the acylanng went is referned to
herein as the "succinic groups)". The succiaic groups are those groups
characterized by the structure '
O O
If I ~ ft
X-C-G-C-C-X' (I)
l I
15 wherein X and X' are the same or different provided that at least one of X
and
X' is such that the substituted succinic acylating agent can function as a
carboxylic acylating agent. That is, at least one of X and X' must be such
that
the substituted acylatiag agent can form, for example, amides, amides or amine
salts with amino compounds, and esters, ester-salts, amides, amides, etc.,
with
2 0 the hydroxyamines, and otherwise function as a conventional carboxylic
acid
acylating agent. Transesterification and transamidanon reactions are consid-
ered, for purposes of this invention, as conventional acylating reactions.
Thus, X and/or X' is usually -OH, $hydrocarbyl, -O-M~" where M+
represents one equivalent of a metal, ammonium or amine canon, -NHZ, -Cl, -Br,
2 5 and together, X and X' can be -O- so as to form the anhydride. The
specific
identity of any X or X' group which is not one of the above is not critical so
long
as its presence does not prevent the remaining group from entering into
acylation
-14-
reactions. Preferably, however, X and X' are each such that both carboxyl
functions of the succinic group (i.e., both -C(O)X and -C(O)X') can enter fnto
acylation reactions.
One of the unsatisfied valences in the grouping
l l
-C-C-
~ l
of Formula I forms a carbon-to-carbon bond with a carbon atom in the
substituent group. While other such unsatisfied valence may be satisfied by a
similar bond with the same or different substituent group, all but the said
one
such valence is usually satisfied by hydrogen, i.e., -H.
The substituted succinic acylating agents are characterized by the
presence within their structure of an average of at least 1.3 succinic groups
(that
is, groups corresponding to Formula I) for each equivalent weight of
substituent
groups. These acylating agents can have from about 1.5 to about 2.5,
preferably
about 1.? to about 2.1, more preferably about 1.8 to about 2.0 succinic groups
for
each equivalent weight of substituent group. For purposes of this invention,
the
equivalent weight of substituent groups is deemed to be the number obtained by
dividing the Mn value of the polyalkene from which the substituent is derived
into the total weight of the substituent groups present in the substituted
succinic
acylating agents. Thus, if a substituted succinic acylating agent is
characterized
by a total weight of substituent group of 40,000 and the Mn value for the
polyalkene from which the substituent groups are derived is 2000, then that
substituted succinic acylating agent is characterized by a total of 20
(40,000/
2000=20) equivalent weights of substituent groups. Therefore, that particular
succinic acylating agent must also be characterized by the presence within its
structure of at least 26 (1.3x20=26) succinic groups.
The ratio of succinic groups to equivalents of substituent groups
present in the acylating agent can be determined by one skilled in the art
using
conventional techniques (e.g., acid number, saponification number).
-15-
In one embodiment, the succinic groups correspond to the formula
v
-CH - C(O)R
I
CH2-C(O)R' (I1)
wherein R and R' are each independently selected from the group consisting of
-OH, -Cl, -O-lower alkyl, and when taken together, R and R' are -O-. do the
latter case, the succinic group is a succinic anhydride group. All the
succinic
groups in a particular succinic acylating agent need not be the same, but they
can be the same. Preferably, the succinlc groups correspond to
O
-CH-COOH -CH C
0
CH2-COOH or ~ / ~ (III)
CH2 C
O
(a) (b)
and mixtures of III(a) and III(b). Providing substituted succinic acylating
agents
wherein the succinic groups are the same or different is within the ordinary
skill
of the art and can be accomplished through conventional procedures such as
treating the substituted succinic acylating agents themselves (for example,
hydrolysing the anhydride to the free acid or converting the free acid to an
acid
chloride with thionyl chloride) and/or selecting the appropriate malefic or
fumaric
reactants.
The preferred characteristics of the succinic acylating agents are
intended to be understood as being both independent and dependent. They are
intended to be independent in the sense that, for example, a preference for a
minimum of 1.4 or 1.5 succinic groups per equivalent weight of substituent
groups
is not tied to a more preferred value of Mn or Mw/Mn. They are intended to be
~~~~~.4~
-is-
dependent in the sense that, for example, when a preference for a minimum of
1.4 or 1.5 succinic groups is combined with more preferred values of Mn and/or
Mw/Mn, the combination of preferences does in fact describe still further more
preferred embodiments of the invention. Thus, the various parameters are
intended to stand alone with respect to the particular parameter being
discussed
but can also be combined with other parameters to identify further
preferences.
This same concept is intended to apply throughout the specification with
respect
to the description of preferred values, ranges, ratios, reactants, and the
like
unless a contrary intent is clearly demonstrated or apparent.
The polyalkenes from which the substituent groups are derived are
homopolymers and interpolymers of polymerizable olefin monomers of 2 to about
16 carbon atoms; usually 2 to about 6 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)" as used herein is inclusive of copolymers, 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 monoolefinic
monomers such as ethylene, propylene, butane-1, isobutene, and octane-1 or
polyolefinic monomers (usually diolefinic monomers) such as butadiene-1,3 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
CA 02091405 2003-05-02
-17
I I I I
-C-C=C-C
I I
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,
pentadi-
ene-1,3 (i.e., piperylene) is deemed to be a terminal olefin for purposes of
this
invention.
Some of the substituted succinic acylating agents (A) useful in
preparing the inventive emulsifiers are known in the art and are described in,
fpr
example, U.S. Patent 4,234,435. The acylating agents described in the '435
patent
are characterized as containing substituent groups derived from polyalkenes
having
an Mn value of about 13()0 to about 5000, and an Mw/Mn value of about 1.5 to
about 4.
There is a general preference for aliphatic, hydrocarbon polyal-
kenes free from aromatic and cycloaliphatic groups. Within this general
preference, there is a further preference for polyalkenes which are
derived.from
the group consisting of homopolymers and interpolymers of terminal hydrocarbon
olefins of 2 to about 16 carbon atoms. This further preference is qualified by
the
proviso that, while interpolymers of terminal olefins are usually preferred,
interpolymers optionally containing up to about 4096 of polymer units derived
from internal olefins of up to about 1S carbon atoms are also within a
preferred
group. A more preferred class of polyalkenes are those selected from the group
consisting of homopolymers and interpolymers of terminal olefins of 2 to about
6 carbon atoms, more preferably 2 to 4 carbon atoms. However, another prefer-
red class of polyalkenes are the latter more preferred polyalkenes optionally
containing up to about 2596 of polymer units derived from internal olefins of
up
to about 6 carbon atoms. 'The polybutenes and polyisobutenes are particularly
preferred. In one embodiment, the polyalkene is a polybutene in which at least
~r~t3~.~~.~:~~s
about 50°Yo of the total units derived from butenes is derived from
isobutene. In
one embodiment, the polyalkene is an interpolymer or copolymer of ethylene and
propylene, or an interpolymer or copolymer of styrene and at least one diene
(e.g., butadiene, pentadiene, isoprene, etc.).
The preparation of polyalkenes as described above which meet the
various criteria for Mn and Mw/Mn is within the skill of the art and does not
comprise part of the present invention. Techniques readily apparent to those
skilled in the art include controlling polymerization temperatures, regulating
the
amount and type off polymerization initiator and/or catalyst, employing chain
terminating groups in the polymerization procedure, and the like. Other
conventional techniques such as stripping (including vacuum stripping) a very
light end and/or oxidatively or mechanically degrading high molecular weight
polyalkene to produce lower molecular weight polyalkenes can also be used.
In preparing the substituted succinic acylating agents of this
invention, one or more of the above-described polyalkemes is reacted with one
or more acidic reactants selected from the group consisting of malefic or
fumaric
reactants of the general formula
X(O)C-Ci d=CH-C(O)X' (IV)
wherein X and X° are as defined hereinbefore in Formula I. Preferably
the
malefic and fumaric reactants will be one or more compounds corresponding to
the formula
RC(O)-CH=CH-C(O)R' (y)
wherein R and R' are as previously defined in Formula II herein. Ordinarily,
the
malefic or fumaric reactants will be malefic acid, fumaric acid, malefic
anhydride,
or a mixture of two or more of these. The malefic reactants are usually
preferred over the fumaric reactants because the former are more readily
available and are, in general, more readily reacted with the polyalkenes (or
derivatives thereof) to prepare the substituted succinic acylating agents of
the
CA 02091405 2003-05-02
-19-
present invention. The especially preferred reactants are malefic acid,
malefic
anhydride, and mixtures of these. Due to availability and ease of reaction,
malefic anhydride will usually be employed.
For convenience and brevity, the term "malefic reactant" 'is
sometimes used to refer to the acidic reactants used to prepare the succinic
acylating agents. When used, it should be understood that the term is generic
to
acidic reactants selected from malefic and fumaric reactants corresponding to
Formulae (IV) and (V) above including mixtures of such reactants.
Examples of patents describing various procedures for preparing
useful acylating agents include U.S. Patents 3,215,70?; 3,219,866; 3,231,587;'
3,912,764; 4,110,349; 4,234,435; and 5,041,662; and U.K. Patents 1,440,219 and
1,492,337 which describe the preparation of substituted succinic acylating
agents.
The acylating agents described above are intermediates in the
process for preparing the emulsifier for the inventive emulsion, the process
comprising reacting (A) one or more acylating agents with (B) ammonia and/or
at least one amine.
The amines (B) useful in making the emulsifiers include primary
amines, secondary amines and tertiary amines, with the secondary and tertiary
amines being preferred and the tertiary amines being particularly useful.
These
2 0 amines can be monoamines or polyamines. Hydroxy amines, especially
tertiary
alkanol monoamines, are useful. Mixtures of two or more amines can be used.
The amines can be aliphatic, cycloaliphatic, aromatic or heterocy-
clic, including aliphatic-substituted aromatic, aliphatic-substituted
cycloalipha-
tic, aliphatic-substituted heteroeyclic, cycloaliphatic-substituted aliphatic,
2 5. cycloaliphatic-substituted aromatic, cycloaliphatic-substituted
heterocyclic,
aromatic-substituted aliphatic, aromatic-substituted cycloaliplmtic, aromatic-
substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic-
substi-
tuted cycloaliphatic and heterocyclic-substituted aromatic amines. These
amines
-20-
may be saturated or unsaturated. If unsaturated, the amine is preferably free
from aeetylenic unsaturation. The amines may also contain non-hydrocarbon sub-
stituents or groups as long as these groups do not significantly interfere
with the
reaction of the amines with the acylating agents (A). Such non-hydrocarbon
substituents or groups include lower alkoxy, lower alkyl, mercapto, vitro, and
interrupting groups such as -O- and -S- (e.g., as in such groups as -CH2CH2-X-
CH2CH2- where X is -0- or -S-).
With the exception of the branched polyalkylene polyamines, the
polyoxyalkylene polyamines and the high molecular weight hydrocarbyl-substi-
tuted amines described more fully hereinafter, the amines used in this
invention
ordinarily contain less than about 40 carbon atoms in total and usually not
more
than about 20 carbon atoms in total.
Aliphatic monoamines include mono-aliphatic, di-aliphatic and tri-
aliphatic-substituted amines wherein the aliphatic groups can be saturated or
unsaturated and straight or branched chain. Such amines include, for example,
mono-, d1- and tri-alkyl-substituted amines; mono-, di- and tri-alkenyl-substi-
tuted amines; amines having one or more N-alkenyl substituents and one or more
N-alkyl substituents, and the like. The total number of carbon atoms in these
aliphatic monoamines preferably does not exceed about 40 and usually does not
exceed about 20 carbon atoms. Specific examples of such monoamines include
ethylamine, di-ethylamine, tri-ethylamine, n-butylamine, di-n-butylamine,
allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyl-
laurylamine, oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine,
and the like.-Examples of cycloaliphatic-substituted aliphatic amines,
aromatic-
substituted aliphatic amines, and heterocyclic-substituted aliphatic amines,
include 2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and
3-(furylpropyl) amine.
Cyclaaliphatic monoamines are those monoamines wherein there
is one cycloaliphatic substituent attached directly to the amino nitrogen
through
a carbon atom in the cyclic ring structure. Examples of cycloaliphatic
~. .~ 0.I
-21-
monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines,
cyclopentenylamines, N-ettryl-cyclohexylamines, dicyclohexylamines, and the
like. Examples of aliphatic-substituted, aromatic-substituted, and
heterocyclic-
substituted cycloaliphatic monoamines include propyl-substituted cyclohexyl-
amines, phenyl-substituted cyclopentylamines and pyranyl-substituted cyclo-
hexylamine.
Suitable aromatic amines include those monoamines wherein a
carbon atom of the aromatic ring structure is attached directly to the amino
nitrogen. The aromatic ring will usually be a mononuclear aromatic ring (i.e.,
one derived from benzene) but can include fused aromatic rings, especially
those
derived from naphthylene. Examples of aromatic monoamines include aniline,
di(para-methylphenyl) amine, naphthylamine, N-(n-butyl) aniline, and the like.
Examples of aliphatic-substituted, cycloaliphatic-substituted, and hetero-
cyclic-substituted aromaticmonoamines includepara-ethoxyaniline, paradodecyl-
amine, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.
Suitable polyamines include aliphatic, cycloaliphatic and aromatic
polyamines analogous to the above-described monoamines except for the
presence within their structure of another amino nitrogen. The other amino
nitrogen can be a prinnary, secondary or tertiary amino nitrogen. Examples of
such polyamines include N-aminopropyl-cyclohexylamine, N-N'-di-n-butyl-
para-phenylene diamine, bis-(para-aminophenyl)-methane, 1,4-diaminocyclohex-
ane, and the like.
Heterocyclic mono- and polyamines can also be used. As used
herein, the terminology "heterocyclic mono- and polyamine(s)" is intended to
describe those heterocyclic amines containing at least one primary, secondary
or tertiary amino group and at least one nitrogen as a heteroatom in the
heterocyclic ring. Heterocyclic amines can be saturated or unsaturated and can
contain various substituents such as vitro, alkoxy, alkyl mercapto, alkyl,
alkenyl,
aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon
atoms in the substituents will not exceed about 2a. Heterocyclic amines can
s f . 1
-22-
contain heteroatoms other than nitrogen, especially oxygen and sulfur.
Obviously
they can contain more than~one nitrogen heteroatom. The 5- and 6-membered
heterocyclic rings are preferred.
Among the suitable heterocyclics are aziridines, azetidines,
azolidines, tetra- and di-hydro pyridines, pyrroles, indoles, piperadines,
imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines,
morpholines, thiomorpholines, N-aminoalkyl-morpholines, N-aminoalkylthiomor-
pholines, N-aminoalkyl-piperazines, N,N'-di-aminoalkylpiperazines, azepines,
azo-
canes, azonines, azecines and tetra-, di- and perhydroderivatives of each of
the
above and mixtures of two or more of these heterocyclic amines. Preferred
heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines
containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially
the
piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the
like.
Piperidine, aminoalkyl-substitutedpiperidines, piperazine, aminoalkyl-
substituted
piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine, and
aminoalkyl-substituted pyrrolidines, are useful. Usually tlae aminoalkyl
substituents are substituted on a nitrogen atom forming part of the hetero
ring.
Specific examples of such heterocyclic amines include N-aminopropyhnorpholine,
N-aminoethylpiperazine, and N,N'-di-aminoethyl-piperazine.
The tertiary amines include monoamines and polyamines. The
monoamines can be represented by the formula
Rl-N-R2
~3
wherein R~, R2 and R~ are the same or different hydrocarbyl groups.
Preferably,
Rl, R2 and R3 are independently hydrocarbyl groups of from 1 to about 20
carbon atoms. Examples of useful tertiary amines include trimethyl amine,
triethyl amine, tripropyl amine, tributyl amine, monomethyidiethyl amine,
monoethyldimethyl amine, dimethylpropyl amine, dimethylbutyl amine, dimethyl-
l P
~~i~.~~'~
-23-
pentyl amine, dimethylhexyl amine, dimethylheptyl amine, dianethyloctyl amine,
dimethylnonyl amine, dimethyldecyl amine, dimethyldicodanyl amine, dimethyl-
phenyl amine, N,N-dioctyl-1-octanamine, N,N-didodecyl-I-dodecanamine tricoco
amine, trihydrogenated-tallow amine, N-methyl-dihydrogenated tallow amine,
N,N-dimethyl-1-dodecanamine,N,N-dimethyl-I-tetradecanamine,N,N-dimettayl-
I-hexadecanamine, N,N-dimethyl-1-octadecanamine, N,N-dimethylcoco, amine,
N,N-dimethyl soyaamine, N,N-dimethyl hydrogenated tallow amine, etc.
Hydroxyamines, both mono- and polyamines, analogous to those
mono- and polyamines described herein are also useful. The hydroxy-substituted
amines contemplated are those having hydroxy substituents bonded directly to
a carbon atom other than a carbonyl carbon atoms that is, they have hydroxy
groups capable of functioning as alcohols. The hydroxyamines can be primary,
secondary or tertiary amines, with the secondary and tertiary amines being
preferred, and the tertiary amines being especially preferred. The terms
"hydroxyamine" and "aminoalcohol" describe the same class of compounds and,
therefore, can be used interchangeably.
The hydroxyamines include N-(hydroxyl-substituted hydrocarbyl)
amines, hydroxyl-substituted poly(hydrocarbyloxy) analogs thereof and mixtures
thereof. These include secondary and tertiary alkanol amines represented,
respectfully, by the formulae:
H
N-R'-OH (VI)
R
and
t I
r.h m r
~~~i~~~~
-24-
R
N-R'-OH (VII)
R/
wherein each R is independently a hydrocarbyl group of one to about eight
carbon
atoms or hydroxyl-substituted hydrocarbyl group of two to about eight carbon
atoms and R' is a divalent hydrocarbyl group of about two to about 18 carbon
atoms. The group -R'-OH in such formulae represents the hydroxyl-substituted
hydrocarbyl group. R° can be an acyclic, alicyclic or aromatic group.
Typically,
R' is an acyclic straight or branched alkylene group such asI an ethylene,
1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. Where two R 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, nitxogen or sulfur) to form a 5-,
6-,
7- or 8-membered ring structure. Examples of such heterocyclic amines include
N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazoli-
dines, -thiazolidines and the like. Typically, however, each R is a lower
alkyl
group of up to seven carbon atoms.
Examples of the N-(hydroxyl-substituted hydrocarbyl) amines
include di- and txiethanolamine, dhnethylethanolamine, diethylethanolamine,
di-(3-hydroxylpropyl) amine, N-(3-hydroxylbutyl) amine, N-(4-hydroxylbutyl)
amine, N,N-di-(2-hydroxylpropyl) amine, N-(2-hydroxylethyl) morpholine and its
thio analog, N-(2-hydroxylethyl) cyclohexylamine, N-3-hydroxyl cyclopentyl-
amine, o-, an- and p-aminophenot, N-(hydroxylethyl) piperazine, N,N'-
di(hydroxyl-
ethyl) piperazine, and the like.
In a particularly advantageous embodiment, the hydroxyamine is a
compound represented by the formula
R
NR'OH
R~
-25-
wherein each R is independently an alkyl group of 1 to about 4 carbon atoms,
preferably 1 or 2 carbon atoms, and R' is an alkylene group of 2 to about A
carbon atoms, preferably about 2 or 3 carbon atoms. In an especially useful
embodiment, the hydroxyamine is dimethylethanolamine.
The hydroxyamines can also be ether N-(hydroxy-substituted
hydrocarbyl)amines. These are hydroxyl-substituted poly(hydrocarbyloxy)
analogs
of the above-described hydroxy amines (these analogs also include hydrox-
yl-substituted oxyalkylene analogs). Such N-(hydroxyl-substituted hydrocarbyl)
amines can be conveniently prepared by reaction of epoxides with afore-des-
cribed amines and can be represented by the formulae:
1-I
~N-(R'O)~ H
R
R
~ N-(R'0)X H
R
wherein x is a nLUnber of about 2 to about 15, and R and R' are as described
above with respect to Formulae (VI) and (VII).
polyamine analogs of these hydroxy amines, including alkoxylated
alkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine), can be used.
Such
polyamines can be made by reacting alkylene amines (e.g., ethylenediamine)
with
one or more alkylene oxides (e.g., ethylene oxide, octadecene oxide) of two to
about 20 carbons. Similar alkylene oxide-alkanol amine reaction products can
also be used such as the products made by reacting the afore-described
secondary
or tertiaay alkanol amines with ethylene, propylene or higher epoxides in a
1:1
or 1:2 molar ratio. Reactant ratios and temperatures for carrying out such
reactions are known to those skilled in the art.
-26-
Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl) ethylenetiiamine, N,N-bis(2-hydroxyethyl)-ethylene-diamine,
1-(2-hydroxyethyl) piperazine, mono(hydroxypropyl)-substituted diethylene
triamine, di(hydroxypropyl)-substituted tetraethylene pentamine, N-(3-hydroxy-
butyl)-tetramethylene diamine, etc. Higher homologs obtained by condensation
of the above-illustrated hydroxy alkylene 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 condensa-
tion 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 mono- or polyamines are also useful.
Hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl
substituents on the nitrogen atoms, are also useful. Useful hydroxyalkyl-
substi-
tuted alkylene polyamines include those in which the hydroxyalkyl group is a
lower hydroxyalkyl group, i.e., having lass than eight carbon atoms. Examples
of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)
ethylene
dfamine, N,N-bis(2-hydroxyethyl) ethylene diamine, 1-(2-hydroxyethyl)-pipera-
tine, monohydroxypropyl-substituted diethylene triamine, dihydroxypropyl-
substituted tetraethylenepentamine, N-(3-hydroxybutyl) tetramethylenediamine,
etc. Higher homologs as are obtained by condensation of the above-illustrated
hydroxy alkylene 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 and condensation through the hydroxy
groups results in products containing ether linkages accompanied by removal of
water.
Useful polyamines include the alkylene polyamines represented by
the formula:
R-N-(Alkylene-N)nR
I I
R R
CA 02091405 2003-05-02
-27-
wherein n is from 1 to about 10, preferably about 2 to about 10; each R is
independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted
hydrocarbyl group having up to about 700 carbon atoms, preferably up to about
100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably
up to about 30 carbon atoms; and the "Alkylene" group has from about 1 to
about
18 carbon atoms, preferably 2 to about 18 carbon atoms, more preferably 2 to
about 4 carbon atoms, with the preferred Alkylene being ethylene or propylene.
Useful alkylene polyamines include those wherein each R is hydrogen with the
ethylene polyamines, and mixtures of ethylene polyamines being particularly
preferred.
Alkylene polyamines that are useful include methylene polyamines,
ethylene polyamines, butylene polyamines, propylene polyamines, pentylene
polyamines, hexylene polyamines, heptylene polyamines, etc. Also included are
ethylene diamine, triethylene tetramine, propylene diamine, trimethylene
diamine, hexamethylene diamine, decamethylene diamine, octamethylene
diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene
pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)
triamine, N-(2-aminoethyl) piperazine, 1,4-bis(2-aminoethyl) piperazine, and
the
like. Higher homologs as are obtained by condensing two or more of the
2 o above-illustrated alkylene amines are useful as amines in this invention
as are
mixtures of two or more of any of the afore-described polyamines.
Ethylene polyamines, such as those mentioned above, are described
in detail under the heading "Diamines and Higher Amines" in The Encyclopedia
of Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages
27-39, Interscience Publishers, Divison of John Wiley and Sons, 1965. Such
compounds are prepared most conveniently by the reaction of an alkylene
chloride
' with ammonia or by reaction of an ethylene imine with a ring-apening reagent
such
as ammonia, etc. These reactions result in the production ofthe somewhat
complex
mixtures of alkylene polyamines, including cyclic condensation products such
as
3 0 piperazines.
.,
~~~~~~~~y':~
_2g~
Also suitable as amines are the aminosulfonic acids and derivatives
thereof corresponding to the formula:
O
(I
(RcRbN)x (Ra) ~ R)y
wherein R is OH, NH2, ONH4, etc.; Ra is ~a polyvalent organic group having a
valence equal to x + y; Rb and Rc are each independently hydrogen, hydrocarbyl
or substituted hydracarbyl with the proviso that at least one of Rb and Rc is
hydrogen per aminosulfonic acid molecule; x and y are each integers equal to
or
greater than one. Each aminosulfonic reactant is characterised by at least one
HN< or H2N- group and at least one
O
i1
-S-R
Ii
O
group. These sulfonic acids can be aliphatic, cycloaliphatic or aromatic
aminosulfonic acids and the corresponding functional derivatives of the sulfo
group. Specifically, the aminosulfonic acids can be aromatic aaninosulfonic
acids,
that is, where Ra is a polyvalent aromatic group such as phenylene where at
least
one
-S-R
Ii.
O
group is attached directly to a nuclear carbon atom of the aromatic group. The
aminosulfonic acid may also be a mono-amino aliphatic sulfonic acid; that is,
an
acid where x is one and Ra is a polyvalent aliphatic group such as ethylene,
propylene, trimethylene, and 2-niethylene propylene. Other suitable aminosul-
CA 02091405 2002-09-18
_. 2 9
fonic acids and derivatives thereof useful as amines in this invention are
disclosed in U.S. Patents 3,029,250; 3,367,864; and 3,926,820.
Hydrazine and substituted-hydrazine can also be used as amines
in this invention. At least one of the nitrogens in the hydrazine must contain
a
hydrogen directly bonded thereto. The substituents which may be present on the
hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like.
Usually, the
substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl
such
as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl. Specific
examples of substituted hydrazines axe methylhydrazine, N,N-
dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-
ethylhydrazine, N-(para-tolyl)-N'-(n-butyl)hydrazine, N-(para-nitrophenyl)-
hydrazine, N-(para-nitrophenyl)-N-methylhydrazine, N,N'-di-(para-
chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the like.
The high molecular weight hydrocarbyl amines, both monoamines
and polyamines, which can be used as amines in this invention are generally
prepared by reacting a chlorinated polyolefin having a molecular weight of at
least about 400 with ammonia or an amine. The amines that can be used are
known in the art and described, for example, in U.S. Patents 3,275,554 and
3,438,757. These amines must possess at least ane primary or secondary amino
group.
Another group of amines suitable for use in this invention are
branched polyalkylene polyamines. The branched polyalkylene polyamines are
polyalkylene polyamines wherein the branched group is a side chain containing
on the average at least one nitrogen-bonded aminoalkylene
H
(1.e., NHZ-R N- -)
sJ
-30-
group per nine amino units present on the main chain; for example, 1-4 of such
branched chains per nine units on the main chain, but preferably one side
chain
unit per nine main chain units. Thus, these polyamines contain at least three
primary amino groups and at least one tertiary amino group. These amines may
be expressed by the formula:
H
NH2-(R N)x RN RNH2
R
C NH z
0
R
NH2
L y
wherein R is an alkylene group such as ethylene, propylene, butylene and other
homologs (both straight chained and branched), etc., but preferably ethylene;
and
x, y and z are integers; x is in the range of from about 4 to about 24 or
more,
preferably from about 6 to about 1~; y is in the range of from 1 to about 6 or
more, preferably from 1 to about 3; and z is in the range of from zero to
about
6, preferably from zero to about 1. The x and y units may be sequential,
alternative, orderly or randomly distributed. A useful class of such
polyamines
includes those of the formula:
H H
I I
NH (R-N)5RN-(R-N) H
R
I
NH2 n
wherein n is an integer in the range of from 1 to about 20 or more, preferably
in the range of from 1 to about 3, and R is preferably ethylene, but may be
CA 02091405 2003-05-02
-31-
propylene, butylene, etc. (straight chained or branched). Useful embodiments
are
represented by the formula:
H H
I
NH2 (CH2CH2N)5-CH2CH2-~l-(CH2CH2N)2 1
CH2
CH2
NH2 n
wherein n is an integer in the range of 1 to about 3. The groups within the
brackets may be Joined in a head-to-head or a head-to-tall fashion. U.5.
Patents
3,200,106 and 3,259,578 contain disclosures relative to said polyamines.
Suitable amines also include polyoxyalkylene polyamines, e.g.,
polyoxyalkylene diamines and polyoxyalkylene triamines, having average
molecular weights ranging from about 200 to about 4000, preferably from about
400 to 2000. Examples of these polyoxyalkylene polyamines include those amines
represented by the formula:
NH2-Alkylene-(-O-Alkylene-)mNH2
wherein m has a value of from about 3 to about 70, preferably from about 10 to
about 35; and the formula:
R-[Alkylene-(-O-Alkylene-)nNH213_6
Z 0 wherein n is a number in the range of from 1 to about 40, with the proviso
that
the sum of all of the n's is from about 3 to about 70 and generally from about
6 to about 35, and R is a polyvalent saturated hydrocarbyl group of up to
about
10 carbon atoms having a valence of from about 3 to about 6. The alkylene
CA 02091405 2002-09-18
-32-
groups may be straight or branched chains and contain from 1 to about 7 carbon
atoms, and usually from 1 td about 4 carbon atoms. The various alkylene groups
present within the above formulae may be the same or different.
More specific examples of these polyamines include:
NHZCH-CHZ( OCH2 i H)xNH2
CH3 CH3
wherein x has a value of from about 3 to about 70, preferably from about 10 to
35; and
CH -(OCH2CH)2NH
~ CH3
CH3-CH2-C-CH2-(OCH2CH)yNH2
CH3
CH -(OCH2 ~ H)2NH
CH3
wherein x + y + z have a total value ranging from about 3 to about 30,
preferably
from about 5 to about 10.
Useful polyoxyalkylene polyamines include the polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines having average
molecular weights ranging from about 200 to about 2000. The polyoxyalkylene
polyamines are commercially available from the Jefferson Chemical Company,
Inc. under the trade name "Jeffamine". U.S. Patents 3,804,763 and 3,948,800
disclose such polyoxyalkylene polyamines.
The carboxylic derivative compositions produced from the acylating
agents (A) and ammonia or the amines (B) described hereinbefore comprise
acylated amines which typically include one or more amine salts, amides,
imides
-33-
and/or imidazolines as well as mixtures of two or more thereof. When the amine
(~) is a hydroxyamine, the' carboxylic derivative compositions usually include
esters and/or ester-salts (e.g., half-ester and half-salt). The amine salt can
be
an external salt wherein the ionic salt linkage is formed between the
acylating
agent (A) and a nitrogen atom from the amine (B); the amine is not otherwise
bonded to the acylating agent. The amine salt can also be an internal salt
wherein the acylating agent (A) and amine (B) are bonded to each other through
a non-salt linkage (e.g., an ester linkage) and a nitrogen atom from the
bonded
amine forms a salt linkage with the acylating agent. Examples of these salts
are
as follows:
O
R-CH-~-O-+N-(CH2CH3)3
H
CHZ-COON
(External Salt)
O H
R-CH-C-O-CH2CH2-N-(CH3)2
O_
CH2 ~C~
I
O
(Internal Salt)
wherein R is a polyalkene (e.g., polybutene) group.
To prepare the carboxylic acid derivative compositions from the
acylating agents (A) and ammonia or the amines(B), one or more acylating
agents
and one or more of ammonia and/or amines are heated, optionally in the
presence
CA 02091405 2003-05-02
-34-
of a normally liquid, substantially inert organic liquid solvent/diluent, at
temperatures in the range of about 30°C up to the decompositiop point
of the
reactant or product having the lowest such temperature, but normally at
temperatures in the range of about 50°C up to about 300°C
provided 300°C does
not exceed the decomposition point. Temperatures of about 50°C to about
200°C
ran be tied.
The acylating agents (A) can be reacted with ammonia and flee amines
(B) in the same manner as the high molecular weight acylating agents of the
prior
art are so reacted, and U.S. Patents 3,172,892; 3,219,666; 3,272,746; and
4,234,435
contain disclosures with respect to the procedures applicable to reacting the
acylating agents (A) with ammonia and amines (B).
In one embodiment, the acylating agent (~~ is reacted with from
about 0.5 to about 3, preferably about 0.5 to about 2, more preferably about
0.5
to about 1.5, more preferably about 0.8 to about 1.2 equivalents of ammonia or
amine (8) per equivalent of acylating agent (A). In otta3r embodiments,
increasing amounts of the ammonia or amine (B) can be used.
The number of equivalents of the acylatiag agent (A) depends on
the total number of carboxylic functions present. In determining the number of
equivalents for the acylatlng agents, those carboxyl functions which are not
z o capable of reacting as a carboxylic acid acylating agent are excluded. In
general, however, ttrere is one equivalent of acylating agent for each carboxy
group in these acylating agents. For example, there are two equivalents in an
anhydride derived from the reaction of one mole of olefin polymer and one mole
of malefic anhydride. Conventional techniques are readily available for deb
2 5 ing the number of carboxyl functions (e.g., acid number, saponification
number)
and, thus, the number of equivalents of the acylatiag agent can be readily
deter-
mined by one skilled in the art.
An equivalent weight of an amine or a polyamine is the molecular
weight of the amine or polyamine divided by the total number of nitrogens
~~~~.4~
-35-
present in the molecule. Thus, ethylene diamine has an equivalent weight equal
to one-half of its molecular weight; diethylene triamine has an equivalent
weight
equal to one- third its molecular weight. The equivalent weight of a commer-
cially available mixture of polyalkylene polyamine can be deteranined by
dividing
the atomic weight of nitrogen (14) by the 96N contained in the polyamine and
multiplying by 100; thus, a polyamine mixture containing 3496 N would have an
equivalent weight of 41.2. An equivalent weight of ammonia or a monoamine is
its molecular weight.
An equivalent weight of a hydroxyamine to be reacted with the
acylating agent under amide- or amide-forming conditions is its molecular
weight
divided by the total number of nitrogens present in the molecule. Under such
conditions, the hydroxyl groups are ignored when calculating equivalent
weight.
Thus, ethanolamine would have an equivalent weight equal to its molecular
weight, and diethanolamine would have an equivalent weight (based on nitrogen)
equal to its molecular weight when such amines are reacted under amide- or
amide-forming conditions.
The equivalent weight of a hydroxyamine to be reacted with the
acylating agent under ester-forming conditions is its molecular weight divided
by the number of hydroxyl groups present, and the nitrogen atoms present are
ignored. Thus, when preparing esters from diethanolamine, the equivalent
weight
of the diethanolamine is one-half of its molecular weight.
The amount of ammonia or amine (B) that is reacted with the
acylating agent (A) may also depend in part on the number and type of nitrogen
atoms present. For example, a smaller amount of a polyamine containing one or
more -NH2 groups is required to react with a given acylating agent than a
polyamine having the same number of nitrogen atoms and fewer or no -NH2
groups. One -NH2 group can react with two -COOH groups to form an amide. If
only secondary nitrogens are present in the amine compound, each >NH group can
react with only one -COOH group. Accordingly, the amount of polyamine to be
reacted with the acylating agent to form the carboxylic derivatives of the
-36-
invention can be readily determined from a consideration of the number and
types of nitrogen atoms in the polyamine (i.e.., -NH2, >Nl-I, and aN-).
In addition to the relative amounts of acylating agent (A) and
ammonia or amine (B) used to form the carboxylic derivative composition, other
important features of the carboxylic derivative compositions used in this
invention are the Mn and the Mw/Mn values of the polyalkene as well as the
presence within the acylating agents of an average of at least 1.3 succinic
groups
for each equivalent weight of substituent groups.
The preparation of the acylating agents (A) is illustrated in the
following Examples 1-10, and the preparation of the carboxylic acid derivative
compositions useful as emulsifiers in the inventive emulsions is illustrated
in
Examples A-D. In the following examples, and elsewhere in the specification
and claims, all temperatures are in degrees Centigrade, and all percentages
and
parts are by weight, unless otherwise clearly indicated.
Example 1
A mixture of 1000 parts of polyisobutene (Mn=1750; Mw=6300) and
106 parts of rnaleic anhydride is heated to 138°C. This mixture is
heated to
190°C in 9-14 hours during which time 90 parts of liquid chlorine are
added. The
reaction mixture is adjusted with chlorine addition, malefic anhydride
addition or
nitrogen blowing as needed to provide a polyisobutene-substituted succinic
acylating agent composition with a total acid number of 95, a free malefic
anhydride content of no more than 0.6°6 by weight, and a chlorine
content of
about 0.896 by weight. The composition has flash point of 180°C, a
viscosity at
150°C of 530 cSt, and a viscosity at 100°C of 5400 cSt. The
ratio of succinic
groups to equivalent weights of polyisobutene in the acylating agent is 1.91.
Example 2
A mixture of 510 parts of polyisobutene (Mn=1845; Mw=5325) and
59 parts of malefic anhydride is heated to 110°C. This mixture is
heated to 190°C
in 7 hours during which 43 parts of gaseous chlorine is added beneath the
surface.
At 190-192°C an additional 11 parts of chlorine is added over 3.5
hours. The
-37-
reaction mixture is stripped by heating at 190-193°C with nitrogen
blowing for
hours. The residue is the~desired polyisobutene-substituted succinic acylating
agent having a saponification equivalent number of 8? as determined by ASTM
procedure D-94.
5 Example 3
A mixture of 1000 parts of polyisobutene (Mn=2020; Mw=6049) and
115 parts (1.17 moles) of malefic anhydride is heated to 110°C. This
mixture is
heated to 184°C in 6 hours during which 85 parts of gaseous chlorine is
added
beneath the surface. At 184-189°C an additional 59 parts of chlorine is
added
10 over 4 hours. The reaction mixture is stripped by heating at 186-
190°C with
nitrogen blowing for 26 hours. The residue is the desired polyisobutene-substi-
tuted succinic acylating agent having a saponification equivalent number of 87
as determined by ASTM procedure D-94.
Example 4
A mixture of polyisobutene chloride, prepared by the addition of
251 parts of gaseous chlorine to 3000 parts of palyisobutene (Mn=1696;
Mw=6594)
at 80°C in 4.66 hours, and 345 parts of malefic anhydride is heated to
200°C in
0.5 hour. The reaction mixture is held at 200-224°C for 6.33 hours,
stripped at
210°C under vacuum and filtered. The filtrate is the desired
polyisobutene-sub-
stituted succinic acylating agent having a saponification equivalent number of
94 as determined by AS'TM procedure D-94.
Example 5
A mixture of 3000 parts of polyisobutene (Mn=1845; Mw=5325) and
344 parts of malefic anhydride is heated to 140°C. This miacture is
heated to
201°C in 5.5 hours during which 312 parts of gaseous chlorine is added
beneath
the surface. The reaction mixture is heated at 201-236°C with nitrogen
blowing
for 2 hours and stripped under vacuum at 203°C. The reaction mixture is
filtered
to yield the filtrate as the desired polyisobutene-substituted succinic
acylating
agent having a saponification equivalent number of 92 as determined by AS'TM
procedure D-94.
',.. .
~~~.4~
_3g_
Example 6
A mixture of 3000 parts of polyisabutene (Mn=2020; Mw=6049) and
364 parts of malefic anhydride is heated at 220°C for 8 hours. The
reaction
mixture is cooled to 170°C. At 170-190°C, 105 parts of gaseous
chlorine are
added beneath the surface in 8 hours. The reaction mixture is heated at
190°C
with nitrogen blowing for 2 hours and then stripped under vacuum at
190°C. The
reaction mixture is filtered to yield the filtrate as the desired
polyisobutene-
substituted succinic acylating agent.
Example 7
A mixture of 800 parts of a polyisobutene falling within the scope
of the claims of the present invention and having an Mn of about 2000, 646
parts
of mineral oil and 87 parts of malefic anhydride is heated to 179°C in
2.3 hours.
At 176-180°C, 100 parts of gaseous chlorine is added beneath the
surface over
a 19 hour period. The reaction mixture is stripped by blowing with nitrogen
for
0.5 hour at 180°C. The residue is an oil-containing solution of the
desired
polyisobutene-substituted succinic acylating agent.
Example 8
The procedure for Example 2 is repeated except the polyisobutene
(Mn=1845; Mw=5325) is replaced on an equimolar basis by polyisobutene
(Mn=1457; Mw=5808).
Example 9
The procedure for Example 2 is repeated except the polyisobutene
(Mn=1845; Mw=5325) is replaced on an equimolar basis by polyisobutene
(Mn=2510; Mw=5793).
Example 10
The procedure for Example 2 is repeated except the polyisobutene
(Mn=F,845; Mw=5325) is replaced on an equimolar basis by polyisobutene
(Mn=3220; Mw=5660).
-39-
Example A
A mixture of~ 4920 parts (8.32 equivalents) of the polyisobutene-
substituted succinic acylating agent prepared in accordance with the teachings
of Example 1 and 2752 parts of a 40 Neutral oil are heated to 50-55°C
with
stirring. 742 parts (8.32 equivalents) of dimethylethanolamine are added over
a
period of 6 minutes. The reaction mixture exotherms to 59°C. The
reaction
mixture is heated to 115°C over a period of 3 hours. Nitrogen blowing
is
commenced at a rate of 1.5 standard cubic feet per hour, and the reaction
mixture is heated to 135°C over a period of 0.5 hour. The mixture is
heated to
and maintained at a temperature of 140-160°C for 14 hours, then cooled
to room
temperature to provide the desired product. The product has a nitrogen content
of 1.3596 by weight, a total acid number of 13.4, a total base number of 54.8,
a
viscosity at 100°C Of 125 cSt, a viscosity at 40°C of 2945
c,.St, a Specific gravity
at 15.6°C of 0.94, and a flash point of 82°C.
Example B
A mixture of 1773 parts (3 equivalents) of the polyisobutene-
substituted succinic acylating agent prepared in accordance with the teachings
of Example 1 and 992 parts of a 40 Neutral oil are heated to 80°C with
stirring.
267 parts (3 equivalents) of dimethylethanolamine are added over a period of 6
minutes. The reaction mixture is heated to 132°C over a period of 2.75
hours.
The mixture is heated to and maintained at a temperature of 150-174°C
for 12
hours, then caoled to room temperature to provide the desired product. The
product has a nitrogen content of 0.7390 by weight, a total acid number of
12.3,
a total base number of 29.4, a viscosity at 100°C of 135 cSt, a
viscosity at 40°C
of 2835 cSt, a specific gravity at 15.6°C of 0.933, and a flash point
of 97°C.
Example C
The procedure of Example B is repeated except that after the
product is cooled to room temperature, 106 parts of dimethylethanolamine are
added with stirring. The resulting product has a nitrogen content of
1.21°l0 by
weight, a total acid number of 11.3, a total base number of 48.9, a viscosity
at
,..
~~1~~
-40-
100°C of 110 cSt, a viscosity at 40°C of 2730 cSt, a specific
gravity at 15.6°C
of 0.933, and a flash point~of 90°C.
Example D
f1 mixture is prepared by the addition of 10.2 parts (0.25 equiva-
lent) of a commercial mixture of ethylene polyamines having from about 3 to
about 10 nitrogen atoms per molecule to 113 parts of mineral oil and 161 parts
(0.25 equivalent) of the substituted succinic acylating agent prepared in
Example
2 at 138°C. The reaction mixture is heated to 150°C in 2 hours
and stripged by
blowing with nitrogen. The reaction mixture is filtered to yield the filtrate
as
an oil solution of the desired product.
Sensitizers
In one embodiment of the invention, closed-cell, void-containing
materials are used as sensitizing components. The term "closed-cell, void-con-
raining 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 1.1 to about 1.3 g/cc. In general, the
emulsions of tla~e subject invention can contain up to about 1596 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 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 g/cc. Useful glass microbubbles or microbailoons
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/cc. Microballoons identified by the industry
CA 02091405 2002-09-18
designation C15/250 which have a particle density of i~.15 gm/cc and 10% of
such
microballoons crush at a static pressure of 250 psig can be used. Also,
microbal-
loons identified by the designation B37/201:)0 which have a particle density
of 0.37
gm/cc and 10% of such microballoons crush at a static pressure of 2000 psig
can be
used. Other useful glass microballoons are sold under the trade-mark
ECCOSPHERES
by Emerson & Gumming, Inc., and generally have a particle 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-mark Q-
CEI, by
Philadelphia Quartz Company.
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
utilized, the microbubbles themselves are a fuel component for the explosive
and their
fuel value should be taken into consideration when designing a water-in-oil
emulsion
explosive composition. Another closed cell, void containing material which can
be
used within the scope of the subject invention is the saran microspheres 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 0.25 to about 1 % by weight
thereof
be used in the water-in-oil emulsions of the subject invention.
Gas bubbles which 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, can also be used can be used to sensitize the
explosive
emulsions. Other suitable sensitizing components which may be employed alone
or in
addition to the foregoing include insoluble particulate solid self explosives
or fuel such
as, for example, grained or flaked T2JT, DNT, RDX and the like, aluminum,
aluminum
alloys, silicon and ferro-silicon; and water-soluble and/or hydrocarbon-
soluble organic
sensitizers such . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . .
J
f~~ ~
~~~~~.~U~
-42-
as, for example, amine nitrates, alkanolamine nitrates, hydroxyalkyl nitrates,
and
the like. The explosive emulsions of the present invention may be formulated
for
a wide range of applications. Any combination of sensitizing components may be
selected in order to provide an explosive composition of virtually any desired
density, weight-strength or rxitical diameter. The quantity of solid self-
explo-
saves or fuels and of water-soluble and/or hydrocarbon-soluble organic
sensitizers
may comprise up to about 5096 by weight of the total explosive composition.
The
volume of the occluded gas component may comprise up to about 5096 of the
volume of the total explosive composition.
Particulatg-Solid OxvrcP,~n-~S pg~yinx Salts
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. These particulate solids can be in the form of
grills, crystals or flakes. Ammonium nitrate grills are especially useful.
In one embodiment ammonium nitrate grills made by the Kalten-
back-Thoring (KT) process are used. This process involves the use of one or
more
crystal growth modifiers to help control the growth of the caystals. It also
involves the use of one or more surfactants which are used to reduce caking.
An
example of a commercially available material made by this process is Columbia
KT ammonium nitrate grills which are marketed by Columbia Nitrogen. The
crystal habit modifier and the surfactant used in the production of Columbia
KT
grills are each available under the trade designation Galoryl.
Ammonium nitrate particulate solids, (e.g., ammonium nitrate
grills), which are availablae in the form of preblended ammonium nitrate-fuel
oil
(ANFO) mixtures, can be used. Typically, ANFO contains about 949'o by weight
ammonium nitrate and about 696 fuel oil (e.g., diesel fuel oil), although
these
proportions can be varied.
~r~~ .,
-43-
The quantities of these particulate-solid oxygen-supplying salts or
ANFO that are used can comprise up to about 8096 by weight of the total
explosive composition. In one embodiment of the invention, explosive composi-
tions comprising about 2596 to about 3596 by weight of the inventive emulsion
and
about 6596 to about 75~Yo of particulate solid, oxygen-supplying salts or ANFO
are
used. In one embodiment, explosive compositions comprising about 4596 to about
55°!o by weight of the inventive emulsion and about 4596 to about 5596
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 2096 to about 3096 of particulate solid; oxygen-
supplying salts or ANFO are used.
Supglement~l 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,
carboxymeth-
yl 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 5096 by weight of the
total explosive composition.
Mme hQd of Makin~~ the Emulsions
A useful method for making the 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 com-
-44-
pounds, 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 mincing
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
rernove 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 grills and ANFO, solid fuels such as aluminum or sulfur, inert
materials
such as barytes 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 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
inventive emulsions. 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
1096 to about 9096 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 hereinabove.
CA 02091405 2002-09-18
-95-
Examples I-IX are directed to explosive emulsions using the
emulsifier prepared in accordance with the teachings of Example A. The
formulations for these explosive emulsions are indicated below in Table I (all
numerical amounts being in grams). The procedure for making these emulsions
involves the following steps. The ammonium nitrate is mixed with the water at
a temperature of 82°C. The emulsifier is mixed with the mineral oil at
a
temperature of 52°C. The mixture of ammonium nitrate and water is added
to
the mixture of oil and emulsifier to form a water-in-oil emulsion. The glass
microballoons are then added. Each of these explosive emulsions are useful as
blasting agents.
_TAHLE~
Example No. ~ I_I Ill )V_ ~I V_~ ~ V,~j
Ammonium Ni-
trate 7440 7636 7636 7200 8500 7700 7200 8500 ?700
Water 1610 1564 1564 2000 1000 1500 2000 1000 1500
Klearol* oil (re-
fined mineral
oil, Witco) 800 ___ ___ ___ ___ ___ _~ _w ___
Mentor* 28 (min-
eral seal oil,
Exxon) __, 700 ___ ___ ~ ___ ___
40 Neutral Oil --- --- 700 700 400 750 100 100 50
C15/250 Glass
Microballoons 100 100 100 100 250 150 100 250 150
Product of Ex. A 150 100 100 100 100 50 700 400 750
~xarOple~
The following emulsion is prepared using Columbia KT ammonium
nitrate grills (a product of Columbia Nitrogen identified as ammonium nitrate
grills made using the Kaltenbach-Thoring process employing a crystal growth
modifier and a surfactant, each of which is available under the trade
designation
*trade-marks
_46_
Galoryl). The formulation for this emulsion is provided in Table II (all
numerical
amounts being in grams).
TABLE II
Ammonium Nitrate 534.52
Columbia KT grills 229.08
Water 156.40
40 Neutral oil 65.00
Product of Ex. A 15.00
The emulsion in Table II is prepared by mixing the ammonium nitrate with the
water and then melting the Columbia KT grills in the ammonium nitrate and
water. The emulsifier from Example A is mixed with the 40 Neutral oil. The
mixture of ammonium nitrate, water and Columbia KT grills is added to the
mixture of oil and emulsifier. The resulting emulsion is creamy (no
graininess)
three months after it is made.
Examples XI-XIX are directed to explosive compositions consisting
of mixtures of the emulsions from Examples I-III and ANFO. The ANFO is a
mixture of ammonium nitrate solids (94% by weight) and diesel fuel oil (6% by
weight). The formulations are indicated in Table III (all numerical amounts
being
in grams).
BLE III
ExamnlgNo. ~I, XII ~~II ~yI ~ '~-'-VI C~VII XVITI ~CIX
Emulsion from
Ex.I . 300 ___ ___ 500 _-_ ___ 750 _-- ___
Emulsion from
Ex. II --- 300 --- --- 500 --- --- 750 ---
Emulsion from
Ex. III _,.- ___ ;300 ___ _a 500 -__ ___ 750
ANFO 700 700 700 500 500 500 250 250 250
-47-
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that variom 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 as fall within the scope of the appended claims.
