Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
lO9S~
Introduction and Summary of the Invention
This invention relates to new magnesium-containing
compositions of matter and methods for their preparation. More
particularly, it relates to non-carbonated magnesium-containing
complexes which are prepared by heating, at a temperature above
about 30C., a mixture comprising:
(A) At least one of magnesium hydroxide, magnesium
oxide, hydrated magnesium oxide or a magnesium alkoxide;
(B) At least one oleophilic organic reagent comprising
a carboxylic acid, a sulfonic acid, a pentavalent phosphorus
acid, or an ester or alkali metal or alkaline earth metal salt of
any of thesei
(C) Water, if any, in an amount at least sufficient to
hydrate a substantial proportion of component A if hydratable to
produce hydrated magnesium oxide; and
(D) At least one organic solubilizing agent for
component B;
the ratio of equivalents of magnesium to component B,
calculated as the free carboxylic or sulfonic acid or as the
phosphoric acid ester, being at least about 5:1.
Several methods are known for the preparation of
basic magnesium compounds for use in lubricants, greases and
the like. For example, U.S. Patent 3,865,737 describes the
formation of a highly basic magnesium-containing liquid dis-
persion by mixing an oil-soluble dispersing agent, magnesium
oxide, a volatile aliphatic hydrocarbon solvent, alcohol,
water and ammonia or an ammonium compound, treating the mixture
with carbon dioxide, adding a non-volatile diluent oil and
removing volatiles. Similarly, U.S. Patent 3,62~,10
Y,~ 1
describes the carbonation of a mixture of an oil-soluble
organic acid or salt thereof, magnesium oxide, a lower ali-
phatic alcohol, water and an organic liquid diluent. The
products obtained by these methods may be characterized, for
the most part, as basic, oleophilic magnesium carbonates
since an essential step in their preparation is reaction
with carbon dioxide.
In accordance with the present invention, it has
been discovered that highly basic magnesium complexes may be
prepared without reaction with carbon dioxide or similar
acidic gases. The-products obtained in accordance with the
present invention, which may be characterized as complexes
of magnesium oxide or hydroxide and a magnesium sulfonate,
carboxylate or phosphate, and which are hereinafter sometimes
referred to merely as "magnesium complexes", have a wide
variety of uses, including additives for lubricants and fuel
oils and corrosion-xesistant coatings or constituents thereof.
A principal object of the present invention,
therefore, is to provide new oleophilic magnesium-containing
compositions and a method for their preparation.
A further object is to provide a method for pro-
ducing magnesium complexes which does not necessitate reaction
with carbon dioxide or a similar acidic gas.
A further object is to provide basic magnesium
compositions which may be obtained either in free-flowing
liquid form or in thickened or solid form.
Still another object is to provide magnesium-
containing compositions useful as greases, as detergent
additives for lubricants or as corrosion inhibitors, vanadium
scavengers and smoke suppressants for fuels, and in the
~09~;886
formulation of corrosion-resistant coatings for metals.
Other objects will in part be obvious and will in
part appear hereinafter.
Component A
Component A used in the method of this invention
is magnesium hydroxide, magnesium oxide, hydrated magnesium
oxide, a magnesium alkoxide, or a mixture of these. Magnesium
hydroxide and magnesium oxide are, of course, represented by
the formulas Mg(OH) 2 and MgO, respectively. Magnesium oxide
exists in an inactive "dead burned" and a hydratable "reactive"
form and the latter is the one which is useful in this
invention although mixtures of the "reactive" form with
minor amounts of the "dead burned" form may also be used.
"Hydrated magnesium oxide", for the purpose of this invention,
is magne8ium oxide which is associated with water in an
amount less than that required for conversion to magnesium
hydroxide; that is, the amount of water is less than one
mole per mole of magnesium oxide. As so defined, "hydrated
magnesium oxide" may actually be a mixture of various propor-
tions of magnesium oxide and magnesium hydroxide and its
exact chemical nature is not critical to this invention.
Typically, the amount of water present in "hydrated magnesium
oxide" is at least about 0.7 mole per mole of the oxide.
The magnesium alkoxides, especially the lower
alkoxides (i.e., those in which the alkyl groups contain 7
carbon atoms or less), are equivalent to magnesium oxide and
hydroxide for the purpose of this invention; they are hydrolyzed
by water to magnesium hydroxide under the conditions described
hereinafter.
11~9S~86i
The equivalent weight of component A is half its
molecular weight, since magnesium is a divalent element.
Component B
Component B is at least one oleophilic reagent
comprising any of several types of organic acidic compounds
or salts or esters thereof. Among the suitable reagents ~or
this purpose are the carboxylic and sulfonic acids. These
acids include many of those known to be susceptible to overbasing
and especially many of those disclosed in a number of U.S. patents
such as 2,616,904; 2,695,910; 3,312,618; 3,746,643; 3,764,533;
and the aforementioned 3,629,109.
The sulfonic acids suitable for use as component B
include those represented by the formulas R ( s03H ) and
(R )xT(SO3H)y. In these formulas, R is an aliphatic or ali-
phatic-substituted cycloaliphatic hydrocarbon or essentially
hydrocarbon radical free from acetylenic unsaturation and
containing up to about 60 carbon atoms. When R is aliphatic,
it usually contains at least about 15-1~ carbon atoms; when
it is an aliphatic-substituted cycloaliphatic radical, the
aliphatic substituents usually contain a total of at least
about 12 carbon atoms. Examples of R are alkyl, alkenyl and
alkoxy-alkyl radicals, and aliphatic-substituted cycloaliphatic
radicals wherein the aliphatic substituents are alkyl, alkenyl,
alkoxy, alkoxyalkyl, carboxyalkyl and the like. Generally, the
cycloaliphatic nucleus is derived from a cycloalkane or a cyclo-
al~ene such as cyclopentane, cyclohexane, cyclohexene or cyclo-
pentene. Specific examples of Rl are cetylcyclohexyl, lauryl-
cyclohexyl, cetyloxyethyl, octadecenyl and radicals derived from
petroleum, saturated ................. .... ............ ........
-- 4 --
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and unsaturated paraffin wax, and olefin polymers including
polymerized monoolefins and diolefins containing about 1-8
carbon atoms per olefinic monome~ unit. Rl can also contain
other substituents such as phenyl, cycloalkyl, hydroxy,
mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower
alkylmercapto, carboxy, carbalkoxy, oxo or thio, or interrupting
groups such as -NH-, -O- or -S-, as long as the essentially
hydrocarbon character thereof is not destroyed.
R2 is generally a hydrocarbon or essentially
hydrocarbon radical free from acetylenic unsaturation and
containing about 4-60 aliphatic carbon atoms, preferably an
aliphatic hydrocarbon radical such as alkyl or alkenyl. It
may also, however, contain substituents or interrupting
groups such as those enumerated above provided the essen-
tially hydrocarbon character thereof is retained. In general,
the non-carbon atoms present in Rl or R2 do not account for
more than 10~ of the total weight thereof.
The radical T is a cyclic nucleus which may be
derived from an aromatic hydrocarbon such as benzene, naph-
thalene, anthracene or biphenyl, or from a heterocyclic
compound such as pyridine, indole or isoindole. Ordinarily,
T is an aromatic hydrocarbon nucleus, especially a benzene
or naphthalene nucleus.
The subscript x is at least 1 and is generally 1-
3. The subscripts r and y have an average value of about 1-
4 per molecule and are generally also 1.
Illustrative sulfonic acids useful as component B
are mahogany sulfonic acids, petrolatum sulfonic acids, mono-
and polywax-substituted naphthalene sulfonic acids, cetyl-
chlorobenzene sulfonic acids, cetylphenol sulfonic
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acids, cetylphenol disulfide sulfonic acids, cetoxycapryl
benzene sulfonic acids, dicetyl thianthrene sulfonic acids,
di-lauryl beta-naphthol sulfonic acids, dicapryl nitro-
naphthalene sulfonic acids, paraffin wax sulfonic acids,
unsaturated paraffin wax sulfonic acids, hydroxy-substituted
paraffin wax sulfonic acids, tetraisobutylene sulfonic acids,
tetra-amylene sulfonic acids, chloro-substituted paraffin
wax sulfonic acids, nitroso-substituted paraffin wax
sulfonic acids, petroleum naphthene sulfonic acids, cetyl-
cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic
acids, mono- and polywax-substituted cyclohexyl sulfonic
acids, postdodecylbenzene sulfonic acids, "dimer alkylate"
sulfonic acids, and the like. These sulfonic acids are well-
known in the art and require no further discussion herein.
For the purpose of this invention, the equivalent
weight of a sulfonic acid is the molecular weight thereof
divided by the number of sulfonic acid groups present therein.
Thus, for a monosulfonic acid the equivalent weight is equal
to the molecular weight.
Carboxylic acids suitable for use as component B
include aliphatic, cycloaliphatic and aromatic mono- and
polybasic carboxylic acids free from acetylenic unsaturation,
including naphthenic acids, alkyl- or alkenyl-substituted
cyclopentanoic acids, alkyl- or alkenyl-substituted cyclo-
hexanoic acids, and alkyl- or alkenyl-substituted aromatic
carboxylic acids. The aliphatic acids generally contain at
least 8 and preferably at least 12 carbon atoms. The cyclo-
aliphatic and aliphatic carboxylic acids can be saturated or
unsaturated. Specific examples include 2-ethylhexanoic acid,
linolenic acid, propylene tetramer-substituted maleic acid,
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1~9~88~ii
behenic acid, isostearic acid, pelargonic acid, capric acid,
palmitoleic acid, linoleic acid, lauric acid, oleic acid,
ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic
acid, myristic acid, dilauryldecahydronaphthalenecarboxylic
acid, stearyl-octahydroindenecarboxylic acid, palmitic acid,
acids formed by oxidation of petrolatum or of hydrocarbon
waxes, and commercially available mixtures of two or more
carboxylic acids such as tall oil acids, rosin acids, and
the like. The equivalent weight of any such acid is its
molecular weight divided by the number of carboxy groups
present therein.
The pentavalent phosphorus acids useful as component
B may be represented by the formula
R3 ~X~
a P-X3H
R4 (X 2 )~
wherein each of R3 and R4 is hydrogen or a hydrocarbon or
essentially hydrocarbon radical preferably having about 4~25
carbon atoms, at least one of R3 and R4 being hydrocarbon or
essentially hydrocarbon; each of Xl, X2, X3 and X4 is oxygen
or sulfur; and each of a and b is 0 or 1. Thus, it will be
appreciated that the phosphorus acid may be an organophosphoric,
phosphonic or phosphinic acid, or a thio analog of any of
these. The equivalent weight of such a phosphorus acid is
its molecular weight divided by the number of hydroxy groups
bonded to phosphorus therein.
Usually, the phosphorus acids are those of the
\ ¦l
formula P-OH wherein R3 is a phenyl radical or
R4 0/
1~9S886
(preferably) an alkyl radical having up to 18 carbon atoms,
and R4 is hydrogen or a similar phenyl or alkyl radical.
Mixtures of such phosphorus acids are often preferred because
of their ease of preparation.
Also useful as component B are the alkali metal
and alkaline earth metal salts (e.g., sodium, potassium,
magnesium, calcium, strontium or barium salts, with mag-
nesium salts being preferred) and esters of the acids previously
described. The suitable esters include those with monohydric
alcohols free from acetylenic unsaturation and having about
1-25 carbon atoms, including monohydric alcohols such as
methanol, ethanol, the butanols, the hexanols, allyl alcohol,
crotyl alcohol, stearyl alcohol and oleyl alcohol, and
polyhydric alcohols such as ethylene glycol, diethylene
glycol, propylene glycol, glycerol, sorbitol, sorbitan and
similar carbohydrates and derivatives of carbohydrates.
When an ester is used as component B, it is converted to the
magnesium salt of the free acid during the reaction with
component A and water. In other words, the acidic portion
of the ester is the operative portion for the purpose of
this invention and the identity of the alcoholic portion
thereof is immaterial. Thus, it will be appreciated that
the equivalent weight of the ester for the purpose of this
invention is its molecular weight divided by the number of
groups present therein which are convertible by hydrolysis
to carboxylate or sulfonate groups or to pentavalent phosphorus
acid groups under the reaction conditions of the invention.
If any of the ester groups remain unconverted, the ester is
considered as inert to that extent for the purpose of calculating
its equivalent weight.
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The preferred compounds for use as component B are
the above-described sulfonic and carboxylic acids, especially
those having an equivalent weight of about 300-500. The
sulfonic acids are most often used, and a particular prefer-
ence is expressed for alkylaromatic sulfonic acids and more
particularly for alkylbenæenesulfonic acids.
It is also within the scope of the invention to
use as component B mixtures of two or more of the above-
described compounds or types of compounds. Examples of
suitable mixtures are mixtures of carboxylic acids, of
sulfonic acids, and of sulfonic with carboxylic acids. Many
such mi~tures will be readily apparent to those skilled in
the art. Particularly preferred are mixtures of alkyl-
benzenesulfonic acids with fatty acids (which may be hydro-
genated) and with carboxylic acids formed by oxidation of
hydrocarbons such as petrolatum.
One of the characteristics of component B is that
it is oleophilic. This means that it is soluble or at least
stably dispersible tas defined hereinafter) in oil or similar
non-polar organic liquids such as hexane, naphtha, Stoddard
solvent, benzene, toluene and the like. While component B
need not be oil-soluble, the oil-soluble sulfonic and car-
boxylic acids and phosphate esters are preferred for the
purposes of this invention. These oil-soluble compounds
constitute a known subgenus of the previously described
compounds useful as component B.
Component C
Component C is water, which may be used in the
liquid or vapor phase as described hereinafter. For the
purpose of the present invention, the equivalent weight of
water is considered to be 9 (half its molecular weight).
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Component D
Component D is at least one organic solubilizing
agent for component B. It may be solid or liquid at room
temperature, although liquids are often preferred. It need
not be a solvent for component B, in the sense that component
B is entirely soluble therein when in the liquid state, but
should be at least a partial solvent in the sense that
relatively small proportions of component B, at least, when
blended with component D in the liquid state will form a
homogeneous mixture.
Materials useful as component D include sub-
stantially inert, normally liquid organic diluents. The
term "substantially inert" as used herein is intended to
mean that the diluent is inert to chemical or physical
change under the conditions in which it is used so as not to
materially interfere in an adverse manner with the preparation,
storage, blending and/or functioning of the magnesium complex
in the context of its intended use. For example, small
amounts of a diluent can undergo minimal reaction or degrada-
tion without preventing the making and using of the invention
as described herein. In other words, such reaction or
degradation, while technically discernible, would not be
sufficient to deter the practical worker of ordinary skill
in the art from making and using the invention for its
intended purposes. "Substantially inert" as used herein is
thus readily understood and appreciated by those of ordinary
skill in the art.
Among the preferred normally liquid diluents are
non-polar compounds or mixtures of compounds such as naphtha,
hexane, kerosene, mineral oil, Stoddard solvent, benzene,
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toluene, xylene, and alkylbenzenes of the type present as
unsulfonated residue in alkylbenzenesulfonic acids. Also
suitable are somewhat more polar liquids such as l-butanol,
2-butanol, ethylene glycol, propylene glycol, ethylene
glycol monomethyl ether, ethylene glycol monobutyl ether,
ethylene glycol dimethyl ether, diethylene glycol and its
ethers, wax-derived alcohol mixtures, methyl ethyl ketone,
chlorobenzene, pyridine, indole, furan and tetrahydrofuran.
Also useful are materials which are chemically
similar to the above-described liquids but solid at ambient
temperature. These include the following, as well as mixtures
of any two or more thereof:
Crystalline (including microcrystalline) and non-
crystalline hydrocarbon waxes, including natural hydrocarbon
waxes such as petrolatum, paraffin and olefin waxes, and
synthetic hydrocarbon waxes such as polyethylene and other
polyolefins.
Waxy alcohol mixtures such as C2 0-4 o aliphatic
alcohols.
Resins such as styrene-butadiene copolymers,
hydrogenated styrene-butadiene polymers, olefin-vinyl car-
boxylate (e.g., vinyl acetate) copolymers, and hydrocarbon
resins.
It is also within the scope of the invention to
use mixtures of any of the materials described above. Such
mixtures may be of materials all of which are liquid at
normal ambient temperatures (e.g., about 20-30C.), such as
mineral oil-toluene, Stoddard solvent-toluene, mineral oil-
alkylbenzene, Stoddard solvent-alkylbenzene; of materials
all of which are solid at normal ambient temperatures, such
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as paraffin wax-polyethylene wax, paraffin wax-polyethylene
wax-C2 0-4 o alcohol wax; or of materials which are both
liquid and solid at normal ambient temperatures, such as
mixtures of the above-mentioned normally liquid diluents and
a resin or hydrocarbon wax (e.g., paraffin wax-toluene,
polypropylene-toluene, polypropylene-mineral oil).
Component Proportions
The relative proportions of components A, B, C and
D are an important feature of this invention since the
physical state in which the magnesium complex is obtained
depends to a great extent on the proportions of the components
used for their preparation.
As previously noted, the ratio of equivalents of
magnesium to the acid portion of component B (free carboxylic
or sulfonic acid, or acidic phosphoric acid ester) is at
least about 5:1. This ratio is hereinafter sometimes referred
to as the "magnesium ratio". (It will be appreciated that
the magnesium ratio is such as to produce a basic magnesium
complex.) If component B is the free carboxylic acid, an
ester thereof, a free sulfonic acid or an acidic phosphate
ester, the ratio of component A to component B will be
identical to the magnesium ratio. If component B is a
magnesium salt of one of the above, the ratio of component A
to component B will be somewhat less than the magnesium
ratio since part of the magnesium is provided by component
B.
It has been found that magnesium complexes with
relatively low magnesium ratios (e.g., about 5-25:1 and
particularly about 5-10:1) are particularly useful as lubri-
cant additives. Complexes with a magnesium ratio above
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about 60:1 and preferably up to about 150:1 find utility
principally as additives for fuel oils. As protective coatings
for metals, it is preferred to employ complexes in which
component D is entirely or predominantly liquid and the
magnesium ratio is between about 25:1 and 60:1, or solid
(e.g., "hot melt") complexes in which component D is entirely
or predominantly solid at ambient temperature and which
typically have a magnesium ratio of about 5-50:1.
The molar ratio of water (component C) to component
A (hereinaftex sometimes designated the "water ratio") is
also critical. If component A is hydratable, the amount of
water should be at least sufficient to hydrate a substantial
proportion of component A, calculated as magnesium oxide. If
component A is magnesium hydroxide or hydrated magnesium oxide,
it already contains at least this amount of water and therefore
water need not be added to produce hydrated magnesium oxide
although water may nevertheless be added and the amount of
additional water will depend on the nature of the product
desired and the intended use thereof. On the other hand, if
component A is anhydrous magnesium oxide, water has to be added
to achieve a water ratio that should generally be at least
about 0.7:1 so as to produce the hydrated magnesium oxide
referred to hereinabove.
Most often, a water ratio between about 0.7:1 and
3.0:1 is adequate to produce a composition of this invention.
If larger amounts of water than this are used, it is frequently
possible to remove excess water, at least some of which
separates from the magnesium complex as a separate layer and
the remainder of which can be removed by azeotropic
distillation or the like. More water may be desirable for
the preparation of the complex in certain instances; for
example, magnesium oxide frequently contains traces of sodium
compounds whose presence may be undesirable in the
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complex, and if so, such compounds may be removed by using
up to about 8 moles of water per mole of component A and
removing the excess, which has dissolved therein the sodium
compounds. When the excess water has been removed, the
molar ratio of remaining water to component A is usually
below about 3:1 as noted above.
As among various magnesium complexes with water
ratios between about 0.7:1 and 3.0:1, those having a water
ratio below about 1:1 are often particularly useful as
lubricant additives or fuel oil additives, while those
having a somewhat higher water ratio (e.g., between about
1:1 and 3:1) may be particularly useful in the preparation
of corrosion-resistant coating compositions.
The ratio of component D to component A is not
critical and may be varied so as to provide magnesium com-
plexes suitable for the particular use to which they are
intended. For example, a complex suitable as a lubricant
additive may frequently be obtained by employing as com-
ponent D solely the unsulfonated alkylbenzene present as an
impurity in the sulfonic acid used as component B. In that
event, the weight ratio of component D to component A will
usually be below about 1:1 and frequently as low as 0.5-
0.7:1. In general, when a lubricant additive product is
desired it is inadvisable to use volatile materials as com-
ponent D.
When the magnesium complex is to be used as a fuel
oil additive, higher amounts of component D are frequently
preferred and these may include relatively volatile materials
such as toluene or xylene, less volatile materials such as
mineral oil or mineral seal oil, and mixtures of volatile
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and less volatile materials. The proportions of volatile
and non-volatile solubilizing agents in such mixtures are
subject to wide variation, but in any event it is usually
found that the total weight ratio of component D to component
A should be about 1.2-1.8:1.
When a product useful in a protective metal coating
is desired, still higher ratios (e.g., about 2-3:1) are
often employed with one of the solubilizing agents being a
substantially volatile aliphatic hydrocarbon such as naphtha
or Stoddard solvent, and the other being a somewhat less
volatile material such as mineral oil. Another useful type
of complex for metal coating is the solid (e.g., "hot melt")
type briefly referred to hereinabove, in which component D
comprises mostly or entirely materials which are solid at
ambient temperature, in which case the ratio of D to A may
be between about 0.5:1 and 6:1.
Preparation of the Magnesium Complex
The magnesium complexes of this invention are pre-
pared by merely blending the components described herein-
above and heating the resulting blend at a temperature above
about 30C. It is important that water remain in the blend
during substantially the entire period of preparation of the
magnesium complex, and the maximum temperature thereof
should be adjusted accordingly. However, said water may be
present in the liquid or vapor state, i.e., as liquid water
or as steam, though it will be apparent to those skilled in
the art that the preparation of complexes involving a relatively
large amount of water will be difficult if not impossible,
at least at atmospheric pressure, if the water is present as
steam. Therefore, it is generally found that temperatures
1~95886
of about 30-125C. are most conveniently employed at atmos-
pheric pressure, and the preparation should be carried out
under superatmospheric pressure if the use of higher tempera-
tures is likely. Most often, a maximum temperature of about
100C. is convenient when component D is entirely or pre-
dominantly liquid and the preferred temperature range is
then about 40-90C. Naturally, the temperature may be
somewhat higher (e.g., about 95-150C.) when component D is
entirely or predominantly a solid at ambient temperature.
The order of addition of the various components is
not critical. It is often convenient to first combine com-
ponents A, B and D and -~ubsequently to add component C
(water) either all at once or incrementally. It is also
often found convenient to prepare an initial mixture containing
only a relatively small portion of component A (e.g., a~out
5-10% of the total amount thereof) and to add the remainder
at a later stage, typically during or after the addition of
water.
The magnesium complexes of this invention, when
prepaxed as described herein, are often conveniently obtained
as thickened compositions, i.e., viscous liquids or hetero-
geneous dispersions in the form of greases or gels, or (when
component D is predominantly solid) as "hot melt" materials.
For many purposes, such as the formation of corrosion-
resistant coatings, it is preferred that they be used in
such thickened or "hot melt" form. However, some other
applications such as those involving lubricants and fuels
may require that the complex be obtained in the form of a
relatively non-viscous, easily flowable liquid. Such liquids
may be obtained by methods well known to those of skill in
~16-
109588~
the art, such as maximizing the amount of liquid diluent
present as component D or by decreasing the relative amount
of component A or component C in the reaction mixture.
Alternatively, a thickened complex can be further diluted
with a substantially inert organic liquid diluent of the
type described hereinabove to produce a homogeneous solution.
One of the unique and desirable characteristics of the
compositions of this invention is their capability of existing
either as heterogeneous thickened compositions or homogeneous,
relatively dilute solutions or dispersion.
A method which is frequently advantageous for
incorporating relatively large amounts of magnesium while
making possible the formation of a homogeneous solution or
dispe~sion in mineral oil or the like is to prepare the com-
plex in the presence of ammonium hydroxide, which may be
prepared from ammonia and the water present as component C.
The amount of ammonium hydroxide required is small, generally
less than about 10% by weight based on the water present.
Insoluble materials can then be removed by diluting with a
non-polar volatile organic liquid such as hexane or naphtha,
centrifuging, and stripping the volatile liquid, or by
equivalent means.
Another method for clarifying the magnesium com-
plex for use in mineral oil, which may be employed in addition
to or in place of preparation in the presence of ammonium
hydroxide, is to add water or an acidic or basic reagent
after preparation of the complex. The acidic or basic
reagent may be organic or inorganic; suitable ones include
sodium hydroxide, potassium hydroxide, ammonium hydroxide,
triethanolamine, tartaric acid and citric acid. The amount
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of water or acidic or basic reagent is generally less than
about 10% by weight of the magnesium complex system.
The molecular structures of the magnesium com-
plexes of this invention are not known and are not a critical
aspect of the invention. The magnesium complexes are, in
general, most conveniently defined in terms of the method
for their preparation.
The preparation of the magnesium complexes of this
invention is illustrated by the following examples. All
parts are by weight.
Example 1
A blend is prepared of 135 parts of magnesium
oxide and 600 parts of an alkylbenzenesulfonic acid having
an equivalent weight of about 385, and containing about 24%
unsulfonated alkylbenzene. During blending, an exothermic
reaction takes place which causes the temperature to rise to
57C. The mixture is stirred for one-half hour and then 50
parts of water is added. Upon heating at 95C. for one
hour, the desired magnesium oxide-sulfonate complex is
obtained as a firm gel containing 9.07% magnesium.
Example 2
A blend of 600 parts of the alkylbenzenesulfonic
acid of Example 1 and 225 parts of magnesium oxide is prepared
and heated for 2 hours at 60-65C. There is then added,
over one hour, a solution of 10 parts of 30% ammonium hydroxide
and 75 parts of water. The mixture is heated for 3 hours at
60-65OC., and then an additional 10 parts of 30~ ammonium
hydroxide solution is added over 5 minutes. Upon heating
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for 2 more hours at 60-65C. and cooling, the desired magnesium
oxide-sulfonate complex is obtained as a dark brown gel.
Example 3
Following the procedure of Example 2, a blend is
made of 600 parts of the alkylbenzenesulfonic acid of Example
1 and 225 parts of magnesium oxide, and a solution of 30
parts of 30% ammonium hydroxide in 75 parts of water is
added. After heating for 4 hours at 60-~5C., the mixture
is cooled and 900 parts of hexane is added. The hexane-
diluted mixture is centrifuged and the hexane is removed by
vacuum stripping at 150C. The residue is cooled to 130C.
and 18 parts of triethanolamine is added. The product is
the desired magnesium oxide-sulfonate complex, a soft brown
gel which contains 11.3% magnesium.
Example 4
Magnesium hydroxide, 233 parts, is added to 600
parts of the alkylbenzenesulfonic acid of Example 1. There
is then added 1250 parts of water and the mixture is heated
gradually to about 80C. over about 2 hours, whereupon a gel
forms. The mixture is allowed to stand and a water layer of
830 parts is decanted; 570 parts of toluene is then added
and an additional 300 parts of water is removed by azeotropic
distillation.
A 602-part portion of the resulting gel is diluted
with 200 parts of toluene. The solution is centrifuged and
the toluene removed by blowing with nitrogen at 160-170C.
to yield the desired magnesium oxide-sulfonate complex as a
soft gel.
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1~958~
Example 5
Magnesium oxide, 600 parts, is added to a solution in
478 parts of Stoddard solvent and 244 parts of mineral oil
of 308 parts of an alkylbenzenesulfonic acid having an
equivalent weight of about 430 and containing about 22%
unsulfonated alkylbenzene. Water, 381 parts, is added and
the mixture is heated under reflux for 15 minutes. It is
then cooled to room temperature, yielding the desired magnesium
oxide-sulfonate complex in the form of a gel.
Example 6
A mixture of 204 parts of the alkylbenzenesulfonic
acid of Example 1, 88 parts of mineral oil and 515 parts of
Stoddard solvent is prepared, and 320 parts of magnesium
oxide is added, followed by 420 parts of water. The mixture
is heated at 95-100C., with stirring, until gelation occurs.
The excess water (about 300 parts) is then removed by azeo-
tropic distillation to yeild the desired magnesium oxide-
sulfonate gel.
Example 7
A mixture is prepared of 1106 parts of water, 54
parts of magnesium oxide, 425 parts of the alkylbenzene-
sulfonic acid of Example 5, 495 parts of mineral oil and 856
parts of Stoddard solvent. An additional 781 parts of
magnesium oxide is then added and the mixture is slowly
heated to 52-55C. There are then added 30 parts of tetra-
propenyl succinic acid and 37 parts of a black pigment~
Upon screening and cooling, the desired composition contain-
ing the magnesium oxide-sulfonate gel is obtained.
Example 8
A mixture of 125 parts of toluene, 225 parts of
-20-
lO~S~386
the alkylbenzenesulfonic acid of Example 5, 680 parts of
mineral oil, 550 parts of magnesium oxide and 200 parts of
water is heated slowly to reflux temperature (about 100C.)
and excess water (about 43 parts) is removed by azeotropic
distillation. The residue is stripped under vacuum at 170C.
as 117 parts of volatiles are re ved. The residue from the
stripping is cooled to yield the desired magnesium oxide-
sulfonate complex in the form of a gel.
Example 9
A mixture of 2050 parts of water, 30 parts of
magnesium oxide, 294 parts of the alkylbenzenesulfonic
acid of Example 5, and 520 parts of oil is heated to 35-40C.,
and an additional 715 parts of magnesium oxide is added
slowly. An exothermic reaction takes place and the magnesium
oxide addition is regulated so as to cause a temperature
increase of about 10C. per hour to a maximum temperature of
about 65C. Heating is continued until the temperature
reaches 85C., whereupon a gel is obtained containing a clear
water layer on top. The excess water (about 1552 parts) is
decanted. To the residue are added 375 parts of mineral oil
and 165 parts of toluene, and an additional portion of water
(259 parts) is removed by azeotropic distillation. Excess
toluene is removed by stripping under nitrogen (180C.) and
the residue is screened to yield the desired magnesium oxide-
sulfonate gel.
Example 10
A mixture of 900 parts of water, 333 parts of mag-
nesium oxide, 266 parts of mineral oil and 132 parts of the
alkylbenzenesulfonic acid of Example 1 is heated to 80-85C.,
with stirring, over about 45 minutes. It is maintained at
-21-
i~9S886
this temperature for about 10-15 minutes after gelation takes
place, after which time stirring is discontinued and a water
layer of about 793 parts is decanted. There are added 135
parts of mineral oil and 75 parts of toluene, and an addi-
tional 43 parts of water is removed by azeotropic distilla-
tion. The toluene is stripped at 180C. by nitrogen blowing
and the residue is screened to yield the desired magnesium
oxide-sulfonate complex as a thick opaque liquid.
Example 11
An acidic phosphate ester is prepared by adding
136 parts of methanol and 744 parts of a commercial mixture
of predominantly straight chain Cl 2-14 alcohols to a suspen-
sion of 284 parts of phosphorus pentoxide in 800 parts of
hexane, with stirring. After the alcohols have been added,
the reaction mixture is heated under reflux for 4 hours and
hexane is removed by distillation. The resulting acidic
phosphate ester has an equivalent weight of about 200.
A mixture of 200 parts of the resulting acidic
phosphate ester, 310 parts of toluene, 880 parts of mineral
oil and 440 parts of magnesium oxide is prepared and heated
to 60C., with stirring, over 1/2 hour. Water, 200 parts,
is then added and the mixture is heated at 94C. for 45 minutes,
with continued stirring. Excess water is then removed by
azeotropic distillation (a total of 90 parts) and the
toluene is removed by vacuum stripping to yield the desired
magnesium oxide-phosphate complex as a pourable gel.
Example 12
A mixture of 754 parts of water, 23 parts of mag-
nesium oxide, 210 parts of mineral oil and 247 parts of
Stoddard solvent is heated to about 40C. and 331 parts of
-22-
1~95886
a carboxylic acid having an equivalent weight of about 350
and obtained by oxidation of petrolatum, which acid has
been preheated to about 50-60C., is added as the tempera-
ture of the mixture is maintained at 40-45C. An additional
350 parts of magnesium oxide is added, with stirring, and
the temperature of the mixture is increased to 75C. An
opaque dispersion is obtained which is screened to afford
the desired magnesium oxide-carboxylate complex.
Example 13
A product similar to that of Example 12 is pre-
pared, substituting about 300 parts of sorbitan trioleate
for the oxidized petrolatum.
Example 14
A reaction vessel is charged with 63 parts of
"Epal* 20+", a solid mixture consisting predominantly of
C20 32 linear and branched aliphatic alcohols and available
from Ethyl Corporation; 83 parts of "Factowax* R-143", a
paraffin wax available from Standard Oil Company (Ohio) and
melting at about 62C.; and 83 parts of "Bareco Polywax*
655", a polyethylene synthetic wax manufactured by Petrolite
Corp. and melting at about 102C. The mixture is melted
and 21 parts of magnesium oxide is added. As the mixture
is agitated at 96-99C., 235 parts of the alkylbenzenesul-
fonic acid of Example 5 is added. Following the sulfonic
acid addition, an additional 185 parts of magnesium oxide is
* Trade Mark
-23-
l~gS88~
added at 96-99C. Mixing is continued at that temperature
for 2 hours and then 69 parts of water is added over 2-1/2
hours at 99-102C. An additional 76 parts of alkylbenzene-
sulfonic acid is added at 96-99C. and mixing is continued
for 1-1/2 hours after which the mixture is heated to 143-
149C. for 3 hours and blown with nitrogen to remove vola-
tiles by distillation. The residue is the desired solid
magnesium oxide-sulfonate complex.
Example 15
A mixture of 1280 part~ of water, 18 parts of
magnesium oxide, 180 parts of the alkylbenzenesulfonic acid
of Example 5, and 215 parts of mineral seal oil is heated
to 45C. and an additional 534 parts of magnesium oxide is
added, with stirring. The mixture is heated to 80-85C.
over two hours whereupon partial coagulation takes place
and a water layer separates. The water layer (about 1050
parts) is decanted and an additional 290 parts of mineral
seal oil is added. The mixture is purged with nitrogen at
140-145C. for 2-1/2 hours to remove excess water and is
then passed through a 20-mesh screen to yield the desired
magnesium oxide-sulfonate complex.
Example 16
A mixture of 16 parts of the alkylbenzenesulfonic
acid of Example 5, 305 parts of mineral oil, 180 parts of
magnesium oxide and 96 parts of "Hydrex* 440", a mixture of
hydrogenated fatty acids obtainable from Union Camp Corporation,
* Trade Mark
-24-
5886
is heated to 95C. and blown with steam for two hours. The
temperature is increaqed to 145-150C., an additional 28
parts of mineral oil is added and the mixture is blown with
air as the temperature is heated to 170C. over 15 minutes.
The mixture is then cooled to room temperature and an additional
44 parts of mineral oil is added to yield the desired magnesium
oxide-sulfonate complex having the consistency of a grease.
Lubricants and Fuels
When in the form of flowable liquids as previously
described, the magnesium complexes of this invention are
stably dispersible in the normally liquid media (e.g., oil,
fuel, etc.) in which they are intended to function. Thus,
for example, compositions intended for use in oils are
stably dispersible in an oil in which they are to be used.
The term "stably dispersible" as used in the specification
and appended claims is intended to mean the magnesium complex
or other material is capable of being dispersed in a given
medium to an extent which allows it to function in its
intended manner. Thus, for example, when a magnesium complex
is used in an oil, it is sufficient that it be capable of
being suspended in the oil in an amount sufficient to enable
the oil to possess one or more of the desired properties
imparted to it by the suspended complex. Such suspension
can be achieved in various conventional ways. For example,
in constantly circulating oil or oil in splash lubricating
systems, physical agitation can keep the complex suspended
in oil. Likewise, conventional dispers~nts (such as the
5886
acylated nitrogen dispersants disclosed in U.S. Patent
3,219,666) often found in lubricating oils and fuels promote
the stable dispersion or suspension of the magnesium complex.
In any event, the complex will be "stably dispersible" in
the normally liquid media in which it will be used in at
least the minimum concentrations set forth elsewhere herein.
Thus, the terminology "stably dispersible" is used in a
conventional manner and will be understood by those of
ordinary skill in the art.
As previously indicated, the magnesium complexes
of this invention may be homogeneously incorporated into
lubricants, in which they function primarily as ash-
producing detergents. The products of Examples 1-4 are
particularly useful for this purpose. They can be employed
in a variety of lubricants based on diverse oils of lubricating
viscosity, including natural and synthetic lubricating oils
and mixtures thereof. These lubricants include crankcase
lubricating oils for spark-ignited and compression-ignited
internal combustion engines, including automobile and truck
engines, two-cycle engines, aviation piston engines, marine
and railroad diesel engines, and the like. They can also be
used in gas engines, stationary power engines and turbines
and the like. Automatic transmission fluids, transaxle
lubricants, gear lubricants, metal-working lubricants,
hydraulic fluids and other lubricating oil and grease com-
positions can also benefit from the incorporation therein of
the magnesium complexes of the present invention.
Natural oils include animal oils and vegetable oils
(e.g., castor oil, lard oil) as well as liquid petroleum oils
-26-
~5886
and solvent-treated or acid-treated mineral lubricating oils
of the paraffinic, naphthenic or mixed paraffinic-naphthenic
types. Oils of lubricating viscosity derived from coal or
shale are also useful base oils. Synthetic lubricating oils
include hydrocarbon oils and halosubstituted hydrocarbon oils
such as polymerized and interpolymerized olefins [e.g.,
polybutylenes, polypropylenes, propylene-isobutylene copoly-
mers, chlorinated polybutylenes, poly(l-hexenes), poly-
(l-octenes), poly(l-decenes), etc. and mixtures thereof];
alkylbenzenes [e.g.,dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.]; poly-
phenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls,
etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides
and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and deri-
vatives thereof where the terminal hydroxyl groups have been
modified by esterification, etherification, etc. constitute
another class of known synthetic lubricating oils. These
are exemplified by the oils prepared through polymerization
of ethylene oxide or propylene oxide, the alkyl and aryl
ethers of these polyoxyalkylene polymers (e.g., methyl-
polyisopropylene glycol ether having an average molecular
weight of 1000, diphenyl ether of polyethylene glycol having
a molecular weight of 500-1000, diethyl ether of polypropylene
glycol having a molecular weight of 1000-1500, etc.) or
mono- and polycarboxylic esters thereof, for example, the
acetic acid esters, mixed C3-C8 fatty acid esters, or the
Cl 3 ~XO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating
oils comprises the esters of dicarboxylic acids (e.g.,
-27-
1~9588~
phthalic acid, succinic acid, alkyl succinic acids and
alkenyl succinic acids, maleic 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,
e~c.). 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-ethylhexanoic
acid, and the like.
Esters useful as synthetic oils also include those
made from C5 to Cl 2 monocarboxylic acids and polyols and
polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils
comprise another useful class of synthetic lubricants (e.g.,
tetraethyl silicate, tetraisopropyl silicate, tetra-(2-
ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate,
tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2-
pentoxy)-disiloxane, poly(methyl)siloxanes, poly(methylphenyl)-
siloxanes, etc.). Other synthetic lubricating oils include
liquid esters of phosphorus-containing acids (e.g., tricresyl
phosphate, trioctyl phosphate, diethyl ester of decylphospho-
nic acid, etc.), polymeric tetrahydrofurans and the like.
-28-
1~958B6
Unrefined, refined and rerefined oils (and mixtures
of each with each other) of the type disclosed hereinabove
can be used in the lubricant compositions of the present
invention. Unrefined oils are those obtained directly from a
natural or synthetic source without further purification
treatment. For example, a shale oil obtained directly from
retorting operations, a petroleum oil obtained directly from
distillation or ester oil obtained directly from an esterifi-
cation process and used without further treatment would be an
unrefined oil. Refined oils are similar to the unrefined oils
except they have been further treated in one or more purifi-
cation steps to improve one or more properties. Many such
purification techniques are known to those of skill in the
art such as solvent extraction, acid or base extraction, fil-
tration, percslation, etc. Rerefined oils are obtained byprocesses similar to those used to obtain refined oils
applied to refined oils which have been already used in ser-
vice. Such rerefined oils are also known as reclaimed or
reprocessed oils and often are additionally processed by
techniques directed to removal of spent additives and oil
breakdown products.
Generally, the lubricants of the present invention
contain an amount of the composition of this invention
sufficient to impart detergency thereto. Normally this
amount will be about 0.05-20.0%, preferably about 0.5-10.0%,
of the total weight of the lubricant. In lubricating oils
operated under extremely adverse conditions, such as lubri-
cating oils for marine diesel engines, the magnesium complexes
of this invention may be present in amounts up to about 30%.
The magnesium complexes of the present invention,
as illustrated by the products of Examples 8-10 and 15, are
-29-
1~9S886
also useful as corrosion inhibitors, vanadium scavengers and
smoke suppressants in fuels. For that purpose, they are
homogeneously incorporated in minor proportions in normally
liquid fuels, usually hydrocarbonaceous fuels such as fuel
oils, bunker fuels and the like. Normally liquid fuel
compositions comprising non-hydrocarbonaceous materials such
as alcohols, ethers, organo-nitro compounds and the like
(e.g., methanol, ethanol, diethyl ether, methyl ethyl ether,
nitromethane) are also within the scope of the invention as
are liquid fuels derived from vegetable or mineral sources
such as corn, alfalfa, shale and coal. Normally liquid
fuels which are mixtures of one or more hydrocarbonaceous
fuels and one or more non-hydrocarbonaceous materials are
also contemplated.
Generally, these fuel compositions contain an
amount of the magnesium complex sufficient to impart corrosion-
resistant properties thereto; usually this amount is about
1-10,000, preferably 4-1000, parts thereof by weight per
million parts of fuel.
The invention also contemplates the use of other
additives in combination with the magnesium complexes.
Other additives useful in lubricants include, for example,
auxiliary detergents and dispersants of the ash-producing or
ashless type, corrosion- and oxidation-inhibiting agents,
pour point depressing agents, extreme pressure agents, color
stabilizers and anti-foam agents.
The auxiliary ash-producing detergents are exempli-
fied by oil-soluble neutral and basic salts of alkali or
alkaline earth metals with sulfonic acids, carboxylic acids,
or organic phosphorus acids characterized by at least one
direct carbon to-phosphorus linkage such as those prepared
-30-
~09~8~
by the treatment of an olefin polymer (e.g., polyisobutene
having a molecular weight of 1000) with a phosphorizing agent
such as phosphorus trichloride, phosphorus heptasulfide,
phosphorus pentasulfide, phosphorus trichloride and sulfur,
white phosphorus and a sulfur halide, or phosphorothioic
chloride. The most commonly used salts of such acids are
those of sodium, potassium, lithium, calcium, magnesium,
strontium and barium.
The term "basic salt" is used to designate metal
salts wherein the metal is present in stoichiometrically
larger amounts than the organic acid radical. The commonly
employed methods for preparing the basic salts involve heat-
ing a mineral oil solution of an acid with a stoichiometric
excess of a metal neutralizing agent such as the metal oxide,
hydroxide, carbonate, bicarbonate, or sulfide at a tempera-
ture above 50C. and filtering the resulting mass. The use
of a "promoter" in the neutralization step to aid the incor-
poration of a large excess of metal likewise is known.
Examples of compounds useful as the promoter include phenolic
substances such as phenol, naphthol, alkylphenol, thiophenol,
sulfurized alkylphenol, and condensation products of for-
maldehyde with a phenolic substance; alcohols such as methanol,
2-propanol, octyl alcohol, cellosolve, carbitol, ethylene
glycol, stearyl alcohol, and cyclohexyl alcohol; and amines
such as aniline, phenylenediamine, phenothiazine, phenyl-
~-naphthylamine, and dodecylamine. A particularly effec-
tive method for preparing the basic salts comprises mixing
an acid with an excess of a basic alkaline earth metal
neutralizing agent and at least one alcohol promoter, and
carbonating the mixture at an elevated temperature such as
60-200C.
1~5886
Ashless detergents and dispersants are so called
despite the fact that, depending on its constitution,
the dispersant may upon combustion yield a non-volatile
material such as boric oxide or phosphorus pentoxide; however,
it does not ordinarily contain metal and therefore does not
yield a metal-containing ash on combustion. Many types are
known in the art, and any of them are suitable for use in
the lubricants of this invention. The following are illus-
trative:
(1) Reaction products of carboxylic acids (or
derivatives thereof) containing at least about 34 and pre-
ferably at least about 54 carbon atoms with nitrogen-
containing compounds such as amine, organic hydroxy com-
pounds such as phenols and alcohols, and/or basic inorganic
materials. Examples of these "carboxylic dispersants" are
described in British Patent 1,306,529 and in many U.S.
patents including the following:
3,163,603 3,351,552 3,541,012
3,184,474 3,381,022 3,542,678
3,215,707 3,399,141 3,542,680
3,219,666 3,415,750 3,567,637
3,271,310 3,433,744 3,574,101
3,272,746 3,444,170 3,576,743
3,281,357 3,448,048 3,630,904
3,306,908 3,448,049 3,632,510
3,311,558 3,451,933 3,632,511
3,316,177 3,454,607 3,697,428
3,340,281 3,467,668 3,725,441
3,341,542 3,501,405 Re 26,433
3,346,493 3,522,179
l~gS886
(2) Reaction products of relatively high molecu-
lar weight aliphatic or alicyclic halides with amines, pre-
ferably polyalkylene polyamines. These may be characterized
as "amine dispersants" and examples thereof are described
for example, in the following U.S. patents:
3,275,554 3,454,555
3,438,757 3,565,804
(3) Reaction products of alkyl phenols in which
the alkyl group contains at least about 30 carbon atoms
with aldehydes (especially formaldehyde) and amines (es-
pecially polyalkylene polyamines), which may be characterized
as "Mannich dispersants". The materials described in the
following U.S. patents are illustrative.
3,413,347 3,725,480
3,697,574 3,726,882
3,725,277
(4) Products obtained by post-treating the car-
boxylic, amine or Mannich dispersants with such reagents as
urea, thiourea, carbon disulfide, aldehydes, ketones, car-
boxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, phosphorus compounds or
the like. Exemplary materials of this kind are described in
the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242
3,087,936 3,312,619 3,502,677 3,649,229
3,200,107 3,366,569 3,513,093 3,649,659
3,216,936 3,367,943 3,533,g45 3,658,836
3,254,025 3,373,111 3,539,633 3,697,574
3,256,185 3,403,102 3,573,010 3,702,757
3,278,550 3,442,808 3,579,450 3,703,536
3,280,234 3,455,831 3,591,598 3,704,308
3,281,428 3,455,832 3,600,372 3,708,522
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1~95886
(5) Interpolymers of oil-solubilizing monomers
such as decyl methacrylate, vinyl decyl ether and high
molecular weight olefins with monomers containing polar
substituents, e.g., aminoalkyl acrylates or acrylamides
and poly-(oxyethylene)-substituted acrylates. These may be
characterized as "polymeric dispersants" and examples there-
of are disclosed in the following U.S. patents:
3,329,65~, 3,666,730
3,449,250 3,6~7,849
lo 3,519,565 3,702,300
Extreme pressure agents and corrosion- and oxida-
tion-inhibiting agents are exemplified by chlorinated ali-
phatic hydrocarbons such as chlorinated wax; organic sulfides
and polysulfides such as benzyl disulfide, bis(chlorobenzyl)
disulfide, dibutyl tetrasulfide, sulfurized methyl ester of
oleic acid, sulfurized alkylphenol, sulfurized dipentene,
and sulfurized terpene; phosphosulfurized hydrocarbons such
as the reaction product of a phosphorus sulfide with
turpentine or methyl oleate; phosphorus esters including
principally dihydrocarbon and trihydrocarbon phosphites such
as dibutyl phosphite, diheptyl phosphite, dicyclohexyl
phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphite,
tridecyl phosphite, distearyl phosphite, dimethyl naphthyl
phosphite, oleyl 4-pentylphenyl phosphite, polypropylene
(molecular weight 500)-substituted phenyl phosphite,
diisobutyl-substituted phenyl phosphite, metal thiocarbamates,
such as zinc dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate; Group II metal phosphorodithioates such as
zinc dicyclohexylphosphorodithioate,
- 34 -
886
zinc dioctylphosphorodithioate, barium di(heptylphenyl)-
phosphorodithioate, cadmium dinonylphosphorodithioate, and
the zinc salt of a phosphorodithioic acid produced by the
reaction of phosphorus pentasulfide with an-equimolar
mixture of isopropyl alcohol and n-hexyl alcohol.
Other additives useful in fuels include deposit
preventers or modifiers such as triaryl phosphates, dyes,
cetane improvers, antioxidants such as 2,6-di-tertiary-
butyl-4-methylphenol, rust inhibitors such as alkylated
succinic acids and anhydrides, bacteriostatic agents, gum
inhibitors, metal deactivators, demulsifiers and the like.
The magnesium complexes of this invention can be
added directly to the lubricant or fuel. Preferably, however,
they are diluted with a substantially inert, normally liquid
organic diluent such as those mentioned hereinabove, par-
ticularly mineral oil, naphtha, benzene, toluene or xylene,
to form an additive concentrate. These concentrates generally
contain about 20-90~ by weight of the magnesium complex and
may contain in addition, one or more of the other additives
described hereinabove.
The lubricants of this invention are illustrated
by the following example. All parts are by weight.
Example 17
Ingredient Parts
Mineral oil (SAE 10W-40 base) 86.83
Product of Example 4 0.49
Mixed ester-amide of polybutenyl
succinic acid 3.02
Zinc dialkylphosphorodithioate 0.82
Sulfurized alkyl cyclohexenecarboxylate 0.39
Tetrapropenylsuccinic acid 0.07
Ethoxylated alkyl phenol 0.29
-35-
- 1095886
Hindered phenol antioxidant 0.34
Polyacrylate viscosity index improver 7.75
Silicone anti-foam agent 0.01
Corrosion-Resistant Coatings and Other Uses
The thickened magnesium complexes of this invention
are useful as corrosion-resistant coatings for metal (e.g.,
ferrous metal, galvanized, aluminum or magnesium) surfaces,
especially in the nature of undercoats for automotive bodies,
coatings for structural members such as automotive frames,
and the like. They may be employed as such alone, in combina-
tion with other basic metal sulfonates and the like known to
be useful in corrosion-resistant coatings, and/or in combina-
tion with known adjuvants for such corrosion-resistant coat-
ings such as acidic phosphate esters, resins, and waxes.
Many of the suitable resins and waxes are the same as those
described hereinabove with reference to component D; they
may be incorporated in varying amounts in the thickened com-
plex but generally comprise a minor amount of the coating
composition, typically about 0.5-2.0% by weight. U. S.
Patents #3,453,124 and #3,671,072 disclose basic compositions
and adjuvants useful in combination with the thickened mag-
nesium complexes.
The products of Examples 5-7 are exemplary of the
magnesium complexes suitable for use as corrosion-resistant
coatings of the undercoat type. Also useful for this pur-
pose is the product prepared by the following example.
Example 18
A product is obtained substantially in accordance
-36-
1~9~
with the procedure of Example 7 by the reaction of 11.61
parts of the alkylbenzenesulfonic acid of Example 5, 9.2
parts of mineral oil, 23.71 parts of Stoddard solvent, 22.61
parts of magnesium oxide and 30.92 parts of water. To the
resulting gel are added 0.97 part of a black pigment com-
position and 1.0 part of a vinyl acetate-ethylene copolymer
comprising about 28% vinyl acetate units.
For coating automotive frames and the like, a
solid "hot melt" composition of the type described in Example
- 10 14 is particularly suitable. Frequently, a dye or pigment
is added to the "hot melt" composition; for example, 17
parts of a black pigment may be added to the product of
Example 14 immediately after the distillation step and
distillation may then be continued to remove volatiles
present in the dye or pigment composition.
For corrosion-inhibiting purposes, the thickened
or solid composition of this invention may be applied to the
metal surface by any ordinary method such as brushing,
spraying, dip-coating, flow-coating, roller-coating and the
like, with heating if necessary (as to liquefy a solid
composition). The viscosity of a thickened composition may
be adjusted for the particular method of application selected
by adding, if necessary, a substantially inert, normally
liquid organic diluent such as those disclosed hereinabove.
The coated metal surface may then be dried either by exposure
to air or by baking, although drying frequently takes place
without a separate drying step. If the coating composition
is of a suitable viscosity to allow direct application to
the metal surface, typically the consistency of a No. 1 or
i~)9S8~6
No. 2 grease, no solvent is used and no drying procedure
need be followed. A more viscous grease can be diluted to
produce a less viscous grease which is suitable for appli-
cation as previously noted. The film thickness i~ not
critical although a coating o~ about 50-2000 mg. per square
foot of surface in the case of an undercoat, and up to about
10,000 mg. per square foot in the case of a coating for
frames or other structural members, is usually sufficient to
provide adequate protection. Heavier coatings can be used
if desired, but they normally contribute little in the way
of additional protection.
The magnesium complexes of this invention are also
useful as lubricant greases and as stabili2ers for resinous
compositions, typically polyvinyl chloride, to protect them
against oxidative degradation.
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