Basic alkali metal sulfonate dispersions, process for their preparation, and lubricants containing same

Solutions or substantially stable dispersions of basic alkali metal sulfonates in an inert organic diluent are prepared by intimately contacting an acidic gaseous material such as carbon dioxide with a reaction mixture comprising a sulfonic acid, an alkali metal, an alcohol and a carboxylic acid. The products are useful as additives for lubricants and fuels.

This invention relates to new compositions of matter, a method for their 
preparation, and lubricants and fuels containing them. The invention may 
be briefly characterized as a stable oil-soluble dispersion of basic 
alkali metal sulfonates having metal ratios of at least about 4 prepared 
by the process which comprises intimately contacting for a period of time 
sufficient to form the desired dispersion, at a temperature between the 
solidification temperature of the reaction mixture and its decomposition 
temperature: 
(A) At least one acidic gaseous material selected from the group consisting 
of carbon dioxide, hydrogen sulfide, sulfur dioxide, and mixtures thereof, 
with 
(B) A reaction mixture comprising 
(i) at least one oil-soluble sulfonic acid, or derivative thereof 
susceptible to overbasing; 
(ii) at least one alkali metal or basic alkali metal compound; 
(iii) at least one lower aliphatic alcohol; and 
(iv) at least one oil-soluble carboxylic acid or functional derivative 
thereof. 
Solutions and/or substantially stable dispersions of basic metal-containing 
compositions, and various methods for their preparation, are well known in 
the art. They are variously referred to by such names as "basic", 
"complex", "superbased" and "overbased" salts, and the method for their 
preparation is commonly referred to as "overbasing". 
The chief property these basic salts have in common is that they contain 
metal in amounts that are in excess, frequently substantially in excess, 
of those equivalent to the organic anion. The term "metal ratio" is often 
used to define the quantity of metal in these basic salts relative to the 
quantity of organic anion, and is defined herein as the ratio of the 
number of equivalents of metal to the number of equivalents thereof which 
would be present in a normal salt based upon the usual stoichiometry of 
the compounds involved. 
These basic salts are known to be useful as detergents and corrosion 
inhibitors in lubricants, particularly those used in internal combustion 
engines, and as smoke suppressants and anti-screen clogging agents for 
petroleum distillate fuels, especially diesel fuels. The basic salts and 
their utility in lubricants and fuels are described in a number of U.S. 
Pat. Nos. including the following: 
______________________________________ 
2,616,905 
3,312,618 
2,723,234 
3,342,733 
2,777,874 
3,410,670 
2,781,403 
3,410,671 
3,031,284 
3,437,465 
3,256,186 
______________________________________ 
These patents are incorporated by reference herein for their disclosures of 
basic metal salts and their use in lubricants and fuels. Also incorporated 
herein for the same purpose is German published application 1,243,915. 
Most of the basic metal salts heretofore produced and used in lubricants 
and fuels have been alkaline earth metal salts, especially those of 
magnesium, calcium and barium. A few patents have suggested that basic 
alkali metal salts can be produced by similar methods. On the whole, 
however, there have been few adequately described procedures for producing 
basic alkali metal salts, and such salts have heretofore not been a major 
factor in the industry because of their relative unavailability. 
The increasing complexity of engines and other units in automotive and 
similar machinery in recent years has materially increased the demands 
made on lubricants and fuels used therein. It is now desirable that 
additives be developed which, in addition to providing detergency and 
other valuable properties, will impart such advantages as suppression of 
oil thickening, reduction of oil consumption and preignition, improvement 
of rust inhibition, and suppression of tendency to stain copper parts and 
to deposit "lead paint"--that is, a thin film of finely divided 
lead-containing material from the lead additives in the fuel--on engine 
parts. 
A principal object of the present invention, therefore, is to produce novel 
compositions of matter. 
A further object is to provide a novel process for the preparation of such 
compositions. 
A further object is to produce new basic alkali metal salt-containing 
compositions which are useful as detergent additives in lubricants and as 
anti-screen clogging and smoke suppressing additives in fuels. 
A still further object is to prepare lubricant additives as described above 
in the form of clear, filterable, homogeneous solutions or substantially 
stable dispersions of basic alkali metal salts in such organic media as 
lubricating oils and normally liquid fuels. 
Still another object is to produce such compositions which, in addition to 
providing detergency when used in lubricants, will inhibit rust formation, 
reduce oil thickening and oil consumption, and inhibit staining of copper 
and "lead paint" formation. 
Other objects will in part be obvious and will in part appear hereinafter. 
The present invention is based on the discovery that basic alkali metal 
salts having the above-described advantageous properties may be prepared 
by a specific method set forth in full hereinafter. The metal ratios of 
the basic salts of this invention are in the range of about 4-40, 
preferably about 6-30 and especially about 8-25. 
Reactant A used in the method of this invention is at least one acidic 
gaseous material which may be carbon dioxide, hydrogen sulfide or sulfur 
dioxide; mixtures of these gases are also useful. Carbon dioxide is 
preferred because of its relatively low cost, availability, ease of use 
and performance. 
Reactant B is a mixture containing at least four components of which 
component (i) is at least one oil-soluble sulfonic acid, or a derivative 
thereof susceptible to overbasing. Mixtures of sulfonic acids and/or their 
derivatives may also be used, but for the sake of simplicity, frequent 
reference hereinafter will be to the individual sulfonic acids and 
derivatives which exemplify those which are useful. They may typically be 
represented by the formulas R.sup.1 (SO.sub.3 H).sub.r and (R.sup.2).sub.x 
T(SO.sub.3 H) .sub.y. In these formulas, R.sup.1 is an aliphatic or 
aliphatic-substituted cycloaliphatic hydrocarbon or essentially 
hydrocarbon radical free from acetylenic unsaturation and containing up to 
about 60 carbon atoms. When R.sup.1 is aliphatic, it usually contains at 
least about 15-18 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.sup.1 are alkyl, alkenyl 
and alkoxyalkyl 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 cycloalkene such as 
cyclopentane, cyclohexane, cyclohexene or cyclopentene. Specific examples 
of R.sup.1 are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, 
octadecenyl, and radicals derived from petroleum, saturated and 
unsaturated paraffin wax, and olefin polymers including polymerized 
monoolefins and diolefins containing about 1-8 carbon atoms per olefinic 
monomer unit. R.sup.1 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 
aliphatic character thereof is not destroyed. 
R.sup.2 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 essentially hydrocarbon 
character thereof is retained. In general, the non-carbon atoms present in 
R.sup.1 or R.sup.2 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, naphthalene, 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 (i) are mahogany sulfonic 
acids, petrolatum sulfonic acids, mono- and polywax-substituted 
naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol 
sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxycapryl benzene 
sulfonic acids, dicetyl thianthrene sulfonic acids, di-lauryl 
beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic acids, 
paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, 
hydroxy-substituted paraffin wax sulfonic acids, tetraisobutylene sulfonic 
acids, tetraamylene sulfonic acids, chloro-substituted paraffin wax 
sulfonic acids, nitroso-substituted paraffin wax sulfonic acids, petroleum 
naphthene sulfonic acids, cetylcyclopentyl 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. 
Sulfonic acid derivatives susceptible to overbasing include their metal 
salts, especially the alkaline earth, zinc and lead salts; ammonium salts 
and amine salts (e.g., the ethylamine, butylamine and ethylene polyamine 
salts); and esters such as the ethyl, butyl, and glycerol esters. 
For the purpose of this invention, the equivalent weight of a sulfonic acid 
or derivative thereof is its molecular weight divided by the number of 
sulfonic acid groups or sulfonic acid derivative groups present therein. 
Thus, for a monosulfonic acid the equivalent weight is equal to the 
molecular weight. 
Component (ii) is at least one alkali metal selected from sodium and 
potassium or basic compounds thereof. Of the two alkali metals sodium 
and/or its compounds are preferred. Illustrative of basic alkali metal 
compounds are the hydroxides, alkoxides (typically those in which the 
alkoxy group contains up to 10 and preferably up to 7 carbon atoms), 
hydrides and amides. Thus, useful basic alkali metal compounds include 
sodium hydroxide, potassium hydroxide, sodium propoxide, potassium 
ethoxide, sodium butoxide, sodium hydride, potassium hydride, sodium amide 
and potassium amide. Especially preferred are sodium hydroxide and the 
sodium lower alkoxides (i.e., those containing up to 7 carbon atoms). The 
equivalent weight of component (ii) for the purpose of this invention is 
equal to its molecular weight, since the alkali metals are monovalent. 
Component (iii) is at least one lower aliphatic alcohol, preferably a 
monohydric or dihydric alcohol. Illustrative alcohols are methanol, 
ethanol, 1-propanol, 1-hexanol, isopropanol, isobutanol, 2-pentanol, 
2,2-dimethyl-1-propanol, ethylene glycol, 1-3-propanediol and 
1,5-pentanediol. Of these, the preferred alcohols are methanol, ethanol 
and propanol, with methanol being especially preferred. The equivalent 
weight of component (iii) is its molecular weight divided by the number of 
hydroxy groups per molecule. 
Component (iv) is at least one oil-soluble carboxylic acid or functional 
derivative thereof. Suitable carboxylic acids are those of the formula 
R.sup.3 (COOH).sub.n, wherein n is an integer from 1 to 6 and 
is.preferably 1 or 2 and R.sup.3 is a saturated or substantially saturated 
aliphatic radical (preferably a hydrocarbon radical) having at least 8 
aliphatic carbon atoms. Depending upon the value of n, R.sup.3 will be a 
monovalent to hexavalent radical. 
Functional derivatives of the acid useful as component (iv) include the 
anhydrides, esters, amides, imides, amidines and metal salts. Mixtures of 
the acids and/or functional derivatives are also useful. 
R.sup.3 may contain non-hydrocarbon substituents provided they do not alter 
substantially its hydrocarbon character. Such substituents are preferably 
present in amounts of not more than about 10% by weight. Exemplary 
substituents include the non-hydrocarbon substituents enumerated 
hereinabove with reference to component (i). R.sup.3 may also contain 
olefinic unsaturation up to a maximum of about 5% and preferably not more 
than 2% olefinic linkages based upon the total number of carbon-to-carbon 
covalent linkages present. The number of carbon atoms in R.sup.3 is 
usually about 8-700 depending upon the source of R.sup.3. As discussed 
below, a preferred series of carboxylic acids and derivatives is prepared 
by reacting an olefin polymer or halogenated olefin polymer with an 
.alpha.,.beta.-unsaturated acid or its anhydride such as acrylic, 
methacrylic, maleic or fumaric acid or maleic anhydride to form the 
corresponding substituted acid or derivative thereof. The R.sup.3 groups 
in these products have a number average molecular weight in the range of 
about 150-10,000 and usually about 700-5000. 
The monocarboxylic acids useful as component (iv) have the formula R.sup.3 
COOH. Examples of such acids are caprylic, capric, palmitic, stearic, 
isostearic, linoleic and behenic acids. A particularly preferred group of 
monocarboxylic acids is prepared by the reaction of a halogenated olefin 
polymer, such as a chlorinated polybutene, with acrylic acid or 
methacrylic acid. 
Suitable dicarboxylic acids include the substituted succinic acids having 
the formula 
##STR1## 
wherein R.sup.4 is the same as R.sup.3 as defined above. R.sup.4 may be an 
olefin polymer-derived group formed by polymerization of such monomers as 
ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-pentene, 1-hexene 
and 3-hexene. R.sup.4 may also be derived from a high molecular weight 
substantially saturated petroleum fraction. The hydrocarbon-substituted 
succinic acids and their derivatives constitute the most preferred class 
of carboxylic acids for use as component (iv). 
The above-described classes of carboxylic acids derived from olefin 
polymers, and their derivatives, are well known in the art, and methods 
for their preparation as well as representative examples of the types 
useful in the present invention are described in detail in the following 
U.S. Pat. Nos. 
______________________________________ 
3,172,892 3,316,771 
3,522,179 
3,216,936 3,373,111 
3,542,678 
3,219,666 3,381,022 
3,542,680 
3,271,310 3,341,542 
3,579,450 
3,272,746 3,344,170 
3,632,510 
3,278,550 3,448,048 
3,632,511 
3,281,428 3,454,607 
3,639,242 
3,306,908 3,515,669 
______________________________________ 
Some of the functional derivatives of the above-discussed acids useful as 
component (iv) are the amides, esters and salts. The reaction products of 
olefin polymer-substituted succinic acids and mono- or polyamines, 
particularly polyalkylene polyamines, having up to about ten amino 
nitrogens are especially suitable. These reaction products generally 
comprise mixtures of one or more of amides, imides and amidines. The 
reaction products of polyethylene amines containing up to about 10 
nitrogen atoms and polybutene-substituted succinic anhydride wherein the 
polybutene radical comprises principally isobutene units are particularly 
useful. These products are disclosed and exemplified in U.S. Pat. Nos. 
3,018,250; 3,024,195; 3,172,892; 3,216,936; 3,219,666; and 3,272,746. 
Included in this group of functional derivatives are the compositions 
prepared by post-treating the amine-anhydride reaction product with carbon 
disulfide, boron compounds, nitriles, urea, thiourea, guanidine, alkylene 
oxides or the like as disclosed and exemplified in U.S. Pat. Nos. 
3,200,107; 3,256,185; 3,087,936; 3,254,025; 3,281,428; 3,278,550; 
3,312,619; and British Specification 1,053,577. The half-amide, half-metal 
salt and half-ester, half-metal salt derivatives of such substituted 
succinic acids are also useful. These products are disclosed in U.S. Pat. 
Nos. 3,163,603 and 3,522,179. 
Also useful are the esters prepared by the reaction of the substituted 
acids or anhydrides with a mono- or polyhydroxy compound, such as an 
aliphatic alcohol or a phenol. Typical esters of this type are disclosed 
in British Specification 981,850 and U.S. Pat. Nos. 3,311,558 and 
3,522,179. Preferred are the esters of olefin polymer-substituted succinic 
acids or anhydrides and polyhydric aliphatic alcohols containing 2-10 
hydroxy groups and up to about 40 aliphatic carbon atoms. This class of 
alcohols includes ethylene glycol, glycerol, sorbitol, pentaerythritol, 
polyethylene glycol, diethanolamine, triethanolamine, 
N,N'-di(hydroxyethyl)ethylene diamine and the like. When the alcohol 
contains reactive amino groups, the reaction product may comprise products 
resulting from the reaction of the acid group with both the hydroxy and 
amino functions. Thus, this reaction mixture can include half-esters, 
half-amides, esters, amides, and imides, as disclosed in U.S. Pat. No. 
3,324,033. 
Suitable monocarboxylic acid derivatives and methods for their preparation 
are disclosed in detail in British Patent Specification 1,075,121 and U.S. 
Pat. Nos. 3,272,746; 3,340,281; 3,341,542; and 3,342,733. 
The foregoing U.S. patents and foreign specifications are incorporated 
herein by reference for their disclosures of suitable acids and 
acid-derivatives and the process for their preparation. 
The equivalent weight of a compound useful as component (iv) is its 
molecular weight divided by the number of carboxy groups (or groups 
derived therefrom) present therein. 
The ratios of equivalents of the constituents of reagent B may vary widely. 
In general, the ratio of component (ii) to (i) is at least 4:1 and usually 
not more than about 40:1, preferably between 6:1 and 30:1 and most 
preferably between 8:1 and 25:1. While this ratio may sometimes exceed 
40:1, such an excess normally will serve no useful purpose. 
The ratio of equivalents of component (iii) to component (i) is between 
about 1:1 and 80:1, and preferably between about 2:1 and 50:1; and the 
ratio of equivalents of component (iv) to component (i) is from about 1:1 
to about 1:20 and preferably from about 1:2 to about 1:10. 
Reagents A and B are generally contacted until there is no further reaction 
between the two or until the reaction substantially ceases. While it is 
usually preferred that the reaction be continued until no further 
overbased product is formed, useful dispersions within the scope of this 
invention can be prepared when contact between reagents A and B is 
maintained for a period of time sufficient for about 70% of reagent A, 
relative to the amount required if the reaction were permitted to proceed 
to its completion or "end point", to react. 
The point at which the reaction is completed or substantially ceases may be 
ascertained by any of a number of conventional methods. One such method is 
measurement of the amount of gas (reagent A) entering and leaving the 
mixture; the reaction may be considered substantially complete when the 
amount leaving is about 90-100% of the amount entering. These amounts are 
readily determined by the use of metered inlet and outlet valves. 
The reaction temperature is not critical. Generally, it will be between the 
solidification temperature of the reaction mixture and its decomposition 
temperature (i.e., the lowest decomposition temperature of any component 
thereof). Usually, the temperature will be 25.degree.-200.degree. C. and 
preferably about 50.degree.-150.degree. C. Reagents A and B are 
conveniently contacted at the reflux temperature of the mixture. This 
temperature will obviously depend upon the boiling points of the various 
components; thus, when methanol is used as component (iii), the contact 
temperature will be about the reflux temperature of methanol. 
The reaction is ordinarily conducted at atmospheric pressure, although 
superatmospheric pressure often expedites the reaction and aromotes 
optimum utilization of reagent A. The process can also be carried out at 
reduced pressure but, for obvious practical reasons, this is rarely done. 
The reaction is usually conducted in the presence of a substantially inert, 
normally liquid organic diluent, which functions as both the dispersing 
and reaction medium. This diluent will comprise at least about 10% of the 
total weight of the reaction mixture. Ordinarily it will not exceed about 
80% by weight, and it is preferably about 30-70% thereof. 
Although a wide variety of diluents are useful, it is preferred to use a 
diluent which is soluble in lubricating oil or normally liquid fuel, 
particularly when the product is to be used as an additive in a lubricant 
or fuel. The diluent usually itself comprises a low viscosity lubricating 
oil or a normally liquid petroleum distillate fuel. 
Other organic diluents can be employed either alone or in combination with 
the lubricating oil or liquid fuel diluent. Preferred diluents for this 
purpose include the aromatic hydrocarbons such as benzene, toluene and 
xylene; halogenated derivatives thereof such as chlorobenzene; lower 
boiling petroleum distillates such as petroleum ether and the various 
naphthas; normally liquid aliphatic and cycloaliphatic hydrocarbons such 
as hexane, heptane, hexene, cyclohexene, cyclopentane, cyclohexane and 
ethylcyclohexane, and their halogenated derivatives. Dialkyl ketones such 
as dipropyl ketone and ethyl butyl ketone, and the alkyl aryl ketones such 
as acetophenone, are likewise useful, as are ethers such as n-propyl 
ether, n-butyl ether, n-butyl methyl ether and isoamyl ether. 
When a combination of oil and other diluent is used, the weight ratio of 
oil to the other diluent is generally from about 1:20 to 20:1. It is 
usually desirable for a mineral lubricating oil to comprise at least about 
50% by weight of the diluent, especially if the product is to be used as a 
lubricant additive. The total amount of diluent present is not 
particularly critical since it is inactive. However, the diluent will 
ordinarily comprise about 10-80% and preferably about 30-70% by weight of 
the reaction mixture. 
The reaction is preferably conducted in the absence of water, although 
small amounts may be present (e.g., those through the use of technical 
grade reagents). Water may be present in amounts up to about 10% by weight 
of the reaction mixture without having harmful effects. 
Upon completion of the reaction, any solids in the mixture are preferably 
removed by filtration or other conventional means. Optionally, readily 
removable diluents, the alcoholic promoters, and water formed during the 
reaction can be removed by conventional techniques such as distillation. 
It is usually desirable to remove substantially all water from the 
reaction mixture since the presence of water may lead to difficulties in 
filtration and to the formation of undesirable emulsions in fuels and 
lubricants. Any such water present is readily removed by heating at 
atmospheric or reduced pressure or by azeotropic distillation. 
The chemical structure of the compositions of this invention is not known 
with certainty. The basic salts may be solutions or, more likely, stable 
dispersions. Alternatively, they may be regarded as "polymeric salts" 
formed by the reaction of the acidic material, the oil-soluble acid being 
overbased, and the metal compound. In view of the above, these 
compositions are most conveniently defined by reference to the method by 
which they are formed.

The oil stable dispersions and the method of preparing them are illustrated 
by the following examples. Unless otherwise indicated, all parts and 
percentages are by weight. 
EXAMPLE 1 
To a solution of 790 parts (1 equivalent) of an alkylated benzenesulfonic 
acid and 71 parts of polybutenyl succinic anhydride (equivalent weight 
about 560) containing predominantly isobutene units in 176 parts of 
mineral oil is added 320 parts (8 equivalents) of sodium hydroxide and 640 
parts (20 equivalents) of methanol. The temperature of the mixture 
increases to 89.degree. C. (reflux) over 10 minutes due to exotherming. 
During this period, the mixture is blown with carbon dioxide at 4 cfh. 
(cubic feet/hr.). Carbonation is continued for about 30 minutes as the 
temperature gradually decreases to 74.degree. C. The methanol and other 
volatile materials are stripped from the carbonated mixture by blowing 
nitrogen through it at 2 cfh. while the temperature is slowly increased to 
150.degree. C. over 90 minutes. After stripping is completed, the 
remaining mixture is held at 155.degree.-165.degree. C. for about 30 
minutes and filtered to yield an oil solution of the desired basic sodium 
sulfonate having a metal ratio of about 7.75. This solution contains 12.4% 
oil. 
EXAMPLE 2 
Following the procedure of Example 1, a solution of 780 parts (1 
equivalent) of an alkylated benzenesulfonic acid and 119 parts of the 
polybutenyl succinic anhydride in 442 parts of mineral oil is mixed with 
800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 
equivalents) of methanol. The mixture is blown with carbon dioxide at 7 
cfh. for 11 minutes as the temperature slowly increases to 97.degree. C. 
The rate of carbon dioxide flow is reduced to 6 cfh. and the temperature 
decreases slowly to 88.degree. C. over about 40 minutes. The rate of 
carbon dioxide flow is reduced to 5 cfh. for about 35 minutes and the 
temperature slowly decreases to 73.degree. C. The volatile materials are 
stripped by blowing nitrogen through the carbonated mixture at 2 cfh. for 
105 minutes as the temperature is slowly increased to 160.degree. C. After 
stripping is completed, the mixture is held at 160.degree. C. for an 
additional 45 minutes and then filtered to yield an oil solution of the 
desired basic sodium sulfonate having a metal ratio of about 19.75. This 
solution contains 18.7% oil. 
EXAMPLE 3 
Following the procedure of Example 1, a solution of 3120 parts (4 
equivalents) of an alkylated benzenesulfonic acid and 284 parts of 
polybutenyl succinic anhydride in 704 parts of mineral oil is mixed with 
1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 
equivalents) of methanol. This mixture is blown with carbon dioxide at 10 
cfh. for about 65 minutes. During this time, the temperature of the 
mixture increases to 90.degree. C. and then slowly decreases to 70.degree. 
C. The volatile material is stripped by blowing with nitrogen at 2 cfh. 
for 2 hours as the temperature of the mixture is slowly increased to 
160.degree. C. After stripping is complete, the mixture is held at 
160.degree. C. for 0.5 hour, and then filtered to yield a clear oil 
solution of the desired sodium salt having a metal ratio of 7.75. This 
solution has a 12.35% oil content. 
EXAMPLE 4 
Following the procedure of Example 1, a solution of 3200 parts (4 
equivalents) of an alkylated benzenesulfonic acid and 284 parts of the 
polybutenyl succinic anhydride in 623 parts of mineral oil is mixed with 
1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 
equivalents) of methanol. The mixture is blown with carbon dioxide at 10 
cfh. for about 77 minutes. During this time the temperature increases to 
92.degree. C. and then gradually drops to 73.degree. C. The volatile 
materials are stripped by blowing with nitrogen gas at 2 cfh. for about 2 
hours as the temperature of the reaction mixture is slowly increased to 
160.degree. C. The final traces of volatile material are vacuum stripped 
and the residue is held at 170.degree. C. and then filtered to yield a 
clear oil solution of the desired sodium salt, having a metal ratio of 
about 7.72. This solution has an oil content of 11%. 
EXAMPLE 5 
Following the procedure of Example 1, a solution of 780 parts (1 
equivalent) of an alkylated benzenesulfonic acid and 86 parts of the 
polybutenyl succinic anhydride in 254 parts of mineral oil is mixed with 
480 parts (12 equivalents) of sodium hydroxide and 640 parts (20 
equivalents) of methanol. The reaction mixture is blown with carbon 
dioxide at 6 cfh. for about 45 minutes. During this time the temperature 
increases to 95.degree. C. and then gradually decreases to 74.degree. C. 
The volatile material is stripped by blowing with nitrogen gas at 2 cfh. 
for about one hour as the temperature is increased to 160.degree. C. After 
stripping is complete the mixture is held at 160.degree. C. for 0.5 hour 
and then filtered to yield an oil solution of the desired sodium salt, 
having a metal ratio of 11.8. The oil content of this solution is 14.7%. 
EXAMPLE 6 
Following the procedure of Example 1, a solution of 3120 parts (4.0 
equivalents) of an alkylated benzenesulfonic acid and 344 parts of the 
polybutenyl succinic anhydride in 1016 parts of mineral oil is mixed with 
1920 parts (48 equivalents) of sodium hydroxide and 2560 parts (80 
equivalents) of methanol. The mixture is blown with carbon dioxide for 
about two hours at 10 cfh. During this period the temperature increases to 
96.degree. C. and then gradually drops to 74.degree. C. The volatile 
materials are stripped by blowing with nitrogen at 2 cfh. for two hours as 
the temperature is increased from 74.degree. C. to 160.degree. C. by 
external heating. The stripped mixture is heated for an additional hour at 
160.degree. C. and filtered. The filtrate is vacuum stripped to remove a 
small amount of water, and again filtered to give a solution of the 
desired sodium salt, having a metal ratio of about 11.8. The oil content 
of this.solution is 14.7%. 
EXAMPLE 7 
Following the procedure of Example 1, a solution of 2800 parts (3.5 
equivalents) of an alkylated benzenesulfonic acid and 302 parts of the 
polybutenyl succinic anhydride in 818 parts of mineral oil is mixed with 
1680 parts (42 equivalents) of sodium hydroxide and 2240 parts (70 
equivalents) of methanol. The mixture is blown with carbon dioxide for 
about 90 minutes at 10 cfh. During this period, the temperature increases 
to 96.degree. C. and then slowly drops to 76.degree. C. The volatile 
materials are stripped by blowing with nitrogen at 2 cfh. as the 
temperature is slowly increased from 76.degree. C. to 165.degree. C. by 
external heating. Water is removed by vacuum stripping. Upon filtration, 
an oil solution of the desired basic sodium salt is obtained. It has a 
metal ratio of about 10.8 and the oil content is 13.6%. 
EXAMPLE 8 
Following the procedure of Example 1, a solution of 780 parts (1.0 
equivalent) of an alkylated benzenesulfonic acid and 103 parts of the 
polybutenyl succinic anhydride in 350 parts of mineral oil is mixed with 
640 parts (16 equivalents of sodium hydroxide and 640 parts (20 
equivalents) of methanol. This mixture is blown with carbon dioxide for 
about one hour at 6 cfh. During this period, the temperature increases to 
95.degree. C. and then gradually decreases to 75.degree. C. The volatile 
material is stripped by blowing with nitrogen. During stripping, the 
temperature initially drops to 70.degree. C. over 30 minutes and then 
slowly rises to 78.degree. C. over 15 minutes. The mixture is then heated 
to 155.degree. C. over 80 minutes. The stripped mixture is heated for an 
additional 30 minutes at 155.degree.-160.degree. C. and filtered. The 
filtrate is an oil solution of the desired basic sodium sulfonate, having 
a metal ratio of about 15.2. It has an oil content of 17.1%. 
EXAMPLE 9 
Following the procedure of Example 1, a solution of 2400 parts (3.0 
equivalents) of an alkylated benzenesulfonic acid and 308 parts of the 
polybutenyl succinic anhydride in 991 parts of mineral oil is mixed with 
1920 parts (48 equivalents) of sodium hydroxide and 1920 parts (60 
equivalents) of methanol. The mixture is blown with carbon dioxide at 10 
cfh. for 110 minutes, during which time the temperature rises to 
98.degree. C. and then slowly decreases to 76.degree. C. over about 95 
minutes. The methanol and water are stripped by blowing with nitrogen at 2 
cfh. as the temperature of the mixture slowly increases to 165.degree. C. 
The last traces of volatile material are vacuum stripped and the residue 
is filtered to yield an oil solution of the desired sodium salt having a 
metal ratio of 15.1. The solution has an oil content of 16.1%. 
EXAMPLE 10 
Following the procedure of Example 1, a solution of 780 parts (1 
equivalent) of an alkylated benzenesulfonic acid and 119 parts of the 
polybutenyl succinic anhydride in 442 parts of mineral oil is mixed well 
with 800 parts (20 equivalents) of sodium hydroxide and 640 parts (20 
equivalents) of methanol. This mixture is blown with carbon dioxide for 
about 55 minutes at 8 cfh. During this period, the temperature of the 
mixture increases to 95.degree. C. and then slowly decreases to 67.degree. 
C. The methanol and water are stripped by blowing with nitrogen at 2 cfh. 
for about 40 minutes while the temperature is slowly increased to 
160.degree. C. After stripping, the temperature of the mixture is 
maintained at 160.degree.-165.degree. C. for about 30 minutes. The product 
is then filtered to give a solution of the corresponding sodium sulfonate 
having a metal ratio of about 16.8. This solution contains 18.7% oil. 
EXAMPLE 11 
Following the procedure of Example 1, 836 parts (1 equivalent) of a sodium 
petroleum sulfonate (sodium "Petronate") in an oil solution containing 48% 
oil and 63 parts of the polybutenyl succinic anhydride is heated to 
60.degree. C. and treated with 280 parts (7.0 equivalents) of sodium 
hydroxide and 320 parts (10 equivalents) of methanol. The reaction mixture 
is blown with carbon dioxide at 4 cfh. for about 45 minutes. During this 
time, the temperature increases to 85.degree. C. and then slowly decreases 
to 74.degree. C. The volatile material is stripped by blowing with 
nitrogen at 2 cfh. while the temperature is gradually increased to 
160.degree. C. After stripping is completed, the mixture is heated an 
additional 30 minutes at 160.degree. C., and then is filtered to yield the 
sodium salt in solution. The product has a metal ratio of 8.0 and an oil 
content of 22.2%. 
EXAMPLE 12 
Following the procedure of Example 11, 1256 parts (1.5 equivalents) of the 
sodium petroleum sulfonate in an oil solution containing 48% oil and 95 
parts of polybutenyl succinic anhydride is heated to 60.degree. C. and 
treated with 420 parts (10.5 equivalents) of sodium hydroxide and 960 
parts (30 equivalents) of methanol. The mixture is blown with carbon 
dioxide at 4 cfh. for 60 minutes. During this time, the temperature is 
increased to 90.degree. C. and then slowly decreases to 70.degree. C. The 
volatile materials are stripped by blowing with nitrogen and slowly 
increasing the temperature to 160.degree. C. After stripping, the reaction 
mixture is allowed to stand at 160.degree. C. for 30 minutes and then is 
filtered to yield an oil solution of sodium sulfonate having a metal ratio 
of about 8.0. The oil content of the solution is 22.2%. 
As previously indicated, the dispersions of this invention are principally 
useful as additives for lubricants, in which they function primarily as 
detergents. When used as such in crankcase lubricants, for example, they 
promote engine cleanliness and reduce wear by neutralizing acidic 
contaminants such as those formed by oxidation of the oil components or 
during combustion. These acidic contaminants, if not neutralized, will 
lead to increased engine wear and the formation of lacquer on engine 
parts. The dispersions of this invention also disperse insoluble materials 
formed in lubricants as a result of fuel combustion or oil oxidation, and 
accordingly reduce sludge formation. 
Additional beneficial properties imparted to lubricants by the dispersions 
of this invention are inhibition of rust and "lead paint" formation and 
staining, reduction of oil thickening and oil consumption, and reduction 
of the preignition tendency in gasoline engines. Reduction of oil 
consumption and preignition may be effected by replacing conventional 
basic alkaline earth metal salt dispersions by the present dispersions in 
full or in part. 
The dispersions of this invention 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 
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 petroleum oils 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 copolymers, chlorinated 
polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), etc. and 
mixtures thereof]; alkylbenzenes (e.g., dodecylbenzenes, 
tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.); 
polyphenyls (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 derivatives 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 C.sub.3 -C.sub.8 fatty acid esters, or the C.sub.13 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 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, 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 C.sub.5 to 
C.sub.12 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-(2ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) 
silicate, tetra-(p-tert-butylphenyl) silicate, 
hexa-(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 decylphosphonic acid, 
etc.), polymeric tetrahydrofurans and the like. 
Unrefined, refined and rerefined oils (and mixtures of each with each 
other) of the type disclosed hereinabove can be used 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 esterification 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 
purification steps to improve one or more properties. Many such 
purification techniques are known to those of skill in the art such as 
solvent extraction, acid or base extraction, filtration, percolation, etc. 
Rerefined oils are obtained by processes similar to those used to obtain 
refined oils applied to refined oils which have been already used in 
service. Such rerefined oils are also known as reclaimed or reprocessed 
oils and often are additionally processed by techniques 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 
advantageous properties mentioned hereinabove, especially detergency. 
Normally this amount will be about 0.001-30% by weight. Most often, an 
amount is used to provide a sulfate ash content in the lubricant of about 
0.01-20%, preferably about 0.1-10%. If the lubricant is for use in the 
crankcase of a gasoline engine, it will normally contain about 1% ash. For 
diesel engines about 0.1-5% ash is required, and in marine diesel engines 
at least about 10% ash may be necessary. 
The invention also contemplates the use of other additives in combination 
with the dispersions of this invention. Such additives 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 ash-producing detergents are exemplified by oil-soluble neutral and 
basic salts of 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 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 calcium, magnesium, 
strontium and barium. They are known in the art and described in a number 
of patents, some of which are referred to hereinabove. 
Auxiliary 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; 
these include the esters, amides, imides, amidines and metal salts 
described hereinabove with reference to component (iv), which are referred 
to hereinafter as "carboxylic dispersants". Other suitable dispersants 
include: 
(1) Reaction products of relatively high molecular weight aliphatic or 
alicyclic halides with amines, preferably polyalkylene polyamines. These 
may be characterized as "amine dispersants" and examples thereof are 
described for example, in the following U.S. Pat. Nos.: 
______________________________________ 
3,275,554 
3,454,555 
3,438,757 
3,565,804 
______________________________________ 
(2) Reaction products of alkyl phenols in which the alkyl group contains at 
least about 30 carbon atoms with aldehydes (especially formaldehyde) and 
amines (especially polyalkylene polyamines), which may be characterized as 
"Mannich dispersants". The materials described in the following U.S. Pat. 
Nos. are illustrative. 
______________________________________ 
3,413,347 
3,725,480 
3,697,574 
3,726,882 
3,725,277 
______________________________________ 
(3) Products obtained by post-treating the carboxylic, amine or Mannich 
dispersants with such reagents as urea, thiourea, carbon disulfide, 
aldehydes, ketones, carboxylic 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. Pat. Nos.: 
______________________________________ 
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 3,533,945 
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 
______________________________________ 
(4) 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 thereof are disclosed in the 
following U.S. Pat. Nos.: 
______________________________________ 
3,329,658 
3,666,730 
3,449,250 
3,687,849 
3,519,565 
3,702,300 
______________________________________ 
The above-noted patents are incorporated by reference herein for their 
disclosures of ashless dispersants. 
Extreme pressure agents and corrosion- and oxidation-inhibiting agents are 
exemplified by chlorinated aliphatic 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, 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. 
In fuel compositions such as petroleum distillate fuels, the dispersions of 
this invention promote engine cleanliness particularly to the components 
of the fuel system, such as fuel lines, carburetors, injectors and pumps. 
In furnace fuel oils, they serve as anti-screen clogging agents. In diesel 
fuels and other fuels which tend to produce black exhaust smoke upon 
combustion, the subject salt dispersions tend to suppress the formation 
and evolution of such smoke. 
The fuel compositions of the present invention contain a major proportion 
of a normally liquid fuel, usually a hydrocarbonaceous petroleum 
distillate fuel such as motor gasoline as defined by ASTM Specification 
D439-73 or diesel fuel or fuel oil as defined by ASTM Specification D396. 
Normally liquid fuel compositions comprising nonhydrocarbonaceous 
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 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 
fuels and one or more non-hydrocarbonaceous materials are also 
contemplated. Examples of such mixtures are combinations of gasoline and 
ethanol or of diesel fuel and ether. Particularly preferred is gasoline, 
that is, a mixture of hydrocarbons having an ASTM boiling point of about 
60.degree. C. at the 10% distillation point to about 205.degree. C. at the 
90% distillation point. 
When the dispersions of this invention are added to fuels as anti-screen 
clogging agents, they will normally be employed in an amount such that the 
sulfate ash content of the fuel will be about 0.0001-0.1% by weight. If 
the dispersion is used in a diesel fuel to suppress the formation of 
smoke, enough additive should be added to impart a sulfate ash content of 
about 0.001-1%, preferably about 0.05-0.5%. 
The fuel compositions can contain, in addition to the dispersions 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 preventers or mcdifiers such as triaryl 
phosphates, dyes, cetane improvers, anti-oxidants 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, upper cylinder lubricants, anti-icing 
agents and the like. 
The dispersions 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, 
particularly mineral oil, naphtha, benzene, toluene or xylene, to form an 
additive concentrate. These concentrates usually contain about 20-90% by 
weight of the dispersion of this invention and may contain, in addition, 
one or more other additives known in the art or described hereinabove. 
The following examples illustrate lubricant and fuel compositions 
containing the dispersions of this invention. Unless otherwise indicated, 
all percentages and parts are by weight. 
EXAMPLE A 
A composition for use as an automatic transmission fluid is prepared using 
an ATF base oil plus 12.36% total additives. These additives are added as 
a concentrate which contains 3% of a conventional commercial seal sweller; 
3.25% of a viscosity index improver derived from mixed esters of a 
styrene-maleic acid interpolymer as disclosed in U.S. Pat. No. 3,702,300; 
4% of a dispersant which is the reaction product (1:1 equivalents) of 
polyisobutenyl succinic anhydride and tetraethylene pentamine, prepared 
according to the procedure of U.S. Pat. No. 3,172,892; 0.71% of a zinc 
isobutylamyl phosphorodithioate oxidation inhibitor; 1% of the product of 
Example 1; 0.2% of a conventional friction modifier based upon 
polyoxyethylene(2) tallow amine (Ethomeen T/12); 0.2% of mineral oil; 200 
ppm. of a conventional silicone based anti-foam agent; and 0.025% of a 
dye. 
EXAMPLE B 
A lubricating composition is prepared using a SAE 90 base oil, 20% by 
volume of the product of Example 5, and 50 ppm. of a conventional silicone 
based anti-foam agent. 
EXAMPLE C 
A lubricating composition is prepared using a SAE 30 base oil, and as 
additives, 4% by volume of a dispersant based upon the reaction product of 
a polyisobutylene succinic anhydride, pentaerythritol, a poly(oxy 
ethylene)-(oxypropylene)glycerol, and polyethylene polyamine, as described 
in Example 11B of British Patent 1,306,529; 0.5% by volume of a commercial 
demulsifier; 0.1% zinc as zinc isobutyl-p-amyl phosphorodithioate as an 
oxidation inhibitor; and 2.5% of the product of Example 8. 
EXAMPLE D 
A lubricating composition is prepared using a SAE 20 base oil, and, as 
additives, 0.2% of a commercial acrylate based pour point depressant; 4.5% 
by volume of the dispersant described in Example C; 0.57% of the oxidation 
inhibitor described in Example C; 0.5% sulfate ash as the product of 
Example 1; and 40 ppm. of a conventional silicone based anti-foaming 
agent. 
EXAMPLE E 
A lubricating composition is prepared using a SAE 30 base oil, and, as 
additives, 2.45% by volume of the product of Example 1; 1% by volume of 
the dispersant described in Example A; 0.6% by volume of the oxidation 
inhibitor described in Example C; and 30 ppm. of a conventional silicone 
based anti-foam agent. 
EXAMPLE F 
A lubricating composition is prepared using a SAE 30 base oil, and, as 
additives, 4% by volume of the dispersant described in Example C; 0.5% of 
a commercial demulsifier; 0.1% zinc as zinc isobutyl-p-amyl phosphoro 
dithioate as an oxidation inhibitor; and 3.17% of the product of Example 
10. 
EXAMPLE G 
A lubricating composition is prepared using a SAE 10W-30 base oil, and, as 
additives, 5.75% of a combination pour point depressant and viscosity 
index improver based upon a mixture of a fumaric-vinyl acetate-ethyl vinyl 
ether copolymer (as described in U.S. Pat. No. 3,250,715) and a 
polyacrylate; 4.5% by volume of the dispersant described in Example C; 
0.57% of the oxidation inhibitor described in Example F; and 0.5% sulfate 
ash as the product of Example 10. 
EXAMPLE H 
A lubricating composition is prepared using a 100N base oil and a total of 
13.36% additives including 3.75% of the viscosity index improver described 
in Example A; 3.5% of a commercial seal sweller; 4% by volume of the 
dispersant described in Example A; 0.71% of a zinc dioctyl 
phosphorodithioate oxidation inhibitor; 0.2% of the friction modifier 
described in Example A; 0.2% mineral oil; and 1% of the product of Example 
3. 
EXAMPLE J 
A lubricating composition is prepared using a SAE 20 base oil and, as 
additives, 4.5% of the demulsifier described in Example C; 0.57% of the 
oxidation inhibitor described in Example C; 0.25% sulfate ash as an 
overbased magnesium petroleum sulfonate; 0.25% sulfate ash as the product 
of Example 1; 0.2% of a conventional commercial pour point depressant 
(Acryloid 150); and 30 ppm. of a conventional silicone based anti-foam 
agent. 
EXAMPLE K 
A lubricating composition is prepared using a SAE 10W base oil and, as 
additives, 12% of a commercial viscosity index improver; 3.42% of a 
dispersant comprising the 1:1 mole reaction product of a polyisobutenyl 
succinic anhydride and pentaerythritol; 1.05% of a dispersant comprising 
the reaction product of a polyisobutenyl succinic anhydride and the 
reaction product of adipic acid and aminoethyl ethanolamine; 0.12% of a 
commercial demulsifier; 1.73% of the product of Example 2; 1.63% of zinc 
methylethyl phosphorodithioate, and 50 ppm. of a silicone based anti-foam 
agent. 
EXAMPLE L 
A lubricating composition is prepared using a 10W-50 base oil and, as 
additives, 8.4% of a hydrogenated butadiene-styrene viscosity index 
improver; 7.25% of the product of Example 2; 2% by volume of the 
dispersant described in Example C; and 0.1% of a conventional pour point 
depressant (PAM-140). 
EXAMPLE M 
A lubricating composition is prepared using a synthetic lubricating oil 
base consisting essentially of the diethyl ether of polypropylene glycol 
having an average molecular weight of about 1500, and 1% of the product of 
Example 1. 
EXAMPLE N 
A diesel fuel composition is prepared containing 1% of the product of 
Example 8 and 100 ppm. of a conventional silicone based anti-foam agent. 
EXAMPLE P 
A jet aviation fuel composition is prepared containing 0.25% of the product 
of Example 1 and 100 ppm. of a conventional anti-foam agent. 
EXMPLE Q 
Three gasoline fuel compositions are prepared using the product of Example 
1 as the additive in concentrations of 67.5 pounds, 33.75 pounds, and 1000 
pounds per 1000 barrels (42 U.S. gallons per barrel) of gasoline. 
As stated earlier, one of the significant characteristics realized from 
lubricants comprising one or more of the oil stable dispersions of the 
present invention is their ability to reduce internal combustion engines 
oil consumption. A well known test utilized by the industry to determine, 
inter alia, oil consumption is Oldsmobile Sequence IIIC Test (described in 
ASTM publication STP 315F "Multicylinder Test Sequences for Evaluating 
Automotive Engine Oils" at pages 53-111.) This IIIC Test which utilizes 
high speed turnpike operation under relatively high ambient conditions 
typical of the southern and southwestern parts of the United States 
involves operating an Oldsmobile V-8 engine for a predetermined period 
under non-cyclic, moderately high speed, high load and high temperature 
conditions, with oil level checks and oil additions every 8 hours. The 
maximum permitted oil consumption after 64 hours, according to the 
industry standard, is 5.88 quarts. 
Three lubricants are tested, each comprising a 10W-30 mineral oil base and 
containing identical amounts of conventional additives including an 
amide-imide type ashless dispersant derived from polybutenyl succinic 
acid, an ethylene-propylene terpolymer viscosity index improver, zinc 
dialkylphosphorodithioates, a silicone anti-foam agent, and a synthetic 
sulfurized product having properties similar to those of sulfurized sperm 
oil. In addition, the lubricants contain alkali metal and/or alkaline 
earth metal detergents in an amount to provide 0.75% (by weight) metal 
sulfate ash, said amount being distributed as follows: 
Lubricant 1--0.30% as the product of Example 2; 0.45% as a basic calcium 
sulfonate having a metal ratio of about 12.25. 
Lubricant 2--0.75% as the basic calcium sulfonate of lubricant 1. 
Lubricant 3--0.75% as a basic calcium sulfonate prepared as the one 
described in Lubricant 1 but having a metal ratio of about 20:1. 
Thus, the detergents in Lubricants 2 and 3 are entirely the previously 
known basic calcium detergents, while the detergent of Lubricant 1 is in 
part a basic sodium detergent of the present invention. 
The oil consumption figures (in quarts) for the above lubricants after a 
test duration of 64 hours are as follows: 
______________________________________ 
Lubricant 1 Lubricant 2 
Lubricant 3 
______________________________________ 
Run 1 4.50 5.20 5.58 
Run 2 4.80 -- 5.39 
Run 3 4.23 -- -- 
Av. 4.51 5.20 5.49 
______________________________________ 
Lubricant 1 provides a reduction in oil consumption of 13+% over Lubricant 
2 and 18+% over Lubricant 3. 
In another series two lubricants are tested, each comprising identical 
amounts of conventional additives including an amide-imide type ashless 
dispersant derived from polybutenyl succinic acid, styrenated succinic 
acid ester as viscosity index improver, zinc dialkyl phosphorodithioates, 
a silicone antifoam agent, and a synthetic sulfurized product having 
properties similar to those of sulfurized sperm oil. Also, these 
lubricants contain alkali metal and/or alkaline earth metal detergents in 
an amount to provide 0.75% (by weight) metal sulfate ash, said amount 
being distributed as follows: 
Lubricant 4--0.30% as the product of Example 2 of the invention, 0.45% as a 
basic calcium sulfonate having a metal ratio of about 12.25. 
Lubricant 5--0.75% as the basic calcium sulfonate of Lubricant 4. 
The following results (single test in each instance) are obtained: 
Lubricant 4--4.83 quarts. 
Lubricant 5--5.66 quarts. 
Lubricant 4 shows a reduction of 14.6% over Lubricant 5. 
It will be apparent from these results that replacement of part of the 
conventional basic calcium detergent in a lubricant by a basic sodium 
detergent results in a significant decrease in oil sonsumption. 
A second test procedure is conducted to determine the effects of lubricants 
containing overbased alkali metal sulfonates on "lead paint" deposits on 
engine parts. Leaded fuels are notorious for forming undesirable gray 
deposits known as "gray paint" or "lead paint". 
The test uses a single cylinder engine [known as a CLR (Committee on 
Lubricant Research) engine which was developed by the Coordinating 
Research Councel of the Society of Automotive Engineers (SAE)] burning 
leaded fuel and lubricated with the lubricants under consideration. The 
test is run for a total of sixty hours after which the various engine 
parts are rated visually for "lead paint". 
In this series three lubricants, 6, 7 and 8 are used; each comprising 
identical amounts of conventional additives including a polyol ester type 
ashless dispersant derived from polybutenyl succinic acid, hydrogenated 
buta diene-styrene copolymer as viscosity index. improver, zinc dialkyl 
phosphorodithioates, a pour point depressing agent, and a silicone 
anti-foam agent. These lubricants contain alkali metal or alkaline earth 
metal detergents in an amount to provide 0.58% (by weight) metal sulfonate 
ash, said amount being distributed as follows: 
Lubricant 6--0.58% of basic calcium sulfonate having a metal ratio of about 
12.25. 
Lubricant 7--0.58% of basic magnesium sulfonate having a metal ratio of 
about 11.0. 
Lubricant 8--0.58% of basic sodium sulfonate as prepared in Example 2 
above. 
The following results are obtained: 
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Engine Rating 
Piston Rating 
50 = Clean 
10 = Clean 
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Lubricant 6 37.2 8.8 
Lubricant 7 38.5 8.7 
Lubricant 8 48.4 9.3 
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From the above it is quite apparent that the basic sodium salt is 
significantly more effective in reducing "lead paint" than either the 
basic calcium or magnesium sulfonates.