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Patented Oct. 15, 1.946
John R. Morris, Lawrenceviile, Ill, and Rush F.
McCieary, Beacon, N. Y., assignors to The Texas
Company, New York, N. Y., a corporation of
‘Io Drawing. Original application
April 26, 1941,
Serial N . 390,540, now Patent N .,
dated April 24, 1945. Divided and this2,374,559,
tion May 12, 1944, Serial
No. 535,362
6 Claims. (01. 252-—42.7)
This invention relates to an improved lubri
cating oil adapted for use in internal combustion
engines and particularly to a lubricating oil
having one or more additives incorporated there
rcsive properties when dissolved or dispersed in
mineral lubricating oils. These anti-oxidant or
anti-corrosive properties are meant to include
all such properties which effect a reduction or
This application is a division of the application
of John R. Morris and Rush F. McCleary, Serial
No. 390,540, ?led April 26, 1941, now Patent No.
2,374,559, dated- April 24, 1945, for Lubricating oil.
It is generally conceded that in the recent de
velopment of internal combustion engines, and
particularly engines designed for heavy-duty
service, the increase in operating temperatures,
bricating oil.
It is the object 01' the present invention to pro
vide a mineral oil composition which possesses
the above-mentioned detergent and anti-oxidant
or anti -corrosive properties by incorporating in a
mineral lubrlcat‘ng oil a novel additive ingre
together with the reduction of clearances and the
use of hard bearing alloys, such as copper-lead, 15 dient of multi-functional activity.
A ‘further object of this invention is to provide
cadmium-silver, etc., have set up such severe op
a mineral oil composition possessing detergent
erating conditions as to necessitate an improve
properties and enhanced anti-oxidant or anti
ment in the highly solvent-re?ned mineral oils
corrosive properties by combining with the above
re?ned for use as crankcase lubricants. These
rigorous operating conditions, which are most
mentioned multi-functional additive an auxiliary
prevalent in Diesel and gasoline engines used in 20 additive ingredient and incorporating the combi
nation in a mineral lubricating oil.
heavy duty bus and tractor service, have serious
ly accentuated such problems as corrosion, oxida
tion and resin formation in the solvent-re?ned
The invention is based upon the discovery of
a novel class of multi-functional additives which
may be broadly described as oil-soluble or oil
mineral lubricating oils with the resultant dele-, 25
terious effect on the emciency of the engines. The
miscible metal derivatives of alkyl-substituted
nature and extent or these problems depend upon
aryloxy or arylthiooxy sul?des. It has been found
the conditions of operation of the particular en
that when small proportions of a compound with
in the scope of the above general class are blended
gine type, the type and extent of re?ning of- the
with a mineral lubricating oil, a mineral oil com
base oil used, and numerous other factors.
30 position is formed possessing eiscellent detergent
The tendency of mineral lubricating oils to
and anti-oxidant or anti-corrosive properties.
deposit gums, resins,ysoot and varnish-like ma
Speci?cally, the compounds of the present in
terials about the valves, rings, pistons, cylinders
vention may be described as oil-soluble or oil
and other engine parts can be largely overcome
by the addition of certain types of additive in 35 miscible metal salts of the class of compounds
having the structure:
gredients which possess detergent properties
when dissolved or dispersed in mineral lubricat
ing oils. By detergent properties is meant not
only that property which aids in dispersing, re
moving or purging foreign materials which ac 40
cumulate on the surface of the engine parts, but
in which R and R’ represent alkyl, aralkyl, cyclo
also that property which prevents the accumula-'
alkyl or naphthenyl or naphthenyl radicals, the
tion or deposition of such materials, as distin
alkyl portion of which contains at least 5 carbon
guished from solvent action upon these accumu
lations or deposits.
atoms. R’ is preferably the same as R, but may
45 also be a different radical within the above group.
In addition thereto the added tendency of these
X and X’ represent either an oxygen or sulfur
oils to corrode the metal surfaces with which
the lubricating oil comes in contact may be over
atom, and n, y, z are integers of 1' or more. 11 and
y are usually 1, 2, 3 or 4, while z‘is usually 1, 2.
come or reduced by the addition of additive com-’
ponents which possess anti-oxidant or anti-cor 50 or 3. Either or both of the aromatic nuclei dia
grammatically shown may be substituted by a
naphthyl, anthracyl or other condensed aromatic
nuclei. The positions of the substltuent in the
Example I
34 grams of sulfur monochloride (0.25 mol) in
formula are purely diagrammatic and may be
a carbon disulfide solution were added to a car
connected to any position in the aromatic nuclei.
The sul?de bond between the nuclei represented
of the following structural
‘ by Sn may be any one
taneous evolution of hydrogen chloride had
bon disul?de solution of 138 grams of tridecyl
phenol (0.5 mol) with stirring. After the spon
ceased, the reaction mixture was heated on a
steam bath at ‘lo-80° C. for two days to evaporate
the solvent and residual hydrogen chloride. 152
The metallic derivatives of this class of com
10 grams of di(tridecylphenol) disulflde. which ap
peared as a dark oil, were obtained.
pounds, in which the hydrogen of the hydroxyl
Example [I
75.4 grams of di(tridecylphenol) disulfide were
(OH) or sulfhydryl group (SH) , illustrated above
as XH and X’H respectively, isreplaced by a 15
added to a solution of calcium ethylate made from
metal, include any of the following metals or
8.8 grams of calcium in 100 cc. absolute alcohol.
combinations thereof: sodium, potassium,
The mixture was stirred for two hours at 75-80°
cium, barium, strontium, magnesium, aluminum, Y
C., then freed of solvent by heating at 80-85° C.
tin, iron, cobalt, nickel, copper, manganese and
an oil
chromium. These derivatives also include the 20 in vacuo. The residual calcium salt wasthe
folsoluble, dark, sticky mass, which gave
partial derivatives wherein the hydroxyl or sulf
lowing analysis:
hydryl groups are only partially converted into
their metallic salts as follows:
R’ I
(Where M is a mono
valent metal)
Ash __________________________________ __ 18.8
Sulfur ________________________________ __ 6.9
Free sulfur __________________________ __ 0.86
Eample 111
To '100 grams of polymer phenol (hydroxyl No.
166) , prepared by the alkylation of phenol with
30 a mixture of ole?ns (Bromine No. 129), with a
boiling range of 350-450“ E, which was separated
from the raw polymer fraction from the cata
lytic polymerization of gasoline, was added an
equal volume of carbon disul?de. A solution of
35 135 grams of sulfur monochloride in an equal
volume of carbon disul?de was added portionwise
to the solution of polymer phenol at room tem
perature while stirring. The resulting solution
was maintained at room temperature until'the
spontaneous evolution of hydrogen chloride gas
As illustrative of the speci?c compounds whose
had ceasedfthen warmed gently on a steam bath
oil-soluble metallic derivatives fall within the
to evaporate off the solvent, unreacted sulfur
scope of the present invention, the following list
monochloride, and residual hydrogen chloride.
(Where M is a di
valent metal)
of compounds is presented:
Di(pentadecy1phenol) disul?de
The resulting di(polymer phenol) disul?de ap
45 peared as a dark residue and gave the following
Di(octylphenol) disul?de
Di(tridecylphenol) sulfide
Di(octadecylphenol) trisul?de
Total sulfur __________________________ -_ 8.13
Free sulfur_____' ______________________ __ Trace
. Di(tridecylphenol)
Di(diamylphenol) disul?de
Di(dioctylphenol) sul?de
Example IV
In the preparation of a partially converted
varium salt of di(polymer phenol) disul?de, 100
grams of di(polymer phenol) disul?de (approxi
in U!
mately 0.135 11101), from Example 111, were re
acted with 11.5 grams of anhydrous barium hy
droxide (approximately 0.0675 mol) in the pres
Octylphenol-amyiphenol sul?de
Cetylnaphthol-isoamylphenol trisul?de
Di(o-phenylphenol) sul?de
Di(p-phenylphenol) di'sul?de
Di(p-phenylphenol) polysul?de
Di(o-benzylphenol) sul?de
Di(p-benzylphenol) disul?de
Di(amylresorcinol) sul?de
Di(octylpyrogallol) sul?de
Dl(o-cyclohexylphenol) disul?de
Di(p-cyclohexylphenol) polysul?de
Di(o-cyclohexylphenol) sul?de
Di(naphthenylphenol) sul?de
Di(naphthenylphenol) disul?de
Di(pentadecyl-thiophenol) sul?de
Di(tridecyl-thiophenol) disul?de
Di(octyl-thiophenol) polysul?de
Di(o-cyclohexyl-thiophenol) disul?de
Di(p-benzyl-theiophenol) disul?de
Di(o-phenyl-thiophenol) disul?de
Di(naphthenyl-thiophenol) disul?de
ence of 200 cc. of toluene. The reaction mixture
was stirred and heated to re?ux under an auto
60 matic water separator for four hours, thereafter
filtering through cloth and ?lter-cel. The ?l-v
trate then was freed of solvent by heating to
80-90° C. in vacuo. In the resulting salt it was
found that only one-half of the phenolic groups
was converted to the barium salt. It analyzed
7.62% sulfur and 7.0% barium. found to impart
These compounds have been
excellent detergent and anti-oxidant or anti
corrosive properties to a mineral lubricating oil
70 when they are blended therewith in proportions
ranging from 0.1-5.0% by weight. These propor
tions vary ‘with the particular type of mineral
oil used and the purpose for which it is intended.
The following examples illustrate suitable
However, the proportions preferred herein are methods for preparing the above-described multi 75 between 0.25 and 2.0% by weight.
functional additives:
' '5
An additional feature of
is the combi
unless otherwise noted, are the normal salts, e. 3.,
containing no free hydroxyl groups. The results
'tional additives with an auxiliary additive ingre
of two runs at 250° F.
and 350?
are presented:
Bearing corrosiom-c'opper lead (10 hours)
Loss of weight in
Oil tested
250° F.
Reference oil ....................... .; _______ ..
oil-+05% barium di (tridccyl pheno
lete) disulfide _____________________________ ._
15 Reference oil-l-0.6% barium di (polymer-phen
olate) disulilde ____________________________ _.
oil+0.5% calcium di (tridecyl phen
olate) disul?de ____________________________ __
Reference oil+0.6% barium di (polymer-phen
, olate) disul?de+l.0% sulfurized terpinoleua.
Reference o1l+0.5% barium di (polymer-phen
20 olate) disulilde+3.0% sulfurized clay tower
polymers .................................. _.
350° F.
38, 39
133, 185
l, 1
67, 71
........ _. '
2, 3 ________ ._
0, l
0. 5
0, 0
functional additive is usually within the propor
tion range of 0.5 to 5.0% by weight and preferably
between 1.0 and 3.0%, depending upon the type
of lubricating oil used.
‘These sulfurized auxiliary additives may be pre
pared in accordance with the copending applica
tions of Edwin C. Knowles and Frederick C.
McCoy, Serial Nos. 358,876, 358,877 and 358,878,
respectively, all ?led September 28, 1940, wherein
pended claims.
We claim:
1. A lubricating composition comprising a min
eral lubricating oil having incorporated therein
0.1-5.0% by
rivative of a compound of the formula
colored compound as against the usual dark
colored sulfurized compounds.
As illustrative of the anti-corrosive properties
in which R and R’
of a lubricating oil containing either or both of
are radicals selected from the
alkyl, aralkyl, cycloalky1 and
suits oi’ the following empincal tests are pre
sented: A copper-lead bearing specimen, incased
in a special non-wear bushing and rotatably
other condensed
of a sulfurized terpene hydrocarbon.
2. A lubricating composition comprising a min
011 having incorporated therein
0.1 to 5.0% by weight of an oil-soluble metal salt
of an alkyl substituted aryloxy sul?de and 0.5 to
bon. by weight of a sulfurized terpene hydrocar
3. A lubricating composition comprising a min
eral lubricating oil having incorporated therein
0.1-5.0% by weight of an oil-soluble metal salt
0.1-5.0% by weight of an7oil-soluble metal derivative of a compound of the formula:
5. A lubricating composition comprising a min
eral lubricating oil having incorporated therein
0.1 to 5.0% by weight of an oil-soluble alkaline
earth metal salt of an alkyl phenol sul?de, and
a 0.6 to 5.0% by weight of a sullurized terpene hy
( )'
in which R and R’ are radicals selected from
the group consisting of alkyl; aralkyl, cycloalkyl
and naphthenyl, the ailryl portion 0! which con- 10
6. A lubricating composition comprising a min
talns at least 5 carbon atoms, X and X’ are ele-
weight of a suliurized terpinolene.
ments from the group consisting of oxygen and
sulfur, ‘1!, v, z are integers 01 at least 1, and 0.5
to 5.0% by weight of sulfurized terpinolene.
eral lubricating oil having incorporated therein
0.1 to 5.0% by weight or an oil-soluble metal salt
of an alkyl phenol sulfide and 0.5 to 5.0% by
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