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Патент USA US3041290

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3,041,280
Patented June 26, 1962
2
operation is frequently an accompaniment of heavy load
3,041,280
Robert K. Smith, Spring?eld Township, Del’aware
SULFUR CQMPOUNDS
conditions, so that corrosiveness in such circumstances
forms an important consideration in determining the
suitability of lubricant compositions. Accordingly, prior
ors to E. F. Houghton & Co., Phiiadeiphia, Pin, a
County, and Charlotte S. Popo?, Ambler, Pa, assign
corporation of Pennsylvania
No Drawing. Filed Sept. 29, 1958, Ser. No. 763,832
23 Claims. (Cl. 252—33.6)
to the production of the compositions of this invention, it
has been impossible to provide satisfactory lubricants for
wide temperature range operation with extremely heavy
loads.
This invention relates to lubricating compositions, and
more particularly, provides novel lubricating compositions
ing compositions of improved performance characteristics,
comprising an oleaginous base and certain chlorinated
aromatic sulfur compounds as further de?ned herein
after, and means of making the same.
known hitherto.
A particular object of this invention is to provide novel
The novel lubricating compositions provided by this
invention are uniquely effective as extreme pressure
It is an object of this invention to provide lubricat
with higher load-carrying properties than have been
lubricant compositions characterized by e?fective lubricity
15 under advanced extreme pressure conditions at ultra high
loads.
Another object of this invention is to provide novel
lubricants. There is a continuing demand in the lubricant
industry for lubricants effective at increasingly higher
loading pressures. With the development of improved
extreme pressure lubricant compositions which are sub
stantially free of corrosive qualities.
lubricating compositions to meet this demand, the opera
A further object is to provide a novel method of im
proving the extreme pressure qualities of an oleaginous
tional range of pressures has been greatly extended. Pres
sures initially denoted as falling in the extreme pressure
base by adding certain chlorinated aromatic sulfur com
range are now many times lower than the maximum which
pounds thereto.
has been reached. To keep pace with engineering de
An additional object is to provide novel high-tempera
velopments, however, it is essential that the upper opera— 25 ture,
heavy load-carrying greases.
tional pressure limit be advanced further than has been
These and other objects, including the provision of
attainable hitherto. Thus for example, higher speed air
craft with larger power plants and changed structural de
sign present stringent requirements for lubricants, for
novel compounds useful as extreme pressure additives
and for other applications, will become evident from a
which the load carrying and wear properties of known 30 consideration of the following speci?cation and claims.
The novel lubricant compositions of this invention com
lubricant compositions are inadequate. In such applica
prise an oleaginous base containing a chlorinated aro
tions, anticipated loads of sliding surfaces such as rod
matic sulfur compound selected from the class con
ends, pulleys, screw jack actuators, hinges, gear boxes
sisting of pentachlorobenzenethiol, heavy metal salts of
and oscillating spherical bearings may range as high as
100,000-150,000 p.s.i., with ambient temperatures from
35
—65° F. to 600° F. The present invention is particularly
valuable in that it provides compositions capable of ef
fective lubrication under these severe conditions.
The requirements which extreme pressure lubricating
compositions, must meet include not only lubricity under 40
high loads, but also good temperature response and sub
stantial absence of corrosiveness.
Natural oils such as
mineral oils are generally of restricted utility: the vis
cosity-temperature characteristics of even highly re?ned
pentachlorobenzenethiol, pentachlorophenylmercaptoace
tic acid, heavy metal salts of pentachlorophenylmercap
toacetic acid, and esters of pentachlorophenylmercapto
acetic acid.
The novel compositions of this invention are prepared
by dispersing a chlorinated ‘aromatic sulfur compound of
the stated nature in an oleaginous base, as further de
scribed hereinafter.
The presently provided novel lubricant compositions
exhibit unique qualities which make possible the effective
lubrication of mechanical components operating under
mineral oils are unfavorable where lubricants must be 45
service conditions which are substantially more severe
operative over a broad temperature range. Synthetic
than
it has been possible to employ advantageously
lubricants, such as silicones, polyesters, and the like, are
hitherto.
The loads which can be e?'ectively lubricated
available which do not have this defect; however, such
With the novel lubricant compositions of this invention
lubricants are less desirable in other respects. Thus syn~
extend up into a higher range than it has ever previously
thetic lubricants such as the silicones rand polyesters are 50 been possible to lubricate satisfactorily. Even under
de?cient in lubricity, and the silicones are also poor in
severe service conditions at high-temperature operating
wear properties. This inferior lubricity limits the pres—
conditions, they exert a high load-bearing capacity while
sures at which such ?uids can be employed; thus, a sili_
remaining substantially free of corrosiveness. A partic—
cone-based grease performs well in the ABEC NLGI
ular advantage of the present invention is that the stated
bearing tester (criterion for high temperature service and 55 aromatic sulfur compounds can be used to produce sub
boundary lubrication at low loads), but fails in the Navy
stantial improvements in the extreme pressure qualities
Gear Test (higher loads). Moreover, these synthetic
of synthetic lubricants; when these additives are introduced
lubricant bases present a particular problem because they
in low ‘concentration, they can produce as much as triple
are only poorly responsive to treatment with additives. 60 the unmodi?ed load carrying capacity of such base ?uids,
Mineral oils generally can be substantially increased in
thereby bringing synthetic base ?uids of this nature into
load-carrying capacity with a variety of extreme pres
the lubricity range requisite for utility under ultra-high
loads.
sure additives. However, only a limited number of such
additives are effective to improve the extreme pressure
The chlorinated aromatic sulfur compounds employed
properties of silicones and like synthetic oleaginous bases, 65 in the practice of this invention as extreme pressure ad
and only a restricted degree of response is produced.
ditives to oleaginous bases are characterized by the
Furthermore, known extreme pressure ‘additives tend to
presence of a pentachlorophenylmcrcapto radical,
be corrosive, and this corrosiveness is especially evident
when lubricant compositions containing such additives are
employed at elevated temperatures. High temperature 70
3..
Ol_O1
s,041,2so
3
One class of the stated compounds comprises penta
chlorobenzenethiol and heavy metal salts thereof. Penta
chlorobenzenethiol is itself very effective in producing
compositions in accordance with this invention; su1pris-_
ingly, in view of the acidic qualities of aromatic thiols
land in view of the usually pronounced corrosive qualities
of chlorine compounds, pentachlorobenzenethiol is sub
stantially non-corrosive, and may be used advantageously
4
acid, heavy metal salts of pentachlorophenylmercapto
acetic acid, or pentachlorophenylmercaptoacetic acid
esters. In the stated substituted acetic acids, the sub
stituents on the alpha carbon atom of the acetic acid,
besides the pentachlorophenylmercapto radical, will pref
erably be hydrogen atoms, but may alternatively comprise
small alkyl substituents.
This series of compounds, as compared to the penta
chlorobenzenethiol compounds discussed above, is par
in lubricating compositions designed for use at elevated
10 ticularly advantageous because these mercaptoacetic acid
pressures and temperatures.
compounds are soluble in oleaginous bases, including syn
The heavy metal salts of pentachlorobenzenethiol have
thetic lubricant ?uids such as silicones. Accordingly, the
additives of this group are readily dispersed in such ?uids
to produce lubricant compositions which are intrinsical
ing the stated salts have good load-carrying properties
and minimal corrosivity even at high temperatures. The 15 ly stable to storage and handling.
The parent compound of this series, pentachlorophen
metals, pentachlorobenzenethiol salts of which are em
also been found to'be efficient extreme pressure additives
for oleaginous bases. Lubricating compositions compris
ployed as lubricant composition components in accord
ance with this invention, are heavy metals, by which are
meant metals having a density of 4 or more. Particular
ylmercaptoacetie acid, is a preferred component of the
lubricant compositions of this invention. It is highly
etfective in raising the load-carrying capacity of oleagi
nous bases, and surprisingly free from corrosivity even at
ly preferred in this connection are heavy metals of group
II of the periodic table, including mercury, cadmium, and
as the salt-forming metal of choice, zinc, and of group IV,
especially tin and lead. Alternatively, the selection de
high temperatures. Homologs comprising oc-alkyl-sub
stituted acetic acids such as u-(pentachlorophenylmer
captoja-a-methylacetic acid, a-(pentachlorophenylmen
capto-u-ethylacetic acid, a-(pentachlorophenylmercapto)
pending on such considerations as the reactivity and avail
‘ability of the metals, there may be employed salts of 25 a-isopropylacetic acid and the like are also effective to
accomplish the objects of this invention.
Heavy metal salts of the stated acid are also useful in
silver and so forth; of group III, like indium and thal
the practice of the present invention. In respect to this
hum; of group IV, like thorium; of group V, like anti
embodiment of the invention, essentially the same con
mony and bismuth; of group Vi, like tungsten and
1 other heavy metals, such as those of group I, like copper,
‘ tellurium; and of the transition elements, like iron, cobalt, 30 siderations apply as have been pointed out in the fore
going discussion with respect to heavy’ metal thiolate
. nickel and so forth.
salts useful in the practice of this invention. Thus, the
salt-forming metal will be a heavy metal having a density
As Will be appreciated by those skilled in the art, when
a salt of a polyvalent metal with an aromatic thiol is
of 4 or more, such as those mentioned above in connec
formed, the arylmercapto radical of the thiol may satisfy
all or less than all of the valences of the metal. Both 35 tion with the pentachlorobenzenethiolates. Any anion
satisfying valences of the metal other than those taken
partial metal salts and metal salts fully substituted by
up by the pentachlorophenylmercaptoacetyl radical, if
the stated arylmercapto radical are useful in the practice
present, will generally be an inorganic anion of low
'of the present ‘invention. When the arylthiol salt is
molecular weight, as set forth above in connection with
formed in aqueous solution for example, a basic salt may
be produced in which one or more of the metal valences 40 the pentachlorobenzenethiolates, preferably a hydroxide
ion. Preparation of the stated salts may be effected by
is satis?ed by a hydroxide ion; other anions may alter
'natively be introduced if desired, although this will usual
rly require additional. manipulative steps without corre
sponding bene?t. For practical purposes, in any case,
anion radicals when present in the arylmercapto salts of
heavy metals will usually be inorganic radicals and gen
erally of relatively low molecular weight, as for example
means well known in the art, such as reacting penta—
chlorophenylmercaptoacetic acid or a salt thereof in
solution with a hydroxide or other salt of a selected
heavy metal. Illustrative of the salts of this nature use
ful in the practice of this invention are zinc pentachloro
phenylmercaptoacetate, zinc a-(pentachlorophenylmer
capto)-a-methylacetate, cadmium pentachlorophenylmer
a halide ion such as .chloride, bromide or ?uoride ion,
or an oxygen-containing radical such as hydroxide or
'carbonate, bicarbonate or sulfate.
-
-
captoacetate, mercury pentachlorophenylmercaptoacetate,
50 copper pentachlorophenylmercaptoaceate, silver penta
p The preparation of the stated salts can be effected, for
‘example, by reacting a convenient salt of pentachloro
benzenethiol, such as the water-soluble sodium salt there
‘of,
solution witha salt of the selected heavy metal to
' eifect a metathetical exchange of ions; or by other means 55
' known in the art for the preparation of aromatic thiolate
metal salts.
_
.
,
.
V
-
-'
Illustrative of ‘the stated heavy metal .salts are zinc
pentachlorobenizenethiolate, cadmium pentachloroben
‘ zenethiolate, mercury pentachlorobenzenethiolate, copper
pentachlorobenzenethiolate, , silver pentachlorobeuzene
' thiolate, tin pentachlorobenzenethiolate, .lead pentachloro
‘ benzenethiolate, thorium pentachlorobenzenethiolate,
antimony pentachlorobenzenethiolate, bismuth penta
chlorobenzenethiolate, tungsten pentachlorobenzenethio
late, cobalt ipentachlorobenzenethiolate, nickel penta
chlorobenze‘nethiolate, basic zinc pentachlorobenzene
tbiolate, basic cadmium'pentachlorobenzenethiolate, basic
‘lead pentachlorobenzenethiolate, lead chloride penta
chlorophenylmercaptoacetate, tin pentachlorophenylmer—
captoacetate, lead pentachlorophenylmercaptoacetate,
thorium w(pentachlorophenylmercapto)-a-ethylacetate,
antimony pentachlorophenylmercaptoacetate, bismuth
pentachlorophenylmercaptoacetate, tungsten pentachloro
phenylmercaptoacetate, cobalt pentachlorophenylmercap
toacetate, nickel pentachlorophenylmercaptoacetate, basic
'zinc pentachlorophenylmercaptoacetate, basic zinc or
(peutachlorophenylmercapto)-a,a-dimethylacetate, basic
cadmium pentachlorophenylmercaptoacetate, lead chlo—.
ride pentachlorophenylmercaptoacetate, tin chloride pen
tachlorophenylmercaptoacetate, zinc sulfate pentachloro
phenylmercaptoacetate, and the like.
The pentachlorophenylmercaptoacetic acid derivatives
65 found to be useful in the practice of this invention also
include substituted acetic acid esters of the stated type.
The nature of the ester radical may vary widely. The
stated ester radical will be an organic radical, containing
at least one carbon atom; and may comprise a hydrocar
- chlorobenzenethiolate, tin sulfate pentachlorobenzene 70 bon radical, such as an alkyl, cycloalkyl, aryl, alkaryl or
aralkyl radical, or a hydrocarbon radical containing any
thiolate, and so forth.
of a wide variety of non-interfering substituents, such
As indicated hereinabove, compounds employed as
as halogen atoms, hydroxy radicals, carboxy radicals,
extreme pressure lubricant additives in accordance with
sulfo radicals, alkoxy radicals, hydroxyalkoxy radicals,
this invention may alternatively comprise substituted
acetic acids including pentachlorophenylmercaptoacetic 75 aryloXy radicals, cycloalkoxy radicals, sulfamoyl radicals,
5
3,041,286
6
mercapto radicals, acyl radicals such as an acetyl or
the oleaginous base alone. Generally a minor amount of
the stated additive as compared to oleaginous base is ef
fective in achieving this improvement. The amount to be
benzoyl radical, cyano radicals and the like. A preferred
class of esters for the present purposes comprises aliphatic
esters such as alkyl, haloalkyl, and oxyalkyl including
used may vary over a fairly wide range depending on the
hydroxyalkyl, alkoxyalkyl and hydroxyalkoxyalkyl esters
type of additive used, the nature of the oleaginous base,
and the severity of the operating conditions under which
the lubricant is to be actually used in service. In general,
containing up to 8 carbon atoms; the effectiveness of
these esters as lubricant additives has been observed to
diminish with increasing chain length, and when the ester
an increase in the amount of additive will produce an in
radical contains above about 8 carbon atoms, the esters
crease in the extreme pressure properties of the base,
are not of the potency required to produce a degree of 10 but for practical purposes, it usually will not be necessary
lubricity of the unusually high order of magnitude which
to employ an amount of additive appreciably above about
may be provided in accordance with this invention. The
15% by weight, based on the weight of the ?nal composi
stated aliphatic phentachlorophenylmercaptoacetic acid
tion. Ordinarily excellent results are achieved with con_
esters, so far as is known, are new compounds which are
centrations on the order of between about 0.1% and
provided by this invention.
The preparation of the stated pentachlorophenylmer
15
captoacetic acid esters can ‘be effected by conventional
procedures for an esteri?cation of an acid with an alcohol,
10% ‘by weight. Generally at least about 0.05% of the
additive will be employed.
The oleaginous base used in the compositions may be
selected from a wide variety of natural or synthetic lubri
such as reaction of the acid and alcohol in the presence
of an acidic or basic catalyst, or by other means adapted
for ester synthesis. Illustrative of the stated esters pro
vided by this invention are alkyl esters such as methyl
cating oils. Thus for example, natural oils can advantage
ously be employed in conjunction with the stated penta
such as cyclopentyl pentachlorophenylmercaptoacetate,
cyclohexyl pentachlorophenylmercaptoacetate, and 1
more desirable properties than natural oils in some re
spects, and also in that only a limited number of additives
are known which are effective to improve the extreme
chlorophenylrnercapto compounds to provide extreme
pressure lubricant compositions. Illustrative of such nat
pentachlorophenylmercaptoacetate, ethyl pentachloro
ural oleaginous bases are mineral oils such as naphthene
phenylmercaptoacetate, propyl pentachlorophenylmer
and para?in base oils; vegetable oils such as cotton seed
captoacetate, isobutyl pentachlorophenylmercaptoacetate,
oil and castor oil; animal and marine oils such as sperm
Z-ethylbutyl pentachlorophenylmercaptoacetate, amyl
whale oil, lard oil, blown ?sh toil and degras; and mix
pentachlorophenylmercaptoacetate, neopentyl pentachlo
tures thereof. Of the natural oil bases, mineral oils are
rophenylmercaptoacetate, octyl pentachlorophenylmer
preferred. A typical mineral oil base for extreme pres
capto acetate, methyl w(pentachlorophenylmercapto)a
lubrication will be characterized by a viscosity of
methylacetate, methyl a-(pentachlorophenylmercapto)ax 30 sure
35-350 Saybolt Universal seconds at 210° F., a viscosity
propylacetate, n-butyl a-(pentachlorophenylmercapto)-a
index in the range of from ——25 to 150, and a ?ash point
ethylacetate Z-ethylhexyl a-(pentachlorophenylmercapto)—
of between about 275 and 600° F.
a-methylacetate and so forth. Carbocyclic esters useful
The synthetic oleaginous bases are of particular inter
in the practice of this invention comprise cycloalkyl esters
est in connection with this invention, in that they offer
methylcyclohexyl pentachlorophenylmercaptoacetate, aryl
and alkaryl esters such as phenyl pentachlorophenylmer
pressure properties of such lubricants to be substantial
degree required, so that the particular bene?ts of this in
vention are of special advantage. Any of a wide variety
of synthetic oleaginous bases may be employed to pro
duce the compositions of this invention.
Polysiloxanes, also known as silicones, or silicone poly
mers, comprise one class of synthetic lubricant bases of
commercial importance which may be improved in ex
treme pressure properties to a substantial degree by modi~
?cation in accordance with this invention. .Polysiloxanes
are compounds comprising essentially silicon atoms con
nected to one another by oxygen atoms. In liquid poly
captoacetate and tolyl pentachlorophenylmercaptoacetate;
and aralkyl esters such‘as benzyl pentachlorophenylmer
captoacetate. Ilustrative of the presently provided esters
of pentachlorophenylmercaptoacetic acid which may be
employed in the practice of this invention wherein the
ester radical is a hydrocarbon radical containing non-in
terfering substituents are oxyalkyl esters such as 2-hy
droxyethyl pentachlorophenylmercaptoacetate, 3-hydroxy
propyl pentachlorophenylmercaptoacetate, 2-(ethyloxy)
ethyl pentachlorophenylmercaptoacetate, 2-(2 - hydroxy
ethyloxy)ethyl pentachlorophenylmercaptoacetate, 2-bu
toxyethyl pentachlorophenylmercaptoacetate, and 2-hy
organosiloxanes, or silicones, of the lubricating oil vis
cosity range, a preponderant number of the remaining
valences of the silicon atoms are satis?ed by the substitu
rophenylmercaptoacetate, 3 ~chlorophenyl pentachloro
tion thereon of organic radicals, attached by a carbon-to
phenylmercaptoacetate, 4-chlorobutyl pen-tachlorophenyl
silicon bond. Examples of such organic radicals are
mercaptoacetate, o-bromohexyl pentachlorophenylmer 55 aliphatic radicals including alkyl radic?s such as methyl,
droxyethyl a-(pentachlorophenylmercapto)-a-methylace
tate; and haloalkyl esters such as 2-chloroethyl pentachlo
captoacetate, 2-chl0rooctyl or-(pentachlorophenylmercap
ethyl, propyl, butyl, and so forth; alicyclic radicals such
as phenyl, cyclohexyl, diphenyl, anthracyl, naphthyl, and
to)-u-methylacetate, and so forth. Illustrative of other
types of presently useful esters are 2-carboxyethyl penta
so ‘forth; aralkyl radicals such as benzyl and alkaryl radi~
cals such as tolyl, xylyl, and so forth; and the like. Rela
tively common oils of this type are dimethylsilicone poly
chlorophenylmercaptoacetate, 4-sulfamoylphenyl penta
chlorophenylmercaptoacetate, 4-cyanopentyl pentachloro
phenylmercaptoacetate, benzoylmethyl pentachloro
phenylmercaptoacetate, Z-mercaptoethyl pentachloro
phenylmercaptoace-tate, 4-acetylbutyl pentachlorophenyl
mer, phenylmethylsilicone polymer, chlorophenylmethyl
silicone polymer, and so forth. Of particular utility for
lubricating purposes are silicones in which the silicon
atoms are substituted by two different organic radicals,
mercaptoacetate, 2 -carboxyethyl a-(pentachiorophenyl
mercapto)-a-methylacetate, 2-sulfoethyl a-(pentachloro
phenylmercapto)-a-propylacetate, and the like.
The lubricant compositions provided in accordance
with this invention will comprise an oleaginous basic stock
compounded with one or more of the pentachlorophenyl
mercapto radical~containiug compounds described above.
The chlorinated aromatic sulfur compound employed
in preparing extreme pressure ?uid and grease-like lubri
cant compositions in accordance with this invention will
be incorporated in amounts su?icient to effect a substantial
65
e.g. methyl and phenyl radicals. Especially effective
properties have been obtained when the organic radicals
substituted on the silicon atoms in the silicone polymers
are in turn substituted by halogen atoms, especially chlo
rine atoms. Thus for example, the silicone may be sub
stituted by chlorophenyl radicals such as dichlorophenyl,
trichlorophenyl and tetrachlorophenyl radicals, other
valences of the silicon atoms being satis?ed by the hydro
carbon radicals such as methyl radicals or the like. As
is well known in the art, the silicones intended for use as
increase in load carrying capacity over that exhibited by 75 oleaginous bases will desirably contain an average of
3,041,280
'from 1.9 to 2.67 organic groups per silicon atom. Re
-maining valences, if any, of the silicon atoms may be sat
is?ed by radicals attached to the silicon atoms in the
compounds from which the silicone polymers are pre
pared, such as hydrolyzable organosubstituted silanes;
or by the product of hydrolysis of such radicals, such as
'8
oxanes of lubricating oil viscosity.
Other synthetic
oleaginous bases which may be mentioned include fluoro
carbon oils such as perfluorinated petroleum oils; tetra
substituted ureas; and esters such as dimethylcyclohexyl
phthalate, trioctyl phosphate; and similar ?uids adapted
for lubricant applications.
Mixtures of oleaginous bases may sometimes be pre
ferred to any single lubricant ?uid. It has been found
that certain advantages are possessed by base stock blends
lar interest in the practice of the present invention com
comprising silicone/polyester blends; and a blend of this
10
prises organic polyesters. On the one hand, these may
composition as described hereinafter will form a preferred
comprise esters of polycarboxylic acids, such as dicar
hydroxide radicals.
Another class of synthetic oleaginous bases of particu
boxylic acid diesters. Thus for example, such synthetic
ester ‘lubricants may have the general formula
base stock for compounding with the stated chlorinated
compounds to form the novel lubricant compositions of
R(COOR1) (COOR2)
this invention.
In the context of severe operating conditions present
Where R is an aliphatic or cycloaliphatic hydrocarbon
radical of from 2 to 8 carbon atoms and R1 and R2 are
ing demands for the ultra-high load bearing capacity of
lubricating compositions obtainable in accordance with
this invention, a form of lubricant composition which will
be of particular importance will comprise a grease. To
alkyl-substituted cycloalkyl radicals of at least 4 carbon
atoms. Such esters may be derived from succinic, maleic, 20 form greases, oleaginous bases as described above are
compounded with a thickener effective to provide a gel
pyrotartaric, glutaric, adipic, pimelic, suberic, azelaic,
structure and raise the dropping point of the composition.
,sebacic, pinic, thiopropionic or oxypropionic acids or
Any of a wide variety of thiekeners may be employed in
the like, speci?c esters of this nature including for exam
the compositions of this invention.
ple di(1-methyl-4-ethyloctyl) glutarate, di(2-ethylhexyl)
the same or dilferent and are branched chain alkyl or
oxydibutyric acid, di(2-ethylhexyl) adipate, di(3-methyl
vbutyl) azelate, di-(Z-ethylhexyl) azelate, di-(2-ethyl
hexyl) sebacate, di(3,5,5-trimethy1hexyl) sebacate, di(2
,ethylhexyl) maleate, di(methylcyc1ohexyl) adipate, 2
One class of thickeners for formation of greases com
prises soaps, that is, alkali metal salts of long chain fatty
acids.
There is a large number of such soaps which are
effective for this purpose. Thus for example, lithium
soaps of hydroxy fatty acids such as hydroxystearic acid,
ethylhexyl l-methylhexyl sebacate and the like. Alter
natively, instead of derivation from a polycarboxylic acid, 30 hydroxypalmitic acid, hydroxymyristic acid and so forth
can be used as lubricant thickeners, alone or in admixture
the polyester synthetic oleaginous bases may be produced
with naphthenic salts such as calcium naphthenate and
by reacting a polyhydric alcohol with a monocarboxylic
acid. Thus for example, a polyhydric alcohol such as
ethylene glycol or pentaerythritol is esteri?ed with an
acid of relatively long chain length such as caproic,
pelargonic, capric, lauric, myristic, palmitic or stearic
acid, to produce a polyester of lubricating oil viscosity.
Speci?c examples of such polyesters derived from polyols
are pentaerythritol tetrapelargonate, pentaerythritol tetra
caprate, pentaerythritol tetrapalmitate, pentaerythritol
tetrastearate, ethylene glycol divalerate, diethylene gly
col dicaprate, propylene glycol dicaprylate, and so forth.
Another type of synthetic polyester lubricants which
may be used ‘as oleaginous bases in accordance with this
the like. Another type of soaps effective for grease for
mation comprises Sodium soaps of carboxylic acids con
taining a high number of carbon atoms, such as the sodium
salt of an eicosanoic acid the sodium salt of gadoleic acid,
the sodium salt of montanic acid, the sodium salt of be
henic acid and the like. The combination of a conven
tional soap thickener such as sodium salt of a hydrogen
ated ?sh oil acid with a salt derived from an aldehyde
such as furfuraldehyde by the Cannizzaro reaction is il
lustrative of another group of thickeners within this gen
eral class. Soaps of the stated nature or any of a wide
variety of other soap thickeners may be used in the com
positions of this invention. In general, however, soap
invention will be complex esters obtained by esterifying
a polycarboxylic acid with a diol, together with a mono
hydric alcohol and/or a monocarboxylic acid. Thus,
complex esters which may be employed as oleaginous
thickeners are not e?icient at substantially elevated tem
peratures; and where performance requirements call for
greases operative at very high temperatures, other thick
eners may be preferred.
bases may be obtained by esterifying one mole of a dicar
boxylic acid with 2 moles of a glycol and 2 moles of a
Silica materials form another class of thickeners useful
in grease formulation. Representative of such thicken
. monocarboxylic acid; or by esterifying one mole of a di
carboxylic acid with one mole each of a glycol, a mono
ers are silica aerogels, which may be treated in various
ways, such as with reactive silicon compounds, to im
carboxylic acid and a monohydric alcohol. Speci?c ex
amples of suitable complex esters are the esters prepared
from one mole of ethylene glycol, two moles of sebacic
acid and two moles of Z-ethylhexanol; and the ester pre
pared from one mole of triethylene glycol, one mole of
adipic acid, one mole of n-caproic acid and one mole of
prove their grease-forming powers. A related type of
thickener comprises a silicate, such as an organic deriva
rtive of bentonite clays.
A class of thickeners of particular importance in the
preparation of lubricating compositions based on syn
thetic oleaginous bases comprises compounds containing
Z-ethylhexanol.
In addition to the above-mentioned classes of synthetic
, lubricating base stocks comprising types of present major
an amide type linkage, including ureides, urethanes, al
commercial importance, there are a number of other
oleaginous bases which can be used if desired in the
, lophanates, carbazides, carbazones and the like. Thick
,eners of this nature are particularly valuable when a
I grease having high temperature stability is required. An
practice of this invention. Thus for example, such lubri
cant bases may comprise hydrocarbon oils prepared by
mula RNHCONHR or RNHCONHRNHCONHR, where
polymerization of unsaturated hydrocarbons. Polyethers
of the nature of high molecular Weight polyoxyalkylene
compounds, derived for example from ethylene oxide,
propylene oxide and like substances, form another useful
class of lubricant bases; similarly, there may be employed
oleaginous bases of related structure, such as propylene
, oxide-tetrahydrofuran copolymers, and polyaryl ethers.
Besides the silicones discussed above, additional silicon
derivatives of interest in this connection comprise silanes,
organosilicates and disiloxanes such as hexaalkoxydisil 75
especially preferred class comprises a ureide of the for
each R is an organic radical, preferably aromatic. Such
ureides may conveniently be prepared by reacting an iso
cyanate with an amine.
These thickeners may be syn
thesized separately and formulated with the oleaginous
base to form a grease or, since the reaction of an iso
cyanate with an amine proceeds very readily, the compo
nents of the thickener may be reacted in situ in the
oleaginous base; the latter is generally preferred. As il
lustrative of the isocyanates which may be employed to
produce such thickeners may be mentioned aromatic iso
3,041,280
9
10
cyanates such as p-chlorophenyl-isocyanate, p-tolyliso
benzenethiolate with an ammoniacal cadmium chloride
solution containing 11.5 parts of CdClz. Cadmium penta
chlorobenzenethiolate sublimes with decomposition at
about 350° ‘C.
(III) For the preparation of the lead salt of penta
cyanate, tolylenediisocyanate, p-biphenylylisocyanate (p
xenylisocyanate), phenylisocyanate, p-carboxyphenyliso
cyanate, p,p'-diisocyanatodiphenyl, 2,5-dichlorophenyliso
cyanate and so forth, as well as alkyl isocyanates such as
hexylisocyanate, 1,6-diisocyanatohexane, cyclohexaneiso
cyanate and so forth.
chlorobenzenethiol, 30.6 parts of sodium pentachloro
Illustrative of amines which can
.benzenethiolate were reacted with an aqueous solution
be employed to produce the stated thickeners are aryl
amines such as p-amino-biphenyl, benzidine, dianisidine,
o-toluidine, p-aminobenzonitrile, p-phenylenediamine, m
phenylenediamine, aniline, p-toluidine, and so forth; and l0
alkyl amines such as 1,6-diaminohexane, 1,3-diamino
propane, diethylenetriamine, triethylenetetramine, hexyl
containing 16 parts of lead acetate.
EXAMPLES ‘IV-X
Pentachlorophenylmercaptoacetic acid esters were pre—
pared by reacting the acid with an excess of the corre
sponding alcohol in the presence of catalytic amounts of
amine, dodecylamine and so forth. Examples of combi
nations of such isocyanates and amines which may be se
p-toluenesulfonic acid at re?ux temperature or a maxi
lected to produce thickeners for use in the presently pro 15 mum of 130° C. The excess of alcohol was stripped un
vided lubricant compositions comprise a diamine such as
der vacuum and the catalyst removed (by washing. The
benzidine with a monoisocyanate such as p-biphenylyliso
esters were isolated in almost quantitative yield and re
cyanate, in a 1:2 molar ratio; a diisocyanate such as
crystallized from the appropriate solvent. A list of the
hexylenediisocyanate with an amine such as aniline, in a
prepared esters with their physical data is given below:
20
1:2 molar ratio; a diisocyanate such as tolylenediisocya
nate with a mixture of amines such as aniline and p
Ester
Recrystallized from
M.P. ° 0.
chloroaniline, in a molar ratio of 1:121, and so forth.
Instead of the above-mentioned thickeners, if desired,
the lubricant compositions of this invention may be for
mulated as greases by the inco1poration of such thick~ 25
eners as phthalimides, phthalocyanines, indanthrene, and
so forth.
To formulate the lubricant compositions of this inven
tion as greases, thickeners will be incorporated in propor
tions and by means usual in the lubricant art. Thus, the 30
oleaginous base is preferably mixed with the thickeners
under conditions of high shear, in a colloid mill, homoge
Methyl _______ ._
Methanol _______ _.
Ethyl _________ __
Petroleum ether"- 83° C.
Isopropyl __________ __do _________ __
2-ethylbuty1 ________ __do ___________ 1.
_. 2-ethylhexyl__-._ None ____________ __
91° C.
83° C.
30~34° C.
Liquid at room tempera
Monoglycol_____ Toluene".
__.__ 204° C'._
4-chloro-1-butyl.
_ _ _ _.
None _ _ _ _ _ _
Not puri?ed.
EXAMPLES XI-XIII
nizer or the like. The proportion of thickener to be used
will vary very widely depending on the nature of the
These examples illustrate preparation of the heavy metal
salts of pentachlorophenylmercaptoacetic acid useful in
With the aryl-sub— 35 preparing the lubricating compositions of this invention.
oleaginous base and the thickener.
stituted urea thickeners, silicone polymer oils are general~
'ly thickened to grease consistency by the addition thereto
(XI) The Zinc salt of pentachlorophenylmercaptoacetic
acid was prepared by reacting an aqueous solution con
of 5 to 70% and preferably to about 10 to about 50% of
taining 36.3 parts of the sodium pentachlorophenylmer
the thickener by weight. For the present purposes, a pro
40 captoacetate with an ammoniacal solution of 13.6 parts
portion of about 15-25% thickener has been found satis—
of zinc chloride. An 87% yield was obtained.
factory in such a system, where the thickener employed
(XII) The cadmium salt was obtained in a 95% yield
was a mixed ureide prepared by reaction of a single aro
using essentially the same procedure as described for the
matic diisocyanate with a mixture of two aromatic amines,
zinc-salt, by reaction of 36.3 parts of sodium pentachloro
reacted in situ in the oleaginous base. It is to be appre 45 phenyhnercaptoacetate with 11.5 parts of cadmium chlo
ciated that with different thickeners and oleaginous bases,
ride.
these proportions will be varied appropriately, as is well
(XIII) The lead salt of pentachlorophenylmercapto—
understood in the art.
acetic acid was prepared by reacting an aqueous solution
The compositions of this invention may also comprise
of the 36.3 parts of corresponding sodium salt with a 2%
other property-modifying components such as antioxi 50 solution of 18 parts of lead acetate. The lead salt was
dants, pour point depressants or viscosity improvers, anti
obtained in the yield of approximately 90%.
foaming agents or the like. Antioxidants which may be
employed may be selected for example from alkyl phenols
such as 2,4,6-trimethylphenol, pentamethylphenol, 2,4,6
tri-tert-butylphenol and the like; aminophenols such as
benzylaminophenol; amines such as dibutyl-phenylenedi
EXAMPLES XIV-XXXI
55
These examples illustrate the improvement in proper
ties of base ?uids which can be obtained using the addi
tives of this invention.
amine, diphenylamine, phenyl-beta-naphthylamine, phe
The lubricant compositions and base ?uids were tested
nothiazine and dinaphthylamine; metal salts such as iron
octoate; and so forth.
for their lubricity properties on a Shell 4-ball extreme
The invention is illustrated but not limited by the fol 60 pressure tester, which comprises a device for holding three
lowing examples.
rigidly clamped 1/2 inch metal balls submerged in a lubri
EXAMPLES I—III
cant in a metal cup. A fourth rotating ball of the same
diameter is then pressed into contact with the three sta
tionary balls by an adjustable ?oating arm attached to .a.
These examples illustrate preparation of the pentachlo
spindle rotating at approximately 1750 rpm. The tests
robenzenethiol heavy metal salts employed ‘as extreme 65 were run at ambient temperatures at increasing loads until
pressure additives in accordance with this invention.
seizure and welding of the balls was observed to occur.
(1) The Zinc salt of pentachlorobenzenethiol Was pre—
The contact points on the three stationary balls Where
pared by reacting 30.6 parts of sodium pentachloroben
they are rubbed by the rotating ball have formed a circu
zenethiolate with an ammoniacal zinc chloride solution
lar scar at this point, the diameter of which is a measure
70
containing 7.5 parts of zinc chloride. A 97% yield was
of the wear properties of the lubricant.
obtained. The zinc salt sublimes with some decomposi
The following tables present the data obtained in this
tion at about 350° C.
test and illustrate the eifectiveness of the additives em
(II) The corresponding cadmium salt was prepared
ployed to produce the compositions of the present inven
similarly by reaction of 30.6 parts of sodium pentachloro 75 tion, in a variety of base ?uids.
73,041,280
Table I
INOIPIENT WELD POINT, SHELL 4-BALL E. P. TEST
,
Example
Base ?uid
Avg.
Corr.
Load, wear scar load,
Additive, percent
kg.
'am.,
kg.
mm.
XIV ...... __ Polymethylphenyl silicone 1
XV
do 1-
126
224
3.13
POBT,B 2% ______ __
XVI _____ _.
do 1 _____________________________________ __
PCPMAA,b 2%
158
2. 36
31. 0
XVII ____ _-
Chlorinated polymethylphenyl silicone 2 ____ ._
126
2. 32
23. 8
-_
17. 6
37
XVTTT
do 2
>316
2. 20
XIX ____ __
d0 2 _____________________________________ -_
>355
1. 23
X _____ __
XXI .... __
(103--___-do 3 _____________________________________ __ PCB'I‘,B 2% ______ __
112
200
2.48
2. 27
89
2. 75
12. 2
158
3. 43
22
X
_ ___.
Polyester L- -
XXIH_-__ __...do 4 _____________________________________ ._ PCPMAA,b 3%_.___
XXIV-_ -_ Didodeoyl dioctyl silane
56
XXV _________ __d?
XXVIXXVII.
>2. 5
85. 4
>100
19.0
45.0
<10
PCBT,“ 3% _______ -_
112
2. 45
19
Didodecyl diphenyl silnne
_____ u
___- o _______________________________________ __ Zn POBT,“ 3%“---
79
158
2. 7
2. 3
11
32
XXVIII--. Octadecyl trideeyl si1ane._
79
2. 55
11
___. -____clo _______________________________________ __ Zn l’OB'I‘;3 3%.-."
178
2.12
41
XXX_____ Hexa (2—ethyl-hexoxy) siloxane ____________________________________ __
79
2.27
13
XXXL... _____do _______________________________________ _- Zn PCBT,° 3%“---
251
2.05
68
XXI
_.
1 A. polymethylphenylsilicone supplied by the Dow Chemical 00., Midland, Mich, kinematic viscosity
16.72 cs. at 210° F., 68.2 cs. at 100° F.; 0.2% evapn. loss in 24 hrs. at 425 ‘’ F., ASTM cell; pour point ~58" F.;
?ash point 575° F.; identi?ed as DC 550.
thermal decompo
'-‘ A chlorinated polymethylphenylsilicone supplied by Dow Chemical 00., which, on
sition, yields p-dichlorobenzene; viscosity, 9.0 cs. at 210° F., 52.6 cs. at 100° F., evapn. loss 20-26% in 22 hrs. at
400° F., ASTltl cell; identi?ed as DC 4140.
.
a A chlorinated polymethyiphenylsilicone supplied by General Electric 00., Schenectady, N.Y.; kinematic
evapn. loss in 6.5 hrs at 400° F., ASTM cell; ?ash point
viscosity 22.8 cs. at 200° F., 61.6 cs. at 10 ‘
F.; identi?ed as GE 81400 and also known as Versilube F-50.
4 A polyester in the lubricant viscosity range, supplied by Emery Industries, Inc, Cincinnati, Ohio, and
reputed to be pentaerythritol tetrapelargonate; viscosity 4.94 cs. at 210° F., 23.97 cs. at 100° F.; evapn. loss 14.6%
in 22 hrs. at 400° F., ASTM cell; pour point —66° F.; ?ash point 515° F.; ?re point 575° F.; identi?ed as poly
ester 3137B.
=- Pcntachlorobenzenethiol.
‘1 Pentachlorophenylmercaptoacetic acid.
I Zinc pentachlorobenzenethiolate.
Table II
EXAMPLES XXXlI-XXXIII
INCIPIENT WELD POINT, SHELL 4-BALL E.P. TEST
These examples illustrate the effect of the present addi
tives in increasing the lubricity of greases.
To incorporate a silica-type thickener in the olcaginous
Avg.
base to provide a grease, the oleaginous base is mixed 50
with the silica thickener in the presence of a solvent.
Example
Additive
Per-
Load,
wear
Corr. MHL
cent
kg.
scar
load
diam,
est.
mm.
For the preparation of the samples testing of which is
described hereinbelow, the selected silica thickener was
XXXIL- None ___________________ _.
126
2. 62
21
15
a product characterized by good high temperature prop
XXXIII. Zinc pentachloro~
250
2.22
40
20
erties known as Bentone 38, supplied by National Lead 55
Company, New York, NY. In. an exemplary prepara
0
benzenethiolate.
The values given under the heading MHL in the fore
going table are the values calculated for the Mean Hertz
was charged with the quantity of oleaginous base to be
Load of the greases, which is a measure of the ability
thickened, such as a silicone polymer. The silica
of an olcaginous material to lubricate under ultra-high
thickener, in an amount equivalent to 15% by weight 60 loads. The Mean Hertz Load is a value calculated from
of the oleaginous base, was added to the fluid and the
data measured by the Shell 4-Ball Extreme Pressure
mixture stirred. Thereafter methanol, in an amount
Machine and provides an index of load-carrying ability
equal to 40% by weight of the thickener, was added
which combines the maximum load which can be im
' tion of silica-thickened greases with this product, a kettle
gradually and the resulting ?uid product passed through
a Morehouse mill ?ve times at 0.002 inch.
posed directly upon the lubricant as well as the wear
Any solvent 65 scar diameters, which are observed during the course
of the test. It is calculated as described in speci?ca
methanol remaining in the grease after milling is elimi
nated by a ?nal heating; after which the desired extreme
pressure additives are milled innto the grease.
The following data illustrate the improvement in prop
erties which may be obtained by the use of the additive
tion MIL-G-71l8.
‘ EXAMPLES XXXlV-LIII
These examples illustrate the effect of the present addi
70
of this invention when the grease is thickened with a
tives in increasing the load-carrying properties of aryl
silica thickener. In this test ‘the oleaginous base was
the polymethylphenylsilicone of Examples XIV~XVI,
thickened with 15% of the above mentioned silica thick
_ ener.
The test procedure was the Shell 4-ball extreme
pressure test described above.
substituted urea thickened greases.
Greases thickened with aryl-suhstituted ureas were pre
pared by dissolving the diisocyanate in a portion of the
75 base ?uid, dissolving the selected amine reactant in the
3,041,280
l3
314
.
remainder of the ?uid, and reacting the isocyanate with
additives provided by this invention produces a substan
the amine reactant by mixing the two solutions at elevated
temperature. Thus, to prepare greases employed in the
tests discussed below, ditolylene diisocyanate was dis
solved in about 30% of the selected base ?uid and equi
molar portions of p-chloroaniline and p-toluidine were
tial increase in the Mean Hertz Load of the greases;
and indeed, with 3.5% of pentachlorophenylmercapto
acetic acid this value is better than tripled for the grease
based on the chlorinated polymethylphenylsilicone, which
even initially has a relatively high value for this ?gure.
dissolved in the remainder of the ?uid in an amount such
as to provide stoichiometric proportions of the diisocya
mate and of the amines. Generally the quantities of
EXAMPLES LIV-LXXIV
these reactants were selected to provide between about
As mentioned in the preceding discussion, experi
15 and about 25%, by weight in the grease, of the aryl 10 ments conducted in the course of the studies leading to
substituted urea product thereof, which in the case of
the present invention have demonstrated that certain
the stated reactants, is 4-[3a(p-chlorophenyl)ureido]-4'
[3-(p-tolyl)ureido]-3,3’-dimethylbiphenyl.
unexpected improvements in the load-carrying ability of
After reac
lubricant compositions can be achieved by the use of ole
tion had occurred, the resulting grease was cooled, passed
aginous base blends as distinguished from single oleagin
ous bases. More particularly, blends of silicone lubri
cant ?uids with ester lubricant ?uids have been found
to provide oleaginous bases with the good wear proper
ties of ester synthetic lubricants combined with the su
once through a Morehouse mill at 0.002 inch, heated 4
hrs. at 450° F, again cooled and remilled. The selected
extreme pressure additive is then milled into the grease.
In the following table are presented Mean Hertz Load
values for an aryl-substituted urea thickened grease in
perior ‘load-carrying capacity of silicone ?uids, and under
which the oleaginous base comprised the polymethyl 20 certain circumstances preserving the good viscosity
phenylsilicone of Examples XIV-XVI.
temperature characteristics of silicone ?uids. With the
stated blends, the load carrying capacity of the lubricant
Table 111
compositions thereby provided may initially ‘be quite
25 high; the values can, however, be still further improved
by introducing the extreme pressure additives of this in
Example
Additive
Per- MHL
cent
vention into the blended oleaginous bases. This is dem
onstrated by the data presented in the following tables,
giving results obtained from greases prepared with the
15
3
30
__
6
6
40
72
XXXVIII . Zine pentachlorophenylmercaptoacetate.
6
27
_____ __do_.______._________.________
Pentachlorophenylmercaptoaceti
XXXVII...
.
indicated oleaginous bases ‘and thickened to a grease by
introduction of the aryl-substituted urea thickener of
Examples XXXIV-LIII, in an amount of about 20%.
Table VII presents data for greases comprising a poly
spectively, as the oleaginous base, the polymethylphenyl
silicone of Examples XIV-XVI: the polyester of Exam
ple XXII-XXIII; and a blend comprising 50% by weight
Table IV gives the Mean Hertz Load values for greases
based on the chlorinated polymethylpheuylsilicone of EX
amples XVII-XIX.
of each of the stated bases.
Table IV
Example
Additive
Per-
MHL
cent
Table V
40
ESTIMATED MEAN HERTZ LOAD OF GREASES
XXXIX- _a
XL _______ __
XLI ______ _.
XLTT
None
_
_
Pentachlorobenzcnetliiol ______________ __
Zinc pentsehlorobenzenethiolate.
_____dn
XLIII _________ __do ____________________________ __
-__
30
3
50
1. 5
36
3
53
6
77
XLIV ____ __
Lead pentachlorobenzenethiolate ______ __
3
54
XLV _____ __
Pentachlorophenylmereaptoacetic acid__
3
72
3.5
94
XLVI ____ __ ____do __________________________________ __
XLVII___-_ Meth?ylc pentachlorophenylmercaptoace a e.
XLVIII____ ISOPI‘éJDtYI
pentaehlorophenylmereaptoace a e.
3
3-6
53
47
XLIX ____ _, Z-ethylbutyl pentachlorophenyl-
3
40
L
6
G3
LI ________ __ 4-chloro-1-hutyl pentachlorophenyl-
3
48
LII _______ __ Zinc pentachlorophenylmercaptoacetate_
LIII ______ __ Lead pentachlorophenylmercaptoacetata
3
3
47
54
mercaptoacetate.
_ "__do
Example
oleaginous base
Additive
Per-
45
LIV___._
LV ____ ._
LVI,_.__
Polymethyl-
______________________________ __
15
Polyester ________________________________________ __
20-30
phenylsilieone.
Blend____
_ ______________________________ »
____.do ___________ __ Zine pentachloro-
mereaptoacetate.
___._do ___________ __ Zinc pentaehlorophenyl~
- going data, the addition of each of the extreme pressure
62
6
80
Table VI presents data for greases comprising respec
55
As will be observed by a consideration of the fore
26
6
benzenethiolate.
mercaptoacetate.
._
MHL
cent
tively, as the oleaginous base, the chlorinated polymeth
ylphenylsilicone of Examples XVII-XIX; the polyester
of Examples XXII-XXIII; and a blend comprising 50%
by weight of each of the stated bases.
Table VI
ESTIMATED MEAN HERTZ LOAD OF GREASES
Example
oleaginous base
Additive
Per; MHL
cen
LIX_____ Chlorinated polymethylphenylsilicona.
30
LX ____ __
Polyester
20-30
LXI_____
Blend ________________________________________________________ _-
___
_-
____ __
35-40
LXIL- . _ _____do _________________________________ ._
Pentachlorobenzenethiol_
3
LXIII___
do.__.
Zine pentachlorobenzenethio
3
58
LXIV____
do
_
6
68
LXV_.___
(in
Cadmium pentachlorobenzenethiolate._.
3
_____do
53
48
LXVI_______ __do _________________________________ ._ Pent-aclllorophenylmercaptoacctic acid...
3
72
Zinc pentachlorophenylmercaptoacetate_
3
52
3
55
Cadrrtu‘ttlm pentaehlorophenylmereapto-
LXIX ______ __do _________________________________ _.
ace a e.
Zinc pentachlorobenzenethiolate ______ __
and
3
Pentachlorophenylmercaptoacetic acid_
3
77
3,041,280
16
15
Materials Test Methods and the tests identi?ed by MIT
members are standard military test methods published by
the Federal Government, as is the oil separation Federal
matic viscosity of 11.8 cs. at 210° F. and 33.2 cs. at 100°
Standard Method mentioned above. The Shell 4-ball test
F.; pour point --85‘’ F.;?ash point 535° F.; supplied by
is conducted by substantially the same procedure as that
Dow Chemical Co., and identi?ed by the supplier as DC
described in a previous example hereinabove, with the
4039. Blend A comprised a mixture of 50% by weight,
di?erence that in this test a steady load is applied rather
each, of the stated polymethylphenylsilicone and the
than
increasing loads.
polyester base of Example XXILXXHI. Blend B com
EXAMPLES LXXVI-LXXVII
prises a mixture of 75% by weight of the stated poly
The following examples illustrate that an improvement
methylphenylsilicone, and 25% of the polyester base of 10
Examples XXII-XXIII. Blend C comprised a mixture of
in extreme pressure properties is achieved by the present
Table VII presents data for greases comprising a poly
"methylphenylsilicone base ?uid characterized by a kine
invention as embodied in compositions comprising a
37.5%, by Weight, of the stated polymethylphenylsilicone;
37 .5 %, by weight, of the chlorinated polymethylphenyl
natural oil as the oleaginous base.
(LXXVI) A grease was prepared by thickening a
silicone of Examples XVII-XIX; and 25%, by weight, of
15 naphthenic base mineral oil characterized by a viscosity
the polyester of Examples XXII-XXEH.
of 725 Saybolt Universal seconds at 100° F. and a vis
Table VII
cosity index of 85 with 8% by weight of a soap thickener
ESTIMATED MEAN HERTZ LOAD OF GREASES
Example
Oleaginous base
Additive
Percent
comprising lithium hydroxystearate.
MHL
20
(LXXVII) Into a portion of this grease of Example
LXXVI, there was incorporated 6% by weight of penta
chlorophenylmercaptoacetic acid as an extreme pressure
LXX_-__
Poiymethyl-
.
______________________________ ._
additive.
The Mean Hertz Load values of the mineral oil based
<15
phenylsilieone.
LXXI--. _____do ___________ ._
Pentachlorophenyl-
6
65
LXXIL- Blend A“
LXXIII- Blend B__
____do _________________ __
__do _________________ __
3
6
90
9O
4
92
.LXXIV_ Blend 0
mercaptoscetic acid.
_____do
grease with and without the stated additive were as fol
25 lows:
Grease of example:
LXXVI _
MHL
__
_
_.._
28.7
LXXVII ______________________________ __ 45
EXAMPLE IJQCV
EXAMPLES LXXVIII-LXXX
This example presents detailed test data for a typical 30
These
examples
illustrate the excellent corrosion prop
lubricating composition provided in accordance with this
erties of the presently provided lubricant compositions.
invention.
Three percent of each of the indicated additives were
The thickener employed in producing the grease, test
incorporated separately into greases prepared with the
data for which follow, comprised 17%, by weight of the
chlorinated polymethylphenylsilicone of Examples XVII
grease, of an aryhsubstituted urea thickener prepared by
XIX as the oleaginous base, thickened with the aryl
reacting ditolylene diisocyanate with p-chloraniline and
substituted urea described in Examples XXXlV-LIII.
p-toluidine in situ in the oleaginous base ?uid by the pro
4340 steel panels were cleaned and polished, then covered
cedure of Examples XXIV-LIII. The oleaginous base
with a 1/s inch layer of grease and kept in a sealed jar
used in this grease comprised a 50:50% by weight blend
comprising respectively the chlorinated polymethyl
phenylsilicone lubricant ?uid of Examples XVII-XIX
40 at 400° F. for a period of 24 hours.
The results are
presented in the following table, in which the rating is a
qualitative comparative value assigned on the basis of
visual inspection of the panels, in which a higher ?gure
and the polyester lubricant ?uid of Examples XXII
)OGII. To this composition was added 3% by weight of
corresponds to greater corrosion or attack on the panels.
zinc pentachlorobenzenethiolate as an extreme pressure
Table VIII
CORROSION TEST, 24 HOURS AT 400° F.
_
Example
Additive
Weight
.
change of
Rating
Comments
panel mg.
LXXVIII _ None
4
200
1
Light oxide stain. No pitting or corrosion.
10
2
Purple heat stain. No pitting or corrosion.
tion.
The properties of this grease were as follows:
Penetrationwworked ‘(60) ASTM method
308.
D217—52T _______________________ __
Penetration—~ 100,000 strokes MILG-3278A- ________________________ _.. 321.
Dropping point ASTM method D566—42__ > 47 5° F.
As will be seen from the foregoing data, the additives
employed to produce lubricating compositions in accord
ance with this invention actually may reduce the corrosiv
ity of the base greases, exerting a corrosion-inhibiting
60 effect. By contrast, greases comprising the same oleagin
ous base in combination with a commercial extreme
pressure additive are found to produce heavy corrosion
Evaporation loss—22 hours at 400° F.
ASTM method D972-42 __________ __
Oil separation-30 hours at 400° F.,
Federal Standard method 321.]. ____ __.
cabinet test MII:—L—4343A,
0
Free
Mean
Surface corrosion.
0
LXXX____ Zinc pentachloro-hcnzenethiolate __________ __
:additive in accordance with the method of this inven
G-
4
LXXLX___ Pentachlorophenyl-mercaptoacetic 301d--."
________________________ _._.
Hertz
G—7118 _________________________ ..
Water washout MIL——G—3278A ______ ..._
within 24 hours at 400° F.
Similar results to those shown in Table VIII were ob
16.7 % .
6.97 % .
65 tained when the grease compositions of this invention
2.
None.
58.
0.69%.
Shell a-hall wear test 2 hours 1,200
52,100 steel balls.
r.p.m. 75° C
10-40.
Load, k
Average scar diameter, mm ____ __
0651-1309.
were tested by Federal Standard Method 79l—5319-T,
run at 100% relative humidity. Greases thickened with
the aryl-substituted urea of Examples XXXIV-LIII com
prising, respectively, the chlorinated polymethylphenyl
silicone base of Examples XVII-XIX, and the blend of
chlorinated polymethylphenylsilicone base ?uid and poly
ester base ?uid of Examples LX'I-LXIX were compounded
Apparent viscosity in poises for 2
with 3% of additives comprising zinc pentachlorobenz
In the foregoing table, the test procedures described
with the pre?x ASTM are American Society for Testing 75
enethiolate, pentachlorobenzenethiol, pentachlorophenyl
mercaptoacetic acid, vzinc pentachlorophenylmercapto
seconds ASTM method D1092-55____.. 15,000 at —--45° F.
17
3,041,280
acetate, and cadmium pentachlorophenylmercaptoacetate.
The greases all gave a test rating of 2; which is an ac
ceptable rating under the stated Standard Method.
While the invention has been illustrated with reference
to various particular embodiments thereof, it is to be ap
preciated that modi?cations and variations can be made
within the scope of the invention.
What is claimed is:
18
the said extreme pressure additive is a heavy metal salt
of pentachlorophenylmercaptoacetic acid.
13. The lubricating composition of claim 8 wherein the
said extreme pressure additive is an ester of pentachloro~
phenylmercaptoacetic acid.
14. The lubricating grease composition of claim 8
wherein said lubricating oil is a silicone ?uid and said
extreme pressure additive is pentachlorophenylmercapto
1. A lubricating composition consisting essentially of
acetic acid.
a lubricating oil and, as an extreme pressure additive, 10
15. The lubricating grease composition of claim 8
from about 0.05 % to about 15% by weight of the total
wherein said lubricating oil is a mixture of a silicone and
composition, of a chlorinated aromatic sulfur compound
a polyester within the lubricating t?uid viscosity range,
selected from the class consisting of pentachlorobenzene
said silicone providing from about 50% to about 75%
thiol, heavy metal salts of pentachlorobenzenethiol, penta
by weight of said mixture, and said extreme pressure ad
chlorophenylmercaptoacetic acid, heavy metal salts of 15 ditive
is pentachlorophenylmercaptoacetic acid.
pentachlorophenylmercaptoacetic acid, and esters of
16. A lubricating composition of claim 10 wherein
pentachlorophenylmercaptoacetic acid.
2. The lubricating composition of claim 1 wherein the
said lubricating oil is a synthetic lubricant ?uid.
3. The lubricating composition of claim 1 wherein 20
the said extreme pressure additive is pentachlorophenyl
mercaptoacetic acid.
4. The lubricating composition of claim 2 wherein the
said synthetic lubricant ?uid comprises a silicone.
5. The lubricating composition of claim 2 wherein the 25
said synthetic lubricant ?uid comprises a mixture of a
silicone and a polyester within the lubricating ?uid vis
cosity range, said silicone providing from about 50% to
the said heavy metal salt is a zinc salt.
17. The lubricating composition of claim 12 wherein
the said heavy metal salt is a zinc salt.
18. A lubricating grease composition consisting essen
tially of a silicone ?uid lubricating oil consisting of a
silicone ?uid, from about 5% to about 70% by Weight
of the total‘ composition, of a thickener consisting of an
aryl-substituted urea, and from about 0.05% to about
15 % by weight of the total composition, of an extreme
pressure additive consisting of pentachlorophenylmercap
toacetic acid.
19. A lubricating composition consisting of a lubri
'
oil and, as an extreme pressure additive,
6. The lubricating composition of claim 2 wherein said 30 cating
an amount which is at least about 0.05% based on the
synthetic lubricant ?uid is a silicone, and wherein said
weight of the total composition, said amount ‘being su?i
extreme pressure additive is pentachlorophenylmercapto
cient :to produce extreme pressure properties, of a chlori
acetic acid.
nated aromatic sulfur compound selected from the class
7. The lubricating composition of claim 2 wherein said
consisting of pentachlorobenzenethiol, heavy metal salts
about 75% by weight of said mixture.
synthetic lubricant ?uid is a mixture of a silicone and a 35
polyester within the lubricating ?uid viscosity range, said
silicone providing from about 50% to about 75% by
weight of said mixture, and wherein said extreme pres
sure additive is pentachlorophenylmercaptoacetic acid.
8. A lubricating grease composition consisting essen
tially of a lubricating oil, from about 5% to about 70%,
by weight of the total composition, of a thickener, and
as an extreme pressure additive, from about 0.05% to
of pentachlorobenzenethiol, pentachlorophenylmercapto
acetic acid, heavy metal salts of pentachlorophenylmer
captoacetic acid, and esters of pentachlorophenylmercap
toacetic acid.
20. The lubricating composition of claim 19 wherein
the said extreme pressure additive is pentachlorophenyl
mercaptoacetic acid.
21. The lubricating composition of claim 19' wherein
the said lubricating oil is a synthetic lubricant fluid.
22. The method of lubricating which comprises inter
about 15% by weight of the total composition, of a 45
posing between load-‘bearing sliding surfaces, a compo
chlorinated aromatic sulfur compound selected from the
class consisting of pentachlorobenzenethiol, heavy metal
salts of pentachlorobenzenethiol, pentachlorophenylmer
sition as de?ned in claim 1.
23. The method of lubricating which comprises inter
posing between load-bearing sliding surfaces, a compo
captoacetic acid, heavy metal salts of pentachlorophenyl
mercaptoacetic acid, and esters of pentachlorophenyl 50 sition as de?ned in claim 8.
mercaptoacetic acid.
References Cited in the ?le of this patent
9. The lubricant composition of claim 8 wherein the
UNITED STATES PATENTS
said extreme pressure additive is pentachlorobenzenethiol.
2,160,273
Loane et a1 ___________ __ May 30, 1939
10. The lubricating composition of claim 8 wherein the
said extreme pressure additive is a heavy metal salt of 55
pentachlorobenzenethiol.
11. The lubricating composition of claim 8 wherein
the said extreme pressure additive is pentachlorophenyl
mercaptoacetic acid.
12. The lubricaating composition of claim 8 wherein 60
2,216,751
2,255,085
2,335,017
2,347,217
2,849,479
2,877,261
2,897,081
Rosen ________________ __ Oct. 8,
Prutton et al. _________ __ Sept. 9,
McNab et a1 __________ __ ‘Nov. 23,
Prutton et a1 __________ __ Apr. 25,
Carmack et al. _______ .._ Aug. 26,
Hardy et al ___________ __ Mar. 10,
Dersch et al ___________ __ July 28,
1940
1941
1943
1944
1958
1959
1959
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent N0. 3,041,280
' June 26, 1962
Robert K. Smith et al-.
It is hereby certified that error appears in the above numbered pat
ant requiring correction and that the said Letters Patent should read as
corrected below.
In the heading to the printed specification, line 2, title
of invention, for "SULFUR COMPOUNDS" read —- LUBRICATING
COMPOSITION CONTAINING CHLORINATED,~'SULFUR COMPOUNDS —"— ; column 6I
line 38, for "be" read —- the -~—; 'column 14, line 32, for "VII"
read —- V -->; same column 14, lines 32 and 33, for "a polyspec—
tively" read -— respectively —-;_ column 15, lines 8 and 9, for
"comprises" read -- comprised —-; column 18' lines 21 and 22I
strike out "consisting of a silicone fluid".
-
Signed and sealed this 27th day of November 1962.
SEAL)
?ttest:
ZSTON G.
O
m3
Lttesting Officer
N
(0
DAVID L. LADD
Commissioner of Patents
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