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Patented June 20, 1950
2,512,359
umreo
PATENT OFFICE
LUBRICANT ‘- COMBO SITIONSiCONTAINING
~ :BERYL'LIUM‘.C‘ARBQXYLATES
John F. McGrogan, Philadelphia; Pa, ,assignor to
The Atlantic ,‘Re?ning Company,’ Bhiladelph‘ia,
Pa., a corporation of Pennsylvania
Noni-owing- ‘Application October 26,1946.
.> SerialrNo. 706,054
v10 Claims.“ (mag-#3217) '
,
1'
,
,
The present invention relates to lubricants,
and particularly to mineral oil lubricantshaving,‘
incorporated therein ininorquantitiesof addi
erence ishadpforjmonc- Or di-salts of saturated
tive materials adapted to improve lubrication
aliphatiocarboxylic, acids of from 1.2 to ,18, car
properties, and toinhibit or retard deposition of
blpnatqms- .iHowcver, a variety of acids ‘may be
employed-in the production of the beryllium
saltsfiineluding, both the mono! and polycar
varnish, lacquer and sludge caused by deteriora
tion of the oil in normal lubrication service.
>
'
Commercial petroleum lubricating oils, no
boxyhlcv acids which are exempli?ed by enanthic
matter how highly re?ned, have. a de?nite tend
ency to deteriorate under the lubricating con;
a1
ditions encountered-in internal combustion en,
waxes. adipic acid, :nimelic . acid, suberic acid,
az'elaic acidsebacic acid; succinic acid, and other
15
Deposits, in the nature of varnish, lacquer and t
sludge, are products of this deterioration, and
iere with proper operation, ,ormay even cause 20
_
the,;nuclear.hydregen atoms. issu-bstituted. byan
acids such as nhthalic acid
gests many ways of accomplishing- these ends, - Ch
3
l
'
beIiatoms; .alkylated aryl carboxylic acids in
cludinebenzcic acid .in which one Qrmore of
alkyl or. alkenyl
group preferably
of ataromatic
,‘least 6 '
. carbon-atoms;
.allsylated
nolycarboxylic
problems oi inhibiting
oil
deterioration, andThe
of maintaining
oil cleanliness
during lubrication service, are, therefore, pies;
ential importance, and while the prior art sue;
further improvement is desirable.
acidsiof that series in which. one. or. more of the
metbvlenc hydroaensare substituted by unsatu
ratedhizdrocarben residues suchas polymers of
presumed butvlene’having from 8 to '18 car-1
in modern engines with close clearances small
amounts of these deposits may seriously._inter-.
engine seizure.
. .caprvlic acid, pelargonicacid, lauricacid,
myristicacid, vgpalrnitic acid, stearic acid‘, acids
derived. brthe oxidation of petroleum oils and
gines. High crank case temperatures, and other
increasingly severe requirements inengine, per
formance, aggravate the rate of oil, deterioration
from thermal decomposition and oxidation.
12
normal .911 basic , salts or mixtures thereofderived
from 9L1? gona mixture of carboxylic acids. ' :Pref
which one or more,
of ethe nuclear hydrogenatoms is substituted by
an allgyior alkenyl group of .6_or_rnore .carbon
It is an object of this invention to‘ provide
atoms; abietic acid, hydrogenated abietic, acid,
particularly of from 12 to 18 carbon atoms, are
excellent detergents for all common lubricating
oils, and that these compounds as additives-in
such as to give either'a normalor a basic salt
;Alternatiuely, a-solublev beryllium icompoundsuch
small concentrations minimize .depositionof- de
terioration products, and thereby improve-the
solution, may be reacted with an aqueous solu
narlithenicacidsl and the like
>
lubricating oil compositions which are eifectively
The beryllium salts of the carboxylic acids may
inhibited against the formation of varnish, lac
beprepared by reacting a basic; beryllium com
quer and sludge deposits.
30
pound, such as beryllium hydroxide or carbonate
I. have fellndthat the beryllium salts. of. earwith‘the oarboxylic acid at elevated temperature,
boxylic acids of from 6 to 18 carbon ‘atoms, and
the ratio of hydroxide or; carbonate to acid being
as the chloride, nitrate or ‘sulfate in. aqueous
tiomondispersionof an alkali metal saltoi a
over-all lubricating properties of the oil. Some
c, ;bo_xylic_i_acld.to?give .awater-ins'oluble beryl
of these salts are inherently soluble in petroleum
oils in an amount su?icient to provide good. de 40 liu .carboxylate. ‘The nrcnarationof the beryl
lium-salts of the carboxylic acids is effected by
tergency action, and those which are less. $91.11.
conventional meanseand formsllQP?-l‘t?f the
ble can be readily'incorporated in oils with‘the
present invention. thereieret further discussion
aid of solubilizing agents, such as aliphatic acids
thereof is not essential.
and alcohols, alkyl esters, or other compounds
The beryllium salts of the carboxylic acids
known to have a solubilizing function. The
may be incorporated in suitable amounts in
actual amount of salt additive necessary to pro
lubricating oil by simply heating the mixture
vide the results intended may vary broadly with
until solution or dispersion is accomplished, and
in a range from about 0.1% to 5.0% by weight of
thereafter cooling the product to ordinary tem-x
the oil, depending upon the properties of the
untreated oil base; and with the more common 50 peratures. When it is desired to increase the
anti-corrosion and anti-rust properties of the
commercial lubricants, additions of about 0.5%
lubricant, various inhibitors may be added to
to 2.0% of the beryllium salts have given very
the oil containing the detergent beryllium car
satisfactory results.
boxylates. The anti-oxidants, anti-corrosion
The beryllium salts which may be employed in
accordance with this invention are either the or agents, and anti-rust agents may be incorporated
in amounts varying from 0.1% to 5% by weight
mass;
of the lubricant, 0.5% to 2.0% being preferred.
These agents include phenolic and amino com
pounds such as the long-chain alkylated phenols
produced by the polymerization of ole?ns or the
condensation of ole?ns or halogenated hydrocar
bons with aromatic hydrocarbons.
and polyhydroxy aromatic compounds; aliphatic
I claim:
and aromatic amines; metal salts and amine salts
of the acid esters of the acids ofv phosphorus,
and particularly metal salts of the acid esters
1; A lubricating oil composition comprising
hydrocarbon oil and a beryllium salt of a car
boxylic acid containing from 6 to 18 carbon atoms,
said salt being present in an amount sui?cient to
improve the detergency of the oil when used in the
of a thio-aoid of phosphorus such as the zinc salt
of cyclohexyl acid thiophosphate; phenol sul?des
and metal salts thereof; sulfurized oils and sul
furized esters of carboxylic acids, such as sul-'
10 lubrication of internal combustion engines.
2. A lubricating oil composition comprising
hydrocarbon oil and from 0.1% to 5% by weight
furized aliphatic abietates, sulfurized higher fatty
acid esters, sulfurized sperm 0'1, and the like‘.
The present invention may be further illus
trated by the following examples, which, however,
of a beryllium salt of a carboxylic acid containing
from v6 to 18 carbon atoms.
‘ - 3. A lubricating oil composition comprising
are not to be construed as limiting the scope
thereof:
4
oils, deasphaltized residual oils, and synthetic oils
and from 0.5% to 2% by weight
of a beryllium salt of a carboxylic acid containing
‘ hydrocarbon oil
"
For the detergency test, there is provided- a.
glass test tube within which are vertically and
concentrically disposed two sand-blasted open
ended steel tubes. Between the steel tubes is in
from 6 to 18 carbon atoms.
4. A lubricating oil composition comprising
hydrocarbon oil and from 0.1% to 5% by weight
of a beryllium salt of a saturated aliphatic car
boxylic acid containing from 6 to 18 carbon atoms.
serted a copper tube of small dimension through‘
which air is delivered to the bottom of the test
5. A lubricating oil composition comprising
hydrocarbon oil and from 0.5% to 2% by weight
of beryllium stearate.
6. A lubricating oil composition comprising
hydrocarbon oil and from 0.5% to 2% by weight
tube .below- the end of the inner steel tube. In
carrying out' the test, the inner steel tube is
weighed and then inserted in the testing appa-v
ratus. '15 cc. of the oil to be tested is then ‘intro
duced into the glass test tube and forms a pool
of beryllium mono-stearate. '
covering the lower ends of the steel tubes and the
7. A lubricating oil composition comprising
copper tube. The apparatus is then placed in an 30 hydrocarbon oil and from 0.5% to 2% by weight
oil bath and heated to 300° F., air being injected
through the copper tube and beneath the surface
of beryllium di-stearate.
8. A lubricating oil composition comprising
hydrocarbon oil, 0.5% to 2% by weight of beryl
lium stearate, and 0.5% to 2% of a metal salt
of the test oil at a rate of 30 liters per hour. After
65 hours heating and blowing, the apparatus is
removed from the oil bath and cooled. The inner 35 of an acid ester of an acid of phosphorus.
steel tube is withdrawn, washed with naphtha,
9. A lubricating oil composition comprising
and weighed, the increase in weight being attrib
hydrocarbon oil, 0.5% to' 2% by weight of beryl
uted to the deposition of sludge. The smaller the
lium stearate, 0.5% to 2% of a metal salt of an
weight increase, the more e?ective the'detergent
acid ester of an acid of phosphorus, and 0.5% to
agent in the oil. The results of the tests are tab?‘ 40 2% of sulfurized ester of a carboxylic acid.
ulated below. The base lubricating oil used was
10. A lubricating’ oil composition comprising
a ra?inate fraction of a nitrobenzene selective
hydrocarbon oil, 0.5% to 2% by weight of beryl
solvent extracted distillate lubricating stock, such
lium stearate, 0.5% to 2% by weight of a metal
base oil having an A. P. I. gravity of 31° and a
salt of an acid thiophosphate, and 0.5% to 2% by
Saybolt Universal viscosity of 175 seconds at
weight of sulfurized sperm oil.
100° F.
JOHN F. MCGROGAN.
Milligrams
Lubricant
sludge de
.
posited
REFERENCES CITED
The following references are of record in the
Base oil ____________________________________________ . _
Base oil+0.5% beryllium mono-stearate. _
..
Base oil+l.0% beryllium mouo-stearate.Base oil+2.0% beryllium mono-srearate
Base oil+l.0% beryllium di-stearate.-Base oil+2.0% beryllium di-stearate ________________ _.
63
13
. 3
' *3
‘ 0
1
While, in the above test, a solvent re?ned lubri
cating oil was employed as the base, other hydro
carbon oils may be used in lieu thereof, including
?le of this patent:
UNITED STATES PATENTS
Number
Name
Date
2,320,392
White ____________ __ June 1, 1943
2,322,307
Neely ____________ __ June 22, 1943
CTHER REFERENCES
‘The
Alkaline
Earth and Heavy Metal Soaps,
straight-run lubricating distillates from paraf?n 00
base, naphthene base, or mixed base crude oils,
ACS Monograph Series No. 103, 1946. p. 165, by
acid treated oils, hydrogenated oils, clay treated
Elliott.
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