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Патент USA US2110281

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2,110,281
Patented Mar. 8, 1938
UNITED. STATES
PATENT‘ oFFicE ‘ j
2,110,281
_ PURE oomoimns A8
LUBRIO
'
Elmer Wade m and George in. annuity.
Hammond, Ind., .assignon to Standard Oil
Company, GhicaIm-IIL, a corporation of Indi
ana
No
' Application March '31, 1934;
\
Serial N0. 718,438
12 Claims. .
This invention relates to an improved lubricant
for use .on bearing surfaces which are subjected
to high. pressures and high rubbing velocities
during
use.
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Y
‘
~
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5 v The present day trend in automotive design
toward smaller rear axles and consequently
smaller gears. On account of the small gears,
tooth pressures and rubbing velocities are rapidly
(cl. va'z-o)
of vthe lubricant. ' These extreme-pressure lu
bricants have substantially no corrosive action
upon metal surfaces. .
added to mineral lubricating o?s or greases to
impart, extreme-pressure lubricating properties
thereto are as follows:
-
-
mineral lubricating oils.
15
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'
20
'
'
approaching a point where rear axles cannot
10 be lubricated satisfactorily with the. ordinary
v
V The sulfur-bearing compounds which may be
-
,
~\
-
I
'
R,—s—s—1_2,
10
Buliideo
The trend toward in-_ ' wherein R and R1 represent alkyl groups‘ con- .
creasing loads on gear teeth in other ?elds has
developed an urgent need for special lubricants.
When hypoid gears, worm gears, heavy duty
taining at least 5 carbon atoms each gr aromatic
under those conditions of use.
The object of our invention is to .provide a lu
disul?des are ethyl disul?de, n-propyl disul?de,
n-butyl disul?de, secondary butyl .disul?de, ter
groups such as phenyl radicals and tolyl radicals, -
however, when It ‘represents a phenyl group, R1,
bearings, planetary automatic shifts, and the - may represent any alkyl group; and. R2 and Rs 15
like are used under conditions of high pressure represent alkyl groups or phenyl groups. ‘The
and high rubbing velocities, special types of ex
term‘ alkyl is intended to include the saturated
treme-pressure lubricants must be provided in - cyclic radicals also, such as the cyclohexyl group.
order to reduce the wear upon such moving parts. Examples of the sul?des are amyl sul?de, hexyl
Extreme-pressure lubricants are likewise im
sul?de, cyclohexyl ‘sul?de, phenyl sul?de, ethyl 20
portant in cutting and drawing operations where phenyl
sul?de, methyl phenyl sul?de, tolyl. sul
the 011 must withstand high pressures encountered ?de, and butylphenyl sul?de. Examples of the
25 bri’cant which will give satisfactory lubrication
to bearing surfaces which are subjected to high
pressures and/or high rubbing velocities. A fur
' ther object is to provide a lubricant which will
tiary butyl disul?de, cyclohexyl disul?de, ethyl
propyl disul?de, amyl disulfide, heptyl disul?de,
tolyl disul?de, and phenyl disul?de.
II
' maintain a lubricant ?lm on bearing surfaces at
30 all times. We have found that if small amounts
of certain types of organic sulfur compounds are
added to theJubn'cating oils and, soft greases,
the lubricant will enable the bearing surfaces to
withstand the high pressures and high rubbing
velocities witho-ut- noticeable wear. Similarly,
these sulfur compounds may be incorporated into
drawing lubricants and cutting oils.
,
We have found that the extreme-pressure lu
bricants can be prepared by adding a small
40 _quantity of ‘an alkyl disul?de, high molecular
weight alkyl sul?des, aryl thiocyanates and aryl
isothioc'yanates, xanthic disul?des, or xanthates
to mineral lubricating oils, preferably, those lu
bricating oils having aviscosity from about 90
25
R4—S—C E N
Aryl thiocyanic esters
R4-—N=C=S
30'
‘ fAryl isothiocyanic esters
wherein R4 represents’ aryl groups such,as_
phenyl, tolyl and naphthyl groups. Examples of
the aryl thiocyanic esters are phenyl thiocyanic
ester, tolyl thiocyanic ester, and naphthyl thio
cyanic ester. Examples of the aryl isothiocyanic
esters or aryl isosulphocyanic esters are?phenyl
isos'ulphocyanic ester, tolyl isosulphocyanic esters,
and naphthyl isosulphocyanic‘ester. The aryl 40
esters of isothiocyanic acid impart excellent ex
treme-pressure lubricating properties to mineral
to 200 seconds Saybolt at 210° F. These com
pounds may be used in oils designated as S. A. E.
45
20, 30, 40, 50, and 60 oils. These sulfuricom
pounds are ‘added in quantities ranging from V2
to 7%, but generally amounts ranging from‘ 1 to 5% are satisfactory. The organic sulfur com
pounds may be dissolved in the oil .by any con->
ventional mixing means. If desired, calcium and
aluminum soaps or other soaps of high molecular
weight fatty acids may be added to the com
55 position to increase the viscosity or consistency
Wherein R5, R6, and R11 represent alkyl groups.
Examples of the xanthic esters are ethyl xanth 50
ate ethyl'ester, methyl xanthate ethyl ester, ethyl . ~
‘ xanthate methyl ester, ethyl xanthate butyl ester
and ethyl xantha-te propyl ester. Examples _'of
the xanthic disul?des are methyl xanthic disul
?de and ethyl‘ xanthic disul?de.
'
’
2
The load-carrying capacity of extreme-pres
captans in the petroleum distillate. Generally
sure lubricants may- be determined by the ex-'
this temperature is below 80 to'100" C. Other
oxidinng agents such as hydrogen peroxide or
potassium permanganate may be used instead of
treme-pressure testing machines such as the
"Almen extreme-pressure lubricant testing ma
chine" described by Wolf and Mougey in their
paper on extreme-pressure lubricants'given at
the 13th annual meeting of the A. P. I. at Hous
ton, Texas, November 17, 1932.
The following table gives the. load-carrying ca
pacity of extreme-pressure lubricants as deter
mined by an extreme-pressure lubricant twting
the oxygen. Also the high molecular. weight alkyl
disulfldes maybe prepared by treating hydro
carbon distillates with sodium plumbite solution
and sulfur, separating the plumbite solution from
the oil containing the dissolved disuliide and re6
covering the alkyl' disul?des by distilling the hy
drocarbon oil from~ the dissolved disul?des.
_ machine designed and operated on the same prin
While we have described our invention with
ciple as the Almen extreme-pressure lubricant 'reference to particular ‘examples, it should be ‘ i
testing machine. 'lhose lubricants withstanding , understood that our invention is not limited
a bearing pressure of 20,000 pounds per sq. inch thereby,‘ except as set forth in thefollowing
are satisfactory. ‘
'
'
,
Table I
'
We
claim:
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'
_
‘
,
>
1. An extreme-pressure lubricant comprising, a
mineral lubricating oil and from $5 to 5% of a
- Sample: 5% of the following compounds dissolved
in zero bright stock (mineral oil having a vis
cosity of 150 Saybolt at 210° F.) .>
disuliide having the following general formula:
R+B—8—R1, wherein R and R1 represent sub
'Speedofpin:150R.P.M.
stituents selected from the group consisting of
alkyl groups or hydrocarbon phenyl vgroups.
- 2. An extreme-pressure lubricant comprising, a
mineral lubricating oil and from ya to 5% of
an alkyl disulflde having the following general
formula: R-B-S-Ri, wherein R and R1 repre
sent substituents selected from the class consisting
Compounds
of methyl, ethyl, propyl, butyl, amyl, hexyl, and
Control
30 Am lsulil
cyclohexyl groups.
‘
80
g
‘ 3. An extreme-pressure lubricant comprising,
a mineral lubricating oil having a viscosity from
90 to 200 seconds Saybolt at 210° F. and from
y sulii
$5 to 5% of a butyl disul?de.
................ ..
'
.
4. An extreme-pressure lubricant comprising,
a mineral lubricating oil and from $5 to 7% of an
Bntyl sulfide--.‘ ....... -_
n-Hoptyl mercaptsnnn
Eth benzene sulionate.
7 Met yl p-toluane sulicnatc.
organic sul?de having the following general
formula: RPS-R1, wherein R and R1 represent
alkyl groups containing at least 5- carbon atoms
As stated hereinbefore, the sulfur compounds
may be added to the viscous mineral oil by any
each.
40
-
suitable means. Generally the sulfur compounds
5.7An extreme-pressure lubricant comprising,
are added to the mineral oil and stirred until a
a mineral lubricating oil having a viscosity from
90 to 200 sec. Saybolt at 210° F. and from 1 to 5%
homogeneous mixture is obtained.
Example I
~
of an organic sul?de having the following general
formula: R—S--R1, wherein R and R1 represent
_
Extreme-pressure lubricants for use under con
substituents selected from the class consisting of
- ditions of 'high- rubbing velocities and pressures V amyl. hexyl, and cyclohexyl groups.
7
can be prepared satisfactorily by mixing 5% by
_ ‘ 6.‘ An extreme-pressure lubricant comprising, a
weight of ethyl disulflde with a mineral oil hav
ing a viscosity of about 150 to -l60 Saybolt at
210° F.. Coastal mineral oils, Mid-Continent oils
and para?in mineral oils may be used'as the base
mineral oil having a viscosity from 90. to 200 sec
onds Saybolt at 210° F. and from 1/2 to 5% of an
organic disulfide selected from the group consist
ing of n-propyl disulfide, and n-butyl disul?de.
7. An improved liquid lubricant composition
comprising a mineral lubricating oil and from $9
to 7% of a disul?de having the following general
formula R—S-_—S—Ri, wherein R and R1 repre
for these extreme-pressure lubricants, Any of
the hereinbefore mentioned compounds may. be
used in the preparation of extreme-pressure lubri
cants instead of ethyl disul?de as set forth in
Example I.
v
. .
sent substituents selected from the group con
The alkyl disul?des may be prepared by any
conventional means‘ but if desired, they may be
prepared from" the ~mercaptans occurring in
petroleum distillates boiling within the gasoline
1 or kerosene-range.
A petroleum distillate, pref
sisting of alkyl groups and hydrocarbon phenyl
.
groups.
8. An improved lubricant composition compris
ing a mineral lubricating oil and from 55 to 7%
of an alkyl disul?de'having the following general - I
erably one containing a high percent of mercap
formula R--S—S-R1, wherein R and R1 repre
tansis agitated with caustic. The caustic solu
- tion is separated from. the hydrocarbon material sent substituents selected from the group con
by decantation and then oxidized with any suit-' sisting of ‘methyl, ethyl, propyl, ‘butyl, amyl,
'
.able chemical reagent, for. example air, or ongen. hexyl and cyclohexyl groups.~
9.
An
improved
lubricant
composition
com
The alkyl disul?des are then removed from the
prising a mineral lubricating oil and from $6; to
oxidized caustic solution by boiling and are col
lected by absorption in a mineral oil solution; if 7% of~ an organic compound selected from the
‘ desired, they may be absorbed in the mineral oil ‘group consisting of organic sul?des having thew ,
_
70
used in the preparation of the extreme-pressure
formula R—S--R1, wherein R and R1 represent
lubricant.
phenyl groups or alkyl groups containing from 5 '
toB carbon atoms each; and- disulfides having the ‘
The-oxidation with air or oxygen is
preferably performed under pressure and ,at a
temperature below the boiling point of the mer
general formula Re-S—S—Ra, wherein R: and u
.
,
2,1 10,9131 '
,_
3
‘R: represent alkyl groups and hydrocarbon '> 'rosive action upon metal surfaces, selected from
phenyl groups.
p
10. An extreme-pressure lubricant comprising
a mineral lubricating oil and from % to'7% of an
organic compound selected from the group con
sisting of organic sul?des having the formula
R—,-S-R1 wherein R and Ru represent alkyl
groups containing from 5 to 6 carbon atoms each
the group consisting of organic, sul?des having
the formula R'—.S--R1 wherein R and’ R1 repre
sent alkyl groups containing at least ?ve carbon
atoms each. and di-sul?des having the general
formula Rg'-s'_s‘-_Ra wherein R2 and R: repre
' sent alkyl-f'groups.
and di-sul?des having the general formula
prising mineral lubricating oil and from % to_‘:
groups.
formula R-S-S-R', wherein Band B’ repre
10 Rz-S-S-R: wherein R: andR; represent alhi
~
_
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~ 11. An improved lubricant composition com
prising a mineral lubricating oil and from lé to
7% of an organic compound, which has no cor
5% of a 'disul?de having‘ ‘e following general
sent alkyl groups.
'
GEORGE M. McNUL'lg'llf." '.
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