Sulfurized compositions, and additive concentrates and lubricating oils containing same

Sulfurized mixtures which include (A) at least one partial fatty acid ester of a polyhydric alcohol, and (B) at least one member of the group consisting of PA0 (1) at least one fatty acid ester of a polyhydric alcohol, which fatty acid ester is different from the partial ester (A), PA0 (2) at least one fatty acid, PA0 (3) at least one olefin, and PA0 (4) at least one fatty acid ester of a monohydric alcohol. The sulfurized compositions are useful in preparing additive concentrates and lubricating compositions.

FIELD OF THE INVENTION 
This invention relates to sulfurized compositions. In particular, this 
invention relates to sulfurized mixtures, which mixtures include at least 
one partial fatty acid ester of a polyhydric alcohol and at least one 
additional reactant as described hereinbelow. The sulfurized compositions 
are useful as additives for lubricating oils. Additive concentrates and 
lubricating oil compositions containing such sulfurized compositions are 
also contemplated. 
BACKGROUND OF THE INVENTION 
In the past, sulfurized sperm oil was widely used as an additive in many 
lubricant formulations such as gear oil, including lubricants for worm and 
spur gears, automatic transmission fluids, metal-working lubricants and 
the like. Sulfurized sperm oil is especially useful for improving extreme 
pressure properties while providing excellent lubricity and some degree of 
rust-inhibition in motor oils, gear lubricants, and rolling oils. However, 
the sulfurized sperm oils have been replaced in recent years by other 
sulfurized compositions as a result of the reduction in availability of 
sperm oil and increased cost. Sulfurized olefins do not always exhibit the 
degree of lubricity which is necessary in many applications. 
Habiby, in U.S. Pat. Nos. 3,926,822 and 3,953,347, describes a composition 
comprising a sulfurized mixture of a fatty acid ester of a mono- or 
polyhydric alcohol, a fatty acid and an aliphatic olefin. Newingham et al, 
in U.S. Pat. Nos. 3,825,495 and 4,180,466, teaches lubrication of 
controlled-slip differentials with a composition comprising a 
co-sulfurized blend of a triglyceride and a monoolefin. Recchuite, in a 
series of U.S. Pat. Nos., for example, patent numbers U.S. Pat. No. 
4,166,796, U.S. Pat. No. 4,166,797, U.S. Pat. No. 4,321,153 and U.S. Pat. 
No. 4,456,540 teaches compositions comprising a co-sulfurized mixture of 
triglycerides and an olefinic hydrocarbon. The '540 patent also recites 
the presence of a fatty acid in the reaction mixture. In U.S. Pat. No. 
4,166,795, Recchuite teaches the reaction product of sulfur, lard oil, 
polyisobutylene oligomers and optionally another unsaturated material. All 
of these patents describe the use of these sulfurized mixtures in 
lubricants. Other sulfurized fatty acid esters are described in Lincoln et 
al, U.S. Pat. No. 2,113,811; Wasson et al, U.S. Pat. No. 2,672,444; Eby, 
U.S. Pat. No. 2,680,718; Wakim, U.S. Pat. No. 3,986,966; Zipf, U.S. Pat. 
No. 4,036,769; Hotten, U.S. Pat. No. 4,053,427; and Jackisch, U.S. Pat. 
No. 4,176,072. The sulfurization described in the above-identified patents 
generally is carried out using elemental sulfur. Several patents describe 
alternative means of incorporating sulfur including reactions with sulfur 
monochloride and phosphosulfurization carried out by addition of small 
amounts of a phosphorus sulfide. 
SUMMARY OF THE INVENTION 
Sulfurized compositions are described which are prepared by reacting at an 
elevated temperature, a sulfurizing agent with a mixture of 
(A) at least one partial fatty acid ester of a polyhydric alcohol and 
(B) at least one member of the group consisting of 
(1) at least one fatty acid ester of a polyhydric alcohol, which fatty acid 
ester is different from the partial ester (A), 
(2) at least one fatty acid, 
(3) at least one olefin, and 
(4) at least one fatty acid ester of a monohydric alcohol. 
The sulfurized compositions prepared in accordance with the present 
invention are useful as additives for lubricating oil compositions, 
providing extreme pressure, antiwear, antioxidant, and increased lubricity 
properties. 
Thus, it is an object of this invention to provide novel sulfurized 
compositions. A further object is to provide a method for preparing novel 
sulfurized compositions. Still another object is to provide useful 
lubricant additives. Other objects will in part be apparent to those 
skilled in the art upon reading this disclosure or are described in detail 
hereinbelow. 
DETAILED DESCRIPTION OF THE INVENTION 
As previously described, this invention relates to a sulfurized composition 
prepared by reacting a sulfurizing agent with a mixture of at least two 
reactants, one of which is (A) a partial fatty acid ester of a polyhydric 
alcohol. These partial fatty acid esters will contain at least one 
hydroxyl group in the alcohol portion of the ester; that is, not all of 
the hydroxyl groups of the polyhydric alcohol are converted to ester 
groups. 
Suitable partial fatty acid esters of polyhydric alcohols are known and 
include, for example, glycol monoesters, glycerol mono- and diesters, and 
pentaerythritol di- and/or triesters. Partial fatty acid esters of 
glycerol are preferred. Of the glycerol esters, monoesters are preferred; 
that is, only one of the hydroxyl groups of a glycerol moiety is converted 
to an ester group. Partial fatty acid esters of polyhydric alcohols can be 
prepared by methods well known in the art, such as direct esterification 
of an acid and a polyol, reaction of a fatty acid with an epoxide, etc. 
While it is possible to prepare the partial esters useful in this invention 
employing any of a variety of methods, they can, in a general sense, be 
considered as having been prepared from the reaction of a fatty acid and a 
polyhydric alcohol. Thus, the partial esters contain a moiety which can be 
considered as being derived from a fatty acid and a moiety which can be 
considered as being derived from a polyhydric alcohol. Although suitable 
sulfurized compositions of this invention can be prepared when reactant 
(A) is a saturated material, i.e., is essentially free of olefinic 
unsaturation, it is preferred that reactant (A) contains olefinic 
unsaturation. Such olefinic unsaturation usually appears in the acid 
moiety of the ester. 
The term "fatty acid" as used in the specification and claims refers to 
acids which may be obtained by the hydrolysis of a naturally occurring 
vegetable or animal fat or oil. These acids usually contain from 8 to 22 
carbon atoms and include, for example, caprylic acid, caproic acid, 
palmitic acid, stearic acid, oleic acid, linoleic acid, etc. Acids 
containing 16 to 20 carbon atoms are preferred, and those containing 16 to 
18 carbon atoms are especially preferred. 
As mentioned hereinabove, it is preferred that reactant (A) contains 
olefinic unsaturation, usually in the acid moiety of the ester. Suitable 
unsaturated acid moieties include those which can be considered as being 
derived from various fatty alkenoic acids, for example, octenoic acids, 
tetradecenoic acids and the like. Oleate esters are especially preferred. 
Suitable polyhydric alcohols will have from 2 to about 12 carbon atoms, 
preferably from 2 to about 5 carbon atoms, and from 2 to about 8 hydroxyl 
groups, preferably 2 to 4 hydroxyl groups, most preferably about 3 
hydroxyl groups. Examples of suitable polyhydric alcohols include ethylene 
glycol, propylene glycol, trimethylene glycol, neopentylene glycol, 
glycerol, pentaerythritol, etc. Ethylene glycol and glycerol are 
preferred; glycerol is especially preferred. Polyhydric alcohols 
containing alkoxy groups, particularly ethoxy groups or propoxy groups, 
are contemplated. 
The partial fatty acid esters may be present as components of a mixture 
containing a variety of other components. The other components may include 
unreacted fatty acid, fully esterified polyhydric alcohols, and other 
materials. From the standpoint of economics, it is preferred that the 
partial fatty acid ester content of such a mixture is at least about 25%, 
more preferably at least about 50% by weight. In a particular embodiment, 
the monoester constitutes at least about 30% by weight of such a mixture, 
more preferably at least about 45% by weight. 
As mentioned hereinabove, suitable partial fatty acid esters can be 
prepared by methods known in the art. One method for preparing 
monoglycerides of fatty acids from fats and oils is described in Birnbaum, 
U.S. Pat. No. 2,875,221. This patent teaches a continuous process for 
reacting glycerol and fats to provide a product having a high proportion 
of monoglyceride. Furthermore, many partial glycerol esters are 
commercially available. Such esters usually contain at least about 30% by 
weight of the preferred monoester, generally from about 35 to about 65% by 
weight monoester, about 30 to about 50% by weight diester, and the 
balance, in the aggregate, usually is no more than about 15%, more often 
less than about 10% by weight of triester, free fatty acid and other 
components.

Another method for preparing compositions comprising partial fatty acid 
esters of this invention is described in the following example. 
EXAMPLE 1 
A mixture of glycerol oleates is prepared by reacting 882 parts of a high 
oleic content sunflower oil which comprises about 80% oleic, about 10% 
linoleic and the balance saturated triglycerides, and which contains less 
than 1% by weight acidity measured as oleic acid, and 499 parts glycerol 
in the presence of a catalyst prepared by dissolving KOH in glycerol to 
yield a material containing about 16.7% by weight alkoxide. The reaction 
is conducted by heating the mixture to 155.degree. C. under a nitrogen 
sparge, then heating under nitrogen, for 13 hours at 155.degree. C. The 
materials are cooled to less than 100.degree. C., then 9.05 parts 85% 
H.sub.3 PO.sub.4 is added to neutralize the catalyst. The neutralized 
reaction mixture is transferred to a 2-liter separatory funnel. The lower 
layer is removed and discarded. The upper layer is the product which 
contains, by analysis, 56.9% by weight glycerol monooleate, 33.3% glycerol 
dioleate (primarily 1,2-) and 9.8% glycerol trioleate. 
Repeating the procedure of this example generally provides products 
containing from about 54-57% by weight glycerol monooleate, about 33-36% 
by weight of glycerol dioleate and about 8-10% by weight glycerol 
trioleate. 
Specific examples of commercially available materials comprising partial 
fatty acid esters of glycerol include Emery 2421 (Emery Industries, Inc.), 
Cap City GMO (Capital), DUR-EM 114, DUR-EM GMO, etc. (Durkee Industrial 
Foods, Inc.) and various materials identified under the mark Mazol GMO 
(Mazer Chemicals, Inc.). Other partial fatty acid esters of polyhydric 
alcohols are described in K. S. Markley, Ed., "Fatty Acids", second 
edition, parts I and V, Interscience Publishers (1968). Numerous 
commercially available fatty acid esters of polyhydric alcohols are listed 
by tradename and manufacturer in the two volumes: McCutcheon's Functional 
Materials and McCutcheon's Emulsifiers and Detergents, North American and 
International Editions (1987). 
As previously described, the method of this invention comprises the 
reaction of a sulfurizing agent with a mixture of at least two reactants. 
Reactant (A), a partial fatty acid ester of a polyhydric alcohol, has been 
described hereinabove. Reactant (B) is at least one member of the group 
consisting of 
(1) at least one fatty acid ester of a polyhydric alcohol, which fatty acid 
ester is different from the partial ester (A), 
(2) at least one fatty acid, 
(3) at least one olefin, and 
(4) at least one fatty acid ester of a monohydric alcohol. 
Reactant (B)(1) is at least one fatty acid ester of a polyhydric alcohol. 
Reactant (B)(1) is different from the partial ester (A). Reactant (B)(1) 
may be a partial fatty acid ester, a full ester, or a mixture thereof. As 
in the case for Reactant (A), these fatty acid esters of polyhydric 
alcohols may be prepared in a variety of ways known in the art. As for 
reactant (A), reactant (B)(1) also may be considered as being derived from 
the reaction of a fatty acid with a polyhydric alcohol. The fatty acids 
and polyhydric alcohols from which reactant (B)(1) may be derived are the 
same as those described hereinabove for reactant (A). These fatty acid 
esters are also available from commercial sources, including several of 
those enumerated hereinabove for reactant (A). It is preferred that 
reactant (B)(1) contains a major amount of the fully esterified ester. 
Particularly preferred is where the fully esterified ester is a 
triglyceride, especially where the acid moiety is derived from oleic acid. 
Especially preferred are the fatty oils, that is, naturally occurring 
esters of glycerol with the above-noted long chain carboxylic acids and 
synthetic esters of similar structure. Still more preferred are fatty oils 
derived from unsaturated acids, especially oleic and linoleic, including 
such naturally occurring animal and vegetable oils as lard oil, peanut 
oil, cottonseed oil, soybean oil, corn oil, sunflower seed oil and others. 
Specially grown sunflowers yield an oil containing high amounts of oleic 
acid (e.g., greater than 80% or more by weight of oleic acid). Such 
sunflower oils are available commercially under the designation 
TRISUN.RTM. from SVO Enterprises Corporation. 
Reactant (B)(2) is at least one fatty acid. Thus, reactant (B)(2) may be at 
least one fatty acid as described hereinabove. It is usually an 
unsaturated fatty acid such as oleic or linoleic acid, and may be a 
mixture of acids such as is obtained from tall oil or by the hydrolysis of 
peanut oil, soybean oil or the like. Such fatty acids are commercially 
available from numerous sources. 
Reactant (B)(3) is at least one olefin. This olefin is preferably an 
aliphatic olefin. That is, it is essentially free of aromatic groups such 
as phenyl groups, naphthyl groups and the like. The olefin usually will 
contain from about 4 to about 40 carbon atoms, preferably from about 8 to 
about 36 carbon atoms. Terminal olefins, or alpha-olefins, are preferred, 
especially those having from 12 to 20 carbon atoms. Olefins having 
internal double bonds are also useful. Mixtures of these olefins are 
commercially available, and such mixtures are contemplated for use in this 
invention. 
Reactant (B)(4) is a fatty acid ester of a monohydric alcohol. Such a fatty 
acid ester is one which may be considered as being derived from a fatty 
acid as described hereinabove with an aliphatic monohydric alcohol such as 
methanol, ethanol, n-propanol, isopropanol, the butanols, etc. Mixtures 
thereof are also useful. Reactant (B)(4) can be prepared by methods well 
known in the art. Such fatty acid esters of monohydric alcohols are also 
commercially available from numerous sources. 
As is apparent from the above discussion, (A) and the materials identified 
as reactants (B) contain various hydrocarbon groups such as alkyl or 
alkenyl groups, alkylene groups, etc. These hydrocarbon groups may contain 
non-hydrocarbon substituents or heteroatoms, provided such non-hydrocarbon 
substituents or heteroatoms do not significantly detract from the 
essentially hydrocarbon nature of the hydrocarbon group. Suitable 
non-hydrocarbon substituents include, but are not limited to, halo groups, 
such as chlorine, bromine, etc., mercapto groups, alkoxy groups, etc., and 
the like. Heteroatoms include, for example, sulfur, oxygen, nitrogen, and 
the like. Generally, there will be no more than one non-hydrocarbon group 
present per 10 carbon atoms in a hydrocarbon group. More preferably, no 
more than one such substituent or heteroatom is present per 20 carbon 
atoms. Preferably, the hydrocarbon groups are purely hydrocarbon; that is, 
they contain carbon and hydrogen, and are essentially free of 
non-hydrocarbon substituents or heteroatoms. 
As mentioned hereinabove, the sulfurized compositions of this invention are 
prepared by sulfurizing a mixture of reactants, reactant (A) identified 
hereinabove, and at least one member of the group of reactants identified 
as reactants (B). The mixture usually contains from about 10 to about 90 
percent by weight of reactant (A), more often from about 40 to about 70 
percent by weight. 
In addition to reactant (A), the mixture to be sulfurized contains at least 
one additional reactant selected from the group identified as reactants 
(B). The mixture may contain from about 10 to about 90 parts, often from 
about 10 to about 50 parts, and more often from about 10 to about 30 parts 
by weight of reactant (B)(1), or about 0.1 to about 15 parts, more often 
about 1 to about 5 parts by weight of reactant (B)(2), or about 10 to 
about 90 parts, often from about 15 to about 60 parts, more often from 
about 20 to about 40 parts by weight of reactant (B)(3), or about 1 to 
about 50 parts, often from about 5 to about 30 parts, more often from 
about 5 to about 15 parts of reactant (B)(4). Often, the mixture contains 
at least two members of the group of reactants identified as reactants 
(B). In a preferred embodiment, the mixture contains reactant (B)(3) and 
at least one other member of the group of reactants identified as 
reactants (B). 
The sulfurization reaction generally is effected at an elevated 
temperature, often from about 50 to about 350.degree. C., more preferably, 
at a temperature of from about 100.degree. to about 210.degree. C. The 
reaction is effected with efficient agitation and often in an inert 
atmosphere such as nitrogen. If any of the reactants are appreciably 
volatile at the reaction temperature, the reaction vessel may be sealed 
and maintained under pressure. Although generally not necessary, the 
reaction may be effected in the presence of an inert solvent such as an 
alcohol, ether, ester, aliphatic hydrocarbon, halogenated aromatic 
hydrocarbon, etc., which is a liquid within the temperature range employed 
for the reaction. 
The sulfurizing agents useful in the process of the present invention 
include elemental sulfur, hydrogen sulfide, sulfur halide, sodium sulfide 
and a mixture of hydrogen sulfide and sulfur or sulfur dioxide, etc. 
Preferably, the sulfurizing agent is elemental sulfur. It is frequently 
advantageous to add the sulfurizing agent portionwise to the mixture of 
the other reactants. When elemental sulfur is utilized as a sulfurizing 
agent, the reaction is in some instances exothermic, which can be utilized 
as a cost-cutting benefit since no, or at least reduced, external heating 
may be required. The amount of sulfur or sulfurizing agent added to the 
reaction mixture can be varied over a wide range although the amount 
included in the reaction mixture should be an amount sufficient to provide 
a sulfurized composition containing the desired amount of sulfur. 
Usually, the amount of sulfur or sulfurizing agent employed in the 
preparation of the sulfurized compositions of this invention is calculated 
based on the total olefinic unsaturation of the mixture. A monoolefinic 
reactant, such as an alpha-olefin or oleic acid, for example, contains one 
mole of olefinic bonds per mole of reactant. A polyolefinic material 
contains 2 or more moles of olefinic bonds. For example, 1,4-hexadiene 
contains 2 moles of olefinic bonds. In general, from about 0.01 to about 6 
moles of sulfur, present as elemental sulfur or as sulfur present in 
another sulfurizing reactant, may be employed per mole of olefinic bonds. 
More often from 0.5 to about 3 moles of sulfur are employed per mole of 
olefinic bonds. 
Accordingly, the sulfur content of any given sulfurized composition of this 
invention depends on the amount of sulfur present in the sulfurization 
mixture and on the nature and amount of the reactants present in the 
mixture comprising reactants (A) and (B). Compositions containing from 2 
to about 40 percent by weight sulfur are common, and preferred are those 
containing from about 5 to about 25 percent by weight of sulfur. 
The reaction may be conducted in the presence of various catalysts such as 
amines and other sulfurization catalysts known in the art. A number of 
useful catalysts are described in U.S. Pat. No. 4,191,659 which is 
expressly incorporated herein by reference for relevant disclosures in 
this regard. 
Following the sulfurization reaction, it is preferred to remove 
substantially all low boiling materials, typically by venting the reaction 
vessel, by sparging with an inert gas such as nitrogen, by vacuum 
distillation or stripping, etc. Insoluble by-products may be removed by 
filtration if necessary, usually at an elevated temperature (about 
50.degree.-120.degree. C.). 
A further optional step in the preparation of the sulfurized compositions 
is treatment of the sulfurized composition obtained as described above to 
reduce any active sulfur which may be present. An illustrative method 
involves contacting the sulfurized composition with an alkali metal 
sulfide. Other optional treatments may be employed to improve product 
quality such as odor, color, and staining characteristics of the 
sulfurized compositions. 
The following examples illustrate the preparation of the sulfurized 
composition of the present invention. These examples are presented for 
illustrative purposes only, and are not intended to limit the scope of 
this invention. Unless otherwise indicated in the examples and elsewhere 
in the specification and claims, all parts and percentages are by weight, 
and temperatures are in degrees Celsius. 
EXAMPLE 2 
To a 2-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser to Dean-Stark trap and a sub-surface sparge tube is charged 330 
parts of a mixture of C.sub.16-18 alpha-olefins (Ethyl Corporation) and 
670 parts of a mixture comprising, by analysis, 56 percent by weight 
glycerol monooleate (51.5% alpha-monooleate), 40.7% glycerol dioleate and 
3.3 percent by weight glycerol trioleate and which has an iodine number of 
74.60. The materials are heated, with stirring, to 150.degree. under a 
nitrogen sparge. The nitrogen sparge is discontinued and 117 parts sulfur 
are added in two increments, 15 minutes apart. The temperature is 
increased to 195.degree. C. and held at 195.degree.-199.degree. C. for 2 
hours. The nitrogen sparge is resumed and heating is continued at 
195.degree.-199.degree. C. for 2 hours. The reaction mixture is cooled and 
filtered through a diatomaceous earth filter aid. The filtrate, containing 
9.94% sulfur by analysis, is the product. 
EXAMPLE 3 
A 3-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser to Dean-Stark trap and sub-surface gas sparge tube is charged 
with 2000 parts of the glycerol oleate mixture described in Example 2. The 
material is heated under a nitrogen sparge to 145.degree. C. The nitrogen 
sparge is discontinued and 116 parts sulfur is added in two increments, 20 
minutes apart. The mixture is heated to 195.degree. C. and held at 
195.degree. C. for 2 hours. The nitrogen sparge is resumed and the 
reaction mixture is held for 3 additional hours at 195.degree. C. The 
reaction mixture is filtered through diatomaceous earth at 75.degree. C. 
The filtrate, containing 5.40% sulfur by analysis, is the product. 
EXAMPLE 4 
Following a procedure essentially the same as that of Example 2, 425 parts 
of a glycerol oleate mixture comprising about 60% glycerol monooleate 
(57.1% alpha-monooleate) and having an iodine number of 72.9, 75 parts of 
a mixture of C.sub.16-18 alpha-olefins (Neodene.TM. 16-18, Shell) and 58.7 
parts sulfur are reacted yielding a sulfurized product containing 9.85% 
sulfur by analysis. 
EXAMPLE 5 
A 1-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser to Dean-Stark trap and sub-surface gas inlet tube is charged 
with 75 parts of the C.sub.16-18 alpha-olefin mixture of Example 4, 50 
parts oleic acid (Pamolyn 100) and 375 parts of the glycerol oleate 
mixture described in Example 4. The mixture is heated to 145.degree. C., 
58.7 parts sulfur are added in two increments, 15 minutes apart, and 
heating is continued while the temperature increases to 195.degree. C. The 
reaction is continued at 195.degree. C. for 1.5 hours followed by an 
additional 2 hours at 195.degree. with a nitrogen sparge. The materials 
are filtered at 90.degree. C. through a diatomaceous earth filter aid. The 
filtrate, containing 9.54% sulfur by analysis, is the product. 
EXAMPLE 6 
Following a procedure essentially the same as that for Example 5, 50 parts 
of oleic acid, 150 parts of C.sub.16-18 alpha-olefin mixture, and 300 
parts glycerol oleate mixture (each reactant as described in Examples 4 
and 5 hereinabove) are reacted with 58.7 parts sulfur yielding a 
sulfurized material containing 10.05% sulfur by analysis. 
EXAMPLE 7 
A 1-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser to Dean-Stark trap and a sub-surface gas inlet tube is charged 
with 45 parts soybean oil, 75 parts of a mixture of C.sub.16-18 
alpha-olefins (Neodene.TM. 16-18, Shell), 50 parts oleic acid (Pamolyn 
100) and 330 parts of the glycerol oleate mixture described in Example 4. 
This mixture is heated to 145.degree. C. under a nitrogen sparge. Nitrogen 
is discontinued, and 58.7 parts sulfur are added in two increments, 15 
minutes apart. The materials are heated to 195.degree. C. and held at 
195.degree. C. for 1.5 hours. A nitrogen sparge is resumed and heating is 
continued at 195.degree. C. for 2 hours. The reaction mixture is filtered 
at 95.degree. C. through a diatomaceous earth filter aid. The filtrate, 
containing 9.95% sulfur by analysis, is the product. 
EXAMPLE 8 
A 1-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser to Dean-Stark trap and a sub-surface gas inlet tube is charged 
with 75 parts of a mixture of C.sub.16-18 alpha-olefins (Neodene.TM. 
16-18, Shell), 95 parts soybean oil and 330 parts of the glycerol oleate 
mixture described in Example 4. This mixture is heated to 145.degree. C. 
under a nitrogen sparge. The nitrogen sparge is discontinued, and 58.7 
parts sulfur are added in two increments, 15 minutes apart. The mixture is 
heated to 195.degree. C. and held at 195.degree. C. for 1.5 hours. The 
nitrogen sparge is resumed and the reaction is continued at 195.degree. C. 
for 2 hours. The mixture is filtered at 90.degree. C. through a 
diatomaceous earth filter aid. The filtrate, containing 9.74% sulfur by 
analysis, is the product. 
EXAMPLE 9 
Following essentially the same procedure as described in Example 8 and 
employing ingredients described in that example, 330 parts soybean oil, 95 
parts glycerol oleate mixture and 75 parts C.sub.16-18 alpha-olefin 
mixture is reacted with 58.7 parts sulfur. The resulting product contains 
10.2% sulfur by analysis. 
EXAMPLE 10 
The glycerol oleate mixture described in Example 2 is distilled employing a 
thin-film evaporator at 240.degree.-250.degree. C. at 0.25 millimeters 
mercury pressure. The distillate obtained contains 95.8 percent by weight 
glycerol monooleate and 4.2 percent by weight glycerol dioleate by 
analysis. A mixture of 425 parts of this distillate, 425 parts soybean oil 
and 150 parts of a C.sub.16-18 alpha-olefin mixture (Ethyl) is heated to 
145.degree. C. followed by the addition of 117 parts sulfur in three 
increments over 0.25 hour. The temperature is increased to 195.degree. C. 
and held at 195.degree. C. for 1.5 hours. A nitrogen sparge is begun and 
heating is continued for 2.5 hours at 195.degree. C. The reaction mixture 
is filtered at 75.degree. C. through a diatomaceous earth filter aid. The 
filtrate, containing 9.66% sulfur by analysis, is the product. 
EXAMPLE 11 
Following essentially the procedure of Example 10, 190 parts of the 
glycerol monooleate distillate described in Example 10, 660 parts soybean 
oil and 150 parts of C.sub.16-18 alpha-olefin mixture (Ethyl) are reacted 
with 117 parts sulfur. The product obtained contains 9.84% sulfur by 
analysis. 
EXAMPLE 12 
Following essentially the procedure of Example 10, 660 parts of the 
glycerol oleate distillate described in Example 10, 190 parts soybean oil 
and 150 parts of C.sub.16-18 alpha-olefin mixture (Ethyl) are reacted with 
117 parts sulfur. The product obtained contains 9.7% sulfur by analysis. 
EXAMPLE 13 
A 2-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser and sub-surface sparge tube is charged with 1000 parts soybean 
oil, 454 parts of glycerol oleate mixture prepared according to the 
procedure of Example 1 and 53 parts oleic acid (Pamolyn 100). The 
materials are heated to 145.degree. C. under a nitrogen sparge. Nitrogen 
sparging is discontinued and 176 parts sulfur are added in three 
increments at 145.degree. C. The mixture is heated to 195.degree. C. and 
held at 195.degree. C. for 1.5 hours. Nitrogen sparging is resumed and the 
reaction is continued at 195.degree. C. for 5 hours. The materials are 
cooled and filtered through a diatomaceous earth filter aid. The filtrate, 
containing 9.34% sulfur by analysis, is the product. 
EXAMPLE 14 
A 2-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser and sub-surface gas inlet tube is charged with 500 parts soybean 
oil, 500 parts of a glycerol oleate mixture prepared according to the 
procedure of Example 1, 454 parts of a C.sub.16-18 alpha-olefin mixture 
(Shell) and 53 parts oleic acid (Pamolyn 100). The materials are heated to 
145.degree. C. under a nitrogen sparge. The nitrogen sparge is then 
discontinued and 176 parts sulfur are added in three increments over a 
period of 0.25 hours. The reaction mixture is heated to 195.degree. C. and 
held at 195.degree. C. for 1.5 hours. The nitrogen sparge is resumed and 
the reaction is continued for 3 hours at 195.degree. C. The reaction 
mixture is then cooled and filtered through a diatomaceous earth filter 
aid. The filtrate, containing 9.71% sulfur by analysis, is the product. 
EXAMPLE 15 
A 2-liter, 4-necked flask equipped with a stirrer, thermowell, reflux 
condenser to a Dean-Stark trap and a sub-surface sparge tube is charged 
with 1000 parts sunflower seed oil similar to that used in Example 1, 500 
parts of the glycerol oleate mixture described in Example 14 and 53 parts 
oleic acid (Pamolyn 100). The materials are heated to 145.degree. C. under 
a nitrogen sparge, then the nitrogen sparge is discontinued. In three 
increments, 176 parts sulfur are added at 145.degree. C. The materials are 
heated to 195.degree. C. and held at 195.degree. C. for 1.5 hours. The 
nitrogen sparge is restarted and the reaction is continued at 195.degree. 
C. for 3 hours. The reaction mixture is cooled and filtered through a 
diatomaceous earth filter aid. The filtrate, containing 9.25% sulfur by 
analysis, is the product. 
EXAMPLE 16 
Following essentially the same procedure as employed in Example 15, 1000 
parts of the glycerol oleate mixture of Example 1, 454 parts of 
C.sub.16-18 alpha-olefin mixture (Shell) and 53 parts oleic acid (Pamolyn 
100) are reacted with 176 parts sulfur. The product obtained contains 
9.40% sulfur by analysis. 
EXAMPLES 17-24 
Examples 2-9 are repeated, replacing the glycerol oleate mixtures with a 
commercial pentaerythritol dioleate described as having an acid number of 
less than 1.5, a hydroxyl value of 120-130 and an iodine number of 81-87. 
The sulfurized compositions of this invention are useful as oil-soluble 
lubricant additives providing friction modification, anti-wear and extreme 
pressure performance. They also impart energy conserving properties to 
lubricants containing them. Thus, they are useful in automotive 
lubricants, such as engine oils and drivetrain lubricants, which are 
intended for use when it is desired to reduce fuel consumption. These 
energy conserving properties are also useful in industrial applications 
when it is desired to reduce the power requirements, such as electrical 
power requirements, and consequently the cost, of operating industrial 
machinery. Depending on the particular nature and composition of the 
sulfurized composition, additional benefits such as anti-oxidancy, 
corrosion inhibition, and the like may be obtained. The sulfurized 
compositions of this invention have been shown to improve wear and extreme 
pressure performance in manual transmission fluids without sacrificing 
friction modification. The lubricating oil compositions of this invention 
comprise a major amount of an oil of lubricating viscosity and a minor 
amount of the sulfurized compositions of this invention. By a major amount 
is meant more than 50%. Thus, 51%, 80% and 99% are major amounts. A minor 
amount is less than 50%. Examples of minor amounts are 1%, 25% and 49%. 
The amount of sulfurized composition used will, of course, depend in part 
on whether it contains a diluent and on other characteristics of the 
composition. The sulfurized compositions of this invention are used in an 
effective amount to provide the above-described properties and benefits. 
Typically, on a neat chemical basis, it is employed to provide from about 
0.25 to about 20% by weight of the sulfurized composition to the finished 
lubricating oil. More often, it is used at about 0.5 to about 10%, 
preferably from about 1 to about 5% by weight of the finished lubricating 
oil. 
The lubricating oil compositions may be prepared by dissolving or 
suspending the sulfurized compositions of this invention directly in the 
base oil, along with any other additives which may be desired. More often, 
the sulfurized composition is present as a component of an additive 
concentrate which may contain other additives as well and which usually 
will contain an inert organic diluent. Such additive concentrates usually 
comprise from about 1 to 90% by weight of the sulfurized compositions of 
this invention. 
The lubricating compositions and methods of this invention employ an oil of 
lubricating viscosity, including natural or synthetic lubricating oils and 
mixtures thereof. 
Natural oils include animal oils and vegetable oils (e.g. castor oil, lard 
oil) as well as mineral lubricating oils such 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. 
Synthetic lubricating oils include hydrocarbon oils and halosubstituted 
hydrocarbon oils such as polymerized and interpolymerized olefins, etc. 
and mixtures thereof, alkylbenzenes, polyphenyl (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 that can be used. 
Another suitable class of synthetic lubricating oils that can be used 
comprises the esters of dicarboxylic acids and those made from C.sub.5 to 
C.sub.12 monocarboxylic acids and polyols and polyol ethers. 
Other synthetic lubricating oils include liquid esters of 
phosphorus-containing acids, polymeric tetrahydrofurans and the like, 
silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or 
polyaryloxysiloxane oils and silicate oils. 
Unrefined, refined and rerefined oils, either natural or synthetic (as well 
as mixtures of two or more of any of these) of the type disclosed 
hereinabove can be used in the compositions of the present invention. 
Unrefined oils are those obtained directly from a natural or synthetic 
source without further purification treatment. 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. 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 often are additionally processed by techniques directed to removal of 
spent additives and oil breakdown products. 
Specific examples of the above-described oils of lubricating viscosity are 
given in Chamberlin III, U.S. Pat. No. 4,326,972 and European Patent 
Publication 107,282, both of which are hereby incorporated by reference 
for relevant disclosures contained therein. 
A basic, brief description of lubricant base oils appears in an article by 
D. V. Brock, "Lubrication Engineering", Volume 43, pages 184-5, March, 
1987, which article is expressly incorporated by reference for relevant 
disclosures contained therein. 
OTHER ADDITIVES 
As mentioned, the lubricating oil compositions of this invention may 
contain other components as additives intended to enhance one or more 
properties of the lubricant. The use of such additives is optional and the 
presence thereof in the lubricating oil compositions of this invention 
will depend on the particular use and level of performance required. The 
lubricating oil compositions may comprise a zinc salt of a 
dithiophosphoric acid. Zinc salts of dithiophosphoric acids are often 
referred to as zinc dithiophosphates, zinc 0,0-dihydrocarbyl 
dithiophosphates, and other commonly used names. They are sometimes 
referred to by the abbreviation ZDP. One or more zinc salts of 
dithiophosphoric acids may be present in a minor amount to provide 
additional extreme pressure, anti-wear and anti-oxidancy performance. 
In addition to zinc salts of dithiophosphoric acids discussed hereinabove, 
other additives that may optionally be used in the lubricating oil 
compositions of this invention include, for example, detergents, 
dispersants, viscosity improvers, oxidation inhibiting agents, pour point 
depressing agents, extreme pressure agents, anti-wear agents, color 
stabilizers and anti-foam agents. The above-mentioned additives are used 
in addition to the sulfurized compositions of this invention. 
Auxiliary extreme pressure agents and corrosion and oxidation inhibiting 
agents which may be included in the lubricating compositions of the 
invention are exemplified by chlorinated aliphatic hydrocarbons, organic 
sulfides and polysulfides, phosphorus esters including dihydrocarbon and 
trihydrocarbon phosphites, molybdenum compounds, and the like. 
Viscosity improvers (also sometimes referred to as viscosity index 
improvers) may be included in the lubricating compositions of this 
invention. Viscosity improvers are usually polymers, including 
polyisobutenes, polymethacrylic acid esters, diene polymers, polyalkyl 
styrenes, alkenylarene-conjugated diene copolymers and polyolefins. 
Multifunctional viscosity improvers which also have dispersant and/or 
antioxidancy properties are known and may optionally be used in addition 
to the products of this invention. 
Pour point depressants are a particularly useful type of additive often 
included in the lubricating oils described herein. See for example, page 8 
of "Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith 
(Lezius-Hiles Company Publishers, Cleveland, OH, 1967). Pour point 
depressants useful for the purpose of this invention, techniques for their 
preparation and their use are described in U.S. Pat. Nos. 2,387,501; 
2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,748; 2,721,877; 
2,721,878; and 3,250,715 which are expressly incorporated by reference for 
their relevant disclosures. 
Anti-foam agents used to reduce or prevent the formation of stable foam 
include silicones or organic polymers. Examples of these and additional 
anti-foam compositions are described in "Foam Control Agents", by Henry T. 
Kerner (Noyes Data Corporation, 1976), pages 125-162. 
Detergents and dispersants may be of the ash-producing or ashless type. The 
ash-producing detergents are exemplified by oil soluble neutral and basic 
salts of alkali or alkaline earth metals with sulfonic acids, carboxylic 
acids, phenols or organic phosphorus acids characterized by at least one 
direct carbon-to-phosphorus linkage. 
The term "basic salt" is used to designate metal salts wherein the metal is 
present in stoichiometrically larger amounts than the organic acid 
radical. Basic salts and techniques for preparing and using them are well 
known to those skilled in the art and need not be discussed in detail 
here. 
Ashless detergents and dispersants are so-called despite the fact that, 
depending on its constitution, the detergent or dispersant may upon 
combustion yield a non-volatile residue such as boric oxide or phosphorus 
pentoxide; however, it does not ordinarily contain metal and therefore 
does not yield a metal-containing ash on combustion. Many types are known 
in the art, and any of them are suitable for use in the lubricants of this 
invention. The following are illustrative: 
(1) Reaction products of carboxylic acids (or derivatives thereof) 
containing at least about 34 and preferably at least about 54 carbon atoms 
with nitrogen containing compounds such as amine, organic hydroxy 
compounds such as phenols and alcohols, and/or basic inorganic materials. 
Examples of these "carboxylic dispersants" are described in British Pat. 
No. 1,306,529 and in many U.S. Pat. Nos. including the following: 
______________________________________ 
3,163,603 3,381,022 3,542,680 
3,184,474 3,399,141 3,567,637 
3,215,707 3,415,750 3,574,101 
3,219,666 3,433,744 3,576,743 
3,271,310 3,444,170 3,630,904 
3,272,746 3,448,048 3,632,510 
3,281,357 3,448,049 3,632,511 
3,306,908 3,451,933 3,697,428 
3,311,558 3,454,607 3,725,441 
3,316,177 3,467,668 4,194,886 
3,340,281 3,501,405 4,234,435 
3,341,542 3,522,179 4,491,527 
3,346,493 3,541,012 RE 26,433 
3,351,552 3,541,678 
______________________________________ 
(2) 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 
______________________________________ 
(3) Reaction products of alkyl phenols in which the alkyl groups 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 
______________________________________ 
(4) Products obtained by post-treating the carboxylic amine or Mannic 
dispersants with such reactants as urea, thiourea, carbon disulfide, 
aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic 
anhydrides, nitriles, epoxides, boron compounds, phosphorns 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 
4,234,435 
______________________________________ 
(5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, 
vinyl decyl ether and high molecular weight olefins with monomers 
containing polar substituents, e.g., aminoalkyl acrylates or 
methacrylates, 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. 
The above-illustrated additives may each be present in lubricating 
compositions at a concentration of as little as 0.001% by weight usually 
ranging from about 0.01% to about 20% by weight. In most instances, they 
each contribute from about 0.1% to about 10% by weight. 
The various additives described herein can be added directly to the 
lubricant. Preferably, however, they are diluted with a substantially 
inert, normally liquid organic diluent such as mineral oil, naphtha, 
benzene, toluene or xylene, to form an additive concentrate. These 
additive concentrates usually comprise about 1 to about 90% by weight of 
the sulfurized compositions of this invention and may contain, in 
addition, one or more other additives known in the art or described 
hereinabove. Concentrations such as 15%, 20%, 30% or 50% or higher may be 
employed. 
The lubricating oil compositions of this invention find utility in many 
areas. Examples are lubricants for internal combustion engines, especially 
fuel economy improving oils, power transmission fluids such as automatic 
transmission fluids, hydraulic fluids, power-shift oils, and tractor oils. 
Tractor oils frequently serve multiple purposes such as hydraulic fluids, 
wet brake lubricants, engine lubricants, etc., all employing a lubricant 
from a common sump. Other areas of application include industrial 
applications such as metal-working fluids and industrial gear oils. The 
sulfurized compositions of this invention may also be employed in aqueous 
fluids including those described in several Forsberg patents, for example, 
U.S. Pat. No. 4,329,429, U.S. Pat. No. 4,368,133, U.S. Pat. No. 4,448,703, 
and in other aqueous compositions. 
The lubricating compositions of this invention are illustrated by the 
following examples. The lubricating compositions are prepared by combining 
the specified ingredients, individually or from concentrates, in the 
indicated amounts and oil of lubricating viscosity to make the total 100 
parts by weight. The amounts shown are parts by weight and, unless 
indicated otherwise, are amounts of chemical present on an oil-free basis. 
Thus, for example, an additive comprising 50% oil used at 10% by weight in 
a blend, provides 5% by weight of chemical. These examples are presented 
for illustrative purposes only, and are not intended to limit the scope of 
this invention. 
EXAMPLE A 
A lubricating oil composition formulated for use as an automatic 
transmission fluid is prepared by combining a mineral oil basestock (100 
neutral oil--Cities Service Stocks), 0.042% of a commercial silicone 
antifoam, 0.025% of a commercial red dye, and 15.70% of an additive 
concentrate contributing 1.16% of the reaction product of polyisobutenyl 
succinic anhydride with ethylene polyamine, post-treated with CS.sub.2, 
0.67% of a borated reaction product of polyisobutenyl succinic anhydride 
with ethylene polyamine, 0.54% basic calcium sulfonate, 0.5% 
hydroxythioether, 0.06% zinc dialkylphosphorodithioate, 0.5% of the 
product of Example 16, 0.08% of an alkylated diaryl amine+0.11% N-tallow 
diethanolamine+5% alkylated benzene (Alkylate A-215, Monsanto)+1.98% of an 
amine treated styrene-maleate copolymer and 5.1% oil diluent. 
EXAMPLE B 
A lubricating oil composition formulated for use as a metal-working fluid 
is prepared by combining a mineral oil basestock as described in Example A 
with 1.35% of a basic calcium sulfonate and 2.5 % of the product of 
Example 16. 
EXAMPLE C 
A lubricating oil composition such as described in Example A is prepared, 
which contains, in addition to the ingredients employed in Example A, 
0.42% of a borated fatty epoxide. 
Typical gear lubricating oil compositions of this invention are illustrated 
in the following Tables and Examples: 
TABLE I 
______________________________________ 
Examples D-K 
Mineral oil (Shell International Petroleum - SAE 80W) 
basestock + 0.40% amine treated styrene-alkyl maleate 
copolymer + 7.70% of an additive concentrate contributing 
2.12% of a zinc salt of an alkyl carboxylic acid - dialkyl 
phosphorodithioate mixture + 0.31% of the reaction product 
of a N,N-dialkyl alkanolamine with polyisobutenyl succinic 
anhydride + 1.76% basic calcium petroleum sulfonate + 
2.51% mineral oil diluent + 1% of the product listed 
below: 
Example Product of Example 
______________________________________ 
D 4 
E 5 
F 6 
G 7 
H 8 
I 9 
J 2 
K 16 
______________________________________ 
TABLE II 
______________________________________ 
Examples L- O 
Mineral oil (Shell International Petroleum - SAE 80W) + 
0.40% amine treated styrene-alkyl maleate copolymer + 
100 ppm of a silicone antifoam + 7.70% of an additive 
concentrate contributing 2.12% of a zinc salt of an alkyl 
carboxylic acid-dialkyl phosphorodithioate mixture + 0.31% 
of the reaction product of a N,N-dialkyl alkanolamine with 
polyisobutenyl succinic anhydride + 1.76% basic calcium 
sulfonate + 0.75% of a borated basic alkali metal 
sulfonate sulfonate + 1% of the product listed below: 
Example Product of Example 
______________________________________ 
L 9 
M 14 
N 15 
O 16 
______________________________________ 
EXAMPLE P 
A lubricating oil composition is prepared by combining in a mineral oil 
(Shell International Petroleum--SAE 90) base, 7.70% of the additive 
concentrate described in Example K and 0.30% of a commercial pour 
depressant identified as Shellswim 140 (Shell International). 
EXAMPLE Q 
A lubricating oil composition is prepared by combining a synthetic oil 
basestock (SAE 80W--4 centistokes polyolefin--Gulf Oil Chem) with 20% by 
weight of a solution of 90 parts polyisobutenes (MW about 1900, measured 
by vapor phase osmometry) in 10 parts mineral oil diluent, 1% by weight of 
a solution of 40 parts amine treated styrene-alkyl maleate copolymer in 60 
parts mineral oil, 15% of an alkylated benzene and 7.70% of the additive 
concentrate described in Example 0. 
EXAMPLE R 
A lubricating oil composition is prepared by combining in the mineral oil 
described in Example P, 0.30% of a commercial pour depressant identified 
as Shellswim 140 (Shell International), 7% of an additive concentrate 
which contributes 1.16% of a C.sub.11-14 t-alkyl amine salt of the 
reaction product of P.sub.2 O.sub.5 with hydroxypropyl 
O,O-di(4-methyl-2-pentyl) phosphorodithioate, 0.56% of a borated reaction 
product of an ethylene polyamine with polyisobutenyl succinic anhydride, 
0.02% of a polyoxyalkylene demulsifier, 700 ppm of a polyacrylate 
antifoam, 0.09% of a fatty amide, 3.5% of a sulfurized isobutylene and 
0.11% of a solution of 80 parts of the reaction product of an alkylated 
phenol, (CH.sub.2 O).sub.x and dimercaptothiadiazole in 20 parts of an 
aromatic diluent, and 1% of the product of Example 16. 
TABLE III 
__________________________________________________________________________ 
Examples S-AA 
A series of lubricating oil compositions for use as 
tractor transmission lubricants is prepared by combining a 
mineral oil basestock (Sun Tulsa J20B), 5.75% of a mixture 
of mineral oil solution (approx. 60% oil) of amine treated 
styrene-alkyl maleate copolymers, 0.02% of a 10% solution 
of a silicone antifoam in kerosene and 6.40% of an addi- 
tive concentrate which contributes the following listed 
components: 
Percent by Weight in Oil Blend 
Example 
Component S T U V W X Y Z AA 
__________________________________________________________________________ 
Zinc salt of alkyl 
1.87 
1.87 
1.87 
1.87 
1.87 
1.87 
1.87 
2.12 
2.12 
carboxylate-dialkyl 
phosphorodithioate mixture 
Basic calcium sulfonate 
1.72 
1.72 
1.72 
1.72 
1.72 
1.72 
1.72 
1.95 
1.43 
Diluent oil 2.01 
2.01 
2.01 
2.26 
2.26 
2.01 
2.26 
2.32 
Boronated basic alkali 
0.75 
0.75 0.75 0.38 
metal sulfonate 
Reaction product - N,N- 
0.3 
0.3 
0.3 
0.3 
0.31 
0.31 
dialkylalkanolamine with 
polyisobutenyl succinic 
anhydride 
Product of Example 2 
0.8 
Product of Example 10 
0.8 
Product of Example 16 
0.8 0.8 
0.8 
1.0 
1.0 
Product of Example 14 0.8 
Product of Example 15 0.8 
__________________________________________________________________________ 
The benefits provided by the sulfurized compositions of this invention are 
illustrated by the test results presented below. The Timken test is a 
well-known procedure used to determine the load-carrying ability of a 
lubricant. It is described in the American Society for Testing and 
Material procedure ASTM D-2782-77. 
Gear Lubricants are prepared from an SAE 80W basestock (Texaco) to which is 
added 15% of an alkylated benzene, 10% of an acrylate polymer viscosity 
improver, (Texaco TC10124), 0.4% of an amine treated styrene-alkyl maleate 
copolymer, 100 ppm of a silicone antifoam and 7.70% by weight of an 
additive concentrate contributing 2.12% of a zinc salt of an alkyl 
carboxylic acid-dialkyl phosphorodithioate mixture, 0.31% of the reaction 
product of a N,N-dialkyl alkanolamine with polyisobutenyl succinic 
anhydride, 1.76% of basic calcium sulfonate, 0.75% of basic borated alkali 
metal sulfonate, 1% of the product listed below and mineral oil diluent: 
______________________________________ 
Timken (ASTM-2782) 
OK 
Example Product of Example 
Load PSI 
______________________________________ 
AB Example 12, 55 lb. 32,850 psi 
U.S. 3,953,347 60 lb. 35,825 psi 
AC Example 13 95 lb. 40,000 psi 
95 lb. 40,000 psi 
______________________________________ 
While the invention has been explained in relation to its preferred 
embodiments, it is to be understood that various modifications thereof 
will become apparent to those skilled in the art upon reading the 
specification. Therefore, it is to be understood that the invention 
disclosed herein is intended to cover such modifications as fall within 
the scope of the appended claims.