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Патент USA US2386206

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Patented Oct. 9, 1945,
J 2,386,206 v '
RATENT' OFFICE
‘ UNITED ~ s'rA'rEs
. 2,386.206\,
MINERAL on. COMPOSITION
John J. Giammaria as Orland M. Reifl, Wood
bury, N. 1., assignors to SoconyI-Vacunm Oil
Company, Incorporated,_a corporation of New
York ,
No Drawing. Application May 21, 1943.
'
‘
Serial No. 488,742 ,
I
'15 Claims. (01.252-323)
This invention has to do in a general way with
to form deposits which interfere with the func
i
tion of the piston rings.
' mineral oil compositions and is more particularly
related to compositions comprised of mineral ‘oil
Aside from the corrosive action which attends
and a minor proportion of an added ingredient
which will improve the oil in one or more impor
the formation of acidic products of oxidation in ,
tant respects.
_
mineral oil fractions of the lubricant range, it has
been discovered that certain types of recently
, developed hard metal alloy bearing metals, such
as typi?ed by cadmium-silver alloy bearings, are
attacked‘ by ingredients in certain types of‘ oils,
.
It is well known to those familiar with the art
that mineral oil fractions re?ned for their vari
ous uses are in and of themselves usually de~
?cient in one or more respects, so that their 10
particularly oils of high viscosity index obtained
by various methods of solvent-V-re?ning. This
?eld for which they have been re?ned. For ex
ample, mineral oil fractions re?ned for use as
lubricants have a tendency to oxidize under con
ditions of use with the formationof sludge or 15
corrosive action on alloys of the aforesaid type
has led to the development of corrosion inhibitors
whichmay be used in solvent-re?ned oils to pro
practical utility is limited even in the particular
acidic oxidation products; also the lighter frac-~
'
tect such bearing metals against-this corrosive
action.
In the'lighter mineral oil fractions, such as
tions such as gasoline and kerosene tend to oxi
dize with the formation of color bodies, gum, etc.
those used for fuel purposes, particularly in in
In order to prevent or retard the formation of
ternal combustion engines, it has been found that
these products and thereby extend the useful life 20 the combustion characteristics of the fuel may be
of the oil fraction, it is common practice to blend
controlled and improved by adding minor pro
with such oil fractions an additive ingredient
portions of various improving agents thereto.
The various ingredients which have been de
which will have the effect of inhibiting oxidation,
such ingredients being generally known to the
- veloped for use in mineral oil fractions to im
trade as oxidation inhibitors or sludge inhibitors, 25 prove such fractions in the various respects
gum inhibitors, etc.
' enumerated above are largely speci?c to their ‘
It is also the practice to add other ingredients
‘particular applications, and it has, therefore,
to mineral oilfractions for the. purpose of im- ,
been the practise to add a separate ingredient for
each of the improvements which is to be effected.
proving "oiliness” characteristics and the wear
reducing actionJ of such mineraloils when they
30 ‘ We have discovered that mineral oil fractions
are used as lubricants, particularly when the oils
are used‘ for the purpose of lubricating metal
such as those referred to above can be improved
in several of the various properties enumerated
- surfaces which are engaged under extremely high
above by’ the incorporation therein of a small
pressures andat high rubbing speeds.
quantity of a m-ulti-functional compound or reac
Other ingredients have been developed for the 35 tion product selected from a new and novel class
purpose of depressing the pour point of mineral
oil fractions which have been re?ned. for use as
lubricants, such ‘re?nement leaving a certain
amount of wax' in the oil, which, without the
v of
phosphorus _
and
sulfur-containing
com
pounds or reaction products. Morev speci?cally,
' we have found that the compounds or reaction
products obtained by the reaction: of substan
added ingredient, would tend to crystallize at 40 tially two mols of alkyl-substituted hydroxyaro
temperatures which would render the oil im
practicable for use under low‘temperature condi
tions.‘ Additive ‘agents have also been developed
pentasul?de; and the metal salts thereof, im
for improving the viscosity index of lubricating
properties. Particularly preferred, however, of
oil fractions. In the case of internal combus
matic carboxylic acids and one mo] of phosphorus
prove such oil fractions in more than one of said
45 these multifunctional oil addition agents ‘are
tion engines, particularly those operating with
' hi'gh cylinder pressures, there is a decided tend
' ency for ‘the ordinary lubricating oil fraction to
those compounds or reaction products of the
aforesaid class which contain one orvmore oil
solubilizing "heavy” alkyl groups, that is, ali
phatic hydrocarbon groups of relatively high
form, under such conditions of use, carbonaceous
deposits which cause the piston 111188 to become 50 molecular weight preferably containing notless
stuck in their slots and which ?ll the slots in the
oil ring or rings, thus materially'reducing the elli
ciency of the engine.‘ Ingredients have, there
fore, been 'develope'dwhich, when added to the
oil, will reduce’ the natural tendency of the oil 55
than 20 carbon atoms, in the aromatic nucleus or
aromatic nuclei.
The multifunctional oil addition agents of this
invention are referred to as compounds and as
reaction products inasmuch as both de?nite com
2 -
2,386,206
_
pounds and products of inde?nite-chemical struc
commercially available as the cerium and yttrium
groups, namely, a. mixture of praseodymium,
ture are obtained by reaction of substantially two
mols of an alkyl-substituted hydroxyaromatic
neodymium,’ Samarium, europium, gadolinium,
terbrium; dysprosium, holmium, erbium, thalium,
. carboxvlic acid and one mol of phosphorus penta
sul?de: On the basis of chemical analyses of the
_ phosphorus- and sulfur-containing products of
_ this reaction, the principal product appears to be
and lutecium.
'
templated herein are barium, tin and cobalt.
'
and salts described above may also be character
10 ized by another substituent group, or groups, on
0
.¢
O—P=S
I,
I’,
.
R,.— -cosn
and the most probable reaction mechanism is "
‘
/OH
.
~
’
/on
_
-11. _ (a), 2Rn-T-OOOH'FP2SB; —_> 2R..—'r—co§11+o,+msi
.
,
'
(I?
/OH
’
’
The combined thiophosphate ester-thiolic acids
a combined thiophosphate esteraryl thiolic acid,
;
‘
Particularly preferred metalsfor the salts con
.
/Q—P=S
(b) 2R,.-,T-—cos11+0,+1>,s; -> 2R.->-'r-‘cosH+m_s
the aromatic nucleus. That is, in addition to the
alkyl, thiophosphate ester (-—OPOS) and thiolic
acid (-—COSH, or metal thiolate --COSM)
groups on the aromatic nucleus, other nuclear hy
15 drogen atoms may be replaced by a monovalent
substituent, ‘or substituents, selected from the
group consisting of hydroxyl, metaloxy, alkoxy,
aroxy, ester, aralkyl, alkaryl, aryl, alkyl, (such as
short-chain groups, methyl, ethyl, etc., in addition
20 to the preferred long-chain R groups), halogen,
wherein‘T is an aromatic nucleus, either mono
nitro and nitroso; all of these substituents will be
or polycyclic, such as phenyl, naphthyl, anthra
hereinafter referred to as Y substituents. Still
cyl, etc.; R.is an oil solubilizing aliphatic hydro
other Y substituents which may be present are
those having a multiple valence and these include
carbon‘radical or group containing at least about
18 carbon atoms, and is preferably a high mo 25 the mono- and poly-sul?de-selenide and -tellu
lecular weight derivative or a heavy alkyl group,
ride groups; of these groups, the disul?de group is
and n is a small whole number, preferably 1 to 4.
As aforesaid, also contemplated herein. are the
particularly preferred.\ Thus the compounds
metal salts_of-the phosphorus- and sulfur-con
taining compounds and reaction products ob
represented by the formula
containing a Y substituent, or substituents, uu‘ll be
80
0
tained by reaction of two mols of the aforesaid
carboxylic acids and one mol of P285, wherein a.
metal (M) replaces the hydrogen of the thiolic
acid group, —COSH. Thus, the metal salts of
mixed thiophosphate ester-aryl thiolic acids may 35
be represented by the following formula,
0
' HI.
‘wherein Y is nuclear hydrogen or a group such as
,
de?ned above; 1' is the numeral 0 or a small whole
, number, from 1 to 3, corresponding to the valences
o-Pi’
40. on the nucleus T not satis?ed by R, --OPOS and
-
' --COOX groups; X is hydrogen or at least one
metal equivalent and the symbols T, R and n are
wherein M represents at least one metal equiva-,
lent, and R and n are asdeflned above.
as de?ned hereinbefore.
As con
'
’ It will be apparent that those compounds con
templated herein the metal salts-represented by 45 templated herein which contain a Y substituent
Formula III, are inclusive of both the neutral
having a multiple valance, such for example as a
disul?de group, will be characterized by more
than one combined thiophosphate ester-thiolic
I metal salts, wherein M will represent a metal
atom such as -Na, -—Ba--, etc., and the basic
metal salts of said acids. In the latter salts,
acid (or metal thiolate) aryl‘ hucleus, and that
the symbol M, which represents at least one metal 50 such compounds wil1~ be represented by the follow
equivalent, is broadly construed to represent a
.ing general formula
basic metal‘ grouping which is defined herein as
a-_polyvalent metal atom having at least one
‘valence satis?ed by. a hydroxide group or an
alcoholate group, and having at least one valence 55
satis?ed as shown in Formula III.
'
r
'
The‘ metal substituent in the thiolic acid group
of the oil-improving agents described herein may
be broadly classified as follows: the alkali metals,
lithium, sodium, potassium, rubidium and cae
sium; the alkaline earth group, beryllium, mag
nesium, calcium, strontium and barium; the met
als' zinc, cadmium and mercury, scandium, yt
wherein Z is a substituent having a multiple va
60 lence and is selected from the group consisting of
mono- and poly-sul?de, -selenide and -telluride
groups; 111. is 0 or a small whole number, prefer
ably from 1 to 2; and all other symbols are as
defined hereinabove.
.
trium, lanthanum, aluminium, gallium, indium,
_ From the foregoing, therefore, it will be appar
thallium, titanium, zirconium, cerium, thorium; 65 ent
that the symbol Y is of such scope-as to in
germanium, tin and lead; vanadium, columbium
and tantalum; arsensic, antimony and bismuth;
chromium, molybdenum, tungsten and uranium;
clude the following groups: nuclear hydrogen and
' the aforesaid monovalent substituents and multi
v alent substituents and the group
rhenium, manganese, iron, cobalt and nickel; ru
thenium, rhodium and palladium; osmium, irid 70
ium and platinum.
_
Some of the rare earth metals are given in
the above group of metals; other rare earths
suitable for the formation of combined thiophose
phate ester-aryl thiolic acid salts are those now
in which 2 is representative of the aforesaid mul
number of aromatic nuclei in the molecules and ‘
tivalent substituents and thesymbols m, T, X, R.
and n are as de?ned hereinabove.
in formula V is always equal' to 1 ‘when u equals 1.
‘Otherwise an R," having a valence greater than
the number (u) of aromatic nuclei would either
'
As indicated above, the particularly preferred
type of compounds or reaction products contem
plated by the "present invention are those repre- ,
have some of its valences unsatis?ed or else would
form a condensed ring or rings of attachment at‘
sented by Formulae I, III and WM) and (b), in
two or more points to one and the same aromatic
which the group represented by R is an aliphatic
nucleus. Such latter compounds, as readily in
dicated from the definition of R”, are not con
sidered as characterizing the product of the pres
ent invention although probably formed in some
hydrocarbon radical of relatively high molecular
weight, preferably containing not less than 20 car
bon atoms. In the foregoing formulae (I, III and
IV(a) and (b)) it will be observed that the all
phatic or alkyl substituent in the aryl nucleus is
a monovalent aliphatic hydrocarbon group, but,
as will appear from the hereinafter described syn
thesis' of our preferred type of ‘ oil-improving
instances in minor amounts as unobiectionable '
by-products by certain of the methods of prepara
tion herein disclosed.
15
agent, part or all of the aliphatic hydrocarbon
material may be comprised of polyvalent aliphatic
.
The type of compounds coming under general
formula V in which only the thiophosphate group
(-0105). one thiolic acid group or metal thio
late group (COSX) and the oil-solubilizing group
hydrocarbon radicals or groups in which the sev
or groups (R?) are present on a monocyclic nu
eral valances are attached to separate aromatic 20 cleus, are illustrated by the following formulae.
nuclear groups. Compounds of this type are in~
_ When v and u are each equal to l and one R
cluded under the following’ general formula rep,- , group is present, the compounds are illustrated by
resentation
0
%
25
in which R, T, X, Y, 21, r and m have the same
A.
signi?cance indicated above; R” represents at
'
0-1’: 8
least one oil-solubilizing aliphatic or alkyl radical
or group, such alkyl group or groups being at 30
tached by one valance only to at least one aro
wherein the ‘chain represents the oil-solubilizing '
matic nucleus T, 2: ‘representing the valance of the
alkyl substituent (1%”), and thesymbol X is as
aliphatic radical R” which may be a small whole‘
hereinabove de?ned.
.
‘
number from 1 to 4‘; and u represents a whole
Since group R has been de?ned as “at least
number from 1 to 4 and indicates the total num 35
one," it will be apparent that there may be more
ber of groups
than one heavy alkyl substituent attached to the
nucleus T, such a compound, where v and .u are
each 1 and in which there are two such mono
present in the molecules represented by the for
mulae and which are attached to the aliphatic
40 valent R" groups, may be represented by the
following formula:
'
groups or groups represented by R" through the
valence or valences c.‘
In the foregoing general formula representa
tion V, it will be seen that the compounds rep
45
resented thereby include those materials in .which
all of the nuclear aliphatic substituent is mono
valent (12:1 and u=1> or in which all of the
aliphatic substituent is polyvalent (v and a being 50
equal to 2,- 3, or 4) and since R” is de?ned as‘
being at least one aliphatic radical or group and
may therefore include'several ‘such groups, it will
be seen that the general formula V is inclusive
of compounds having nuclear aliphatic groups or 66
radicals of different valences (from 1 to 4) in the
same molecule. Also it will be observed that since
u may be any whole number from l'to 4, the
number of aromatic nuclei T in said molecules
may likewise vary from 1 to 4. It will be seen, 00
therefore, that the relationship between u and v
in formula V, in its broadest aspect, is such that
when u/is equal to l, v is equal to l; and when
u is greater th°an 1, the valence '1: of at least one
of the R's is equal to u (in order to tie the several 65
nuclei or T's together), the valence of any re
maining R's being any whole number equal to or
less than ‘u.
‘
-
~
in which the chains and X are as de?ned above.
Compounds of the type satisfying the general
formula V in which R" is polyvalent and v and u
are more than one and in which there is only one
such polyvalent R" group, may be illustrated by
the following formula, in which the aryl nucleus
T is again indicated for illustration as being
-
In the above general formula V, it will be un
derstood that since the groups R” ‘are aliphatic 70
hydrocarbon radicals of the chain type and are
each attached by one valence only to each cor
responding aromatic nucleus, the valence v of
such radical or radicals is of necessity never
Under this same type of compound-indicated
by formula C there may be more than one poly
valent R" group (represented by the chain), such
greater‘ than the number u, which indicates the 76 a compound in which there are,_ for example. two
r4.
'
'
2,886,206
polyvalent R? groups being illustrated by the
following formula:
11
no
u
-
.~
_
hydrogen in the aromatic nucleus T substituted
-with predominantly aliphatic material which
I
H
---------------------------------- --c11
0
/o
D
/o H
0-1’:\s
0-1’:\s
_{_cosx
--'-c0sx
n
at“- 2<_/. ______ no
11
______ "CH
n
11
Another possible molecular structure of compounds coming under formula V is that for a
compound having more than one polyvalent R1:
group, at‘ least two of which have diiferent
comprises a su?lcient'proportion of the composi
tion as a whole to renderthe same miscible with
the mineral oil fraction in which the improving
agent is- used under normal conditions of han
valences, such as the following:
dllng and use.
11
H
'
‘
H
C
H
It appears from the results of’ our
H
With regard to the possible number of R" - 30 research that there is a critical range in the de
' gree of alkylation of these improving agents below '
groups which may make up a single molecule.
this will vary to the extent to which it is desired
to e?ect ‘substitution of the nucleus with _oilsolubilizing alkyl groups for obtaining the de-
which the product or agent will not satisfy the
requirements for oil-miscibility. Expressing this
' in another way, it appears that the hydroxyaro
sired properties in the product and is, of course, 35 matic constituent (T—'0H), of the alkylated hy
limited by the number of valences on the aromatic nucleus which are available for substitution. As will be apparent to those skilled in the
droxyaromatic carboxylic acid. from which the
Combined thiODhOSDhate ester-thielic acid is de
rived should not exceed a certain percentage of
art, the maximum possible number of R” groups
such alkylated hydroxyaromatic carboxylic acid.
which can be attached to a single aromatic nu_ 4" This critical range of alkylation may be roughly
cleus will vary as the nucleus is mono- or polyexpressed as the ratio by weight of (T(OH) )u to cyclic and also as the nucleus is otherwise sub-
R” (T(OH)).u. ,
-
stituted. It will also be apparent that available
The degree ‘of alkyletion and the critical range
valances on the nuclei may allbe attached to
withinwhich operative or preferred compounds
polyvale'nt aliphatic substituents.
45 can be obtained may also be expressed as the
It will be understood that the oil-improving
number of carbon atoms contained in the ali
agents contemplated by this invention may be
phatic substituents for each aryl nucleus in a ‘
pure compounds satisfying the general Formula
given molecule 01‘ meleelllar Structure.
V (and the general formulae I, III, ‘and IV(a)
The critical range inthe degree of alkylation,
and (b) ), described above with any one of the 50 as de?ned above, of the aryl nucleus in the im
various mono- and polycyclic aromatic nuclei as
preving agents contemplated herein may Vary I
T and the various substituents R”, (OPOS),
(COSX), (COOX) and Y described, the only
with: (a) the mineral oil fraction in which the
improving agent is to be used; (b) the aryl n11
requisite being that at least one nuclear hydrogen
cleus T (mono- or poly-cyclic) ; (c) the hydroxyl
be substituted with a thiophosphate ester group, 55 ‘content of the aryl nucleus from which the thio
another nuclear hydrogen being substituted with
- a thiolic acid or metal thiolate group (COSX),
phosphate ester substituent is derived (mono- \or
poly-hydric); (d) the character of aliphatic ma
and at least one nuclear hydrogen be substituted
terial comprising the IR") substituent (straight
with an oil-solubilizing aliphatic radical or
or branched chain); (e) mono- or poly-substi
group (Ru); However, in manufacturing thepre- 60 tution of the aryl nucleusyand 0‘) other substit
ferred oil-improving product of the present in—
uents on the nucleus T, which may be of positive
vention by the preferred method of procedure, as
or negative or of neutral solubilizing activity.
will appear hereinafter, the ?nal oil-improving
In general it may be said that a polycyclic nu
product obtained is normally or usually a mixture
cleus appears to require a higher degree of alkyla
of different compounds corresponding to different 65 tion than a moneeyelie nucleus; that a pelyhydric
values of ‘12 and u and to different numbers of
aliphatic groups R". It is for this reason that we
have designated the oil-improving agents con-
nucleus requires a higher ' degree of alkylation
than’ a monohydric nucleus; and that branched
chain aliphatic substituents have a somewhat .
templated herein as compounds and as reaction
greater‘ solubilizing action than straight-chain
products, and intend the designation "reaction 70 solubilizing substituents.
products” broadly to encompass the compounds
In view of ‘the foregoing variables it would be
obtained herein.
_
Y
'
impracticable and probably misleading to attempt
As has been emphasized hereinabove, it is imto give an expression and ?gure which would in
portant that the preferred oil-improving agents
dicate accurately the proper ratio of hydroxy
as represented by general formula V have nuclear 75 aromatic constituent to the ‘alkylated hydroxy
9,380,206
naphthyl methyl ether. chlorphenol and the like.
aromatic constituent which would express a de
gree of aliphatic substitution satisfying. all cases
' Preference is given to the monohydroxy phenols
taking these variables into account. As a guide‘
for preparing the improving agents of this inven
otherwise unsubstituted, particular preference be
ing given‘ to phenol and alpha- and beta-naph
tion, however, our research indicates that for a
thol.
, product having pour depressing and viscosity in;- ‘
dex (V. I.) improving properties in addition to
other valuable properties the ratio, expressed as:
vi.
should not be greater than 0.20 when the weight
’
h
1
'
'
_As indicated ‘in said patent’ (2,197,837)‘, the
alkylation of the hydroxyaromatic compound may
'be accomplished in various’ways, such as by.
Friedel-Crafts synthesis using a halogenated ali
10 phatic hydrocarbon; by reaction with unsaturated
. high molecular weight aliphaticcompounds or
higher alcohols in the presence of a suitable
catalyst such as sulfuric acid, etc. The ll'rie'del
Crafts type of alkylation reaction. howev'er, is
of the hydyroxy-aromatic component (T(OH).): 15 particularly adapted to the preparation of the
is expressed in terms of its chemically equivalent
alkylated hydroxyaromatic compounds from
‘weight of phenol. It will be observed that the
the corresponding acids are obtained be
ratio as expressed by Formula VI above does not ' which
cause the Friedel-Crafts synthesis affords a con
take into account any other substituent in the nu
venient means of controlling the degree of alky
cleus than the aliphatic substituent and the hy 20 lation and obtaining the desired phenolic ratio.
droxyl group (which appears as a thiophosphate
‘In this latter type of synthesis an appropriate ,
ester group in the ?nal product), but since the
mono- or poly-chlorine-substituted aliphatic
aliphatic substituent is primarily relied upon as
compound or material is reacted with the desired
the solubilizing medium in the_combined thio
hydroxyaromatic compound in the presence of a ‘ '
phosphate ester-thiolic acids (and salts thereof) 25 Friedel-Crai'ts catalyst such as a catalytic amount
derived from the aforesaid hydroxyaromatic'acids,
of aluminum chloride. Pure or substantially
it vis believed that the foregoing expression and
pure chlorinated aliphatic compounds may be
limits will serve as a working guide for the prepa
used.
As will be readily understood by those
ration of oil-soluble materials and particularly of
- skilled in'the art, it is usually di?lcult to prepare
the preferred multifunctional reaction- products 30 or obtain high molecular weightaliphatic hydro
and compounds contemplated herein.
5
The ratio of 20 per cent‘, which we may term
' the "phenolic ratio,” represents what we consider
carbons in a pure or substantially pure state and,
correspondingly di?icult to prepare the chlorine
or other halogen-substituted products in a pure >
a maximum. ?gure for the preferred products of
' or substantially pure state. -It is preferred, there
this invention, and in general it will be found that 35 fore, to employ a mixture of such halogenated
this ?gure will be lower. The actual ratio, of
hydrocarbons, such as halogenated petroleum
course, depends upon the variable factors enum
fractions, as the starting material. In general it
erated above. For example, as will appear here
‘may be said that the high molecular weight ali
.inafteryan oil-soluble combined thiophosphate
phatic hydrocarbons contemplated as- preferred
ester-thiolic acid (and the metal salts thereof) of 40 sources for the alkyl substituent R” in Formula
the multifunctional type in which the aliphatic
substituent is derived from petroleum wax, a pre
V for obtaining the multifunctional phosphorus
and sulfur-containing oil addition agents of this
dominantly straight-chain aliphatic hydrocarbon
invention, may be pure or mixed compounds typi
of at least 20 carbon atoms, and in which the
?ed by those which characterize the heavy prod
aromatic nucleus was derived from phenol other 45 ucts of petroleum, such as heavy petroleum oils,
. wise unsubstituted should have a phenolic ‘ratio,
crystalline petroleum wax, etc., or other com
. as expressed above, not substantially greater than
pounds or materials which will result in rela
about 16 per cent.
- tively long hydrocarbon chain substituents. Spe
The degree of alkylation for these preferred
cial ‘preference is given to petroleum wax having .
multifunctional oil-improving agents may also be 50 a melting point not substantially less than about
expressed by the number of carbon atoms con
~120° F. and having a molecular weight of about
tained in the aliphatic substituent for'a given
300 and at least‘ twenty carbon atoms in the
hydroxy-aromatic nucleus T-OH. As a general ,
characterizing molecules.
guide in this connection it may be said that the
Since the product of a Friedel-Crafts reac
substituents represented by Rv in the above gen 55 tion between a chlorinated aliphatic materialof
eral Formula V should, for these preferred com
the type referred to above and a hydroxyaromatic
pounds or reaction products, contain at least
compound will be a mixture of different values of
twenty ‘carbon atoms for each aromatic nucleus.
v and u in the formula R" (T(OH) )u shown above
The alkylated hydroxyaromatic carboxylic
in describing the "phenolic ratio,” and the ?nal
acids which are reacted herein with P285 in the 60 thiophosphate ester-thiolic acids (and salts
molar proportion of 2:1 are preferably obtained
thereof) derived therefrom will likewise be a mix
by the procedures described in Patent 2,197,837,
ture of compounds corresponding to different
‘issued for ‘one of the present inventors, 0, M.
values of v and u in general formula V, it will be
Reiff. vAs described therein, numerous hydroxy
understood thatthe specific values for v and u
aromatic compounds may be used as the starting
in the above formula ‘as well as the general for
materials and alkylated, and thereafter carboxy- '
lated. Examples of the hydroxyaromatic com
pounds which may be used as starting materials
for the alkylation reaction are: phenol, resorcinol,
_ mula V relate to the different specific compounds
present in such a mixture which characterize it as
a reaction product of this invention.
_
Following alkylation of the desired hydroxy
hydroquinone, catechol, cresol, xylenol, hydroxy 70 aromatic compound, the alkylated reaction prod
diphenyl, 'benzylphenol, phenyl - ethyl - phenol
uct thus obtained is carboxylated according to
phenol resins, methyl hydroxydiphenyl, guaiacol,
‘the procedures outlined in Patent 2,197,837. As
alpha- and beta-naphthol, tolyl naphthol, xylyl
indicated therein, one suitable procedure involves
naphthol,, benzyl naphthol, anthranol, phenyl
?rst forming an alkyl-substituted metal hydrox
methyl naphthol, phenanthrol, anisole, beta 75 ylate from‘ an alkyl-substituted hydroxy-aromatic
2,380,906
6
compound and a metal such as an alkali or alka
Patent 2,197,837, is mixed with P285, the mol ratio
~sot‘ acid to Pass being about 2:1, in a reaction
vessel equipped with stirrer and re?ux condenser.
The mixture is diluted with 1/2 part of ethylene
dichloride, 200 grams, and heated at the re?ux
temperature for about 10 hours to bring about
line earth, and then carboxylating the hydrox
ylate (obtained in the preceding operation) with
carbon dioxide gas to form the alkylated hydroxy
aromatic carboxylic acid. The latter product is
available for reaction with P285 to provide the
multifunctional oil-improving agents of this in
vention. Typical alkylated hydroxyaromatic car
boxylic acids which maybe reacted with P285 as
hereinafter described, include the carboxylic acids
reaction of said acid with Pass. The mixture is
then ?ltered and the ethylene dichloride solvent"
is distilled from the ?ltrate whereby the ?nished
product, the combined thiophosphate esterthiolic
,of the representative hydroxy-aromatic com
acid of wax-phenol carboxylic acid is obtained __
pounds enumerated above. Preferred herein are
in mineral oil. Chemical analysis of the product
indicates that the formula, for such product is,
alkylated phenol and naphthol carboxylic acids.
In the event that an aliphatic material such
as petroleum wax described above is used as the 15'
alkyl substituent on the hydroxyaromatic com-'
pound and corresponding hydroxyaromatic car
boxylic acid derived therefrom, and is reacted in
the form or halogenated wax containing, for ex
ample, three atomic proportions of chlorine and 20
14 per cent chlorine, with one mol of said by
OPP
\
B
'R»——- ———COSH
droxyaromatic compound, the alkylated hydroxy
aromatic compound and the alkylated hydroxy
wherein R» is wax.
aromatic carboxylic acid will be, for conven
EXAMPLE 2
25
ience, designated hereinafter as “wax-hydroxy
aromatic compound (ii-14)” and "wax-hydroxy
Reaction of wax-substituted phenol carboayltc
aromatic carboxylic acid (3-14),” respectively.
acid disul?de and P285
Parenthetical expression of the type (A-B) may
be used hereinafter in connection with such com‘- - (a) Reaction mixture:
_ pounds to designate (A) the number of atomic 30,
‘
'
Grams
Wax-phenol carboxylic acid disul?de
proportions in the chloraliphatic material which
(3-14) in solution in 300,grams of
mineral oil (67 secs. S. U. V. at 310°
was reacted with one mol of hydroxyaromatic
compound in the Friedel-Crafts reaction and (B) ‘
the chlorine content of the chloraliphatic mate
F.)
rial. In the above illustrations 11:3 and 13:14. 35
,PzSs
This same designation will also apply ,to the
____________________________ __ 100
_________________ "a _____ _;\____.
13.1
Ethylene dichloride ____________ __\___ 200
alkylated thiophosphate ester-thiolic acids,,and
i (b)
their metal salts, derived from these alkylated
Procedure:
“
‘
The reaction of wax-phenol carboxylic acid
compounds.
1
The multifunctional phosphorus- and sulfur 40 disul?de, obtained as described in co-pending ap
plication of Serial No. 330,532, ?led by O. M.
containing oil improving agents of this invention
Rei?
on April 19, A940, now issued as Patent No. ,
are obtained by reaction of substantially two
2,319,189 of May 11, 1943, was carried out accord
mols of an alkylated hydroxyaromatic carbox
ing to the procedure given in Example 1, and
ylic acid of the type described above and one
here ‘again the molar ratio of the acid disul?de
mol of P285. They ‘"may also be obtained by
to P285 was‘ about 2:1. The reaction product,
reaction of the alkali or alkaline earth _metal
in mineral oil blend, is believed to be the com
salts of the aforesaid alkylated hydroxyaromatic
bined thiophosphate ester-thiolic acid of wax
carboxylic acid and P285 in the same molar ratio,
phenol carboxyllc acid disul?de and the formula
but the preferred procedure is that one in which
the metal-free carboxylic acid reactant is used. 50, for such product is believed to be,
The procedures outlined above will be illustrated
by the following examples, wherein reaction prod
ucts typical of the aforesaid reaction products
are prepared.’
Y
' 0\
\
/ _
.
s/
REACTION OF ALKYL-SUBSTITUTED HY
DROXYAROMATIC CARBOKYLIC ACIDS
AND PzSs
acid and P235
.
\s
R‘X/
RN
60
Reaction of wax-substituted phenol ca‘rboaylic
’
_
HSOC—— -l--s-s-— -—c0sn
'
EXAMPLE 1
)0
0-1,:
'
wherein Ra is wax.
As aforesaid, the neutral and basic metal salts
of the aforegoing reaction products are also con
templated by this invention. These metal-con
- taining products are obtained by reaction of the
(a) Reaction mixture: _
Grams
Wax-phenol carboxylic acid (3-14) in
solution in 300 grams of mineral oil
(67 secs. S. U. V. at 120° F.) _____ __ 100 _
Pass
_
Ethylene
v
13.5
dichloride _______________ .__ 200
combined thiophosphate ester-thiolic acids of the
alkyl-substituted hydroxyaromatic
carboxylic
acids with alkali or alkaline earth metal alco
holates or hydroxides. In the use of the metal
70 alcoholates, the thiophosphate ester-thiolic acid
reaction product is diluted with one part of bu-,
tanol, followed by adding the metal alcoholate,
preferably as the metal ,butylate, heating the re
(6) Procedure:
action mixture to the re?ux temperature for one
The wax-phenol carboxylic acid in mineral oil
. blend, prepared according to the procedure in 75 hour and then distilling off the alcohol—-such as
2,386,206
7
acid-(344), is approximately a 25%, solution‘in
butanol-to obtain the ?nished product, the cor
responding metalisalt. In the use 01' metal hy-f
droxides. the combined thiophosphate‘ ester
thiolic acid reaction product is diluted with 1/2
mineral oil, and is characterized by the repre- _
sentation,
’
' part of benzol, followed by adding the metal hy
droxide. The reaction mixture is heated gently
at the distillation temperature of benzolwhere
upon the water of reaction is removed. Any hy
droxide ‘residue is removed by ?ltering the re
action mixture and then distilling oil’ the remain_ lo
ing benzol from the ?ltrate to obtain the ?nished
product.
‘
a.
-
Metal salts of the phosphorus- and sulfur
containing reaction vproducts described above,
15 wherein Rm is wax. ‘
other than those of the alkali or alkaline earth
metals, are formed by double decomposition of
Exmtr 4'
St'annous salt of the thiophosphate ester-thiolic
an alkali or alkaline earth metal salt with- an
alcohol'solution of the chloride of (the desired
metal. The general procedure consists of dis
' acid of wax-phenol carbocylic acid? (3-14)
solving the metal chloride in butanol and slowly 20
adding the butanol solution thus obtained to the
(a) Thiophosphate
Reaction mixture:
‘ester-thiolic acid
of
alkali (or alkaline earth) metal salt of the thio-'
wax-phenol
carboxylic
acid
(3-14)
phosphate ester-thiolic acid reaction product.
in ‘solution in 300. grams of mineral
The mixture thus formed is heated at the re?ux
oil (67 secs. 8. U. V. at 210° F.)
g
temperature for about 30 minutes and the alco 25
a
'
grams... _100.
hol solvent is then distilled oil’. ‘The solvent-free
Butanol __- _____ __-, ____________ -_cc_- 200
mixture is then ?ltered through a suitable ?lter
. medium such as Hi-F'low to remove alkali (or
alkaline earth) chloride formed as a by-product; ‘
‘the ?ltrate is the ?nished metal salt of ‘said
reaction product.
.
Metallic sodium____t ______ -_grams__
6
Stannous chloride ___________ __do____ 24.8,
3o‘ (11) Procedure:
-
The mineral oil blend containing the combined
The alcoholate method -of forming metal de
, rivatives, as outlined above, is also applicable to
metals other than the alkali or alkaline earth
group. The desired metal alcoholates are formed 3
by double decomposition of alkali alcoholate with
an alcohol solution of the chloride of the desired
metal. This mixture can then be reacted direct
thiophosphate ester-thiolic acid of wax-phenol
carboxylic acid (3-14), obtained in'Example 1,
is diluted with 100 cc. of butanol. Sodium, in the
form of thin strips, is then added and the mix
ture is heated at the re?ux temperature ‘until all
of the sodium has reacted. Stannous chloride in
‘ solution in butanol is then added and the reac
ly with the combined thiophosphate' ester-thiolic
acid reaction product described above to form 40 tion mixture heated at re?ux for about 30 min
utes. Butanol is distilled from the reaction mix
the metal derivative. The alkali chloride formed
ture and the butanol-free mixture is then cooled,
as a by-product in preparing the alcoholate of
diluted with benzol and ?ltered. The ?ltrate is
then distilled to remove benzol therefrom to ob
' the desired metal is ?ltered from the reaction
product to give the ?nished material.
The metal salts contemplated herein :are illus
trated by the following examples.
tain a mineral oil blend of the ?nished product,
the combined thiophosphate ester-stannous thio
late of wax-phenol carboxylic acid (3-14) which
-.
is characterized by the representation,
EXAMPLE 3
Barium salt of the thiophosphate ester-thiolic 60
acid of wax-phenol carbowylic acid (3-14)
(a)Reaction mixture:
'
_ Grams
Thiophosphate ester-thiolic acid of wax
65
phenol carboxylic acid (3-14) in solu
tion in 300 grams of mineral oil (67
secs. _S. U. V. at 210° F.) ____________ __ 100
Benzol
____ ________________________ __ '200
Ba(OH)2.8H2O
____ __; _____________ __
wherein Rm is wax. -
60
Ex'lmru: 5
37
Barium salt of the thiophosphate ester-thiolic
~ ( b) ' Procedure:
‘The mineral oil blend containing the combined
thiophosphate ester-thiolic acid of wax-phenol
c‘arboxylic acid (3-14)‘, obtained in Example 1,
acid of wax-phenol carboxylic acid disul?de
65
was diluted with benzol and then treated with
the barium hydroxide. The reaction mixture
was then heated so that the benzol slowly dis
tilled off carrying with it the water of reaction.
Any barium hydroxide residue is removed by ?l 70
tering the reaction mixture through Hi-Flow be
fore distilling off the remaining benzol. The
?nished product, the combined thiophosphate
ester-barium thiolate of wax-phenol carboxylic
‘
(3-14)
I
(a) Reaction mixture:
,
'
Grams
Thiophosphate ester-thiolic acid of wax
phenol carboxylic acid disul?de (3-14)
in solution in 300 grams of mineral oil
(6'? secs. S. U. V. at 210° F.) _______ __ 100
37
amonnamo ____________________ __,_
(b) Procedure:
_
The method of preparation is the same as in
2,886,206
the present inventors, o. M. Rei?, was reacted
Example 4 and the ?nished product in this case
‘ with P285, in mol proportion of about 2:1 and
is characterized by the representation
the reaction product worked .up' as described in
Example 6 above. The ?nal reaction product is
presumably the same as the ?nal reaction prod
uct obtained in Example 5, namely, the thiophos¢
00
phate ester-barium thiolate of wax-phenol car
boxylic acid disul?de; and, therefore, the formula
given in Example 5 also represents the reaction
product obtained in this example.
REACTION OF ALKALI .IVIETAL SALTS OF‘ -
where Rnl is wax. .
A L K Y L - SUBSTITUTED H‘YDROXYARO
MATIC CARBOXYLIC ACIDS AND‘ P285
'
REACTION OF ALKALINE EARTH METAL‘ 15
SALTS OF ALKYL-SUBSTITUTED HY
DROXYAROMATIC
CARBOXYLIC
EXAMPLE 8v
ACIDS
VReactioa of sodium carboxylate salt ‘of diamyl
ANDPaSs '
phenol carbon/lie acid and P285
EXAMPLEB
20
Reaction of barium salt of diiamyl-phenol car
(a) Reaction-mixture:~
-
bozylic acid and PzSs
" ‘_ ‘
‘
Grams
Sodium carboxylate salt of‘ diamyl
(a) Reaction mixture:
phenol carboxylic acid in 100 grams
.
of .mineral oil (67 secs. S. U. V. at
Grams
Barium salt of diamyl phenol carboxylic
210° F.) '_ _______________________ __
acid in solution in 50 grams of min
_
Benzol
eral oil-(67 secs. S. U. V. at 210° EL- 50
Be'naol _
P285
_____________ _._' ____________ __
50
100
-‘- ---------- --_-_----l-w--_____ ____ -'
50
(b) Procedure:
The procedure here is the same as in Example
(b) Procedure:
.
6 and the ?nal reaction product corresponds to
The barium salt of diamyl phenol carboxylic
the combined thiophosphate ester-sodium thio
acid in mineral oil blend, obtained as described
late of diamyl-phenol carboxyl'ic acid which may
in a co-pending vapplication Serial No. 452,054,
be represented by the formula _' '_
35
?led July 23, 1943, in which one of the present in
ventors, O. M. Reiff, is a ‘joint-inventor, is mixed
with P285 in a' reaction vessel equipped with
stirrer and re?ux condenser. The mol ratio of
the salt and Pass is about 2:1. The mixture is
diluted with benzol and heated at the re?ux tem
perature for about 24 hours to bring about the
P255 _.
.___ 12.8
30
reaction of said acid with PzSt.v The benzol is ,
' then distilled from the reaction mixture'and the
HuCs
temperature is raised thereafter. to 125° C.-, and 45
maintained for several hours to remove the H28
formed in the reaction. The ?nished product,
To demonstrate the e?ectiveness of these com
the combined thiophosphate ester-barium 'thio
pounds or reaction products obtained by the re
late of diamyl phenol carboxylic acid; is thus ob
action of substantially two mols of an alkyl-sub
tained in a 1:1 oil blend, and is- characterized by
stituted hydroxyaromatic carboxylic acid and one
‘the representation
mol of P285, and the metal salts thereof, in min
eral oil compositions, we have conducted several
comparative tests with representative mineral oils
alone and with the same oils'blende'd with typi
cal compounds or reaction products of the class
55
contemplated herein. ‘These tests, which with
their results are described below, show that min
eral oil compositions containing these materials
\/ °
are improved as to pour point, viscosity index,
ExAmPLs'I
60
Reaction of barium salt of wax-phenol carboaylic
and acidity during engine operation.
Pour point depression
‘ acid disul?die (3-14) and P285
The oil used in this test was a mineral lubri
cating oil fraction having a Saybolt Universal
(a) Reactionmixture:
~
Grams
65 viscosity of 67 seconds at 210° F., and a pour
Barium salt of wax-phenol carboxylic
acid disul?de (3-14) in solution in
point of +20° F. Using this oil, blends were pre
pared containing typical reaction products or
compounds of this invention, namely, a combined
200 grams of mineral oil (67 secs.
thiophosphate ester-thiolic acid containing a
' S. U. Vlat 210° F.)__>_ ___________ _.. 100
Past
12.4 70 "wax” substituent, and metal salts thereof, and
the pour points of said blends determined. The
(b) Procedure:
results listed below in Table 1 demonstrate that
The barium salt of wax-phenol 'carboxylic acid ‘
the reaction products or compounds contem
disul?de (3-14), in mineral oil blend, prepared
plated herein are extremely effective in lowering
as described in Patent 2,256,443, issued to one of 75 the pour point of the oil.
-
I
‘
2,386,206
TABLE 1
A
Y
,
i
"
‘blends are listed in Table 3 below.
A. S. 'l‘. M. pour point,
.
Improving agent
6F‘
-
0%
946%
Combined th‘iosphospliate estcrthlolic
+20
5
.
56% %%
Improving agent blended
Concf,
1 with motor oil
percent
'
(3714) ............ --. ............... -.
_ _ _ _ . _ . -.
(‘obalt salt
_
0
—15
—15
+20
+5
—10
~15
0
—l0
—5.
-—15
—20
0
—-l5
-20
+20
0
0
Barium salt __________________________ .. +20
0
—10
Combined thiophosphate este
lic
acid of wax-phenol carboxylic acid
disul?de (3-14) _____________________ -.
____ .
15
—20
wax-phenol
carboxylic
‘
TABLE 2
thiophosphate
Cone
’
motor oil
by '
'
phenol
carboxylic acid
disul?de (3—14)......._.....
Combined
thiophosphate
stokes, at-
v I
0
so. 17
'
as
thiolic acid of wax-phenol car
boxylic acid (3-14) ............. ._
‘ 'I‘in salt...
_ Cobalt salt.
Calcium sal
Combined
__
t
phosphat
l
5. 10
85. 0
1
37. 22
5. 63
97. 2
1
1
1
31. 67
32. 02
31. 78
4. 99
5. O0
4. 97
86. 0
84. 2
83. 3
ester-
33. 10
‘
1
None ...................... ..
so
Combined thiophosphate
ester-barium thiolate of
wax-phenol carboxylic acid
0.25
as
it
6. 46
tual operating conditions. Such data also show
79.8
Combined thiophosphate ester
Barium salt __________ _.
‘
35 the improving agents of this invention e?ect sub
stantial improvement in mineral oil during ac
‘
100° F. 210° F.
None __________________ _. ________ --
1
‘
The data tabulated in Table 3 clearly show that
eosity, centi
weight
n
v
ester-thiolic acid of wax
(3-14) (1:2 ratio) _________ _ .
Kinematic vis
7
1
acid (Example 6)
20
ester-barium tliiolate of
tor lubricating oil fraction having a kinematic
wax-phenol cerboxylic acid
viscosity of 30._l7 and 4.80 at 100° F. and at 210° 25 disultide (3-14) ........... . .
F., respectively, and a viscosity index of 79.8. It
Combined thiophosphate
ester-barium thiolate of
is apparent from these results that the oil im
wax- henol carboxylic acid
proving agents of this invention e?ect an ,ap
(3—14 (1:4 ratio) ......... . _
preciable improvement in the viscosity index of
'
acid (3A4) (Example 3) ....
thiophcsphate
ester-barium thiolate of
diamyl-phcnol carboxylic
motor oils. The oil used in these tests was a mo- _
'
6. 05
tliiophosphate
ester-barium tliiolate of
'
strate ‘the comparative e?ectiveness of the re
action products or compounds contemplated here
in as improvers of the viscosity index '(V. I.) of
Improving agent blended with
8.68
3-14) .................... . .
Combined
Vzscoszty index
The results tabulated below in Table 2 demon;
the oil.
vis. at
210° F.
Combined thio hosphate
ester-thiolic so! of wax
phenol carboxyllc acid
-'—20
+21)
+20
Calcium salt...
run.
None .................... ._
+20
+20
Tin salt ...... __
‘ Kinematic
Hrs.
.................. ..
acid of wax-phenol carboxylic acid
Barium salt _ . . _ _ . .
’
‘TABLE 3
I
-
.
None ................................ .-
9.
210° "F. The results on the blank oil and the oil
the superiority of these improving agents over
related materials obtained by using a different
40 molar ratio of reactants, namely, one mol of
P285 to four mols of an alkyl-‘substituted hy
doxyaromatic'carboxylic acid (or metal carbox
ylate thereof).
_
,
It will be apparent from the foregoing descrip
‘
thiolic acid of wax-phenol car
boxylic acid disul?de (3-l4).__._._
1
31. 98
4. 98
82. 6
Barium salt _______________ _; _____ __
l
33. 06
5. l3
0
45 tion that we have developed a new class of min
eral oil compositions characterized by the pres
ence of a minor proportion of a combined thio
Operation test
phosphate ester-thiolic acid of an alkylated hy
droxyaromatic carboxylic acid, which is obtained
We have also made comparative tests between 50 by the reaction of substantially two mols of an
an oil and oil blends containing representative
alkylated hydroxyaromatic carboxylic acid and
improving agents of the type contemplated here
one mol of phosphorus pentasul?de, and the metal .
in to determine the comparative behavior of the
salts thereof. It- is to be understood that the
unblended oil and the improved oil under the ac
properties of the added agent may. be varied by
tual operating conditions of an automotive en 55 the degree of alkylation and the substituent
gine. In order to determine the comparative ef
groups on the aromatic nucleus in addition to the
fectiveness of an oil blend of the type contem
oil-solubilizing alkyl, thiophosphate ester, and
plated herein, namely, one containing a metal
thiolic acid (or metal thiolate) groups. It will be
salt prepared by using the aforesaid molar ratio
‘further understood that‘ the improvement ef
of one mol of P285 to two mols of an alkyl-sub 60 fected inthe mineral oil composition may be var
. stituted hydroxyaromatic carboxylic acid, and of
ried by the amount of agent added. In general,
an oil blend containing a metal salt prepared by
it appears that the desired improvement can be
using a di?erent molar ratio, namely, one rise
effected by amounts varying from about 116 of one
to .four of said acid, similar comparative tests
per cent to about 10 per cent, but the invention
were carried out.
.
‘
contemplates the use in amounts varying from
The tests were carried out in asingle-cylinder
:1; of one per cent to 2 per cent.
Lauson engine operated continuously over a time
- We claim:
‘ interval of either 16, 24 or 36 hours with the cool
1. An improved mineral oil composition com
ing medium held at a. temperature of about 212°
prising a mineral oil fraction having in admix
F. and the oil temperature held at about 280° F. 70 ture therewith a minor proportion, su?lcient to
The engine was operated at a speed of about 1830
stabilize said oil fraction against oxidation, of a
R. P. M. .At the end of the test .the oil was tested
compound characterized by the‘ presence-of an
for acidity (NIN). and viscosity.
aromatic nucleus containing at least one oil-sol
The oil used in the test was a lubricating oil‘
ubilizing alkyl group, a thiophosphate ester group,
having a kinematic viscosity of 5.8 centistokes at 75 (—-OPOS,), and'a group selected ‘from the group
1O
0
2,886,208
consisting of a thiolic acid group and a metal ,
said 011 fraction against oxidation, or a compound
thlolate group (—COBX) wherein X is selected
from the group, consisting of hydrogen and at
representedby the formula
¢o
least one metal equivalent, said compound being
obtained by the reaction of substantially two mols
o! a compound selected from the group consisting
O—-P=S
R..—'r—cosx
_
of an alkyl-substituted hydroxyaromatic carbox
wherein T is an aromatic nucleus; X is selected
ylic acid and an alkyl-substituted hydroxyaro
from the group consisting of hydrogen and at
matic metal carboxylate, the alkyl substituent
least one metal equivalent; R is at least one oil
being at least one oil-solubilizing alkyl group, and 10 solubilizing alkyl group; 11. is the number of said
one mol of phosphorus pentasul?de.
‘
R groups and is a small whole number from 1
2. .An improved mineral oil composition com- :
to 4; said compound being obtained by the reac-.
prising a mineral oil fraction having in admixture
tion of one mol of phosphorus pentasul?de and
therewith a minor proportion, su?icient to sta
substantially two mols of a compound selected
bilize said 011 fraction against oxidation, of a com 15 from the group of compounds consisting of an
pound charatcerized by the presence of an aro
alkyl-substituted hydroxyaromatic carboxylic acid
matic nucleus containing at least one oil-solu
and an alkyl-substituted hydroxyaromatlc metal
bilizing alkyl group having at least twenty carbon
carboxylate, the alkyl substituent of said com
atoms, a thiophosphate ester group (-OPOS),
pound being at least onev oil-solubilizing alkyl
and a group selected from the group consisting of 20 group (R). a
a thiolic‘ acid group and a metal thlolate group
6. An improved mineral oil composition 'com
(—COSX) wherein X is selected from the group
' prising a mineral oil fraction having in admix
consisting of hydrogen and at least one metal
ture therewith a minor proportion, su?icient to
equivalent, said compound being obtained ‘by the
stabilize said all fraction against‘ oxidation, of a
reaction of substantially two mols of a compound 25 compound represented by the formula
selected from the group consisting of an alkyl
R"[T(OPOS) (COSX) ]u
substituted hydroxyaromatic carboxylic acid and
an alkyl-substituted hydroxyaromatic metal car
wherein R" represents at least one oil-solubiliz
ing alkyl group, attached by one valence only to
boxylate, the alkyl substituent being at least one
oil-solubilizing alkyl group having at least twenty 80 at least one aromatic nucleus T; ‘0 represents the
valence of said alkyl group R and is a small whole
carbon atoms, and one mol of phosphorus penta
number from 1 to 4; X is selected from the group
sul?de.
‘
consisting of hydrogen and at least one metal
3. An improved mineral oil composition com
equivalent; u is a small whole number from 1
prising a mineral oil fraction having in admixture
therewith a minor proportion, su?lcient to sta 35 to 4 and represents the total number of groups
bilize said 011 fraction against oxidation, of a
[T(OPOS) (COSX) ]
compound characterized by the presence of an
attached
to
said
alkyl group R" through the va
aromatic nucleus containing at least one oil-solu
lence 1); said compound being obtained by the
bilizing alkyl group of the type which character
izes petroleum wax, a thiophosphate ester group 40 reaction of one mol of phosphorus pentasuliide
and substantially two mols of a compound se
(,—OPOS), and a group selected from the group
consisting of a thiolic acid group and a metal
lected from the group of compounds consisting ‘
thlolate group (-COSX) whereinX is selected
from the group consisting of hydrogen and at
least one metal equivalent, said compound being
obtained by the reaction of substantially two mols
of a compound selected from the group consist
ing of an alkyl-substituted hydroxyaromatic car;
boxylic acid and an alkyl-substituted hydroxy
aromatic metal carboxylate, the alkyl substitu
alkyl group.
_ out being at least one oil-solubilizing alkyl group
of the type which characterizes petroleum wax,
‘ and one mol of phosphorus pentasul?de.
4.‘ An improved mineral oil composition com
, prising a mineral oil fraction having in admix
ture therewith a minor proportion, from about
11; per cent to about 10 per cent, of a compound
characterized by the presenceyof an aromatic
of an alkyl-substituted hydroxyaromatic carbox
ylic acid and an alkyl-substituted hydroxyaro
matic metal carboxylate, the alkyl substituent of
said compound being at least one oil-solubilizing
'
. '7. An improved mineral oil composition com
prising a mineral oil fraction having in admix
ture therewith a minor proportion, su?lcient to
stabilize said oil fraction against oxidation, of a
compound represented by the formula
v
R"[T(OPOS) (COSX) lu
55 wherein R” represents at least one oil-solubiliz
.ing alkyl group having at least twenty carbon
atoms, attached by one valence only to at least
one aromatic nucleusT; 1: represents the valence
of said alkyl group R and is a small whole num
nucleus containing at least one oil-solubilizing
alkyl group, a thiophosphate ester‘ group 60 her from 1 to 4; X is selected from the group
consisting of hydrogen and at least one metal
(—-OPOS), and a group selected from the group
equivalent; u is a small whole number from 1 to
consisting ‘of a thiolic acid group and. a metal
'4 and represents the total number of groups
thlolate group (—COSX) wherein X is selected
from the group consisting of vhydrogen and at
[T(OPOS) (COSX) ]
least one metal equivalent, said compound being 65
attached
to
said
alkyl group R” through the
obtained by the reaction of substantially two mols
valence 12; said compound being obtained by the
of a compound selected from the group consist
reaction of one mol of ‘phosphorus pentasul?de
ing of an alkyl-substituted hydroxyaromatlc car
and substantially two mols of a compound se
boxylic acid and an alkyl-substituted hydroxy
aromatic metal carboxylate, the alkyl substituent 70 lected from the group of compounds consisting'of
an alkyl-substltuted hydroxyaromatic carboxylic
being at least one oil-solubilizing alkyl group, and
acid and an alkyl-substituted hydroxyaromatic
one mol of phosphorus pentasulfide.
metal carboxylate, the alkyl substituent of said
5. An improved mineral oil composition com
compound being at least one oil-solubilizing allwi
prising a mineral oil fraction having in admixture
therewith a minor proportion, su?icient to stabilize 75 group having at least twenty carbon atoms. .
11.
2,386,206
8. An improved‘ mineral oil composition com
prising a mineral oil fraction having in admixture
therewith a minor proportion, suiiicient to sta
bilize said oil traction against oxidation, of a
compound represented by the i’ormula
.
(-COSH), and. of at least one oil-soiubilizing
alkyl-substituent. and said compounds di?ering
from each other with respect to the nature of said
aiiryl substituents which are comprised essentially
of aliphatic hydrocarbon groups corresponding
substantially to the di?erent aliphatichydrocab
bons contained in paraiiin wax.
.
wherein R” represents at least one oil-solubilizing ‘
11. An improved mineral oil composition com
alkyl group of the type which characterizes pe
prising a mineral oil fraction having in admix
troleum wax, attached by one valence only to at 10 ture therewith a- minor proportion, su?lcient to
least one aromatic nucleus T; 1) represents the
stabilize said all fraction against oxidation, of
valence of said alkyl group R and is a small whole 7 an intimate mixture of oil-soluble alkyl-substi
number from 1 to 4; X is selected from the group
tuted aromatic compounds obtained by the re
consisting of hydrogen and at least one metal
action of one moi of phosphorus pentasuliide and
equivalent; u is a small whole number from 1 to 4 15 substantially two mols of an alkyl-substituted
and represents the total number of groups
hydroxyaromaticpmetai carboxylate, said oil-sol
uble alkyl-substitutcd aromatic compounds oi’ re
[T(OPOS) (COSX) ]
‘
attached to‘said alkyl group‘ R" through the , action- being characterized by the presence or a
valence u: said compound being obtained by the 20 .thiophosphate ester group (—OPOS), of a metal
thiolate group (-COSM), and of at least one
reaction of one mol of phosphorus pentasul?de
oil-solubilizing
alkyi substituent, and said com~
and substantially two mols of a compound selected
pounds differing from each other with respect to
from the group of compounds consisting of an.
the nature of said aikyl substituents which are
alkyl-substituted hydroxyaromatic ,carboxyiic
comprised essentially of aliphatic hydrocarbon
acid and an alkyl-substituted hydroxyaromatic
corresponding substantially to the di?erent
metal carboxylate, the alkyl substituent of said 25 groups
aliphatic hydrocarbons contained in para?in wax.
compound being at least one oil-solubilizing group
12. An improved mineral oil composition com
of the type which characterizes petroleum wax.‘
prising
a mineral oil fraction having in admix
9. An improved mineral oil composition com
prising a mineral oil fraction having in admix 30 ture therewith a'minor proportion, su?icient to
stabilize said oil fraction against oxidation, of
ture therewith a minor proportion, su?icient to
an intimate mixture of oil-soluble aikyl-substi
stabilize said oil fraction against oxidation, of
tuted
aromatic compounds obtained, by the re-‘
an intimate mixture of oil-soluble‘alkyl-substi
action of one mol of phosphorus pentasul?de and
tuted aromatic compounds obtained by the re
‘substantially two mols oi’ a disuliide of an alkyl
action of one moi of phosphorus pentasul?de and
35 substituted hydroxyaromatic carboxylic acid, said
substantially two mols of a compound selected
oil-soluble alkyl-substituted aromatic compounds
from the group consisting of an alkyl-substituted
of reaction being characterized by the presence of
hydroxyaromatic carboxylic acid and an alkyl
a thiophosphate ester group (—-OPOS,) ,_ oi‘ a
substituted hydroxyaromatic metal carboxylate,
and mono- and poly-sul?des of said carboxylic 40 thiolic acid group (-COSH), and of at least one
oii-solubilizing alkyi substituent, ‘and said com
acid and of said metal carboxylate, said oil-solu- .
pounds diifering from each other ‘with respect to
ble aikyl-substituted aromatic compounds of re
the nature of said alkyl substituents which are
action being characterized by the presence of a
comprised essentially of -aliphatic hydyrocarbon
thiophosphate ester group (—-OPOS), of a group
selected from thegroup consisting of a thiolic 45 groups corresponding substantially to the di?er
acid group and a. metal thiolate group (-COSX)
wherein X is selected from the‘ group consisting
of hydrogen and at least one metal equivalent,
and of at least one oil-solubilizing alkyl substit
uent, and said compounds differing from each
other with respect to the nature of said alir'yl sub-' 50
stituents which are comprised essentially of allphatic hydrocarbon groups corresponding sub
stantially to the diiierent aliphatic hydrocar
bons contained in para?ln wax.
'
10. An improved mineral oil composition com
prising a mineral oil fraction having in admix
ture therewith a minor proportion, sufficient to
stabilize said oii fraction against oxidation, of
an intimate mixture oi.’ oil-soluble alkyl-subst'i- i‘
tuted aromatic compounds obtained by the re
action of one moi of phosphorus pentasul?de'and
substantially two mols of an alkyl-substitu'ted
ent aliphatic hydrocarbons contained in paramn
wax.
.
13. An improved mineral oil composition com
prising a mineral oil fraction having inadmix- ’
ture therewith a'minor proportion, su?icient to
stabilize said oil fraction against oxidation, of a
thiophosphate ester-thiolic acid of wax-phenol
carboxylic acid disulfide.
14. An improved mineral oil composition com
prising a mineral oil fraction having in admix
ture therewith a minor proportion, suilicient to
stabilize said 011 traction against oxidation, of a
thiophosphate ester-barium thiolate of wax
phenol carboxyiic acid.
a
15. An improved mineral oil composition com
prising a mineral oil fraction having in admix
. ture therewith a minor proportion, su?lcient to
stabilize said oil fraction against oxidation, of a
thiophosphate ester-barium thlolate oi diamyl
hydroxyaromatic carboxylic acid, said oil-soluble
phenol carboxylic acid.
alkyl-substituted compounds of reaction being
- JQHN J. GIAMMARIA.
characterized by the presence of a thiophosphate 65
ORLAND M. REIFF.
ester group (-OPOS), or a thiolic acid group
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