Note: Descriptions are shown in the official language in which they were submitted.
The present invention relates to lubricant and fuel
compositions having improved demulsifying properties. In
particular, the invention is concerned with a demulsifier
additive for use in lubricants such as power transmitting
fluids, crankcase, gear, marine diesel, and fuels such as
gasoline and diesel coming into contact with water and
moisture, especially during storage and/or handling and
reclaiming operations~
It is w~ll known that water is an undesirable con-
taminant in fuels, and lubricants. For, not only does waterreduce the eectiveness of the fuel or lubricant, it tends
to form delèterious by-products, particularly in relation to
the engine or parts in contact with or utilizing the lubri-
cant. For instance, water present in a crankcase lubricant is
responsible for the formation of objectionable mayonnaise-
like sludge which in turn promotes the formation of hard-to
remove deposits from engine parts. Presumably the formation
of the sludge is preceded by the water forming an emulsion
with the lubricant oil. While water should be separable
rom an oil or lubricant due to immiscibility, often the
additives in many lubricants have water solubility suffi
cient to orm emulsions which are difficult to remove. Thus,
it is important to minimize the presence of water in lubri~
cants to thereby reduce or eliminate the formation of such
emulsions.
Naturally, lubricants having minimum contact with
water would not present the serious problems of water/oil
emulsions. However, it is difficult to eliminate contact
with water, particularly during storage and/or handling.
One particular procedure which gives rise to water contami-
nation involves factory-fill transmission fluids. During
~4~g~
assembly and testing of automotive drive-train parts, the
transmissions, especially automatic transmissions, are
filled with the proper water-free transmission fluid for
testing and inspecting under running and operating con-
ditions. ~fter such testing, the fluid is allowed to draininto exposed trou~hs or collecting stations leading td a
main collecting tank. The drained oil is not protected from
the immediate environment and often contains, among other
things, a considerable amount of water. For eficiency and
economy the collected oil should be re-used with minimal
processing including filtering and centrifugation. To do so
an effective demulsifier must be added to the lubricant.
In the prior art many demulsi~iers have been
suggested and used. Mainly these demulsifiers have com-
lS prised a polyoxyalkylene glycol or a polyoxypolyamine.These glycols and polyamines have not been entirely satis-
factory because of their limited use and inability t~ LUllC-
tion except in specific lubricants or fuels. Thus/ there
has been the need to "custom-make" specific demulsifiers,
which is costly.
The demulsifiers of the present invention have
overcome many such disadvantages. They have shown effec-
tiveness in a variety of lubricants and fuels by substan-
tially reducing the formation of emulsions in such lubricants
and fuels. They have been of particular benefit to water-
contaminated factory-fill automatic transmission fluids
referred to above.
Thus it is a primary object of the present invent~on
to provide fuel and lubricant compositions comprising one or
~3~
more effective demulsifier additives in accordance with the
invention.
Another object is to pro~ide concentrates contain-
ing such demulsifier additives ~o the extent that each of
said concentrates is capable of providing demulsifying
properties to the fuel or lubricant into which it is incor-
porated.
Another object of the invention i5 to provide a
method of making the demulsifier additives, and concentrates,
fuels and lubricants containing said additives.
Other objects and advantages o~ the present inven-
tion will be apparent to those skilled in the art from con-
sideration of the following description.
Briefly, the present invention is directed to fuel
and lubricant compositions having a major proportion o~ a
lubricating oil or normally liquid fuel and a minor propor-
tion of at least one demulsifier additive comprising (A)
one or more reaction products of a hydrocarbon-substitute~
succinic acid or anhydride with one or more po!yalkylene
~lycols or monoethers thereof, (B) one or more organic baslc
metals salts, and (C) one or more alkoxylated amines.
Component (A) is an ester wherein the acid com-
prises a hydrocarbon-substituted succinic acid or anhydride
in which the hydrocarbon substituent is generally a sub-
stantially saturated aliphatic group of 4 to about 50 carbon
atoms in the chain, preferably from 6 to about 30 carbon
atoms, and most preferably, from 8 to about 16 carbon atoms.
The hydrocarbon substituen~ may contain polar groups pro-
vided/ however, that such groups are not present in pro-
portions sufficiently ~arge to alter significantly the
hydrocarbon character of the substituent. The polar groups
are exemplified by ~he chloro, bromo, keto, ethex, aldehyde,
nitro, etc. The upper limit with respect to the portion of
such polar groups in the substituent is approximately 10~
based on the weight of ~he hydrocarbon portion of the sub-
stituent.
The sources of the succinic acid or anhydride hydro-
carbon substituent include a variety of monomers, oligomers,
prepolymers, and even polymers. Oligomers can be a combina-
tion of two or more monomers; prepolymers refer to polymericspecies capable of undergoing the addition reaction with the
maleic acid or anhydride. Monomers comprise any N-monoolefin
of 4 to 50 carbon atoms. ~-Monoolefins such as l-butene,
isobutene, l-hexene, 1 octene, 2-methyl-1-heptene, 3-cyclo-
hexyl-l-butene, and 2-méthyl-5-propyl-1-hexene are quite
useful. Preferably dimers, trimers, or tetramers of ethylene
or propylene are usea to an especial advantage. Polymers of
medial olefins, i.e., olefins in which the olefinic linkage
is not at the terminal position, likewise are useful. They
are illustrated by 2-butene, 3-pentene, and 4-octene~ It is
preferred that polymers derlved from 3 to 6 carbon atom mono-
olefins are used, such as polypropylene or polybutene.
The hydrocarbon-substituted succinic acid or anhy-
dride is reacted with one or more polyalkylene glycol to
form the ester. The polya]kylene glycols, or their mono-
ethers, contemplated by the present invention are illustrated
by, for example, several polyethylene glycols having molecu-
lar weights in the range o~ about 200 to about 1500. Speci-
fically, polyethylene glycol of 200, 300 and 600 molecular
weights are especially useful. Similarly, polypropylene
2~
glycols having molecular weights in the same range of about
200 to 1500 are likewise useful. These polyalkylene glycols
and their monoethers which are commercially available products
(marketed by Union Carbide Corp., New York, N.Y. under the
trade mark Carbowax) can be obtained by xeacting the glycol with
ethylene or propylene oxide. Me~hods o preparing such glycols
are known to those skilled in the art.
As to the monoethers of said polyalkylene glycols, they
are illustrated by ethers such as monomethyl ether of polyethylene
~lycol, monoethylether of polyethylene glycol, monopropyl- and
monobutyl ethers of polyethylene glycols. Generally, monoalkyl
ethers wherein the alkyl group contains from 1 to about 12 carbon
atoms are contemplated herein with the proviso that the average
molecular weight does not exceed about 1500.
The esterification reaction is conducted under conventional
esterification conditions whereby the hydrocarbon-substituted acid
or anhydride is reacted with the glycol at temperatures above
about 100C., preferably between about 110 to about 150C.
Higher temperatures of about 150-300C can be used, if desired.
Of course, the extent of esterification can be controlled to
produce substantially neutral esters, acidic esters, or mixtures
of these. It has been found that the acidic esters are generally
most effective and they are thus much preferred. Therefore,
in conducting the esterification the reactants are introduced
into the reactor at ratios designed to favor the production of
the acid ester. For clarity, the acid ester is defined as the
product formed from the reaction of a dibasic a~id (or
anhydride~ with a polyol in such ratios that the
L~
carboxylic acid moieties are never completely esterified.
Thus when one mole of a dibasic acid is reacted with one
mole of alcohol, the half ester or acid ester is formed.
Similarly, if 2 moles of a dibasic acid (or anhydride) are
reacted with a diol the half or acid ester is formed. The
latter can be illustrated by the following representative
reaction.
O O O
H
RIC ~ C RlC C--O--R2--OC--CH2
\
2 O + HO-R2-OH
HC -- C HC - COH HOC- C R
H il H
O O O
wherein R~ (4-50C) is the hydrocarbon substituent of the
succinic anhydride and R2 represents the polyalkylene group
of the glycol. In the event the mono-ether such as methoxy
polyalkylene glycol is used -then to prepare the acid ester
the ratio becomes one mole of acid to one mole of the mono-
ether as the latter has one hydroxyl moiety available for
reaction.
Referring to component (B) of the demulsifier
additive it clescribes the well known class of basic me-tal
organic salts in which the metal is present in a stoichio-
metrically greater amount than necessary to produce the
neutral salt. These salts are often referred to as "basic
salts", "overbased sal-ts", "super-bas0d salts" and "hyper-
based salts".
Such basic metal salts are known in the art. Those
which are contemplated herein include salts derived from oil-
soluble sulfonic acids, oil-soluble carboxylic acids,
oil-soluble phosphonic acids, oil-soluble phenolic acids and
mixtures thereof, such as are described in U,S. Pat~ Nos.
2,501,731; 2,616,904; 2,616,905; 2,616,906; 2,616,911;
2,616,924; 2,696,025; 2,617,049; 2,777,87~; 3,207,325;
3,256,186; 3,282,835; 3,384,585; 3,373,108; 3,365,396;
3,342,733; 3,320,162; 3,312,618; and 3,318,809. These patents
describe the preparation and identification of such compounds.
As an example of a particularly convenient process for
the preparation of the basic salts used, an oil-soluble
sulfonic acid, such as a synthetically prepared didodecyl-
benzene sulfonic acid, is mixed with an excess oE lime (e.g.,
10 equivalents per equivalent of the acid) and a promoter such
as methanol, heptylphenol, or mixture thereof, and a solvent
such as mineral oil, at 50C - 150C and the process mass is
then carbonated until a homogeneous mass is obtained. Basic
salts derived from sulfonic acids, carboxylic acids, and
mixtures thereof are obtainable by processes such as are
described in U.S. Pat. No. 3,312,618. Another example is the
preparation of a magnesium sulfonate basic salt by carbonating
a mixture of a sulfonic acid or normal magnesium sal~ thereof,
an excess of maynesium oxide, water, and preferably also an
alcohol promoter such as methanol.
The carboxylic acids useful for preparing sulfonate-
carboxylate basic salts, and carboxylate basic salts, i.e.,
those obtainable from processes such as the above wherein a
mixture of sulfonic acid and carboxylic acid or a carboxylic
acid alone is used in lieu of the sulfonic acid, are oil-
soluble acids and include primarily fatty acids which have
at least about 12 aliphatic carbon atoms and not more than
about 2~ aliphatic carbon atoms. Examples of these acids
include: palmitic, stearic, myristic, oleic, linoleic,
dodecanoic, behenic, etc. Cyclic carboxylic acids may also
be employed. These include aromatic and cyclo-aliphatic
acids. The aromatic acids are those containing a benzenoid
structure (i.e., benzene, naphthalene, etc.) and an oil-
solubilizing radical or radicals having a total of at least
about 15 to 18 carbon atoms, preferably from about 15 to
about 200 carbon atoms. Examples of the aroma~ic acids
include: stear~l-benzoic acids, phenyl stearic acid, mono-
or polywax-substituted benzoic or naphthoic acids wherein
the wax group consists o~ at least about 18 carbon atoms,
cetyl hydroxybenzoic acias, etc. The cycloaliphatic acids
contemplated have at least about 12, usually up to about 30
carbon atoms. Examples of such acids are petroleum naph-
thenic acids, cetyl cyclohexane carboxylic acids, di-lauryl
decahydronaphthalene carboxylic acids, di-octyl cyclopentane
carboxylic acids, etc. The thiocarboxylic acid analogs of
the above acids, wherein one or both of the oxygen atoms of
the carboxylic group are replaced by sulfur, are also con~
templated. The ratio of the sulfonic acid to the carboxylic
acid in sulfonate-carboxylate mixtures is a~ least 1:1 (on a
chemical equivalent basis) and is usually less than S:l,
preferably from 1:1 to 2:1.
In general, basic salts having metal ratios from
about 1.1 to about 30 are contemplated for use in the present
invention. Those prepared from Mg, Ca, Ba, Li, or Na and
having metal ratios ranging from 2 to 20 are preferred.
The alkoxylated amines (Component C) of the present
invention which comprise alkylene oxide derivatives of ali-
phatic amines. These alkoxylated amines are secondary or
tertiary amines hav.ing one or more groups of the formula
-NRlR2 wherein Rl is ~ alkylene-O ~ H, wherein alkylene
is straight or branched chain and contains up to 6 carbon
atoms and usually 2 to 4 carbon atoms and n is a number of
1 to about 10, and R2 is selected from hydrogen, an alkyl
group of up to about 18 carbon atoms, and Rl. Representative
alkoxylated amines are the ethoxylated amines which are
tertiary amines having one alkyl group and two polyoxyethylene
groups attached to the nitrogen:
~(CH2CH20) xH
R'N
\ (CH2OEI20) yH
wherein R' represents an alkyl group of up to 18 carbon atoms,
x and y are numbers ranging each from 1 to about 8 with the
proviso that the sum of x~y equals at least 2 and not greater
than about 15. The source o the alkyl group R' is preferably
a ~atty acid such as coco, oleic, soya, tallow, or stearic
fatty acids.
Also contemplated as the alkoxylated amine (Component C)
are the ethoxylated amines obtainable by reacting ethylene
oxide with a diamine. For example, N-alkyl trimethylene
diamine can be reacted with ethylene oxide to produce a compound
represented by the following:
(I 2 2 )z / (CH2CH2O)XH
R'-N-CH2OEI2CH2N \
~ (CH2CEI20) yH
wherein R', x, and y are as above described and z is a number
from 1 to 8 with the proviso that the sum of x, y, and z does
not exceed about 15.
-
_ g _
The alkoxylated amines of the present invention arecommercially available products obtainable from varlous
sources. Those marketed under the trade marks ETHOMEEN and
ETHODUOMEEN (made by Armak Co., part of Akzona, InC . ) are
particularly preferred.
Because of their availabilit~v ethylene oxide and
propylene oxide represent the most practical alkylene oxide
reagent for preparing the above alkoxylated amines. ~owever,
butylene oxide, pentene oxide and others can be used, also.
For most efficient use ethylene oxide (to make the
corresponding ethoxylated amine) is preferred.
In preparing the demulsifier additive oE the present
invention Components (A), (B) and (C) are mixed physically to
make up a substantially homogeneous mixture for incorporation
into lubricants or fuels or to make up concentrates for
subsequent addition to lubricants or fuels. Preferredly, the
demulsifier additive is formed in stages whereby Components
(A) and (B) are admixed and heated at about 50-125C for
sufficient time, usually up to about 3 hours. Component (C),
the alkoxylated amine, then is mixed ~ith the above initial
mixture/product of (A) and (B) just prior to preparation of
the concentrate or prior to addit.ion to the lubricant~ Of
course, the three components can be admixed together and
heated at about 50-125C for up to about three hours to
provide the demulsifier additive. While heating at about
50-125C is not essential, it has been found beneficial in
providing optimum demulsifier additives. For best results J
Components (A) and (B) are heated at the prescribed temperature
range with (C) being admixed subsequentl~.
3Q In terms of the lubricant composition the demulsifier
additive comprises from about 0.05 to about 2.0% by
~; ~ - 10 -
~. ~
weight of the total weight of the composition. ~igher amounts
can be added, if desired, but it is believed that amounts
greater than 2~ are not necessary and can contribute to
hi~her costs. Specifically Component (A) can be from about
0.03 to about 1% by weigh~ of the lubricant. Similarly,
Component (B) can be from about 0.01 to about 1% by weight,
and Component (C) can be from about 0.001 to about 1% by
weight, respecti~ely, of the lubricant.
The fuels to which the demulsifier additives of the
invention are added are the normally liquid fuels, such as
gasoline, diesel fuels, jet fuels, fuel oils, alcohols,
alcohol mi~tures, and distillate oils which do not utilize
as much demulsifier additive as do lubricants. Thus, for
effective demulsification of the fuel, usually about 1 ppm
to about 200 ppm (parts per million) of the demulsifier
additive is incorporated into the fuel.
The demulsifier additives of the present invention
generally are soluble or stably dispersible in the normally
liquid lubricant or fuel in which it is intended to func-
tion. Lubricant compositions, by and large, contain lubri-
cating oil as a major proportion. Thus, the demulsifier
should be at least stably dispersible in such lubricating
oils. To function properly the demulsifier need not be oil
soluble. For clarity, the term "oil soluble" as used herein
does not necessarily mean that all of the compositions in
question are miscible or soluble in all proportions in all
oils. Rather, it is intended to mean that the demulsiEier
additive composition herein described is soluble in an oil
which is used for lubricating purposes at the concentrations
described hereinbefore. Similarly, it is not necessary that
such solutions be true solutions in the strict physical or
chemical sense. They may be instead microemulsions or
colloidal dispersions which, for the purposes o~ this inven-
tion, would exhibit properties sufficiently close to those
of true solutions to be for practical purposes nterchange-
able within the context of this invention. Also, the term
"stably dispersible" in the normally li~uid media as used
herein is intended to mean a demulsifier composition which
is capable of being dispersed in a given medium to an
extent which allows it to function as a demulsifier. Thus,
the demulsi~ier additives of the present invention can be
dispersed stably in a lubricating oil and impart to it the
desired demulsifying properties. Such stable dispersion
of the demulsifier can be achieved in various conventional
ways, such as by physical agitationO Other means of sus-
pending and/or dispersing a minor component in a major
liquid component are very well known to those of ordinary
skill in the art, that need not be described herein ~nr
example, conventional dispersants and detergents normally
present in lubricants promote the solubility and/or stable
dispersion of the herein described demulsifier additivesO
This invention is exemplified in the following
examples. Of course, these examples are not intended as
limiting this invention as modification of the examples by
ordinary expedient will be readily apparent to those of
ordinary skill in the art.
In all examples, unless otherwise stated, all tem-
peratures are in degrees Cen-tigrade; all parts are parts by
weight; and all percentages are percentages by weight.
-12-
Example 1
.
A mixture of 133 parts (0.5 mole) of a tetrapro-
penyl substituted succinic anhydride, 375 parts (0.5 mole)
of a commercially available methoxy polyoxyethylene glycol
(Carbowax 750 obtained from Union ~arbide Corp.) having an
average formula molecular weight of about 750, and 200 parts
of toluene is heated to 100C. ~he reaction mixture is held
at 10~-120C. for 8 hours, then stripped at 120C. undex
vacuum for one hour. The reaction mixture is filtered to
yield the filtrate as the desired acid ester product.
Example 2
The procedure for Example 1 is repeated except the
methoxy polyoxyethylene glycol (Carbowax 750) having an
average formula molecular weight of about 750 is replaced on
equimolar basis by one having a formula molecular weigh-t of
350 (Carbowax 350). The filtrate is the desired acid ester
product.
Example 3
A mixture of 347 parts (1.3 moles) of a tetra-
propenyl substituted succinic anhydride and 261 parts (0.65
mole~ of a commercially available polyoxyethylene glycol
(Carbowax 400) having an average formula molecular weight of
about 400 is heated at 120C. for 6 hours. The product is
filtered to yield the filtrate as the desired acid ester
product.
Example 4
A mixture of 4256 parts (32 equivalents) of a
tetrapropenyl substituted succinic anhydride and 2400 parts
~13-
(16 equivalents) of a commercially available polyoxyethylene
glycol (Carbowax 300) having an average formula molecular
weight of about 300 is heated at 120C. for 3 hours. The
residue is the desired ester product.
Example 5
. _ _
The procedure for Example 4 is repeated except the
polyoxyethylene glycol (Carbowax 300) having a formula
molecular weight of about 300 is rep]aced on an equimolar
basis by a polyoxyethylene glycol (Carbowax 200) having a
formula molecular weight of 200. The product is the desired
ester product.
Example 6
The procedure for Example 4 is repeated except
the polyoxyethylene glycol (Carbowax 300) having an average
formula molecular weight of about 300 is replaced on an
equimolar basis by a polyoxyethylene glycol (CarbnTA~a~ lnnn)
having an average formula molecular weight of about 1000.
A similarly desired ester product is obtained~
Example 7
The procedure for Example 3 is repeated except the
polyoxyethylene glycol (Carbowax 400) is replaced on an
equimolar basis by polyoxypropylene glycol having an average
formula molecular weight of about 425. The ester obtained
is the desired ester product.
Example 8
The procedure for Example 3 is repeated except the
polyoxyethylene glycol (Carbowax 400) having an average
-14-
formula molecular weight of about 400 is replaced on an
equimolar basis by a polyoxypropylene glycol having an
average ~ormula molecular weight of about 1000.
Example 9
A mixture of 466 parts (1 equivalent) o~ the acid
ester prepared in Example 4 and 114 parts of a basic mag-
nesium sulfonate commercially available from Witco Chemical
Company, Chicago, Illinois as ~Iybase M-400*Magnesium Sul-
fonate is heated at 120-130C. for 3 hours. The residue
is the desired product.
Example 10
A mixture of 6656 parts (16 equivalents) of the
acid ester product prepared in Example 4 and 2272 parts ~16
equivalents) of a basic magnesium sulfonate commercially
sold by Witco Chemlcal Company as Hybase M-400 Magnesium
Sulfonate is heated at 12~-130C. for 2 hours. The residue
is the desired product.
Example 11
.
A mixture of 4~6 parts (1 equivalent) of the acid
ester product prepared in Example 4 and 28~ parts (2 equi-
valents) of a basic magnesium sulfonate commercially avail-
able from Witco Chemical Company as ~ybase M-~00 Ma~nesium
Sulfonate is heated at 120-130C. for 3 hours. The residue
is the desired product.
Example 12
. _
The procedure for Example 9 is repeated except the
acid ester product of Example ~ is replaced on an equivalent
basis by -the acid ester product of Example 1.
* trade mark
-15-
Example 13
.
The procedure of Example 11 is repeated except the
acid ester product of Example 4 is replaced on an equivalent
basis by the acid ester product of Example 5.
Example 14
A mixture of 331 parts of mineral oil, 69 parts of
heptylphenol, 50 parts of water, 54 parts of a polybutenyl
(Mn = 1000) substituted succinic anhydride, 58 parts of
lithium hydroxide monohydrate and 465 parts of an alkyl
benzene sulfonic acid having a molecular weight of about 330
is heated at reflux for one hour. An additional 150 parts
lithium hydroxide monohydrate is added to the reaction mix-
ture, which is then dried at 150C. At 150-155C. the
reaction mixture is blown with 210 parts (5 equivalents) of
carbon dioxide over a two-hour period. The reaction mixture
is stripped at 155-160C. under nitrogen for one hour. The
reaction mixture is filtered to yield the desired kaclc
lithium sulfonate having 25% lithium sulfate ash.
`~~xample 15
.
A mixture of 416 parts (l equivalent) of the acid
ester product prepared in Example 4 and 261 parts (1 equi-
valent) of the basic lithium sulfonate prepared in Example
14 is heated at 100C. for 3 hours. The residue is the
desired product.
Example 16
The procedure for Example 15 is repeated except
the acid ester product prepared in Example 4 is replaced on
an equivalent basis by the acid ester product of Example 3.
-16-
Example 16A
A mixture is prepared from 200 parts each of poly
ethylene glycol (200), polyethylene glycol (300) and poly-
ethylene glycol (400) and 1000 parts of tetrapropenyl sub-
stituted succinic anhydride, said mix~ure is heated at
120C. for about three hours. The residue is the desired
mixed aeid ester.
To 400 parts of the mixed acid ester prepared in
Example 16A is added 75 parts of basic magnesium sulfonate
(Hybase M-400) and 25 parts of the basic lithium sulfate
prepared in Example 14. The admixture is heated at 100C.
for about 3 hours to yield the desired product.
Example 17
.
A mixture is prepared by the slow addition of 187
parts of-a basic, carbonated calcium sulfonate having a
conversion ratio of 1200 and prepared from a 430 molecular
weight petroleum sulfonic acid according to the procedure
described in U.S. Patent 3,350,308 to 416 parts (1 equiva-
lent) of the acid ester product prepared in Example 4 and
200 parts of mineral oil at 60C. The reaction mixture is
then heated at 110-120C. for 1/2 hour. The residue is the
desired product~
Example 18
A mixture of 51 parts o ~he product prepared
according to the procedure of Example 10 and 39 parts of
Ethomeen C/15 (a product of Armak CoO, part of Akzona~ Inc.)
is heated to 50C. for 1 hour. The residue is the desired
demulsifier product.
-17-
Example 19
-
A mixture of 70 parts of the product prepared
according to the procedure of Example 11 and 70 parts of
Ethoduomeen T/13 (a product of Armak Co.) is heated at 50C.
for 1 hour. The residue is the desired demulsifier product.
Example 20
A mixture of 60 parts of the product prepared
according to the procedure of Example 16 and 40 parts of
Ethomeen C/12 (a product of Armak Co.) is heated at 50C.
for 1 hour. The residue is the desired demulsifier product.
Example 20A
A mixture of 120 parts of the product prepared
in Example 16B and 60 parts of Ethomeen C/12, and 60 parts
of Ethoduomeen T/13 is prepared and heated at 50C. for
1 hour. The product obtained i5 the desired demulsifier
product.
The fuel compositions of the present invention con-
tain a major proportion of a normally liquid fuel, usually
a hydrocarbonaceous petroleum distillate fuel such as motor
gasoline as defined by ASTM Specification D~439-73 and
diesel fuel or fuel oil as defined by ASTM Specification D-
396. Normally liquid fuel compositions comprising non-
hydxocarbonaceous ma~erials such as alcohols, ethers~ organo-
nitro compounds and the like (e.g., methanol, ethanol,
~5 diethyl ether, methyl ethyl ether, nitromethane) are also
within the scope of this 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 ~uels and one or
more non-hydrocarbonaceous materials are also contemplated.
Examples of such mixtures are combinations of gasoline and
ethanol, diesel fuel and ether, etc. Particularly preferred
is gasoline, that is, a mixture of hydrocarbons having an
ASTM boiling point of about 60C. at the 10~ distillation
point to about 205C. at the 90~ distillation point.
Generally, these fuel compositions contain an
amount of the demulsifier additive of this invention suffi-
cient to impart the desired demulsifying properties to the
fuel; usually this amount is about 1 to about 200 preferably
1 to 40 parts by weight of the reaction product per million
parts by weight of fuel. The preferred gasoline-based fuel
compositions generally exhibit e~cellent demulsifying pro-
perties.
The ~uel compositions of this invention can con-
tain, in addition to the demulsifier of this invention,
other additives which are well known to those of skill in
the art. These can include antiknock agents such as tetra-
alkyl lead compounds, lead scavengers such as halo alkanes
~e.g., ethylene dichloride and ethylene dibromide), deposit
preventors or modifiers such as triaryl phosphates, dyes,
cetane im~rovers, antioxidants such as 2,6-di-tertiary-
butyl-4-methylphenol, rust inhibitors such as alkylated
succinic acids and anh~drides, bacteriostatic agents~ gum
inhibitors, metal deactivators, upper c~linder lubricants,
anti-icing agents and the like.
In certain preferred fuel compositions of the
present invention, the afore-described demulsi~ier And
--19--
additives are combined with an ashless dispersant in
gasoline. Such ashless dispersants are preferably esters of
a mono~ or polyol and a high molecular weiyht mono- or pol~-
carboxylic acid acylating agent containing at least 30 carbon
atoms in the acyl moiety. Such esters are well known to
those of skill in the art. See, for example, French Patent
1,396,645, British Patents 981,850 and 1,055,337 and U.S.
Patents 3,255rlO8; 3,311,558; 3,331,776; 3,346,354; 3,522,179;
3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428;
3,708,522; and British Patent Specification 1,306,529. These
patents describe suitable esters and methods for their
preparation. Generally, the weight ratio of the demulsifier of
this invention to the aforesaid ashless dispersants is about
0.1 to about 10.0, preferably about 1 to about 10 parts of
demulsifier to 1 part ashless dispersant. In still another
embodiment of this invention, the inventive additives are
combined with Mannich condensation products formed from
substituted phenols, aldehydes, polyamines, and substituted
pyridines. Such condensation products are described in U.S.
patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and
3,725,277.
As previously indicated, the compositions of this
invention are useEul as additives for lubricants, in which
they function primarily as demulsifier additives. 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
- 20 -
2~
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 trans-
mission fluids, transaxle lubricants, gear lubricants,metal-working lubricants, hydraulic fluids and othex lubri-
cating oil and grease compositions can also benefit from the
incorporation therein of the compositions of the present
invention.
Natural oils include animal oils and vegetable
oils (e.g., castor oil, lard oil) as well as liquid petro-
leum oils and solvent-~reated or acid-treated mineral lubri-
cating oils of the paraffinic, naphthenic or mixed parafinic-
naphthenic types. Oils of lubricating viscosity derived
from coal or shale are also useful base oils. Synthetic
lubricating oils include hydrocarbon oils and halo-substi-
tuted hydrocarbon oils such as polymerized and interpoly-
merized olefins [e.g., polybutylenes, polypropylenes,
propylene isobutylene copolymers, chlorinated polybutylenes,
poly(l-hexenes), poly(l~octenes), poly(l-decenes), etc. and
mixtures thereof]; alkylbenzenes (e.g., dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl~ben~
zenes, etc.); polyphenyls (e.g., biphenyls, terphenyls,
alkylated polyphenyls, etc.3, alkylated diphenyl ethers and
alkylated diphenyl sulfides and the derivatives, analogs and
homologs thereof and the like.
Alkylene oxide polymers and interpolymers and
derivatives ~hereof where the terminal hydroxyl groups have
been modified by esterificakion, etheri~ication, etc~ con-
stltute another class of known synthetic lubricating oils.
-21-
These are exemplified by the oils prepared through poly-
merization 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 C 3-C 8 fatty acid
esters, or the Cl 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating
oils comprises the esters of dicarboxylic acids (e.g.,
phthalic acid, succinic acid, alkyl succinic acids and
alkenyl succinic acids, maleic acid, azelaic acid/ suberic
acid/ sebacic acid, fumaric acid, adipic acld, 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, etc.). Specific examples of these esters include
dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl
fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl
azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
sebacate, the 2-ethylhexyl diester of linoleic acid dimer,
the complex ester formed by reacting one mole of sebacic
acid with two moles of tetraethylene glycol and two moles of
2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those
made from C5 to Cl2 monocarboxylic acids and polyols and
-22-
polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, poly-
aryl-, polyalkoxy-, or polyaryloxy-silo~ane oils and sili-
cate oils comprise another useful class of synthetic lubri-
cants (e.g., tetraethyl silicate, tetraisopropyl silicate,
tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)
silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(~- -
methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanes, poly-
(methylphenyl)siloxanes, etc.). Other synthetic lubricating
oils include liquid esters of phosphorus-containing acids
te.g., tricresyl phosphate, trioctyl phosphate, diethyl
ester of decylphosphonic acid, etc.3, polymeric tetrahydro-
furans and the like.
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 esteri-
fication process ana 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
purification steps to lmprove one or more properties. ~lany
such purification techniques are known to those of skill in
the art such as solvent extraction, acid or base extraction,
filtration, percolation, etc. Rerefined oils ~re o~tained
~y processes similar to those used ~o obtain r~fined oils
-23-
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 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 provide it with the desired demulsifying
properties. Normally this amount will be about .05 to about
2.0~, preferably about 0.1 to about 1.0 of the total weight
of the lubricant. In lubricating oils operated under extremely
adverse conditions, such as lubricating oils for marine
diesel engines, the reaction products of this invention may
be present in amounts of up to about 10% by weight.
The demulsifier of this invention can be added
directly to the fuel or lubricant to form fuel or lubricant
compositions of this invention or they can be diluted with a
substantially inert, normally liquid organic solveriL/di;-uent
such as mineral oil, xylene, or a normally liquid fuel as
described above, to form an additive concentrate which is
then added to the fuel or lubricant in sufficient amounts to
form the inventive fuel or lubricant composition described
herein. These concentrates generally contain up to about
50~ by weight, and preferably from about 2 to 30 percent
of the demulsifier additive of this invention. Moreover,
these concentrates can contain in addition any of the above-
described conventional additives, particularly the afore-
described ashless dispersants in the aforesaid proportions.
The remainder of the concentrate i5 the solvent/diluent.
Lubricating and fuel compositions made according
to this invention are exemplified by the following:
~24-
Example A
The lubricating composition suitable for use as an
automatic transmission fluid, is prepared, using as ~he base
oil a mixture of 90% by volume of a llON mineral oil and 10~
by volume o~ a 200N mineral oil, and as additives, by weight;
4% of a mixed ester of a styrene maleic anhydride copolymer
reacted with a nitrogen-containing compound (prepared as in
U.S. Patent No. 3,702,300); 3.0% of a commercially avail-
able, proprietary seal swell agent; 1% of the reaction
product of a polyisobutenyl-substituted succinic anhydride,
commercial tetraethylene pentamine, and boric acid prepared
as in U.S. Patent No~ 3,25~,025; 0.3% of a commercially
available diphenylamine-based oxidation inhibitor; 0.1% o a
dialkylphosphite; 0.5% of a conventional friction modifier
based on polyoxyethylene tallow amine (Ethomeen T/12); 0.3
of hydroxy thioether as described in U.S. Patent 4,031,023;
3.0% of the reaction product of polyisobutenyl succinic
anhydride and ethylene-polyamine; and as the demulsifier
0.2% of the product of ~xample 10 and 0.05% of Ethomeen
C/15.
Exam~
A lubricating composition suitable for use as an
automatic transmission fluid is prepared using an ATF base
and, as additives, 0.13% of the xeaction product of a
dialkylphosphite and an alkyl alpha-olefin epoxide as
described in U.S. Patent 3,932,290; 1.75% of the reaction
product of a polyisobutenyl succinic anhydride and ethylene
polyamine; 0.67~ of the reaction product of boric acid with
the reaction product of polyisobutenyl succinic anhydride
. -25-
and polyethylene polyaminei 0.52% of a zinc salt of a
phosphorodithioic acid; 0.10~ of a tallow-substituted
diethanol amine; 1.20% of a mixed ester-amide of maleic
anhydride-styrene copolymer ~12% in solution), 3~00% hydro-
carbon resin seal swelling agent; 0.20% substituted di-
phenylamine; 0.02% of a silicone anti-foam agent; and as the
demulsifier 0.25~ of the product of Example 15 and 0.09% of
Ethomeen C/15.
E~ample C
A lubricating composition suitable for use as a
gear lubricant is prepared using an SAE 90 base mineral oil,
and as additives: 2.0% of a dialkylphosphite derived from
Cl4-l~ alcohols; 0~25% of a commercially available aliphatic
primary amine, wherein the aliphatic groups are a mixture of
tertiary alkyl radicals having 11 to 1~ carbon atoms; 0.08%
of a conventional anti-foaming agent based upon a polymer of
2-ethylhexyl acrylate and ethyl acrylate; and 4.1~ of
sulfurized isobutylene; and as a demulsifier 0.7~ of the
product oE Example 11.
Example D
A gasoline having a Reed vapor pressure of 8.4 psi
and containing 2.0 grams of lead per gallon and as additives:
20 ppm of a Mannich base prepared from tetrapropenyl-substi-
tuted phenol, formaldehyde and diethanol amine as in U.S.
Patent No. 3,877,889; 89.6 ppm of the reaction product of
polyisobutenyl (Mn = 1000) succinic anhydride with poly-
ethylene polyamine mixture; 2.9 ppm of an ethoxylated
reaction product o~ oleic-naphthenic acid mixture with
-26-
polyethylene polyamine mixture; 42 ppm i500ctyl alcohol;
118.5 ppm xylene; 3.0 ppm Nalco Proprietary Dehazer Com-
position; and as the demulsifier 4.0 ppm of the product of
Example 20.
Example E
-
A diesel fuel containing 15 parts per million
parts of fuel of the product of Example 11.
Example F
-
A lubricating composition suitable for use as a
crankcase lubricant is prepared using a lOW-~0 mineral
lubricating oil base and, as additives: 5.41% of a poly-
isodecyl acrylate viscosity improver; 4.2~ of an ashless
dispersant based on the reaction product of a polyisobutenyl
(Mn = 1000) succinic anhydride, pentaerythritol, and poly~
ethylene polyamines; 1.57% of an overbased calcium sulfonate
detergent; 0.82~ of a zinc salt of a phosphorodithioic acid;
40 ppm of a conventional anti-foam agent; and as a demul-
sifier 0.25~ of the product of Example 17 and 0.05% of
Ethoduomeen T/13.
Example G
A lubricating composition suitable for use as an
industrial gear lubricant is preparea using a SAE 90 base
mineral lubricating oil, and as additives: 0.5% of a di-
alkylphosphite derived from long-chain alcohols; 0.02% of a
conventional anti-foaming agent based upon a polymer of 2-
ethylhexyl acrylate and ethyl acrylate; 0.25% of a sul-
furized isobutylene; and as a demulsifier 0.04% of the
product of Exampie 12 and 0O01% o~ Ethomeen C/12.
.2~9
Example H
A lubricatin~ composi~ion suitable ~or use as a
marine diesel lubricant is prepared using a SAE 90 base
mineral lubricating oil and 5.7% of an additive concentrate.
The additive concentrate is mineral oil based and comprises
the following additives: 23.44% of the reaction product of
a polybutenyl (Mn = 1000) succinic anhydride, zinc oxide,
and ethylene polyamines as in U.S. RE 26,433; 17.05% of a
calcium overbased sulfurized alkyl phenol; 1.56~ of a zinc
salt of a phosphorodithioic acid; 2.87% mineral oil; 8.2% of
a slightly basic calcium sulfonate; 46.88~ of an overbased
calcium sulfonate detergent; and as a demulsifier 0.9% of
the product of Example 19.
Example I
A lubricating composition suitable for use as a
crankcase lubricant is prepared using a lOW-40 mineral
lubricating oil base and, as additives: 5.41% of a poly-
isodecyl acrylate viscosity improver; 4.2% of an ashless
dispersant based on the reaction product of a polyisobutenyl
(Mn = 1000) succinic anhydride, pentaerythritol, and poly-
ethylene polyamines; 1.57% o an overbased calcium sulfonate
deter~ent; 0.82% of a zinc salt of a phosphorodithioic acid;
40 ppm of a conventional anti foam agent; and as a demul-
sifier 0.30% of the product of Example 20A.
To determine the efectiveness of the demulsifier
additive in the exemplified lubricants and fuels, the stan-
dard method for "Demulsibility Characteristics o Lubri-
cating Oils" as described in ANSI/ASTM D2711-74 is followed~
-28
Modification in terms of liquid and/or demulsifier quan-
tities have been made to provide more meaningful data for
certain lubricants or fuels. In particular, 200 ml of the
test fluid is utilized, which fluid is placed into a blender
at room temperature. The blender is operated at low speed
for 30 seconds after which 20 mls. of distilled water is
added and mixed for one more minute. ~he mixture is poured
into 400 ml. beaker, covered and placed into an oven at 160
~ 2F. Extent and rate of separation of water and oil, as
well as the interface (cuff) is observed at 2 and 4 hour
intervals.
In the foregoing examples the lubricants and fuels
containing the demulsifier additive have shown excellent de-
mulsifying properties. Automatic transmission fluids con-
taining about 0.1 to about 1~ of the demulsifier of theinvention can be expected for use in factory filled opera-
tions with minimal filtering and centrifuging to remove the
included water. Thus, the demulsified fluids provide con-
venience and economy unavailable heretofore.
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