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Patented Nov. 5, i946
2,41%,659
HUBBKCANT CQEIPGSEEI‘KQN
.‘ichn ,3. Giaminaria, Weodhm'y, N.‘ 3., asngnor
to Balcony-Vacuum @il Qompuny, incorporated,
a corporation of New York
No Drawing, Application March 39, 194d,
:‘derial No. 528,783
- 9 Claims.
(oi. ass-sac)
ii
ri’his application is a continuation-in-part of
substituted with relatively long-chain alkyl
copending application Serial No. 390,586, ?led
April 26, 194i, and relates to hydrocarbon olls‘of
the type employed as lubricants, dielectrics, and
groups, such as those characterizing parafin wax
(predominantly alkyl groups or" at least twenty
carbon atoms).
'
‘
the like. Primarily, the present invention is con-_ 5
A compound or reaction product of the type
cerned with improving certain characteristics of
contemplated herein may be broadly described
such oils, particularly pour point and viscosity
as an oil-miscible metal salt of a thio acid of
phosphorus or, more speci?cally, as a metal salt of
index, and stabilizing the oils against the deteri- -
crating in?uences encountered under operating
conditions.
’
~
\
a partial ester‘ ofv a ‘chic acid of phosphorus, ob~
10 .tained by reacting Pass with a compound having
as is well known to those skilled in the art,
petroleum oils of the viscous type re?ned for use _
as lubricants or the like are generally subject
to deterioration in service with theiiormation of
the general formula ROH wherein R represents
an alkaryl oil soluhilizing hydrocarbon group of
the type described above and then reacting the
- product thus obtained with a reactive metal com
acidic materials, sludge, and other oxidation prod 15 pound. Although, as aforesaid, we do not wish
ucts which reduce their usefulness. li/l'otor oils,
to be bound by any theory of reaction or formula
for example, and particularly those used in the
of the product, it does appear that under certain
lubrication of Diesel engines, are subjected to
conditions of reaction and reactants the ultimate
'relatively severe conditions which accelerate the
products obtained are the metal salts of wax
development of acid and sludge in the crank case 20 substitut'ed diaryl dithiophosphcric acid, the gen
and the accumulation of lacquer and carbona
eral structural formula of which may be expressed
ceous material about the piston rings, which cause - as follows:
the rings to stick and which obstruct the oil slots
therein. The acidic materials developed tend to -
corrode certain hard alloy bearing metals such
as those having the corrosion-susceptibility of
cadmium-silver alloys and the like.
.
This invention is based upon the discovery of
a novel class of addition agents which when
wherein R ‘and R’ represent alkaryl hydrocarbon
groups in which the alkyl substituents correspond
to high molecular Weight aliphatic hydrocarbon
blended in minor proportions with hydrocarbon 30 materials, such as para?in wax and are predomi
, oils of the type above-referred to will effectively
retard the deterioration imposed-by either mild
or severe conditions of use and will therefore .
nantly groups of at least twenty carbon atoms;
and M represents the hydrogen equivalent of a
metal.
greatly increase the useful life of the oil.
These materials which, as aforesaid, possess
The class of compounds or reaction products 35 pour-depressing
properties in addition to other
contemplated herein as addition agents for lubri
oil characterizing properties may, for purposes of
cating oils and the like are organic compounds
illustration, betypiiied by the metal salt of a
containing sulfur, phosphorus, and metal in
chemical combination or a mixture thereof pre
waxnsubstituted diphenyl dithiophosphoric acid
and may be represented by the following general
dominantly comprised of compounds obtained by 40 formula
reacting phosphorus pentasul?de with an alkyl
substituted phenol. and then introducing metal
into the product thus obtained by reaction with
a metal hydroxide or the like. These compounds
or reaction products contain a hydrocarbon group
or groups of a character which will impart oil
. miscibility or oil-solubility to the compound or
reaction product.
The present invention contemplates compounds
of the class described wherein the oil-solubilizing
action is obtained from an alkylated aryl nucleus
wherein Rn represents at least one alkyl group
having at least twenty carbon atoms or an alkyl
depressant properties to the compound or reac
group corresponding to the aliphatic hydrocar
tion product. The pour-depressant property is
bons characterizing parai?n wax, and M is as
obtained by employing an aryl nucleus which .is 55 de?ned above. As aforesaid, howeventhe for
which, in addition to oil-solubility impartspour
2,410,650
3
phenyl dithiophosphoric acid (3-16) in approxi
mulae and nomenclature 'used herein are based
upon our theory of the reaction and are intended
mately 25 per cent mineral oil- blend.
to represent the reaction product obtained rather
than a speci?c chemical compound in each in
stance.‘
-
The stannous salt of "Wax-substituted diphenyi
.dithiophosphoric acid”'was obtained by dissolv
ing 100 grams of the acid product obtained by
the procedure last described above (dissolved in
‘
It is to be understood that the aryl nucleus in
compounds of the type represented by the fore
going general formulae (I and 11) may be mono
or poly-cyclic and, as aforesaid, the alkyl sub
300 grams of mineral oil) in 100 cc. of butyl
alcohoLadding 1.5 grams of metallic sodium, and
' heating the mixture at the re?ux temperature of
stituent thereon should correspond to an alkyl 10 the alcohol until the sodium was all reacted. A
group of su?iciently high molecular weight to im
part to the compound pour point-depressing and
butyl alcohol solution of stannous chloride (6.2‘
.- viscosity index-improving action in addition to ,
ture slowly heated to 150° C. while the alcohol
grams of SnClz) was then added and the mix
oil miscibility. For alkyl substituents that will
impart these properties, particular preference‘ is
was distilled oil. The mixture was then cooled,
diluted with benzol, and ?ltered through a ?lter- _
' given to alkyl groups of at least twenty carbon
aid clay to remove NaCl, after which the solvent
atoms.
was distilled o? to obtain the ?nished product.
As to the metallic constituent M, it ‘appears
The barium salt of, “wax-substituted diphenyl
that any metal may be used. The alkaline earth
dithiophosphoric acid” was prepared by forming
metals are preferred, with particular preference 20 a reaction mixture consisting of 100 grams of the
given to barium. Other representative metals
“wax-substituted diphenyl dithiophosphoricacid"
which may be used are zinc, tin, aluminum, co
in 300 grams of mineral oil, 11 grams of
balt, nickel, chromium, the alkali metals, etc.
,
Ba(OH)2.8Hz0 and 100 cc. or benzol. The mix
As aforesaid, the reaction products contem
ture was gradually heated to 150° C., the benzol
plated herein as typi?ed by the metal salts of the 25 and the water formed in the reaction thereby be;
partial esters of dithiophosphoric acid may be
ing distilled off. ,'After the reaction mixture was
prepared by ?rst forming the corresponding par
cooled, it was diluted with benzol, ?ltered through
tial ester of dithiophosphoric acid by any known
‘ a ?lter-aid clay to remove unreacted
method, such as that described by P. S. Peshchi
Ba (OH) 28H2O,
muka (J. Russ. Phys. Chem. Soc. 56, 11 (1925) ); 30
_ (Chem. Ab. 19, 2808) , wherein phosphorus penta~
and the solvent was distilled oi! to obtain the
sul?de is reacted with an alcohol, and then re
-
?nished product.
acting the partially esteri?ed acid thus formed
a
Typical metal salts of partial esters of dithio
with a metallic hydroxide to form the metal salt
phosphoric acid which have been synthesized and
of the partial ester of dithiophosphoric acid. 35 demonstrated to be effective addition agents for
The reactions involved can probably be expressed
hydrocarbon oils of the type used in lubricants
by the following equations, although, as afore
and the like are the following:
- said._we do not wish to be bound :by any theory of.
Stannous _di(wax-phenyl) dithiophosphate
reaction.
Barium di(wax-phenyl) dithiophosphate
(A)
4ROH+P2S5+2 (R0) zPSSH-I-HaS
(B) (R0) aPSSH-i-MOH.» (R0) zPSSM-I-HaO
40
As a modi?cation of the foregoing procedure
reaction (B) may be carried out with sodium or
to stabilize and improve the various properties of
various viscous hydrocarbon oils.
45
EXAMPLE 2
potassium hydroxide (M'OH) to form the corre
sponding salt (R0): PSSM', which can then be
reacted with a water-soluble salt of another metal,‘
CORROSION Tssr v
The corrosion-inhibiting action of these com
pounds was demonstrated in the so-called cata
such; as’ zinc chloride or stannous chloride, to
yield “by metathesis‘; the substituted dithiophos
phoric ‘acid saltj'of the‘ second metal.
Further detailsfwfthe procedure which may be
50 lyzed Underwood oxidation test, which is de
scribed in a pamphlet, dated August 1, 1938, of
the Research Laboratories Division of the Gen
followed in synthesizing the compounds contem
plated herein, may be obtained from the follow
' eral Motors Corporation, entitled f‘Underwood ox
ing illustrative examples.
idation testing apparatus.” The following results
EXAMPLE 1
Min-AL SALTS or
55 were obtained by using a motor oil of 210 seconds
Dn'mornosrnoarc
-
The following examples will illustrate the effec
- tiveness of the compounds contemplated herein
~Acm
Saybolt viscosityat 130° F. with the addition of
su?icient iron naphthenate to be equivalent to
0.01 per cent iron oxide to act as a catalyst.
Bearings containing a cadmium-nickel surface
Wax-substituted
‘was ?rst prepared by 60 were used and the Mg loss in bearing weight and
the acidity bf the oil (N. N. value) were deter
the Friedel-Crafts condensation of chlorinated
mined after ?ve hours of test. '
para?in wax (16 per cent chlorine content) with
phenol in the ratio of 1 molecular part phenol to
3 atomic parts chlorine in the chlorwax. The‘
Compound added
egg‘;
N. N.
65
wax-substituted diphenyl dlthiophosphoric acid
was obtained by making a reaction mixture of 100
grams of the wax-phenol, 8.1 grams of Past, and
300 grams of mineral oil of Saybolt viscosity of
6'? seconds at 210° F. This‘ mixture was heated
at 100° C. until the evolution of H28 had sub
stantially stopped (about 15 or 20 hours). The
clear solution was then blown with a stream of
nitrogen to remove entrained H118, to obtain the ‘
product which, for purposes of identi?cation
herein we may refer to as wax-substituted di
None _______________________________________ __
Ba salt of wax-substituted diphenyl
dithiophosphoric acid (3-16) ________ ._
1
789
13.4
40
_
2. l
EXAMPLE 3
Form Dnrxsssam AND V. I. IMPROVEMENT‘
As aforesaid, the so-called “wax”-substituted
compounds have‘the properties of acting as pour
point-depressants and viscosity index-improvers.
2,410,650
6
2. A lubricant composition comprising a major
These properties are demonstrated by the re
sults set forth in, Tables 11 and m below showing
proportion of a viscous hydrocarbon oil and an
oil-miscible metal salt of a wax-phenyl-sub
pour point-depressing and V.. I. results, I respec
stituted thio' acid of phosporus in an amount suf
tively. on typical motor oils with and without the
addition agent.
Table II
'
g
A. S. 'I‘. M. pour
.Compound blended with motor oil of 67 sec. points on on Hands
Baybolt viscosity at 210° F.
'
‘
'
*
9%
340%
° F.
None _______________________________________ ._
+20
° F.
%% .
?cient to exert detergent and anti-corrosive prop
erties in the oil under heavy duty service, said
wax group containing at least twenty carbon
atoms.
dithiophosphoric acid (3-16) ____________________ _.
—10
-20
-
to exert detergent and anti-corrosive properties
° F.
in the oil under heavy duty service, said wax group
............ __
Barium salt of waxsubstituted *diphenyl
.
3. A lubricant composition comprising a major
10 proportion or a viscous hydrocarbon oil and an
oil-miscible metal salt of a wax-aryl-substituted
thio acid of phosphorus in an amount su?lcient
15 containing atleast twenty carbon atoms.
4. A lubricant composition comprising a major
proportion of a viscous hydrocarbon oil and an
oil-miscible‘ metal salt of a wax-substituted
diphenyl dithiophosphoric acid in an amount suf
Table III
\
Kinematic viscosity
Compound blended with
C
v ‘I
lubricating oil‘
20 ?cient to exert detergent and antil-corrosive prop
erties in the oil‘ under heavy duty service, said
‘
100° F.
Per can't
None ____________________ __
210° F. ,
,
o
wax group containing at least twenty carbon
atoms.’
5. A lubricant composition comprising a major
.
29. 56
4. 72
76. 7
32. 28
5. 04
-
86. 0
proportion of a viscous hydrocarbon oil and an .
Waxeuhstituted diphenyl
dithiophosphoric acid
(3-1 _______________ __,___
Barium salt of wax-substt‘
tuted
diphenyl
1
dithio-
-
phosphoric acid (3-16)...
1
oil-miscible alkaline earth metal salt of a wax
substituted diphenyl dithiophosphoric acid in an
amount 'su?icient to exert detergent and anti=
I
33.06
I5. 15
89.6
corrosive properties in the oil under heavy duty
The'parenthetical expression “(3-16)” used in 30 service, said wax group containing at least twenty
carbon atoms.
6. A lubricant composition comprising a major
Tables I, II and III and in Example 1 above indi
cates the number of atomic proportions (3) of I
chlorine in the chlorwax reacted with 1 molecular
proportion of a viscous hydrocarbon oil and an
oil-miscible barium salt of a wax-substituted
part of phenol and the percentage (16) of chlorine 35
diphenyl dithiophosphoric acid in an amount
in the chlorwax used in this reaction from which
su?icient to exert detergent and anti-corrosive
the wax phenol was obtained. This wax'phenol
properties in the oil under heavy duty service.
(3-16) provides the wax-substituted phenyl sub
said wax group containing at least twenty carbon
stituents in the salts disclosed herein, as described
in Example 1.
‘
atoms.
'
‘
'
7. A lubricant composition comprising a majo
The compounds or reaction products contem
plated herein may be used in various amounts de
pending upon the character of the. oil and the
severity of the conditions under which it is to be
proportion of a viscous hydrocarbon oil and an
oil-miscible zinc salt 01’ an acidic reaction prod
used. In general it appears that satisfactory im- ,
having the formula:
uct obtained ,by reacting PzSs with a compound
'
provement may be obtained with amounts rang
ing from about 0.01 per cent to about 5.0 per cent.
It ‘is to be understood that while I have herein
described certain speci?c compounds and pro
cedures to illustrate the invention, such speci?c ,,
examples are illustrative only and the invention,
inv an amount sumcient to exert detergent and
anti-corrosive properties in the oil under heavy
duty service, wherein Rn represents at least one
embraces within its scope such changes and modi
?cations as fairly come within-the spirit of the
appended claims.
I claim:
.
I
I
oil-solubilizing alkyl group containing at least
-
1. A lubricant composition comprising a major
proportion of a‘. viscous hydrocarbon oil and an oil
miscible metal salt of a substitutedthio acid of
twenty carbon atoms.
8. A lubricant composition comprising a major
proportion of a viscous hydrocarbon oil and an
oil-miscible stannous salt of an acidic reaction
phosphorus having the general formula
60 product obtained by reacting Pass with a, com
pound having the formula?
R. ——
0 ~
1 1
P£SM
Ra'
in amounts sumcient to exert detergent and anti
corrosive properties in the oil under heavy duty
service, wherein ‘Rn represents at least one oil
solubilizing alkyl group containing at least twenty
carbon atoms and M represents the hydrogen
equivalent of a metal.
65
in an amount suii‘icient to exert detergent and
anti-corrosive properties in the oil under heavy
duty service, wherein Rn represents at least one
oil-solubilizing alkyl group containingv at least
twenty carbon atoms.
'
'
,9. A lubricant composition comprising a major
proportion of a viscous hydrocarbon oil and from
about 0.01 per cent to about 5.0 per cent of an oil
2,410,050
7
miscible metal salt 01' a substitutedthio acid of I
'phosphorus having the general formula:
Esq-o \/
Ego
8
'
'
1
wherein Rn represents at least one oil-solubiiizing
_alkyl group ‘containing at least twenty carbon
atoms vand M represents the hydrogen equivalent
01a metal.
.
JOHN J. '
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