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11.5673
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Patented Oct. 22, 1946v
2,409,878
UNITED STATES PATENT
Eric's
2,409,878
LUBRICATING OIL
Robert L. May, Chicago, 111., assignor to Sinclair
Re?ning Company, New York, N. Y., a corpora
tion of Maine
No Drawing. Application July 15, 1944,
Serial No. 545,195
5 Claims. (Cl. 252—32.7)
1
2
This invention relates to a lubricating oil com
What depending upon the characteristics of the
position having improved characteristics espe
cially with respect to oxidation and corrosion.
In my Patent No. 2,379,313 I have described
and claimed a new class of organic-metal com
pounds comprising the zinc salts of organic com
pounds resulting from the reaction of an alkyl
turpentine-P285 condensation product, the nature
and proportions of the alkylated phenols reacted
therewith to form the intermediate material, the
conditions under which the reactions are effected
and to some extent upon the proportions of zinc
oxide and the intermediate material used in its
ated phenol with a condensation product of a
production. Also the character of the inhibitor
terpene, such as is present in turpentine, and
is in?uenced by the conditions under which the
phosphorus pentasul?de. The turpentine-phos 10 zinc oxide is reacted with the intermediate ma
phorus pentasul?de condensation products are
terial.
the subject of my co-pending application, Serial
The reaction temperature employed in the last
No. 494,688, ?led July 14, 1943, and the materials
mentioned reaction, in the preparation of my in
resulting ‘from the reaction thereof with alkylated
phenols are the subject of my Patent No. 2,379,312. 15 hibitor, is with advantage maintained within the
range of about 275° F. to about 300° F., although
I have now discovered that the zinc salts of my
reaction temperatures somewhat outside of this
?rst said patent are especially effective in re
range are permissible. Particularly desirable re
pressing or inhibiting the deterioration of lubri
sults have been obtained where the temperature
eating oil compositions and the corrosion of metal
parts in contact therewith.
.
20 has been raised to about 280° F. during this reac
tion. Also I have found it desirable to use an
I am at present unable de?nitely to identify by
amount of zinc oxide somewhat in excess of that
chemical formula either the zinc salts or the con
equivalent to the acid number of the intermediate
densation products of turpentine and phosphorus
material and to ‘filter 01? unreacted excess zinc
pentasul?de or the products resulting from (“the
oxide as previously indicated.
reaction of said condensation product with the
The lubricating composition of my present in
alkylated phenol. For convenience and brevity,
vention may consist solely of the lubricating oil
I shall herein refer to the former as my inhibitor,
constituent and my inhibitor. However, the in
to the condensation product as the turpentine
hibitor of my present invention has been found
P2S5 condensation product and to the composi
tion resulting from the reaction of the alkylated 30 to be compatible with other desirable lubricating
oil addends and the inclusion of such other ad~
phenol with the turpentine-P285 condensation
dends, especially addends of the type known as
product as the intermediate material, each of
detergents, is within the contemplation of my
which is hereinafter more fully described.
present invention and constitutes an important
Although the intermediate material itself has
aspect thereof.
been found to be a desirable component of lubri
eating oil compositions, the use of such inter
The inclusion of certain so-called detergents,
mediate materials for this purpose is subject to
for instance, in internal combustion engine lubri
certain disadvantages. For instance, it is subject
cants, has been found highly advantageous. An
to the objection that they have somewhat acidic
especially effective lubricating oil composition for
characteristics, due to phosphorus acidity which 40 the lubrication of internal combustion engines
and the like, contemplated by my present inven
has been found to have a tendency to promote
sludging of mineral oil compositions. The lubri
cating oil compositions of my present invention
are free from this objection.
tion, is one comprising, in addition to the lubri
cating oil constituent and my inhibitor, a minor
proportion of a calcium-containing detergent, for
In general, my inhibitor may be prepared by 45
instance, the calcium salt of various alkyl esters
reacting zinc oxide with the intermediate ma
of aromatic acids, particularly the calcium salt
terial by intimately admixing the zinc oxide with
of iso-octyl salicylate and the calcium salt of
the intermediate material with, moderate heating.
capryl salicylate. These and various other or
The product of this reaction is then with advan
tage diluted and ?ltered to remove any excess or 50 garlic-calcium salts have been found particularly
effective as detergents in lubricating oil composi
unreacted zinc oxide present. In the preparation
tions used in internal combustion'engines, the two
of such compounds for use as a constituent of my
improved lubricating oil compositions, the diluent
particularly named calcium salts being more fully
is with advantage a light neutral lubricating oil
described in Letters Patents 2,347,547 and 27,339,
fraction which may be permitted to remain in 55 692, issued on applications of Willard L. Finley.
the product.
A further highly effective lubricating oil com‘
The characteristics of my inhibitors vary some
po'sition ‘contemplated by my present invention"
2,409,878
is one comprising, in addition to the lubricating
oil constituent and my inhibitor, a calcium petro
leum sulfonate, as a detergent. Other detergents
which may be used with advantage include the
barium phenolate of sulfurized diamyl phenol,
such as currently marketed under the trade name
of “Aerolube B,” metallic phenolates of sulfurized
4
should be a saturated aliphatic group. Each
molecule of the alkylated phenol may contain one
or more such groups.
The number of carbon
atoms in each aliphatic group is not critical. De
sirable products may be obtained where each such
group contains from 1 up to 12 to 16, or even up
to 25 to 35 carbon atoms. Alkylated phenols con
tertiary amyl phenol, such as currently marketed - , taining 5 or more carbon atoms in .each alkyl
group have been found especially desirable, be
under the trade names “Calcium Paranox” and
“Barium Paranox” and various metallic soaps, 10 cause of the greater oil solubility of the resultant
product. The alkyl group or groups may be either
either basic or neutral, metallic sulfonates, alco
normal or branched chain.
holates and alkoxides and metallic derivatives of
alkylated salicylic acid.
When used in conjunction with these deter- '
gents, particularly the calcium salts, including
Alkylated phenols, herein designated codimer
alkylated phenols, such as prepared by the reac
tion, in the presence of sulfuric acid, of phenols
with the ole?nes in commercial codimer, resulting
‘from the phosphoric acid polymerization of mixed
calcium petroleum sulfonates previously men
tioned, these detergents and my inhibitors have
olefines of 4 carbon atoms or less per molecule and
been found to complement each other so that the
comprising propylene, butene-l, butene-Z and
effectiveness of each is promoted. The tendency
of the detergent to promote oxidation of the oil 20 iso-butylene, the codimer consisting of a major
portion of Ca ole?nes, together with some 06- C71
at the termination of its oxidation induction pe
C9, C10, C11, C12 and higher ole?nes, have been
riod is minimized by the presence of my inhibitor
used with advantage. These codimer alkylated
without destroying the effectiveness of either the
phenols are comprised primarily of mono- and
detergent or the inhibitor.
The proportions of the inhibitor used in the 25 poly-alkylated phenols having alkyl groups, as
noted above, but with Ca alkyl groups predomi
compounding of my improved lubricating oil com
position may be varied somewhat but in any case
nating.
I have further used with advantage in the prep-,
only a minor proportion is used. The optimum
aration of my improved lubricating oil composi
proportion to be used will depend upon whether or
tion, alkylated phenols, prepared by the method
not a detergent, such as previously mentioned, is
just described for the preparation of codimer al
present and the particular use to which the lu
kylated phenols except that the phenol was re
bricating oil composition is to be put. The opti
mum proportion will also vary, depending upon
acted with codimer bottoms, the codimer bottoms
used being the bottoms obtained by a redistilla
the particular member of my new class of in
tion of the previously described codimer to a 350
hibitors used.
In the preparation of my improved lubricating
to 360° F. end point overhead. Thisbottom was
oil composition, I have found itadvantageous to
comprised primarily of C12 ole?nes, but contains
prepare the inhibitor in solution in about an equal
some somewhat lower and some somewhat higher
weight of a petroleum lubricating oil fraction, as
molecular
weight ole?nes.
As previously noted, I'am at- present unable
hereinafter more fully described. As a motor oil 40
which does not contain detergents, 0.2 to 05% of
de?nitely to identify by chemical formula either
the 50% concentrate of my inhibitor may, with
the inhibitor used in the preparation of my im
advantage, be admixed with the lubricating oil
proved lubricating oil compositions or the inter
constituent. When used as an anti-oxidant in
mediate material or the turpentine-P285 conden
turbine oils or hydraulic oils, the 50% concentrate 4,5 sation product from which they are prepared.
maybe added to the lubricating constituent in
However, I have found it desirable that the tur
proportions‘ advantageously ranging from about
pentinewPzss condensation product used in ac
0.1 to about 0.3% by weight. In heavy duty oils
cordance with my present invention contain no
containing detergents, such as previously men
'
,
60 unreacted Pass.
tioned, for use in gasoline or Diesel engines, the
Since the characteristics of my improved lubri
50% concentrate of my inhibitor may, with ad
cating oil composition are somewhat in?uenced
vantage, be added in proportions ranging from
about 1% to about 10% by weight, depending
upon the nature and concentration of the deter
gent, the severity of the service for which the
lubricating oil composition is to be used and the
particular inhibitor employed.
The molar proportions of PzSs, turpentine and
alkylated phenol used in the preparation of the
intermediate material, which I react with zinc ox
ide in the preparation of my new class of in
hibitors, may be varied over aconsiderable range.
Molar proportions of 2:6:3 have been used with
by the characteristics of the particular‘ inhibitor
used, which in turn are influenced by the charac
teristics of the intermediate materials from which
my inhibitors are prepared, a detailed description
of the preparation and the character of the par
ticular inhibitor'used will be included in the spe
ci?ic illustrations 'of my invention hereinafter set
forth. However, it will be understood that my in
vention is not limited to the use of these particu
lar inhibitors illustrated nor‘with respect to the
method by which the inhibitor is prepared, but in
cludes lubricating oil compositions ‘comprising
particular advantage, assuming the molecular
the inhibitors herein described by whatever proc
65
weight of the turpentine to be L36. However, for
ess the inhibitor may be made.
each two moles of P255 there may be used 5 to 7
moles of turpentine and 1 to 5 moles of alkylated
phenol, but it is desirable that the sum total of
the number of moles of turpentine and the moles
of alkylated phenol for each two moles of P285 fall
within the range of about 8:10.
In the preparation of my novel class of inhib
Generally, in the preparation of the turpentine
PzSs condensation product used in the prepara
tion of my inhibitors, the molar ratio of turpene
tine-P2555 is with advantage approximately 3:1.
However, this ratio may vary somewhat in either I
direction. For instance, highly desirable prod
ucts
may be produced from intermediate material
itors considerable latitude is permissible in the
which
in turn have been produced from turpen
selection of the alkylated phenol used. In gen
eral, the alkyl radical of the alkylated phenol 75 tine-P255 condensation products in which the
liviti’il‘dl l “lllbllii
Search Room
ice
2,409,878
5
6
ratio of turpentine to P285 is within the range of
about 5:2 to about 7.: 2, as previously noted.
The reaction of turpentine with P2555 is highly
added and the mixture stirred for one hour, at the
endof which time 225 grams of zinc oxide was
added, the mixture stirred for an additional hour
exothermic and proceeds spontaneously after be
ing initiated by slight heating. A desirable meth
and thereafter the temperature increased slowly
to 280° F.
In ‘order to facilitate ?ltration, the resulting
od of effecting this reaction is to heat the turpen
tine in a vessel to about 200° F. and then, without
product Was thinned by intimately admixing
further heating, slowly stirring in the phosphorus
therewith 4380 grams of a light petroleum lubri
pentasul'?de in the powdered form. The heat of
cating oil fraction. The mixture was then ?l
reaction is great and, consequently, the sul?de 10 tered and the ?ltrate was found by analysis to
should be added slowly so as toavoid the possi
have an acid number of 30.0 and an A. P. I. grav
bility of the reaction’s becoming uncontrollable.
ity of 11.1 and to contain 3.19% phosphorus,
3.04% sulfur and 0.48% zinc.
sirable that the temperature during this addition
Example II
not be permitted to exceed about 250° F., although 15
higher temperatures are permissible.
To a turpentine-P285 condensation product pre
‘After the addition of phosphorus pentasul?de
pared, as in Example I, from 2040 grams of steam
is completed and the exothermic heating is 1ess~
distilled wood turpentine, 1110 grams of powdered
phosphorus pentasul?de, at a temperature of 230°
ened, it is usually necessary to apply heat exter
nally‘ to complete the reaction. The temperature 20 F., there was added 1755 grams of diamylphenol
during this last stage is preferably maintained at
and the mixture heated and stirred at a tempera
about ‘300° F., though temperatures of about 200
ture of 200° F. for one hour. Thereafter, 225
to about 400° F. may be employed. The second
grams of Zinc oxide was added and the mixture
stage of the reaction should be continued until
stirred for one hour. The temperature was then
all of the Past is dissolved. The material thus 25 gradually raised to 280° F‘. to complete the reac
prepared is a viscous liquid at elevated tempera
tion.
The product of the reaction was then thinned,
tures, but, in the absence of excess turpentine,
For the purpose of my present invention, it is de
to facilitate ?ltration, by intimately admixing
solidi?es on cooling to room temperature.
In general, the intermediate material used in
therewith 4905 grams of a light petroleum lubri
the preparation of my inhibitors may be prepared 30 cating oil fraction and the mixture ?ltered. The
by adding the alkylated phenol gradually to the
?ltrate was found by analysis to have an acid
number of 28.3, an A. P. I. gravity of 13.1 and to
turpentine-BS5 condensation product, advan
tageously at a temperature of about 230° F. The
contain 3.0’? % phosphorus, 7 .82% sulfur and
optimum temperature of the condensation prod
0.24% zinc.
uct for the introduction of the alkylated phenol 35
Example III
will vary, depending upon the particular alkyl
ated phenol used. During the ?nal step of the
production of the turpentine-Pass condensation
product, the temperature will usually be substan
The product was prepared using the procedure,
ingredients and proportions thereof identical with
those of Example II, with the exception that the
tially in excess of 230° F., usually about 300° F., 40 diamylphencl constituent was added to the tur
pentine-PzSs condensation product while the lat
and in commercial operations two to three hours
ter was at a temperature of 300° F. The prod
would normally be required for lowering the tem
uct was thinned and filtered, as previously de
perature to 230° F. by natural cooling.‘ Such
scribed, and the ?ltrate was found by analysis to
cooling is usually unnecessary and may be avoided
since these alkylated phenols are relatively sta 4-3 havean acid number of 26.2. an A. P. I. gravity of
13.3 and to contain 3.11% phosphorus, 8.28% sul
ble toward heat and may be safely admixed with
fur and 21% zinc.
the turpentine-Pass condensation products at
temperatures as high as 300° F.
Ermnple I V
In reacting the alkylated phenols with the tur
A
product
was
prepared
by the procedure of
pentine-Pzss condensation products, very little 50
Example II from 1‘200 grams of turpentine, 1110
heat is evolved. After the alkylated phenol has
grams of P285, 1755 grams of diamylphenol and
been added. the mixture is maintained at an ele
56 grams of zinc oxide. The product was thinned
vated temperature, advantageously at about 200°
by intimately admixing therewith 4565 grams of
F. or higher, for about one hour with stirring.
a light petroleum lubricating oil fraction and was
The following speci?c examples of various
then ?ltered. The ?ltrate was found by analysis
members of my new class of inhibitors and the
to have an acid number of 33.3, an A. P. I. gravity
procedure by which they have been successfully
prepared, are given as illustrative of the class.
Example I
2040 grams of turpentine was placed in a ?ask
of 13.1 and to contain 3.67% phosphorus, 10.28%
sulfur and 0.182% Zinc.
60
Example V
equipped with a stirrer, a thermometer and a
funnel, and heated therein to 240° F. There was
then added to the turpentine 1110 grams of phos
phorus pentasul?de at such a rate that the tem
perature of the reaction mixture did not rise above
275° F. The mixture was stirred during this addi
tion. When all of the P255 had been added, the
temperature of the mixture was raised to 300° F.
and the mixture held at this temperature for two
hours with stirring. At the end of this period, all
of the phosphorus pentasul?de had dissolved
and the product was ‘a viscous, amber—celored liq
uid. Thereafter, the mixture was cooled to 230°
F. and 1230 grams. of p-tert-amyl phenol was ”
r
I
A product was prepared by the procedure of
Example II from 2040 grams of turpentine, 1110
grams of P265, 1172 grams of diamylphenol and
» 56 grams of Zinc oxide. The product was thinned
by intimately admixing herewith 4.322 grams of a
light petroleumlubricating oil fraction and there
after ?ltered. The ?ltrate was found by analysis
to have an acid number of
an A. P. I. gravity
of 11.9 and to contain 3.20% phosphorus, 9.36%
sulfur and 0.090% zinc.
Example VI
A product was prepared by the procedure of
Example II using the constituents and propor
.
1e
‘
2,409,878
8
7
ample VIII except for using as the alkylated
phenol constitutent 2570 grams of ‘a codimer
bottoms alkylated phenol consisting of a mix
tureof a codimer bottoms alkylated phenol'hav
ing a phenol number of 134.9, an apparent mo
lecular weight of 415 and a codimer bottoms
alkylated phenol having a phenol number of
tions therein described except that, in place of
the diamylphenol, 1425 grams of a butene alkyl
ated phenol having a phenol number of 294.3
and an apparent molecular weight of 190 was
used and the resulting product was thinned by
admixing therewith 4575 grams of the light petro
leum lubricating oil fraction.~ After ?ltration the
?ltrate was found to have an acid number of 31.3,
an A. P. I. gravity of 12.8 and to contain 3.13%
phosphorus, 7.19% sulfur and 0.46% zinc.
Example VII
127.5 and an apparent molecular weight of 441.
Prior to ?ltration, the product was diluted by
10 the addition of 5090 grams of the lubricating
oil fraction. The ?ltration was found by analysis
to have an acid number of 20.5, an A. P. I. gravity
of 16.5 and to contain 2.84% phosphorus, 6.43%
A product was prepared by the procedure of Ex
sulfur 0.07% zinc.
ample II, using the constituents and proportions
therein described except that, in place of the di 15
Example XII
amylphenol, 2050 grams of a codimer alkylated
phenol having a phenol number of 203.7 and an
apparent molecular weight of 275 was used and
This product was prepared by the method and
from the ingredients and proportions used ‘in
Example VIH except for using as the alkylated
the product was thinned by intimately admixing
therewith 5,200 grams of the light petroleum lu 20 phenol constituent, 1920 grams of a codimer‘loot
toms alkylated phenol having a phenol num
bricating oil fraction. The product was then
ber of 116.2 and an apparent molecular weight of
?ltered and the ?ltrate was found by analysis to
483. Prior to ?ltration the product was diluted
have an acid number of 23.7, an A. P. I. gravity of
by the addition of 4440 grams of the lubricating
14.4 and to contain 2.70% phosphorus, 7.83% sul
25 oil fraction. The product was found by analysis
fur and 0.13% zinc.
to have an acid number of 22.5, an A. P. I. gravity
Example VIII
of 15.2 and to contain 2.62% phosphorus, 7.68%
sulfur and 0.115% zinc.
A product was prepared by the procedure de
The light petroleum oil fraction used‘ in each
scribed in Example II from 1632 grams of turpen
of- the foregoing examples to facilitate ?ltration
tine, 888 grams of Past, 2,149 grams of a codimer
was a Mid-Continent neutral having the follow-v
bottoms alkylated'phenol, and 180 grams of zinc
oxide. ‘ The codimer bottoms alkylated phenol
used had a phenol number of 151.2 and an appar
. ent molecular weight of 371. The resulting prod
uct was diluted by intimately admixing therewith
4669 grams of the light petroleum lubricating oil
fraction and was ?ltered. The ?ltrate was found
by analysis to have an acid number of 21.3, an
A. P. I. gravity of 15.2, and to contain 2.86% phos
40
phorus, 6.70% sulfur and 0.12% zinc.
Example IX
This product was prepared by the method and
from the ingredients and proportions used in
Example VIII except for using as the alkylated
phenol constituent 1765 grams of codimer alky
lated phenol having a phenol number of 190.9
and an apparent molecular weight of 294. The
product was diluted prior to ?ltration by inti
mately admixing therevidth 4285 grams of the
light lubricating oil fraction. The ?ltrate was
found by analysis to have an acid number of
25.0, an A. P. I. gravity of 14.5 and to contain
ing characteristics:
Gravity, °A. P. 1: __________ _; __________ __
27.9
Flash, °F _____________________________ __
Fire, "F _______________________________ __
365
405
Viscosity at 100°,F., SUS-__.._v ___________ __ 107.8
Viscosity at 210° F., SUS _______________ __
Pour, °F
__
Color _____________________________ _'____
39.5
20
2—
rI‘he codimer alkylated phenol and the codimer
bottoms alkylated phenol were prepared as pre
viously described herein. From the foregoing
speci?c illustrations, it appears that the com
'bining ratios of zinc oxide and the intermediate
materials vary somewhat with the excess of zinc
oxide present. The duration of the reaction
period also appears to in?uence the zinc content
of‘ ‘the ?nished product. The presence of a
considerable excess of zinc oxide during the
reaction is usually desirable.
The turpentine -P2S5 condensation product
from which the members of my new class of in
2.68% phosphorus, 7.51% sulfur and 0.23% zinc.
55 hibitors are prepared is, in the absence of excess
Example X
turpentine, normally a brittle, resinous solid.
It‘ is with advantage prepared from‘turpentine,
This product was prepared by the method and
from the ingredients and proportions used in
Example VIII except for using as the alkylated
phenol constituent 2670 grams of a codimer bot
toms alkylated phenol, consisting of a mixture
of a codimer bottoms alkylated phenol having a
phenol number of 125.9 and an apparent molecu
either steam-distilled wood turpentine or gum
5.88% sulfur and 0.11% zinc.
Example XI
This product was prepared by the method and
from the ingredients and proportion used in Ex 75
Mid-Continent _ or South Texas neutrals or a
spirits, consisting mainly of alpha pinene, a
bicyclic terpene having the empirical formula
ClOHlS. Pure alpha pinene and other more costly
terpenes will react similarly with P285 but, for
reasons including economic considerations, I pre
fer to use the more readily available turpentine.
lar weight of 445 and a codimer bottoms alkylated
phenol having a phenol number of 124.7 and an 65 The turpentine used in the speci?c examples
herein was a technical grade steam-distilled wood
apparent molecular weight of 448. Prior to .?l
turpentine comprising about 90% alpha pinene.
tration 5,190 grams of the lubricating oil diluent
As the lubricating oil constituents, various
was added. The ?ltrate was found by analysis
petroleum lubricating oil fractions may be used.
to have an acid number of 19.8, and A. P. I.
gravityof 16.6 and to contain 3.12% phosphorus, 70 For instance, solvent treated or acid treated
blend of such neutrals with‘ bright stock or a
solvent re?ned lubricating oil fraction from a
Pennsylvania crude or various blends of such
lubricating oil fractions may be employed. Char-1
i: billresinous.
that‘ 0
Search Room
' UKUBD mil‘ LKENUE
I)
C.
2,499,878
9'.
10
acteristics of several such’ oils which have been
identi?ed, was 255.6,- milliliters and the bearing
metal corrosion, loss. was» 5.8 milligrams. By- in
corporating in, this. base oil 0.1% of my inhibitor
prepared as described in Example II, the mean
used with advantage and. which were used in the
compounding of my ‘lubricating oil: compositions
hereinafter set forth, as illustrative of my in
veniiion, appear in the following Table I in which 5 oxygen absorption rate‘ was reduced .to 12.7 milli
ibase .oilA. is. a. solventetreated Mid:Continent,
liters and the bearing metal corrosion loss was
S. A. E.. 10011 and base. oil. B. is. a. sn?onated MidContinent S.. A. E. 30- 035k prepared: by treating a
raw Midecontinent stock with 40 pounds of
99.3%. suliuric acid per. barrel, separating the in
reduced to $3. milligrams. ‘.By compounding with
this same base oil 0.25% of said inhibitor, the
mean oxygen absorption rate was reduced to 4.6
milliliters and the- bearing~ metal corrosion loss
sludge formed, neutralizing the acid oil with
reducedto 2.6.- ~
lime, heating the mixture to drive off all water
5
’
Further illustrations of my improved lubri
present and ?ltering the dehydrated oil.
eating oil compositions and the characteristics
Base oil C is an- S'. A. E. 30 sol-vent treated
thereof with respect‘to oxygen, absorption rates
neutral’. Base oil D is a solvent treated aircraft 1'5 and bearing metal corrosion losses are set forth
oi-l. Base Oil E‘ is a Mid-Continent base oil con~
in the following Table II. In each instance the
ventionally re?ned by» acid treatment. Base oil
F is also an acid treated Mid-Continent base oil.
Base oil G is an acid treated aircraft lubricating
' oil fraction.
inhibitor was compounded with the previously
identi?ed base oil B, the characteristics of the
base oil B without the inhibitor being included
2Q for comparison.
Table I
Base oil
A
Gravity, at. P.I __________ ..
Flas
13
29.5 " 25.5 ’ 27.0
°F
405
‘:
'
,
435
500
512.1
0.20
Calcium, percent _________________ _.
D
E
25.3
F I
G
25.0
24.7
540
305
450
510
515
010
432.3 1934.6
455
200.5
510
402.9
505
2,011.0
120.5
450
24.0
00.2
50.9
124.1
44.5
53.7
77.0
5,
80.3
5
88.7
10
51.4
15
54.0 1
10
0.03
0.58
0.02
0.05
1.15
0.127
0. 20
0. 39
0 49
0.25
__ ____________ __
Sulfur, percent ____________ _.
o
0.35
0.061
Neutralization No _______________________ __
81.3
-5
__________________________________ __
0.00
0.04
0.00
0 03
0.00
For the purpose of further illustrating my in-
Table II
vention and the advantage derived therefrom, I 40
have herein set forth the results of oxygen ab.
.
.
.
sorpt1on
and bearing
corrosion
tests of vanous
. ,
.
Inhibitor
7'
of my improved lubricating oil compositions.
‘Identity
The advantages of my present invention with re-
' "
_
.
Mean me Of ‘ Beam
Ozabsorpg_
tipnmiper
rglseigllcgs
Pg’eg‘getffini mm'ggesf 10°
mgs. ’
'
spect to oxidation and corrosion characteristics
2L6
M
illustrated
of my improved
by their
lubricating
mean oxygen
oil compositions
absorption rates,
are
‘é:.5- 0
0- 2
.
.
as compared with
the oxygen absorption
rates of>
3.00
4.15
+0.1
metal
the base
in oil,
contact
and the
withcorrosion
the respective
losses lubricants.
of bearing
2:
These tests were carried out in a closed sys
tem in which pure oxygen was circulated through
+0.1
Fromthe results oi these tests, it appears that
though the base oils had high corrosion rates
156 grams of the lubricant being tested. The
and high oxygen absorption rates, the lubricating
pressure of the system'was maintained constant 55 oil compositions prepared therefrom, in accord
by introducing oxygen from a burette, and the
time With my invention. showed in each instance
sample was maintained at 360° F. and in con
tact with two pieces of copper-lead bearings hav
substantially reduced oxygen absorption rates
‘bearing metal corrosion losses.
The .e?ectiveness of. my improved lubricating
ing an approximate combined area of one square
inch of copper-lead alloy surface and one square 60 01.1‘ compositions inhibiting-oil deterioration and
bearing. metal corrosion further appears- from re
inch of steel surface. The rateof oxygen absorp
tion is calculated as milliliters of oxygen ab
sorbed per minute per 100 grams of oil, measuring
5141118 of tests made in accordance with the pro
cedure recommended by the American Society of
Testing Materials, published October 1942, and
the oxygen under standard conditions of temper 65 entitled‘ “Proposed method of test for oxidation
ature and pressure. The bearing corrosion loss is
reported as milligrams, the plus sign indicating
characteristics of heavy duty crankcase'oils” and
conventionally known as the “Chevrolet engine
gain in weight.
test.” The improved characteristics of my lubri
,
The proportions of inhibitor indicated as used
in each of the tests herein are based on the weight
of the undiluted inhibitor, as distinguished from
cating oil compositions are further shown by the
results of tests carried onin accordance with the
method conventionally known as “Heavy duty oil
oxidation test,” a modification of the test usually
the 50% concentrate previously described,
designated “Best,” herein‘designated HDOOT; for
iwhensubjected to the foregoing test, the mean
brevity.
'
’
oxygen absorption rate of base oil A, previously 75. Various lubricating oil compositions, such as
-
.
_
i1
This lubricating oil composition was composed
just identi?ed, will further illustrate my inven
tion.
1-2
Composition D
contemplated by my present invention and the
characteristics thereof, as indicated by the tests
of the following:
-
Per cent
77.7
'
Composition A
Base oil C___‘
Base oil D
'
6.0
Calcium sulfonate detergent ____________ __ 14.0
Inhibitor of Example II _________________ _.. 2.2
This lubricating oil composition was composed
of the following:
Per cent
Base oil C _____________________________ __ 83.9 10 Pour depressant ________________________ __' 0.1
Sodium sulfonate detergent _____________ .._ 14.8
Inhibitor of Example II ____________ __‘_____
When tested by the previously identi?ed
HDOOT, the roof deposit was’ 1.2 grams and the
CuPb bearing metal corrosion loss 8 milligrams.
1.3
The composition contained 0.09% sodium and
the equivalent of 0.15% of P285. When tested
by the previously identi?ed I-IDOOT, there re
After the test the used oil was found to contain
0.23% naphtha insoluble, to have increased in
viscosity at 210° F. by 2.7 seconds and to have'a
neutralization number of 1.6.
Composition E
This lubricating oil composition was composed
sulted a roof deposit of only 3.2 grams, and a
CuPb bearing metal loss of 30 milligrams. At the
end of the 135 hours test, the oil was found to
contain 0.34% of 86° naphtha insoluble material.
Its increase in viscosity at 210° F. was 2.0 seconds
and its neutralization number was 0.6.
of the following:
Composition B
This lubricating oil composition was come 25
posed of the following:
Per cent
Base oil C ____________________________ __ 83.34
Sodium sulfonate detergent ____________ __ 14.71
Inhibitor of Example II ________________ __ _ 1.95
'
7
Per cent
Base oil F _____________________________ __ 62.3
Base ‘oil G _____________________________ __ 15.0
Calcium sulfonate detergent ____________ __ 20.0
Inhibitor of Example II.v ________________ __
2.5
Pour depressant ________________________ __
0.2
The composition contained 0.10% calcium and
the equivalent of 0.31% P2S5. The depressant
30 used was that previously identi?ed.
When tested by the previously described
HDOOT, the roof deposit was 1.9 grams and the
CuPb bearing metal loss was 1 milligram. Fol
scribed HDOOT, the roof deposit was found to '
be 0.14 gram and the CuPb bearing metal loss 27 35 lowing the test, the oil was found, tocOntain
It contained 0.09% sodium and the equivalent of .
When tested by the above de-,
0.22% of P285.
0.42% naphtha insolubles, to have increased in
milligrams. The naphtha insoluble in the used
viscosity at 210° F. by 3.2 seconds and to have a
oil was 0.44%, the viscosity rise at 210° F. was 2.9
neutralization number of 1.7.
and the neutralization number was 0.3.
When subjected to the previously identi?ed
Base oil C alone when subjected to said tests
resulted in a roof deposit of 37.5 grams anda 40 “Chevrolet engine test,” the combined sludge
and varnish rating was Bland the CuBb bear
CuPb bearing metal loss of 204 milligrams. The
ing corrosion loss for the complete bearing was
oil after the test of 135 hours was found to con
0.095 gram. At the end of the 36 hour test, the
tain 1.2% of naphtha insoluble material, to have
increased in viscosity at 210° F. by 4.2 seconds and
used oil was found to have a neutralization num
to have a neutralization number of 1.5.
ber of 1.65 and to have increased in viscosity at
100° F. by 149 seconds.
In compositions of this type, proportions of
'
A blend of this same base oil, containing 15%
of sodium sulfonate and 85% base oil, when sub
jected ‘to the foregoing test resulted in a roof
deposit of 29.1 grams and a CuPb bearing metal
loss of 665 milligrams. After the test, the oil was
found to contain 1.5% of naphtha insoluble ma
terial, to have increased in viscosity at 210° F. by
4.3 seconds and to have a neutralization number
of 2.2.
the addencl as high as 4% have been used with
advantage.
Composition F
This lubricating oil composition was composed
of the following:
Per cent
'
Composition C
This lubricating oil composition was composed
of the following:
Base oil C ____________________________ __ 96.05
Detergent (“Aerolube B”) ______________ __
Inhibitor of Example II ________________ __
The composition contained 0.20% barium and
the equivalent of 0.22% P285.
When tested by the previously described
Per cent
Base oil C _____________________________ __ 79.3
Base oil D-
__
_
2.0
1.95
5.0
I-IDOOT, the roof deposit was 1.8 grams, the sump
was clean and the CuPb bearing metal loss was
3 milligrams. Following the test, the used oil
Pour depressant______________________ __‘__ 0.2
was found to contain. 0.3% naphtha insoluble, to
The composition contained 0.07% calcium and 65 have increased in viscosity at 210° F. by 1.5 sec
onds and to have a neutralization number of
the equivalent of 0.19% P285. The depressant
contained in the oil was a commercial product
0.10.
Calcium sulfonate detergent ____________ __ 14.0
Inhibitor of Example II _________________ __ 1.5
Composition G
marketed under the trade-name “Santopour.”
When tested by the previously described
This lubricating oil composition was composed
HDOOT, the roof deposit was 2.4 grams and. the 70
of the following:
CuPb bearing metal loss 28 milligrams. Follow
Per cent
ing the test, the oil was found to contain 0.26%
Base
oil
C
____________________________
__ 84.86
naphtha insoluble. to have increased in viscosity
at 210° F. by 4.3 seconds and to have a neutrali
zation number of .1.7. y
-
75
Calcium sulfonate detergent ___________ __ 13.81
Inhibitor of Example‘IV___n_ ___________ __ 1.33
1 nine.
QRUSS Rtl’ tlitNUt
4c
1
.
2,409,878
13
14
When tested by the previously identi?ed
When tested by the HDOOT, the roof deposit
HDOOT, the roof deposit was 5.3 grams, the con
dition of the sump was clean and the CuPb bear
ing loss was 15 milligrams. Following the test
the used oil was found to contain 0.31% of
was 1.8 grams. the sump was clean and the bear
ing corrosion loss was 4 milligrams.
The used
oil contained 0.47% of naphtha insoluble, showed
a rise in viscosity at 210° F. of 1.0 and had a
neutralization number of 0.4.
naphtha insoluble, to have increased in viscosity
at 210° F. by 3.6 seconds and to have a neutral
In each of these and numerous other tests, it
ization number of 1.7.
has been found that lubricating oil compositions
prepared in accordance with my present inven
Composition H
10 tion are superior with respect to the oxidation
This lubricating oil composition was composed
and corrosion characteristics of the composition.
of the following:
These results are obtained whether the composi
Per cent
tions consist solely of the lubricating oil con
Base oil C____-_ _______________________ __ 84.92
Calcium sulfonate detergent ___________ __ 13.82
Inhibitor of Example V ______ __- ________ __
1.26
stituent and my inhibitor or also contain a deter
15 gent such as previously noted, for instance cal
cium petroleum sulfonates. However, the latter
When tested by the previously described
HDOOT, the roof deposit was 3.2 grams, the con
dition of the sump was clean, and the CuPb bear
ing loss was 8 milligrams. The used oil con
compositions are particularly advantageous, as
previously noted herein.
I claim:
1. A lubricating oil composition comprising a
major proportion of a petroleum lubricating oil
in viscosity at 210° F. by 2.6 seconds and had a
and a minor proportion, e?ective to retard oxida
neutralization number of 1.3.
tion of the oil, of the reaction product of zinc
Composition I
oxide and an organic compound resulting from
25 the reaction of an alkylated phenol with the con
The lubricating oil composition was composed
densation product of turpentine and phosphorus
of the following:
pentasul?de, the alkyl group of the alkylated
Per cent
phenol being a saturated aliphatic radical.
Base oil E _____________________________ __ 37.4
2. A_lubricating oil composition comprising a
tained 0.37% of naphtha insoluble, had increased
Base oil G _____________________________ __ 25.0
Calcium sulfonate detergent ____________ __ 34.9
Inhibitor of Example VII _______________ __ 2.5
Pour depressant ________________________ __
0.2
20
30 major proportion of a petroleum lubricating oil
and a minor proportion, effective to retard oxida
‘ tion of the oil, of the reaction product of zinc
oxide and an organic compound resulting from
the reaction of an alkylated phenol with the con
HDOOT, the roof deposit was 1.0 gram, the sump 35 densation product of turpentine and phosphorus
was clean and the bearing metal loss was 4 milli
pentasul?de, the alkyl group of the alkylated
grams. The used oil contained 0.55% naphtha
phenol being a saturated aliphatic radical con
insoluble, showed a decrease in viscosity at 210°
taining at least 5 carbon atoms.
F. of 2.7 seconds and had a neutralization num
3. A lubricating oil composition comprising a
40 major proportion of a petroleum lubricating oil
"oer of 1.4.
When subjected to the “Chevrolet engine test,”
and a minor proportion, effective to retard oxida
the sludge and Varnish ratings were each 49,
tion of the oil, of the reaction product of zinc
the bearing corrosion loss for the entire bearing
oxide and an organic compound resulting from
was 0.132 gram, the viscosity rise at 100° F. was
the reaction of a polyalkylated phenol with the
62.2’ and the neutralization number of the used 45 condensation product of turpentine and phos
oil was 2.2.
phorus pentasul?de, the alkyl groups of the
Composition J
alkylated phenol being saturated aliphatic radi
cals.
This lubricating oil composition was composed
4. A lubricating oil composition comprising a
of the following:
major
proportion of a petroleum lubricating oil
Per cent
and a minor proportion, e?ective to retard oxida
Base oil C ____________________________ __ 82.86
tion of the oil, of the reaction product of zinc
Sodium sulfonate detergent ____________ __ 14.62
oxide and an organic compound resulting from
Inhibitor of Example XI ________________ __ 2.52
When tested by the previously identi?ed
the reaction of diamyl phenol with the condensa
When tested by the HDOOT, the roof deposit 5. tion product of turpentine and phosphorus penta
was 2.5 grams, the sump was clean, the bearing
corrosion loss was 5 milligrams, the naphtha
insoluble material in the used oil was 0.40%, the
viscosity rise at 210° F. was 1.3 and the neutral
ization number of the used oil was 0.5.
60
Composition K
This lubricating oil composition was composed
of the following:
Per cent
Base oil C---
____
83.14
Sodium sulfonate detergent______________ 14.67
Inhibitor of Example XII ______________ .._
2.19
sul?de.
5. A lubricating oil composition comprising a
major proportion of a petroleum lubricating oil
and about 0.1 to about 5%, based on the weight
of the oil constituent, of the reaction product of
zinc oxide and an organic compound resulting
from‘ the reaction of an alkylated phenol with the
condensation product of turpentine and phos
phorus pentasul?de, the alkyl group of the alky1~
ated phenol being a saturated aliphatic radical.
ROBERT L. MAY.
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