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Патент USA US2354536

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Patented July 25, ‘1944
2,354,536 ‘
UNITED STATES ' PATENT
ONE‘ '
2,354,536
LUBRICATIN G OIL COMPOSITION
-
.
a
}
Joseph F. Nelson, Elizabeth, N. J., assignor to
Standard Oil Development Company, a corpo
ration of ‘Delaware
,
No Drawing.~ ApplicationJanuar-y 2, 1941, a
.
‘
Serial No. 372,893
4
'9 Claims. ; (01. 252-48)
This invention relates to the preparation of im
the number- of such alkyl carbons should be in- ‘
creased correspondingly. In general there is no
proved lubricating compositions and is particu
larly concerned with certain new types of addi
tion agents which, whenincorporated in lubri
cating compositions, impart thereto
able stability characteristics.
. advantage in
having a larger portionof the mole
cules in the form of alkyl chains thanis re
highly desir- ‘
1
.
quired to obtain adequate oil solubility, though
in certain instances the alkylportion may be
The maintenance of satisfactory automobile
performance requires that a ?lm of. lubricating
increased to obtain'special properties such as
the ability to depress the pour .point of the oil
composition be present‘ on moving engine sur
or to increase the viscosity index.
faces, and that the composition be of good lubri
10
cating quality, and satisfactory chemical stability.
' ‘
_
Among the various suitable compounds em‘
played in the invention, those having the phos
This film must be maintainableon exposed sur
phorus acid esteri?ed with'at least one alkylated
faces over periods of prolonged stoppage of ‘the
aromatic alcohol or a phenol aresuitable and,
engine, even when the surfaces are vertical, and
also sustainable or rapidly replaceable under se 15 of these compounds, the oxyphosphites and 'thlo
phosphites are particularly desirable. In the case
vere operating conditions so as to prevent con
tact of unprotected metallic surfaces with each
other. Desirable properties, therefore, of auto
mobile engine lubricants include rapid formation
of tenacious ?lms, high penetrating and lubri
cating capacity, and homogeneity and stability
of mixed phosphitesjthat-is, those which con
tain dissimilar groups attached to‘the phosphorus
atom, the compounds which contain at least one
alkylated aromatic radical attached through the
20 oxygen or sulfur to the phosphorus atom or at '
least
in the presence of acidic and oxygen-containing
an‘ alkylated
aromatic radical
in
the ~
xanthogen group or groups of the compounds
gases at elevatedtemperatures.
are particularly suitable. The various alkyl and
The present invention is concerned with the a '
.alkylated aromatic groups in these various com
preparation of highly stable lubricating compo
sitions by the addition of small quantities of oil 25 pounds may contain‘halogenconstituents, espe
cially chlorine. When Z1 and/or Z: are xantho
soluble or oii-dispersible compounds of anew
type to mineral lubricating oils.
gen groups the class of compounds may be rep
A group of
resented by the formulae
'30
7
_
i
(RXC s s),
\PY
s
, RX-iL-S
and (RXCSSMPY.
Z1—X>PY
z,—x/
>
'
.
in which R is an organic radical, usually pre
dominantly hydroc'arbon in character, X is oxy~
gen or sulfur, Y is oxygen or sulfur when'phos
phorus is pentavalent or it is omitted when phos- - 40
phorus is trivalent. and Z1 and Z: may be simi
lar or dissimilar metals, onium bases, unsubsti
.,
' .
Instead of phosphorus in the above general
35 class of compounds; arsenic, antimony or bis
muth may be substituted and the compounds are
advantageous lubricating‘ oil ‘addition agents
within the scope of the invention. The com
pounds of the invention therefore include certain
‘phospho-xanthogen compounds, that is, certain
xanthogen-containing phosphates,
vthiophosphates, thiophosphites, the
phosphites, '
correspond
tuted or substituted, organic radicals, especially. ing arsenic, antimony and bismuth compounds;
hydrocarbon or heterocyclic radicals, or xantho
and substituted derivatives thereof. The man
gen groups. By the term xanthogen group is 45 thogen-containing compounds of this invention '
designated the monovalentgrouping (RXCS)-'+
in which R is an organic radical and X may be
either oxygen or sulfur. The organic radical R
are those which have physical properties which
insure adequate blending quality in the particu- '
lar type of vehicle used in the lubricant. Such,
properties are largely determined by the molecu
50 lar weight of the particular compound and ‘in;
tuted or substituted alkyl radical or a benzyl
in thexanthogen group is usually an unsubsti
group or homolog, thereof. The total alkyl radi~
cals in the compound should containrat least 6
carbon-atoms to provide the desired oil solubility,
clude adequate oil ‘solubility or oil dispersibility,
suitable boiling point and satisfactory chemical
stability. Anotherclass of compounds falling
. and when many non-organic groups are present 65 within the scope of the invention are those in
which the element represented by X in the xan~
2,354,586
2
These radicals can replace hydrogen in acids
such as phosphorous acid, thiophosphorous acid,
thogen group in the general formula may be ni
trogen. In this latter case, the R in the general
formula must be replaced by two monovalent
phosphoric acid, thionphosphoric acid,
(S=P(0H)a),
groups such as two hydrogen atoms or two mon
' ovalent hydrocarbon groupings, or it must be re
monothiolphosphoric acid
placed by a divalentrradical such as the penta
methylene group.
All the compounds of the invention may be
classified in terms of the following more general -
thiontrithiolphosphoric acid, S=P(SH)3, etc.
formula:
Thus, classes of compounds within the scope
of this invention include: carboalkoxy phos
phites, thiolphosphates and thionphosphates;
thiocarboalkoxy phosphites, thiolphosphates and
16 thionphosphates; carbodialkylamino phosphites,
thiolphosphates and thionphosphates, thiocar
in which B. may be a hydrogen atom or a hydro- '
bodialkylamino phosphates, thiolphosphates and
thionphosphates; carboalkylmercapto phos
phites, thiolphosphates and thionphosphates;
thiocarboalkylmercapto phosphites, thiolphos
phates and thionphosphates; carboallwlamino
carbon or substituted hydrocarbon radical; X
may be oxygen, sulfur, or'nitrogen; ,Y maybe
oxygen or sulfur; D may be phosphorus, or a
metalloid like arsenic, antimony, or bismuth; Z
may be an organic radical which may contain
phosphites, _ thiolphosphates
andv thionphos
phates; ‘and thiocarboalkylamino phosphites,
halogen, nitro, amino, hydroxy, keto, mercapto,
carboxy, nitroso, ,amido, alkoxy, aroxy, or other
thiolphosphates and thionphosphates; and cor
responding derivatives bearing substituents in
the alkyl groups and containing ordinary phos
phite, thiophosphite, phosphate, or thiophos
,phate linkages; or compounds of the latter type
substituent groups; may be a metal or a group
containing a metal or an onium base like am
monium, sulfonium, phosphonium, or it maybe
a xanthogen group; a may be either 1 or 2,; b
may be 1, 2 or 3;lc is 0 or 1, d is 0, 1 or 2; the‘ 80 containing no hydrocarbon groups in the “thio
carboxy” portions of their molecules. In addi
choice of the value of ,these' subscripts vfor these
tion to these phosphorus compounds, the corre
groups depends on the valency requirements of
spondingarsenic, antimony and bismuth are also
the various atoms and radicals in the compounds.
included within the scope of the invention.
The following radicals are examples of the
Examples of individual compounds within the
scope of this invention are diamylphenylthiocar
groups
7
.
boethoxy
Y.
'(RIXC)
,
C5Hn0!3—
I
Carbopentoxy
(CzHsOCSS) :As:
lauryl dicarbomethylmercapto dithiophosphite,
S
' ‘ 053110 g—
'
>
I
0
o
,
v (CHr-s JQL shP-O CnHu
' Thiocarbopentoxy
H
(Cal-111C050):
phate, ,(CzHsOCSSMPO; trithiocarboethoxy tri
thiophosphite, (CzHsOCSS) 3P; trithiocarboethyl
mercapto trithiophosphite (CzHsSCSShP; tri
thiocarboethoxy trithioarsenite,
in the above formula:
V
monothiophosphite,
(C2H5OCSS)P; trithiocarboethoxy trithiol phos
phosphoryl octyl xanthate,
'
(CsH1i):N-gv"
Csrbodiamylamino
>
50
'
S
(clunoili-snko
di-isobutoxy thiophosphoryl dilauryl monothiol
carbamate,
I
Thiomrbocyclohexylamino
Ca-KDg-i
,
,
-
s
(C1|Hu)rN("]>—S-—Ig—(O 01H’)!
-
and the calcium salt of lauryl carbothiopentoxy
monothiol phosphoric acid,
0
,
so,
Thiocarboethoxyphenylsmino '
65
O
causti
Carboamylmercapto
S
V
0 ‘Hi1 S H-‘—
Thiocarboamylmercapto
When compounds of this invention are incor
porated in lubricating compositions in small
70 amounts, that is in concentrations ranging be
tween 0.05% and 2% and preferably between
0.1% and 1.0%, the resulting lubricating oil com
positions a_re highly stable, especially as regards
resistance to breakdown in an oxidizing atmos
15 phere and to the development of corrosiveness
9,354,536
. towardlalloy bearings of the cadmium-silver or
copper-lead type.
The lubricating oil base stock ‘of the composi
tions of the invention maybe any lubricating
oil, wax or grease, of natural or synthetic origin.
It a mineraloil, it may be wholly a distillate or
may contain residual products and may be any
such material that has been refined by a re?ning
‘process, such as acid treating, solvent extraction,
tion.
tion agents of this invention may be used as the
junction with other materials capable of en
hancing, as for example,» the viscosity index, the
pour point, extreme pressure, oiliness, rust pre
venting, spreading, detergent, dispersing and
solvent characteristicsof the oils.
.
.
,
Lasn TOLERANCE Tas'r
hydrogenation, clay contacting, etc.‘ The -addi-‘ 10
, sole addition agents or they may be used in con
3
under oxidizing conditions. The procedure oi‘
the test is described in Proc. A. S. T. M., v. 24, II,
page 964 (1924): the only exception to this pro
cedure wasthat theoxidation was conducted for
24 hours in testing the compounds of this inven
‘ (Underwood test)
This testis used to determine the tendency of
an oil to corrode bearings. In this test, 1500 cc.
of the oilis maintained at 325° F. and sprayed
for5 hours upon four alloyed half-bearings, two
being of copper-lead and two being cadmium
silver. The oil droppingfroin the bearings is
recirculated. The bearings are weighed before
and after the test to determine any_ loss in'
The lubricating compositions thus prepared . 7 weight.
The test is then repeated with various
are investigated for quality by certain recognized
additions of soluble lead compoundj"usually lead
standard tests of the vpetroleum industry. The
1 oleate, to the oil ‘in increments .of 0.005% by
tests by which the lubricants of 1the present in
weight of lead. When the lossin weight of a
vention were rated were the Oxygen absorption,
half bearing amounts to 50 mg., the “lead toler
Cone, Bligh and Lead tolerance tests. These
ance” of the oil has been exceeded and the
tests are brie?y described below:
amount of lead added in the previous test is re
OxYeaN Ansonrriou Tasr
corded asthe "lead tolerance". A lead toler-'
ance of above 0.02% is generally considered
This test is used for'the most part in judging
the oxidation susceptibility of a lubricating oil
at engine operation temperatures. In this-test
satisfactory.
‘
I’
'
,
The preparation of the compounds employed
as addition agents in this invention, may be 11
a known amount of oxygen is bubbled at atmos
pheric pressure through 10 cc. of the lubricating 30 lustrated by the preparation of di-amylphenyl-
oil maintained at 200° C. The oxygen is ‘con
tinuously recycled. At the end of succeeding 15
minute periodsthe amount of oxygen absorbed
thiocarboethoxy mono thio phosphite; 9.2 grams
tendency of an oil to deposit solid matter upon
heated metallic surfaces ‘such as are present'in
of another phase of 'the preparation, 32 grams
(0.2 mole) of potassium ethylxanthate were add
~
(0.4 mole) of sodium were added to 200 cc, of
absolute ethyl alcohol and to the resulting solu
tion were added_65.6 grams (0.4 mole) jot ter
by the oil is measured. The oxidation rate of
the oil is given as the number'of cubic ‘centi 35 tiaryamylphenol dissolved in 100 cc. of absolute
ethyl alcohol. The resulting sodium amylphe
meters of oxygen absorbed by 10 cc. of the oil
nate was obtained in'a dry state by distilling oil’
per 15 minute interval at 200° C.
the alcohol, the last traces of which were removed
CONE TEST
under vacuum. The sodium amylphenate was
This ,test is the meansv for determining the
dissolved in 350 ‘cc. of dry ethyl ether. As part
the ‘combustion chamber of spark-ignition type
ed to 27.5 grams (0.2'mole) of phosphorus tri
engines. It consists in slowly dropping the oil V chloride dissolved in 100 cc. of dry carbon tetra—
to' be tested upon a heated metal (generally (5 chloride. The mixture was gently heated until
all of the solid materials had dissolved. A gela
steel) cone having a circumferential ‘groove
milled out in screw fashion uponjthe periphery,
' tinous mass formed,V and this was carefully add-'
the time or contact between the heated steel sur
ed to the ether solution‘ of sodium amylphenate.
faceand the oil being about one minute. A
During vthis addition, heat was evolved. After
total of 60 cc.‘ of oil is dropped onto a cone from 50 re?uxing the resultant mixture for 1 hourand
a' dropping funnel during a period of Zhours.
washing it with water, the solution was washed
The cone may be maintained at any desired
temperature but, in testing automobile crankcase
with potassium xanthatesolution to remove all
traces of acid. After being washed further with
lubricating oils, a temperatureofl250° C. is pref
. water and dried, the product was obtained as a
erable. The cone is weighed before the test. 55 residue by distilling oil.’ the solvents.~ Analysis of
After 60 cc. of oil havebeen passed over the
the product established the sulfur content as be
cone, the latter is washed with naphtha to .re
move the adhering oil and the amount of solid
deposits formed is determined by the weight
diil'erential.
,
'
'
The test does not appear to vhave any relation
to the oxygen absorption test since lubricating
oil blends of two separate compounds may give
the same cone deposits but have widely different
oxygen absorption rates, and vice versa.~ The
test is, however, an important indication of the
ing 5.51%
formula:
and the following approximate
(CsHuCeHsO) 2.5 (C2H5QCSS) o,sP
Thus, the product was presumably'a mixture of
two or more compounds. The sulfur contained
therein was su?ficiently stable that the product
was not corrosive to copper when a 0.5% solution
or the compound in a hydrocarbon vlubricating
oilwas heated to 210° F. for 3 hours in the pres
ence of a copper strip. '
_
'
'
ability» of an oil to resist deterioration at high
temperatures. It has been found that the Cone
Another example or the preparation of a com
test gives data which closely. approximate the ' pound suitable for use as an ‘addition agent for
results obtained in the C. F. 1%. (Cooperative 10 lubricating oils, accordingv to this invention,,is
Fuel Research) test engine.
the preparation of trithiocarboethoxytrithiol
phosphate. 240 grams (1.5 mole) of potassium
SLIGH Tnsr
ethylxanthate were suspended in 1500 cc. of ben
This test is used as an indication of the tend
ency of a lubricating composition to form sludge 1| zene. While the suspension ‘was being agitated,
a benzene solution of 80 grams (about 0.5- mole)
.
4 .
9,854,586
ducing the oxidation rate of the oil and also it
. of freshly distilled phosphorus oxychloride was
added through a dropping funnel. The resulting
improved the corrosion resistance or the oil.
mixture was heated to insure completion of the
A lubricating oil blend of, di-amylphenylthio
carboethoxy monothio phosphite was tested by
theCone test; the following data were obtained:
reaction. Small quantities of potassium ethyl
xanthate were added to the reaction mixture un
til a sample of the latter gave a basic reaction 7
,
of hydrolysis. The reaction products were iso
lated by adding ice to the reaction mixture and
then washing the benzene layer free of base.‘
Calcium chloride was employed to dry the ben
Blended S. A. E. 40 mineral oil composition.. 0.39
These data indicate that di-amylphenylthio
. carboethoxy monothio phosphite reduced residue
zene solution. They benzene was‘then distilled 0115
and the residue heated under vacuum to remove
formation from the oil‘ under conditions similar
traces of low-boiling impurities. The product,
trithiocarboethoxy trithiol phosphate was a clear
liquid, containedv'l.39% of phosphorus and cor 15
responded in composition to'the formula
Cone test-Gain in weight of cone, g.
Unblended S. A. E. 40 mineral oil ________ __ 0.50
'
(czrnocss'nro '
to thoseexisting during automobile engine opera
tion.
-
i
-
'
'
EXAMPLE 2
The following oxidation rate data were ob
tained on an 0.25% blend of trithiocarboethoxv
trithio phosphite (CzH5OCSS)aP in an S. A. E.
20 mineral oil:
A further example according to the present in
'
‘
Oxidation rate
vention is the preparationof trithiocarboethoxy 20 Unblended S. A. E. 20 mineral oil___ 20, 38, 37, 31
Blended S. A.-E. 20 mineral oil com
trithio phosphite. 160 grams (1 mole) of potas
.
position _____ __‘_______________ -_
sium ethylxanthate were suspended in 500 cc. of
3, 4, 5, 9
benzene and 46 grams (1/5 mole) of phosphorus
ExAMru: 3
.
trichloride dissolved in benzene was added to the
The e?ect of the thiocarboxy group is shown
mixture from a dropping funnel while the mix 26
by the following comparative Cone test data on
ture was agitated vigorously. Agitation was con
0.25% blends of paratolyl phosphite and di-amyl
tinued until all of the potassium ethylxanthate
phenylthiocarboethoxy
monothio phosphite in an
vhad reacted and then the benzene layer was
‘
'
'
water~washed. The benzene solutionwas then 30 S. A. E. 40 oil:
Cone test-Gain, in
dried and the benzene was removed by distilla
_ _
' '
.
weight of cone, g.
tion. \iTheji product trithiocarboethoxy trithio
S. A. E. 40 Oil ______ "7-; __________ _‘_ _____ .._ .50
phosphite ‘was a‘ yellow-liquid, contained 8.79%
+0.25% p-tolyl phosphite ____ _'_ __________ __ .43
of phosphorus and corresponding in .composition
to the formula (C2H5OCSS)3P.
v Trithiocarboethoxy
,
r'
;
trithioarsenite,
another
as
+0.25 %' di-amylphenylthiocarboethoxy
monothio phosphite ___________________ __ .39
The following results were obtained in the Sligh
compound suitable as an addition agent,,accord
test on blends of these compounds in an S. A. E.
ing to the present invention, was preparedas fol
20
lows:
.
i
-
_
oil:
'
'
"
'
,
A suspension of '240 grams (1.5 mole) of potas
sium 'ethylxanthate in 1200' cc. of benzene .was
40
rapidly stirred while 90.5 grams (0.5_mole) of
Sligh test
S. A. E. 20 mineral oil + 0.25% para-tolyl
32.5
' phosphite
__________ __;_ _______________ _.
S. A. E. 20.mineral oil + 0.25% di-amyl- V
arsenic trichloride wasv added from a dropping
' 'phenylthiocarboethoxy‘ monothio 'phos- _
funnel over a period of 30minutes. The benzene
phite ______________ __' _______________ __ 19.7
in the mixture was re?uxed for, 1.5 hours. A 45
benzene solution of the product was washed with
Thesedata demonstrate that the thiocarbo
ethoxyphosphite compound has a greatere?ect in
reducing the formation of hard deposits from an
dried over'anhydroussodium sulphate, the hem '
oil upon heated-metallic surfaces of spark-igni
zene was distilled from the dried mixture. The
product, trithiocarboethoxy trithioarsenite, was 50 tion type engines and also inhibits the formation
of sludge in an oil to a greeted extent than d
a yellow solid. A yield of 95% was obtained; An- ,
‘
'
.water
to remove salts.
After the; mixture was
alysis of the product established the presence of
18.2% of arsenic, whereas. the theoretical value
for the compound is 17.1%.
-
V 7' EXAMPLE 1
the simple organic phosphites.
sented merely to illustrate and convey an ap
preciation of the invention. It is possible to
formulate other embodiments of ‘the invention
In order to. demonstratethe "advantages in-:
herent' in the use of the compounds of this inf
vention as blending agents for lubricating oils,
and employ compounds other than those speci?
cally mentioned as additives in lubricating oils
the oxidation rateand lead tolerance of a lubri
, cating oil composition prepared by blending 0.25%
' without departing from the scope of the inven
tion described herein. It is therefore desired to
claim all the novelty inherent in the disclosure
of di-amylphenylthiocarboethoxy monothio phos
phite, the preparation of which was previously
described, in an S. A. E. 20 oil were determined.
The following results were obtained :7.
Oxidation
Lead tol- >
‘rate
cranoe‘
Unblended S. A. E. 20 mineral oil _______ __
74,40, 35, 38
Blended S. A..»E. 20 mineral oil com osition _________________ _. ............. .;_
_
'
724,26,22,l8
. 0.010
‘
‘
'
‘The present invention is not limited to the
speci?ccompounds previously mentioned since
56 these, embodiments of the invention’ are pre
0,5
which has been made;v
What is claimed is:v
"
.
~ '
1. An improved lubricating composition which
‘comprises a mineraloil lubricant and between
0.05% and 2% of a‘compound of formula
(R.X(")Y)|
70
'
0.035
'
-
V
/DY.
-(ZY)I
These datashow that di-mnylphenylthiocarbo
ethoxy monothio phosphite was effective .in re
75 »
in which R is a radical of the class consisting of
hydrogen and organic radicals. X is an element
2,364,538
of the class consisting of oxygen, sulfur and nitro
gen, Y is an element of the class consisting of
oxygen and sulfur, D is an element of the class
5
0.05% and 2% of a phospho-xanthogen com
pound of formula
consisting of phosphorus, arsenic, antimony and
bismuth, Z is a grouping selected from the vclass
if metals, monovalent organic radicals and onium
bases; and the subscripts, a, b, c and d have
numerical values in accordance with valency re
in which R is an alkyl group. .X is an element
selected from the class of oxygen and sulfur and
quirements.
Z1 and Z2 are alkylated aromatic groupings.
2. An improved lubricating composition which 10 5. An improvedlubricating composition which
comprises a mineral oil lubricant and between
comprises a mineral oil lubricant in between
0.05%. and 2% of a phospho-xanthogen compound
0.05% and 2% oi’ diamylphenylthiocarboethoxy
of fonnula
V monothio phosphite.
(Rx-o s s )
6. An improved lubricating composition which
15 comprises ‘a mineral oil lubricant and between
0.05% and 2% of a phospho-xanthogencompound
Z1—X7PY
z,-x
'
of formula
-
in which R. is an organic radical, X is an element
(RXCSS) 3P
selected from the class of oxygen and sulfur, 20 in which R is a grouping selected from the class
Y when phosphorus is pentavalent is an element
of alkyl and alkylated phenyl groups and X is an
selected from the class of oxygen and sulfur and element selected from the class of oxygen and
Z1 and Z2 are groups selected from the class of
sulfur.
xanthogen groups and organic radicals. !
7. An improved lubricating composition which Y
3. An improved lubricating composition which 25 comprises a mineral oil lubricant andbetween
comprises a mineral oil lubricant and between
0.05% and 2% of phospho-xanthog’en compound
- 0.05% and 2% of
of formula -
phospho-xanthogen compound
'
of formula
'
(RXCSS) 3P
(RX-C s s)
Zr-X-P
30 in‘ which R is an alkyl group and X is an element ,
_, selected from the class of oxygen and sulfur.
8. An improved lubricating composition con
Zr
taining a mineral oil lubricant and a small quan
in which R is an organic radical, X is an element
tity of trithiocarboethoxy trithio phosphite.
selected from the class of oxygen and sulfur and 35
9. An improved lubricating composition which
Z1 and Z: are groupings selected from the class
comprises a mineral oil lubricant and a small
of xanthogen groups and organic radicals.’
4. An improved lubricating composition which
comprises a mineral oil lubricant and between
/
quantity of trithiocarboethoxy' trithioarsenite.
JOBEPH F. NELSON.
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