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Патент USA US2405608

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Patented Aug. 13, 1946‘ I
' accuses
‘ I
cooonnpn LUBRICANT '
Dilworth'l‘. Rogers, Plain?eld, N. 3., assignor to
Standard Oil Development Company,’ a oorpo-l
ration o! Delaware
' No
Application-ch 31, 1944, '
Serial No. 528,953
'12 Claims. , (c1. 252-3211) '
.
.
I
_
1
v
This invention relates to a method of preventfi
- conversion of the resulting product to a salt, as
- ing the deterioration of organic materials, and it
by reactionwith a metallic base. As pointed out ' Y
relates more'particularly to a new type oi addi
application Serial Number 457,1“, cheer the
tive for improving the properties of mineral lubri~ ' - in
functions of the aromatic material is to stabilize
‘ eating oils.
_
é the sulfur present in the reaction product of the
In co-pending application Serial No. 457,146,
filed September 3,1942, the same being a joint
application of Carl Winning and the present applicant, there were described additives ‘for lubris
'
sulfur halidewith the ‘unsaturated compound.
Although all or a greater part oi'the halogen
presentlis removed by the second reaction as hin
.drosen halide, thearomatic compound does not
eating oils which were. prepared by reacting an m act-solely as a dehydrohalogenatingagent, since
- unsaturated compound, such as ,diisobutylenaV an appreciable Proportion of the same actually
, with a sulfur halide and further reacting the
. enters into the ‘reaction and becomes a constitu~
product thus'tormed with an aromatic compound,
ent of the reaction product, The resulting mate~
' e. a. phenol. These products were shown to have
, rial is a. mixture of compounds some of which
the property of notably reducing‘ the corrosion of. ware believed to possess an aromatic ring strucq
copper-lead and similar bearings when blended
ture with a side chain containing sulfur in a sta
into lubricating oils, and of notably improving
engine cleanliness and reducing ring sticking, pigton' skirt varnish formation and the sludging
‘tendencies of oils used in automotive engines. 20
bilizecl form. Although the ‘Structure of the
materials obtained in the ‘third step is not de?
nitely known, the products do contamwmbine?
phosbhoruswhich enhances their desirable Prop
- ._ The- products were also found to be useful, as ' _ cities. and it is believed that organo-substituted
general anti-oxidants fororganic materials.
.
' thio acids of phosphorus are present. Itis not
It has'now been found, in accordance with the
' intended that the invention be limited by any
present invention, that when products of the type
theory as to ‘the exact nature of the chemical
described in application Serial Number 457,146 25 reactions that take. place was to any particular
are further reactedwith a combination of the ole‘
> chemical structure of the intermediate or ?nal
merits. phosphorus and sulfur, either in the form . .-
products.
'
_
-
oia mixture of elemental phosphorus and ele
. In the ?rst reaction of the process any sulfur
mental sulfur or, more preferably, a phosphorus
halide may be reacted with a ‘compound contain
sul?de‘, the resulting products have properties to lug one or more unsaturated carbon-to-carbon
which are notably superior to those shown to be ' [ linkage, e. g., a 0:6’ group or a CEC~ groupr
possessed by the products before reacting with i
which forms apart of a non-hcnzenoid organic
the phosphorus and sulfur, particularly with re»
group. -By- the term “non-benzenoid”'is meant
gard to their e?ectiveness as blending agents for
any organic group other than a ring structure
.,mineral lubricating oils, since they are distinctly 35 having the typical benzene-like linkage found in
superior in the property of reducing the corrosion . benzene and its homologs and in condensed struc~
' of alloy bearings and in promoting engine cleans
tures such as those of naphthalene, anthra/cene,
liness. These products are described fully and
and the like. 'The desired reactive unsaturated
claimed in my 'co-pending application of even c1 ' . linkages may be found in'many types of groups
lng date. It has further been found that salts
ing, such as in ele?ns. in ole?nic side chains of
or such products, obtained by reacting the prod
aromatic compounds, in cycle-oleflns, in terrenes,
nets with a metal, a metallic base or an organic
in hetercyclic compcunds,_ etc. Thus,
ylene,
base, or in any other manner, are equally valu= 1 isobutylene, diisobutylene, triisobutyleue, the co‘
able.'especially as corrosion inhibitors, extreme
dimer‘ of isobutylene and normal butene, cracked
‘ ‘ pressure agents and antieoxidants and as agents
for promoting engine cleanliness, and in some
cases distinctly superior; and these salts, their .
preparation and uses form the subject matter of
thepresent application.
' I
'The preparation of the new additives of the
4 present invention thus involves Your fundamental
steps: (1) the reaction of an unsaturated organic
compound with a sulfur halide; (2) a further re
action with an aromatic compound: (3) a further
gasoline fractions, cracked paramn wax,'medium
or ‘high ‘molecular weight polybutene or. other
viscous ole?n mlymers, cyclopentene, cyclohcx
ene, butadiene, pentadiene, isoprene, styren .3, oleic
acid, oleyl alcohol, pine oil; terpcnes and similar
unsaturated materials may be ‘used. Oie?ns of
less than four carbon atoms are in general not
considered particularly suitable for the present
invention, although This not intended that their
use be excluded. Derivatives of the above de
reaction with phosphorus and sulfur; and (4) 55 ‘scribed compoundscontainlng various substitueut
_ _
2,405,608
3
since the substituent groups normally do not in
terfere with the principal reaction.
The most suitable sulfur halides are sulfur di
chloride and monochloride, especially the mono
chloride. The ole?nic material and sulfur halide
may be reacted in. any desired proportions, but
4
related compounds are phenol itself and its al
kylated derivatives, such as the cresols, xylenols,
groups and atoms may also be used to advantage, ‘
' mesitol, butyl phenol, tert.—amyl phenol, di-tert.
amyl phenol, tertiary octyl phenol, cetyl phenol,
cashew nut shell phenol (cardanol), wax alkyl
ated phenols, phenyl phenol, petroleum phenols}
, and the like, as well as the naphthols.
the more preferred ratio of ole?nic material to > '
Deriva
tives of ‘such phenols containing substituents,
such as halogen, nitro groups, amino groups, keto
sulfur halide is within the range from about 3:1
groups, carboxyl groups, ester groups, aroxy
10
to 1:1 (molal ratio). Higher ratios may often
groups, etc, may also be used, as well as the cor
be used when a portion of the ole?nic material is
responding thiophenols and compounds having
to serve as a solvent to be. removed later as un
more .than one hydroxyl or mercaptan group at
reacted material. The temperatures which have
Likewise metal
been found most satisfactory for this reaction > , tached to the aromatic nucleus.
are from about 20° to about 50° C. (about 70-125° 15 salts of the phenolic compounds may be em
ployed.
F), but the method may be carried out at con
It may be mentioned that the chlorophenols
siderably higher or lower temperatures if desired.
and chlorinated aromatic hydrocarbons are par
Catalysts are not required.
'
ticularly valuable in forming compounds useful
In the second reaction of the process, in which
the reaction product of the sulfur halide with an 20 in extreme pressure lubricants.
Another particularly preferred class of aro—
ole?n or like material is further reacted with an
matic compounds are the arylamines, such as
aromatic compound, the ratio of about one part
aniline, diphenyl amine, phenylene-diamine, ami
by weight of aromatic materialto one-half to
nophenols and the like. These are particularly
ten parts by weight ofsulfur halide-ole?n reac
because of the additional antioxidant prop
tionproduct may be used. When the aromatic 25 useful
erties of the attached amino groups.
material is a phenol, the most preferred ratio is
Aromatic compounds containing other substit
about one part by weight of the phenol to three
uent groups are also contemplated for use in
to ten parts by weight of the sulfur halide-ole?n
accordance with this invention. These include
reaction product. a In reacting phenol itself with
the diisobutylene-sulfur monochloride conden
sate the most desirable ratio is about one part
30
of phenol to eight to ten parts of the conden
sate. The temperature of the reaction may range
from aboutfi0° to about 160° C. (about 100-320°
F.) , but the most desirable range has been found
to be between about 80° and about 140° C. (about
175-285" F.).
'
'
'
,
.
compounds containing aryl, nitro, nitroso, nitrile,
thiocyanate, aldehyde, carboxyl and ether groups,
as well as groups containing sulfur which par
tially ‘or wholly replaces the oxygen of these
groups. Included also are compounds in which
a'metal is present, as in a metal carboxylate
group, an organo~metallic group, a metal alcohol
ate group, or the like.
'
'
..
Another particularly preferred class of aro
matic compounds which may be reacted with the
the first or second steps of the process because‘ of
the nature of the reactants employed; For ex 40 sulfur halide-ole?nic reaction products to pro
duce unusually valuable addition agents are the
ample, when diisobutylene is used as the ole?n
aromatic sul?des, particularly the phenol sul
source, any excess of this which .is present un
In general, solvents are not required in either
doubtedly acts in a solvent capacity. Where an
ole?nic material of higher molecular weight is
used or where the reaction mixture is not suffi
ciently' fluid the reaction may be aided by the
fides in which two groups are combined with one
or more sulfur atoms. The phenol sul?des are
conveniently prepared by reacting phenols and
alkylated phenols with sulfur halides. Such ma
terials are known to be useful in' themselves as
anti-corrosion agents, and their usefulness is in
hydrocarbon or the like. Also, with some types
creased by reacting them or their metal salts with
of reactants the presence of water, an alcohol
50 the sulfur halide product of the present inven
or an ether will be found to'be bene?cial.
_ tion to form products containing additional sul
The aromatic materials which may be used in
fur in stabilized form and further reacting these
the process include all types. The aromatic hy
products with a phosphorus sul?de.
drocarbons, such as benzene, naphthalene, amyl
If desired, the products after the reaction with
benzene, wax alkylated naphthalene, and the like,
the aromatic compound as described above may
may be used, although compounds containing
be further treated before reacting with a phos
substituent groups, such as phenols, aniline, sal
phorus sul?de or with phosphorus and sulfur.
icylic acid, substituted salicylic acids, alpha
For example, those obtained by reaction with
naphthol, diphenyl oxide, etc., are more‘ readily
phenols or with phenol sul?des may be con
reacted. In such substituted compounds, how—
verted
to metal salts, such as those of tin, bari~
ever, there must always be present in the arc
um, calcium, magnesium, zinc, nickel or alumi
matic nucleus at' least one replaceable hydrogen
num, and the metal derivatives thus formed fur
atom. When unsubstituted hydrocarbons, par
ther reacted with a phosphorus sul?de. Like
ticularly those having no alkyl groups, are sinuse of an organic solvent such as a chlorinated
wise, any free phenolic groups prcsent'may be
to ester or ether groups.
chloride, stannic chloride or the like, is usually 65 converted
In the third basic step of the process the prod
ployed, a condensing agent, such as aluminum ‘
necessary. In the case of more active compounds
no catalyst is needed.
ucts of the foregoing reactions are further re
acted with the elements'phosphorus and sulfur.
This may be accomplished by adding a mixture
use‘ in accordance with thepresent invention are
the phenols. vThese may be reacted with the 70 of the substances in elementary form to ‘the
A preferred group'of aromatic‘compounds for
sulfur halide-ole?nic reaction product without
the use of a catalyst, and the products of reac
tion are particularly useful in improving the
properties of lubricating oils.
The more desir
able and readily obtainable types of phenols and
heated reaction products, or by- adding a sul?de
of phosphorus, such as P283, PzSs, P4S3, P487, eta,
or-the like, or by treating with amixture of sul
fur and/or phosphorus and a sul?de of phos
phorus. or by treating with any other substance
2,405,808
5
5
or substances containing essentially only the ele
ments phosphorus and sulfur, or phosphorus and
sulfur in combination with elements-which do
base. This may be done by heating the reactants
in the presence of a suitable'solvent, such as an
alcohol or lubricating oil. It is insome cases
possible and desirable to conduct the third and
fourth steps of the process simultaneously, e.
not interfere with the reaction and which are
not harmful to the ?nal product. When ele
mentary phosphorus is used it may be either in
the white (yellow) or red allotropic form, and
sulfur may likewise be used in any of its allotropic
forms.
by reacting the ole?n~sulfur halide-aromatic
condensate with a mixture of a phosphorus sul?de"
and‘ a metallic oxide.
.
The salts which " r. em»
ployed in accordance with the present; invention
However, it is ordinarily more convenient to 10 include salts of all types, i. e., metal-salts as well
as salts of non-metallic bases,v such as ‘onium
use a sul?de of phosphorus in carrying out the
reaction. The proportions of phosphorus sul?de
to the sulfur halide—ole?nearomatic condensate
salts of all‘ types, including ammoniun'i, alliyl~
ammonium, quaternary" ammonium, sulionium
may vary over a considerable range. In general,
and phosphonium salts, as well as amine salts
and salts of organic bases generally. The most
about 5% to about 25% and preferably about 8%
to about 15% of phosphorus sul?de may be used,
- preferred metallic salts are the salts of metals
based on the weight of the product from the
of group II, particularly the salts of caliciun,
previous condensation of aromatic material with
the sulfur halide-ole?ne product.
'
‘
.
barium, magnesium and zinc, also the alkali
,
metal salts and salts of tin and aluminum.‘ It
Although the reaction can be brought about 20 has been found to be somewhat preferable to
by fusing the phosphorus and sulfur or phos4
react an amount of metal or base with the phos
phorus sul?de with the above described reaction
phorus sul?de treated product which is _at least
productjit is‘more convenient to carry out. the
equivalent to one atom of ‘a monovalent metal
reaction with the aid of ‘solvents, particularly
petroleum hydrocarbon solvents, or by the use‘
of an excess of the ole?nic reaction product
when the entire series of reactions take place‘in
for each atom of phosphorus present.
'
As noted above, the additives oi the‘ present
‘ invention are particularly useful for reducing
corrosiven‘ess of oils toward alloy bearings and.
one reaction vessel. Chlorinated or aromatic
for improving engine cleanliness as indicated by
solvents may also be used. In'the reaction with
the reduced quantities of deposits found in ring
sul?des of phosphorus, temperatures in the range 30 grooves, on piston skirts and in other parts of
of 60° to 200° C. may be employed, but tempera
they engine in which lubricants compounded with
tures of 90° to 150° C. are preferred.
'
the additives are used.
.
_
,
If desired, the reaction with'thesulfideof phos
.Another noteworthy advantage of the additives
phorus‘ may be conducted in a lubricating oil
prepared in accordance with the presentr‘invenv
medium. For example, a 50% concentrate of 35 tion is their ability to reduce exhaust valve stick
the ole?n-sulfur halide-aromatic condensate may - ing in engine operation. In certainlts’pes of
be prepared in lubricating oil as described ‘in
service, such as in railway Diesel engines, oils
Example 1 of the aforementioned ‘co-pending
of otherwise satisfactory characteristics are often
application Serial Number 457,146,, and then
objectionable because of their tendency to cause
treated with the sul?de of phosphorus and ?nally
sticking or erratic action of the exhaust valves,
?ltered.
_
’
‘.19.
‘
Ingen'eral', the preferred method of carrying
out the ?rst three basic steps of the presentin
vention is first to treat ‘the ole?n or other un
saturated material with the sulfur halide, then
react with the aromatic material, and ?nally add
the phosphorus and sulfur or phosphorus sul?de.
However, variations of this procedure may be
employed, as by adding the sulfur halide to a
mixture of the ole?n and aromatic material,
provided the ole?n and aromatic material do not
react directly with each other, and then further
reacting with the phosphorus sul?de.
‘
It is to be understood that any of the products
disclosed in or prepared by the methods den
scribed in application Serial Number 451ml’; 1119;.’
be further reacted with a combination of phos
phorus and sulfur to form a product which may
be converted to a salt additive of the present
invention.
'
'
‘
position
presur'nabl;r
products
throughonthethe
building
hot portions'of
up of oil
the
valve'stems. Additives of the present invention
markedly retard this tendency in oils in which
they are blended. Since fuel combustion prod~
ucts also come into contact with the valve parts.
the additives may likewise be added to the fuels
for both Diesel and gasoline engines to prevent
or minimize the sticking of valves.
Generally, the additives or" the present inven~
tion are most advantageously blended with lubri;
eating oil base stocks in concentrations between
the approximate limits of 9.02% and 5.0%, and
preferably from 0.1% to 2.0%, although larger
amounts may be employed. The exact amount
to be used depends to a certain extent on the
particular compounds used, the character of the
mineral oil base and the operating conditions of
the engine in which the lubricant is' to he em
'
Products which, in the form of their salts, are
especially adapted for use in extreme pressure
lubricants may be‘ prepared by halogenating the
extreme
ployed. pressure
‘When thelubricants,
additives concentration
are to be usedof l
to ‘15% are desirable and concentrations of 2 to
10% are preferred.
'
phosphorus sul?de reaction products; or, the
Concentrates
of
the
additives
oil may also
halogen may be introduced by using compounds 65, be prepared in, say, 25% to. 75%in concentration
containing phosphorus, sulfur andhalogen, e. g., - of additiveand the concentrate later'blended
PSC13, PSBrg, PSBrClz, PzS'zBm, and the like, in
with other oils‘to give a ?nal blend of lubricating
place of or in addition to the phosphorus sul?de
oil containing the desired precentage of additive.
in the third step of the preparation.
_' '
Such concentrates are often desirable, to save
The fourth and final basic step of the process, 70 shipping weight and space ' and to vfacilitate
i. e., the conversion of the‘ product of the ?rst
blending operations.
three steps into a salt, is generally accomplished
Examples of the'preparation and utilization of
simply'by reacting the product with a metal,
useful products in ‘accordance iv"?! the method
metal oxide, metal hydroxide, or other suitable
metal compounds, or with a suitable non-metallic
exampleswhich
of the ‘present invention
follow, but
will
it be
is to
desbe--under
ed in
2,406,608
}
the bearings used in a given test at the end of
the various four-hour periods are given in
that these example; do not limit the scope of
the invention in any way.
the table.
“’
-
I
'
Example - 1
I
1233 grams of diisobutylene was placed in a‘
reaction ?ask equipped with a‘ heater, stirrer
Table
Cumulative bearing weight loss (mg.
and re?ux condenser. Then, over a period of
three to four-‘hours, 472 grams of S201: was added
.
with stirring, the reaction temperature being
kept at 40°-45° C. After stirring for an addi 10
tional period of approximately an hour 94 grams
-' of phenol was added rapidly, the temperature
Oil
4
8 12 16 20 24 28 32 86
hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs. _
Base
BaseoiLoil 1%‘ product
'
of
Exampei .......... .l_._
' - raised to 100° 0., and the stirring continued for
per25sq.cm.aurtace)
.
5' 181
0
0_
0
0
0
0
0
10
29
an additional period of about two hours. 71
grams ofPzsa was then added over a 15 minute 15
The products of the present invention may
period while the temperature was maintained at ‘
be employed not only in ordinary hydrocarbon
> 100° 0. Heating was continued with stirring at
. lubricating oils but also in the "heavy duty" type
100°-105° C. for an additional period of about
two hours. ‘The product was allowed to cool to
room temperature 1 and then ?ltered through
of lubricating oils which have been compounded
so
with such detergent type additives as metal
soaps, metal petroleum suli'onates, metal phen
ates, metal alcoholates, metal phenol sulfonates.
metal alkyl phenol sul?des, metal organo phos
‘ one portion was steam distilled at 100° 0., yield
phates, thiophosphates, phosphites and thio
ing 282 grams of colorless, water-insoluble dis
tillate. The distillation residue was separated as phosphites, metal salicylates, metal xanthates
Hy-?o, leaving a-very slightresidue. The ?ltrate
was divided intovtwo parts (850 cc. each) and
and thioxanthates, metal thiccanbamates, reac- .
from the water presentand then dried‘ in a
stream of nitrogen fornan hour at 105° C. The
?nal product had the following analysis:
Percent
so
- 26.94
0.52
tion products of metal phenates and sulfur, re
action products of metal phenates- and phos
phorus sul?des, and the like. Thus the new ad
ditives of this invention may be used in lubricat
ing oils containing such addition agents as
To 300 grams of the product prepared as de
barium tern-cetyl phenol sul?des, calcium tert
amyl phenol sul?de, nickel oleate, barium octa'e
decylate, calcium phenyl stearate,‘ zinc diiso
scribed above 10 grams of zinc oxide was added
and the mixture heated to 80° 0. Then 250 cc.‘
cium cetyl phosphate, barium di-tert.-amyl
0.30
r
propyl salicylate, aluminum naphthenate, cal
phenol sul?de, calcium petroleum sulfonate,
of isopropyl alcohol was added and heating was
continued for two hours at 100° C, while a stream
of nitrogen was blown through the mixture. The
material, which had become free of the alcohol
by heating,- was then ?ltered through Hy-?o,
giving as a. ?nal product a light-colored, viseo
liquid soluble in lubricating oil.
'
zinc methyl cyclohexyl thiophosphate, calcium
dichlorostearate, etc. -
asphaltic 'or mixed base crudes, or, if desired,
~
_
_ Example
'
The lubricating 011 base stocks of this inven
tion may be straight mineral lubricating oils, or
distillates derived from paraf?nlc, naphthenic,
2 -
' various blended oils may be employed as well
45 as residuals, particularly those from which as
‘ ' . ‘ The e?ectiveness ‘of the product prepared as
phaltic. constituents have been carefully removed.
described in Example 1 in inhibiting the cor
, The oils may be re?ned by conventionalnmethods
rosion of a typical lubricating oil toward the.
surfaces of copper-lead bearings was determined
‘such as aluminum chloride, or they may be ex
- by a test which will be‘ described below. The
base oil used was a re?ned mineral lubricating:
‘oil of SAE 20 grade. A blank sample of, this
oil as well as a sample of the oil. to which 1%
of the additive vwas added were submitted to the
following corrosion test:
' V
‘500 cc. of the oil were placed in a glass oxi
dation tube (13" long and 2%’! diameter) ?tted
at the ‘bottom with a 1/4", bore air inlet tube
perforated to ‘facilitate air distribution.» The
using acid. alkali and/or clay or other agents
tracted' oils produced, for‘ example, by solvent
vextractionwith solvents of the type of phenol,
sulfur dioxide, furfural, dichloro ethyl ether,
propane, nitrobenzene, crotonaldehyde,"'etc. Hy
drogenated oils or white oils may be employed
65 as well‘ as synthetic oils prepared. for example,
by the'polymerization oi oleiins or by the re- _ .
action of oxides of carbon with hydrogen or by
the hydrogenation of coal or its products. In
certain instances cracking coal tarfractions and
oxidation tube was then immersed in a heating so coal tar or shale oil 'distillates may also be used.
Also, for special'applications, animal, vegetable
bath so that the oil temperature was maintained
- or-?sh oils or their hydrogenated or voltolized
at 325° F. during the test. Two'quarter sec
tions of automotive bearings of copper-lead alloy
products may beemployed, either alone or in
of known weight having a total area of 25 sq. cm. - admixture with mineral oils.
For the best results the base stock chosen
were attached to opposite sides of a stainless steel 65
should normally be that oil which without the
rod which was then immersed in the test oil and
rotated at 600 R. P. M., thus providing su?icient
agitation of the sample during the test. Air
new additives present gives the optimum perform
ance in the service contemplated. However, since
one‘advantage of the additives is that their use
also makes feasible the employment or less satis
was then blown through the oil at the rate of
2 cu. ft. per hour. At the end of each four 70
factory mineral oils or other oils, no strict rule
hour period the bearing surfaces were repolished.
can
be laid down for the choice of the base stock.
Each time the bearings were removed they were
washed with naphtha and weighed to determine
the amount of loss by corrosion (prior to re
Certain essentials must of course-m observed.
The oil must possess the viscosity and volatility
polishing). The cumulative weight losses of all 75 characteristics known to be required for the
2,405,608
seryice contemplated. The oil must be a satis
factory solvent for the additive, although in some
synthetic rubber compounding both as vulcaniza
tion assistants and as antioxidants, and generally
cases auxiliary solvent agents may be used. ,The '
they may be used many organic materials subject
lubricating oils, however they may have been
produced, may vary considerably in viscosity and
to deterioration by atmospheric oxygen.
The present invention is not to be considered
as, limited by any of the examples described here,
in, which are given by way of illustration only,
but'is to be limited solely by the terms, of the appendedv claims.
- other properties depending upon the particular
use for which they are desired, but they, usually
range from about 40 to 150 seconds .Saybolt
viscosity at 210° F. For the lubrication ofcertain
low and medium speed Diesel engines the general
practice has often been to use a lubricating oil
> _1. A lubricant comprising a mineral lubricating
oil base stock and a small proportion, sufficient
to stabilize the said oil against deterioration, of
. base stock prepared from naphthenic or aromatic
crudes and having a Saybolt viscosity at 210° F.
of 45 to 90 seconds and a viscosity index of 0 to 50.
a metal salt of a reaction product of a combi
However, in certain types of Diesel service,
particularly with high speed Diesel engines, and
iii-gasoline engine service, oils of higher viscosity
nation of the elements sulfur and phosphorus
with a product'obtainecl by reacting phenol with ’
sulfur chloride derivative of an ole?n.
index are often required, for example up to 75 or
, _ 2. ,A lubricant comprising a mineral lubricating
‘100, or even higher, viscosity index.
oil base stock and a small proportion, sufiicient
' In additionto the materials to be added ac
cording to the. present invention, other agents 20. to stabilize the said oil against deterioration, of
may also be. used such as dyes, pour depressors,
heat thickened fatty oils, sulfurized fatty oils,
organo metallic compounds, metallic or other
'l. soaps, sludge dlspersers, antioxidants, thickeners,
viscosity index improvers,‘ oiliness agents, de
foaming or antifoaming agents, resins, rubber,
ole?n polymers, voltolized fats, voltolized mineral
a metal salt of a reaction product of a combie
_
nation of-the- elements sulfur and. phosphorus
with a product obtained by reacting phenol with
' a sulfur monochloride derivative of diisobutylene.
25»'
3. A lubricant comprising a minerallubricating
oil base stock and about 0.1% to about‘ 2.0%by
weight of a metal salt of a reaction product of
‘a
vcombination of the elements sulfur and phos
waxes and colloidal solids , _
phorus with a product obtained by reactingabout
such as graphite or zinc oxide, 'etc. Solvents and 30 one
part by 'weightof phenol with about eight
assisting agents, such as esters, k'etones, alcohols, I '
to ten parts by weight of a sulfur monochloride
aldehydes, halogenated 0r nitrated compounds,
oils, and/or voltolized
and the like, may also be employed.
derivative of diisobutylene.
,
,
.
4. A lubricant comprising a mineral lubricating '
Assisting agents which are particularly desir~
able are the higher alcohols‘ having eight or more
carbon atoms and preferably 12 to 20 carbon
atoms. The alcohols may be saturated straight
‘-
oil base stock and asmali proportion, sumcient
to stabilize the ,said oil against deterioration, of
a metal salt of a reaction product of a'phos
. phorus sul?dewith a product obtained by react
' ing a phenol with a sulfur chloride derivative of
_ and branched chain aliphatic alcoholssuch as
octyl alcohol, CsHrzOH, lauryl alcohol, ClilHiibOH, , an ole?n; ‘
cetyl alcohol, CrcHaaOH, stearyl alcohol, some .40 " 5. 'A lubricant comprising a mineral lubricating
times referred to as octadecyl alcohol, CmHa'rOI-I, . ~
oil base stock and a small proportion, su?icient
and the like; the corresponding ole?nic alcohols
‘to stabilize the said-oil against deterioration, of
such as oleyl alcohol; cyclic alcohols, such' a
metal saltfof a reaction product of a phos
' as naphthenic , alcohols; and aryl substituted
alkyl alcohols, for instance, phenyl octyl 1 45 phorus sul?de with'a product obtained by re
acting phenol with a sulfur .monochloride deriv
or octadecyl benzyl alcohol or mix
ative of diisobutylene.
, - alcohol,
tures of these various alcohols, which may be
pure 'or substantially pure synthetic alcohols.
’ One may also use mixed naturally occurring -
.6. A composition according to claim 5 in which
' the metal of the salt is a metal of group II of
alcohols such as those found in wool fat (which 50
is known to contain a substantial percentage of
' alcohols having about 16 to
18 carbon atoms) and
in sperm oil (which contains a high percentage of
the periodic table.
-
.
-
'7.‘ A lubricant comprising a mineral lubricating
- oil base stock and about 0.02% to about 5% of .
a, product obtained by reacting about 1 to about
3 molecular propo
rtions of an ole?n with 1 mo
cetyl alcohol); and although it is preferable to
lecular proportion
isolate the alcohols from those materials, for some 55 acting about -3' to of a sulfur halide, further re
about 10 parts by weight of
purposes, the wool fat, sperm oil or other natural
> the product thus formed with 1 part by weight
products rich in alcohols may be used per se.
of a phenol, further reacting the product thus'
Products prepared synthetically by chemical
formed with about 5% to' about 25% of its weight
processes. mayalso be used, such as alcohols pre
pared by the ‘oxidation of petroleum hydro 60.' of a phosphorus sulfide, and ?nally ‘converting
the product thus formed into a metal salt of the
carbons, e. g., parafiin wax, petrolatum, etc. same by reaction with a' metal-containing sub
vIn addition to being employed in crankcase
stance, the amount of metal so reacted being at
lubricants and in extreme pressure lubricants, the '
least equivalent, on a valence basis, to 1 atom of .
additives or the present invention may also be
a monovalent metal‘ for each atom of phosphorus
used in spindle oils, textile oils, metal cutting oils,
introduced by means of the said phosphorus
engine ?ushing oils, turbine oils, insulating and
transformer oils,‘ steam cylinder oils, slushing
compositions, and greases.
Also their use ,in
sul?de.
-
I
'
,
’
-8. A lubricant comprising a mineral lubricating
' oil base stock and
a small proportion, sumcient
motor fuels, Diesel fuels and kerosene is con
to stabilize the oil against deterioration, of a
templated. Since these additives exhibit anti 70 metal
salt of'a reaction product of phosphorus
oxidant properties and‘are believed also to possess - pentasul?de with a product obtained by reacting
~‘ability to modify surface activity, they may be
a phenol with a sulfur chloride derivative of an
employed in asphalts, road oils, waxes, fatty oils
ole?n, ‘the metal of the salt being a metal of
of animal or vegetable origin, soaps, and plastics,
Similarly, they may be used in natural and ‘it group II of the periodic table.
9. A lubricant comprising a mineral lubricating
'
2,405,608
'
oil base stock and a small proportion, sufilcient
to stabilize the oil against deterioration, of a
metal salt ot-a reaction product of phosphorus
pentasul?de with a product obtained by reacting
phenol with a sulfur monochloride- derivative of Cl
diisobutylene, the metal of the salt being a metal
of group H of theperiodic table.
10. A lubricant composition vaccording to claim
12
of a phosphorus sul?de with a product obtained
by reacting a phenol with a sulfur halide deriv
ative of a compound containing an ole?nic
linkage.
.
e
'
12. An extreme pressure lubricant comprising
a mineral lubricating oil base stock and about 2
to about-10% or a metal salt of a reaction product
of a phosphorus sul?de with a product obtained
by reacting a chlorophenol with a sulfur halide
.11. An extreme pressure lubricant comprising 10 derivative of anole?n.
a 'mineral lubricating oil base stock and about 2
Dniwort'm 'r.- ROGERS. toabout 10% of a metal salt of a reaction product
9 in which the metal salt is a zinc salt.
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