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Патент USA US3098834

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United States Patent 0 ”" cc
3,098,824
Patented July 23, 1963
1
7
2
reaction of _a phosphoroamido acid with ‘an unsaturated
carbonyl compound. In order that the invention may be
clearly understood, the general reactants are described and
3,098,824
LUBRICATING COMPOSITION
Allen F. Millikan, Crystal Lake, and Gifford W. Crosby,
River Forest, Ill., assigno‘rs to The Pure Oil Company,
speci?c examples given.
Chicago, 111., a corporation of Ohio
The phosphorodiamidodithioic acids are prepared by
reacting primary or secondary amines with phosphorus
pentasul?de._ Useful amines include the methylamines,
No Drawing. Original application Nov. 15, 1957, Ser.
No. 696,604, now Patent No. 2,996,532, dated Aug. 15,
1961. Divided and this application Aug. 24, 1960,
Ser. No. 51,494
.
the ethylamines, aniline, m~benzylaniline, p~benzylaniline,
.
benzylamine, propylamine, ,isopropylamine, dipropyla
22 Claims. (Cl. 252-467)
10 mine, di-isopropyl'amine, butylamine, di-bu-tylamiue, iso
- butylamine, di-isobutylamine, amylamine, isoamyl-amine,
(V This invention relates to lubricating compositions con
tain-ing certain new compounds, their method of prepara
p-isopropylaniline, dodecylamine, and the like. The re
action between primary or secondary amines and P285 re
sults in phosphorodiamidodithioates which may be used
15 as intermediates for preparing the subject compounds.
Mixed diamides are obtained when dia-lkyl amines react
with P255 at about 130° C.
tion, and to lubricating oil compositions comprising or
containing the products thereof, namely, carbonyl-substi
tuted alkyl phosphoroamidothioates, particularly phos
phorodiamidodithioates.
,
.
_
In copending application Serial Number 630,088, ?led
December 24, 1956, certain formylalkyl thiophosphate
S
esters are described which are prepared by the reaction
of an O, O-diester of a dithiophosphoric acid with anal 20 “cinema + Piss -—-> zwtHmué-il-su + melanin + HIS
kena-l such as acrolein, crotonaldehyde, 2~pentenal, etc.
“
The reaction is carried out in such a manner that instead
of condensation, wherein the alkenal serves to provide a
04mm;
_
With primary amines, symmetrical diamides can be pre
pared. Aniline reacts vwith P285 at 30° C. to give N,N'
linking nucleus between the thiophosphate esters, and the
diphenylsphosphorodiamidodithioic acid:
0x0 group of the aldehyde is removed by the formation 25
of water, the 0x0 group of the aldehyde reactant is re
i
tained in the reaction product to impart unusual proper
ties thereto.
4CoHsNHa + PzSs —% 2(>O¢H5NH):P—'SH + Has
I
The products" resultingfrom the reaction of the amine
This invention is directed to the discovery that the re
action product of an amine with a phosphorus sul?de can 30 with P285, after separation and puri?cation, or in their
semi-pure state, are treated with an unsaturated conjugated
be converted to a carbonylalkyl derivative by‘reaction
with a carbonyl compound having a, B unsaturation. This
application is a division of application Serial Number
696,604, ?led November 15, 1957, now US. Patent
2,996,532.
It becomes, therefore, a primary object of this inven
tion to provide oil-soluble, al'koxycarbonylalkyl phos~
carbonyl compound, of the following formula:
0
R"-C=C—"C%
R" R” \X
35
phoroamido esters for use in lubricating oil compositions
and a method of preparing same.
wherein X is a group as heretofore de?ned and R" may be
hydrogen, C, to C8 alkyl groups, including methyl, ethyl,
propyl, butyl, isobutyl, pentyl, isopentyl, heiryl, heptyl and
Another object of this invention is to provide oil~soluble, 40 octyl, or combinations thereof. The alpha carbon atom
may carry a hydrogen atom and the beta carbon atom
carbonyl-substituted phosphorodiamidodithioic esters for
may carry one or two alkyl groups, or the alpha carbon
atom may carry an alkyl group and the beta carbon atom
may carry one or two hydrogen atoms. Since X may be
hydrogen, an alkyl group,‘ alkoxy group or amino group,
use as lubricating oil additives.
An additional object of this invention is to provide a
lubricating oil additive having minimum deposit-forming
properties which will enhance the load-carrying and anti
etc., the unsaturated conjugated carbonyl compounds in
wear properties of a mineral lubricating oil.
A further object of this invention is to provide a lubri
cluded in this invention are of the class of unsaturated
cating oil composition having increased load-carrying and
antiwear properties.
the unsaturated amides as general examples.
aldehydes, unsaturated ketones, unsaturated esters, and
The
According to this invention, it has been found that 50
the carbonyl-substituted phosphorodia-midodithoic esters
group in the above formula, having an upper limit of 25
of the general formula,
carbon atoms, becomes R’ in the end product through the
addition of the dithioic acid. Speci?c non-limiting exam
ples of unsaturated carbonyl compounds coming within
the foregoing general formula are:
Acrolein
n-Butyl acrylate
Crotona-ldehyde
where R groups are hydrogen or alkyl groups containing 1
Beta-methylcrotonaldehyde
to 25 carbon atoms, or are aryl groups, alkylaryl or aryl
alkyl groups containing from 6 to 25 carbon atoms, R’ 60 A-lpha-methylcrotonaldehyde
Alpha-methyl-beta-ethylacrolcin
is a divalent alkyl radical containing from 1 to 25 carbon
Vinyl methyl ketone
atoms, and X is selected from the group of hydrogen,
alkyl groups (including lbenzyl, methyl, ethyl, propyl, iso
propyl, isobutyl, n-butyl, t-butyl, cyclohexyl, and octyl),
and alkoxy, amino, alkylamino and dialky-l-amino groups,
are ‘useful as ‘lubricating oil additives.
65
Compounds meet- ,
ing the foregoing general formula can be formed by the
Vinyl ethyl ketone
Mesityl oxide
Methyl methacrylate
Benzyl acrylate
Cyclohexyl acrylate
Ethyl acrylate
Methyl acrylate
Octyl acrylate
Acrylamide
N-t-buty-lacrylamide
N,N~diethylacrylamide
Z-ethylhexyl acrylate
From the foregoing illustrations, it is apparent that X in
3,098,824.
4
percent N, .60 wt. percent P, 12.3 wt. percent S. Found:
3.8 wt. peiicent N, 1.5 wt. percent P, 2.7 wt. percent S.
0
the general formula may also include the met-hoxy, ethoxy,
acetoxy, methylamino, ethylamino, dimethylamino and di
ethyl-amino groups as further speci?c examples.
The S/P/N ratio was 1.9/1/2.9; this indicates the ex
cepted amine dilution, as theory would be 2/1/2.
In order to illustrate the invention, a number of non
limiting examples are given:
EXAMPLE V
EXAMPLE I
N,N’-tri-n-buitylphosphorodiamidodithioic acid was pre
N-t-Octylcarbamylethyl N,N'-Tri-n-Bwtyl
phosplzorodiamidodithioate
The N-t-octylcarba-mylethyl N,N’-tri-n-butylphos
pared as follows: One hundred forty-seven g. (1.14
moles) of di-n-butylamine and 20.4 g. (0.092 mole) of
phorodiamidodithioate ester of the acid from Example
I, another representative compound of our invention, was
prepared as follows: Exactly ten g. (0.034 mole) of
re?ux condenser. As a reaction mixture was stirred, the
the acid prepared above and 6.6 g. (0.036 mole) of N
temperature rose to 80° C. spontaneously, and heat sup
plied by a heating mantle brought the pot tempertaure 15 t-octylacrylamide were charged, along with 200 ml. of
toluene, to a 500 ml. ?ask equipped with sealed stirrer,
to 160-165 ° C. The system was re?uxed for three hours
thermometer and a reflux condenser. With heat supplied
at this temperature. A white solid product started to
phosphorus pentasul?de were charged to a 500 ml. ?ask
equipment with a mercury-sealed stirrer,‘thermometer, and
by a mantle, the reaction mixture was stirred and re?uxed
at 110° C. for 25 hours. The product was ?ltered and
form at 145° C. and its production appeared to be com
plete at the end of this period. The product was washed
vacuum-nitrogen stripped. Analysis of pr0duct.—Cal—
with methanol and dried. Analysis.—Calc’d for
N, 9.5%; P, 10,5%; S, 21.6%. Found: N, 9.3%; P,
‘culated for C23H5oN3OPS2: N, 8.8 wt. percent; P, 6.5
wt. percent; S, 13.4 wt. percent. Found: N, 7.2 wt.
percent; P, 5.6 wt. percent; S, 9.7 wt. percent.
10.3%; S, 19.8%. This product was found to increase
the wear rate of a base oil in which it was blended and
was therefore of no value as an antiwear additive.
EXAMPLE II
2-Ethylhexyloxycarbonylethyl Ester of N,N'-Tri
n-Butylphosphorodiamidodithioate
EXAMPLE VI
N,N-tricyclohexylphosphorodiamidodithioic acid was
prepared as follows: 160.2 g. (0.88 mole) of dicyclo
hexylamine and 16.5 g. (0.074 mole) of P285 were
charged to a 500 ml. ?ask equipped with thermometer,
30 mechanical stirrer and heating mantle. The reaction
The product of Example I was converted to the Z-ethyl
hexyloxycarbonylethyl ester by [addition to Z-ethylhexyl
acrylate as follows: Twenty g. (0.07 mole) of the N,N'_~
mixture was stirred and heated.
At about 80° C. a
precipitate began to form. This coagulated as the reac
tion continued, making stirring very di?icult. The re
action was suspended temporarily and the supernatant
18 g. (0.10 mole) of 2-ethylhexyl acrylate, and 200 ml. 35 liquid poured off. The semisolid lower phase was re
of toluene were charged to a 500 ml. ?ask equipped with
moved and formed a glass-like solid on cooling. The
supernatant liquid was returned to the ?ask and heated
a mercury-sealed stirrer, thermometer, re?ux condenser,
and heating mantle. The reaction mixture was stirred
to 160° C. with stirring. The solid was pulverized and
and re?uxed with a pot temperature of 1104115 ° C. for
added at this temperature as stirring continued. After
twenty-four hours. At the end of this time the solution 40 15 minutes of reaction, the two-phase reaction product
was completely clear. Under vacuum, the product was
was separated while still hot. The lower phase cooled
stripped with nitrogen to remove solvent. Analysis of
to ‘a glass-like product, which was pulverized. The acid
product.—Calc’d for 86% concentrate of C23H49N2O2PS2:
number of this material was 155, near to theoretical for
N, 5.0 wt. percent; P, 5.5 wt. percent; S, 11.4 wt. per
N,N’-tricyclohexylpbosphorodiamidodithioic acid, viz.,
cent. Found: N, 4.7 wt. percent; P, 5.1 wt. percentyS, 45 149.2. The analysis of this product was, calculated:
8.5 wt. percent.
7.5 wt. percent N; 8.3 -wt. percent P; 17.1 wt. percent S.
EXAMPLE III
Found: 5.0 wt. percent N; 8.1 wt. percent P; 14.2 wt. per
cent S.
Exactly 142.4 grams (0.59 mole) of di-Z-ethylhexyl
amine and 11.5 g. (0.052 mole) of phosphorus penta
EXAMPLE VII
tri-n-butylphosphorodiamidodithioic acid thus prepared,
sul-?de were charged to a 500 ml. ?ask equipped with 50
heating mantle, motor-driven stirrer, and thermometer.
Z-Ethylheadyloxycarbonylet/1yl N,N’—Tricyclohexyl
phosphorodiamidodithioaz‘e
Stirring was applied at once and there was some spon
The above product was treated with a r1.6 molar por
taneous generation of heat. Heat was applied by means
of the mantle, and the temperature was raised to 180°
C. The temperature was maintained in that range for
The product was a
tion of 2~ethylhexyl 'acrylate at 90° C. in toluene solution.
A very slow reaction took place, and after 4 days a 60%
yield of oil-soluble product was obtained by removal of
clear liquid with an acidity which. indicated that 0.091
mole of acid had been formed (as against 0.104 mole in
the liquid phase and solvent stripping with nitrogen.
Although a number of organic phosphorus compounds
45 minutes as stirring continued.
theory).
have been proposed as 'antiwear additives ‘for lubricating
EXAMPLE IV
60 oils, the subject class of compounds has been found to
be particularly effective in reducing wear between metal
surfaces. In the following table is shown the results of
Formylethyl N,N’-Tri-2-Ethylhexylphosphor
odiamidodithioate
Three-hundredths mole of the above acid was charged
wear tests on two kinds of lubricating blends. Base oil
A was composed entirely of extract from manufacture of
85 vis., 100 V.I., neutral oil. Base oil B was composed
of 4.8 ‘wt. percent of the above extract, 5.7 wt. percent
to a 500 ml. ?ask equipped with stirrer and a tube for
delivering acrolein beneath the liquid surface. Then 18.5
g. (0.34 mole) of acrolein was distilled into the reaction
mixture with stirring. There was some generation of
heat and marked darkening of the color. The reaction
was complete in an hour.
The product was vacuum
nitrogen stripped. The product, formylethyl N,N’-tri-2
ethylhexylphosphorodiamidodithioate, could be expected
to be diluted with amine and acrolein polymer since neither
of these would be completely removed by the stripping
employed: Analysis.-Calc. for C26H57N2O-PS2: 5.4 wt.
barium-‘calcium phenol sul?de-sulfonate ‘detergent add-i
tive, 6.4 wt. percent of acrylic polymer (Acryloid #618)
and 83.1 wt. percent 170 vis., 100‘ V.I., neutral oil.
70
Wear tests were carried out in triplicate on the four
ball E.P. machine in which the average wear-scar diam
eter was determined after a ?ve-minute test at 1800
rpm, room temperature, 20 kg. load. The subject com
pounds are shown to be effective antiwear compounds
compared to amine-P285 products before conversion to
3,098,824
the carbonyl-substituted ester, or to a commercial metal
N-hexylcarbamylmethyl N',N"-tri-isopropylphosphoro
diamiidodithioate
N-t-octylcarbamylethyl N',N"~tricyclohexylphosphoro
phosphorodithioate.
TABLE I.-—FOUR-BALL wlgigs TESTS ON LUBRIOATING
diamidodithioate
[5 min., 20 kg., 1800 r.p.m., room temp. Phosphorus in blend, 0.10 wt.
Z-acetylethyl N’,N"—tri-ethyloctylphosphorodiamido
dithioate
Carbamylethyl N’,N"-tri-n-octylphosphorodiamidodi
percent]
Additive type
.
Additive description
Avg.
Base
wear
oil
thiate
scar
N~t-octylcarbamylethyl N',N"-tetra-n-octylphosphoro
diamiidodithioate
N~octadecylcarbamylethyl N’,N"-tetra-n-propylphos
phorodiamidodi-thioate
N-pentacosylcarbamylethyl N’,N"-tri-n-propylphos
diam.
Example II.
B
0.261
i
3:
Example V __________ __
B
0.272
Example III ________ __
B
0.311
Products of this invention.... E225: g? _
Amine-P185 products_______ __ €§g$g§g $12
Example I. ___
Commercial P-S.ester ...... _. Zinc dlalkyl phos-
phorodlthloate.
None _______________ ._
-____do _______________ ._
2
3:232
A
1 0. 546
B
0. 278
A
B
0. 505
0. 280
phoroCtia-midodithioate
N-octadecylcarbamylethyl N',N"-tri-pentacosylphos
phorodiamidodithioate
N-dodecylcarbamylethyl N',N"-tri-heptadecylphosphoro
15
diamidothioate
These compounds represent the new and novel compo
sitions of matter of this invention, whether present in a
20
S011I]{?xer
phosphorous concentration in blend due to low
1
.
reaction mixture, or in semi-puri?ed or puri?ed form.
These new compounds ?nd particular use in lubricating
oil compositions as antiwear agents. When used for
son with the diameter of elastic indentation of the balls
under the test load. In the case of the tests at 20 kg. 25 this purpose, they may be incorporated in the oil in
amounts ranging from about 0.1 to 5.0 weight percent.
load, this diameter is 0.236 mm. and the increase in diam
In some applications, less than 0.1 weight percent of the
eter above this value is an accurate measure of the wear
carbonyl-substituted phosphoroarnidodithioates may be
under the test conditions. The above data show that
used and in others more than 5.0% by weight may be
mineral oil alone, or oils containing amine-P285 products
of the phosphorodiamidodit-hioic acid type, allow rela 30 necessary or give better results. Some of these com
pounds have limited oil solubility but are effective when
tively high wear rates. Although additives such as com
used in an amount s‘u?‘icient to incorporate about 0.1
mercial phosphorodithioates and others, including those
weight percent of phosphorus in- the total composition.
in base oil B, lower the wear rate substantially from that
For applications where the appearance of the end com
of mineral oil alone, the subject compounds give uni
position is not important, the compounds of this inven
formly still lower wear rates in either base oil.
tion may be used as suspensions in the oil-carrier or lu
The foregoing examples describe the preparation and
bricity agent.
use of several carbonyl-substituted phosphoroamido
As indicated by the wear tests herein, other addends
dithioates coming within the broad de?nition of the inven~
and ingredients may be used with the compounds of this
tion. The species tested as represented by Examples II,
IV, V and VII are the preferred embodiments of the in 40 invention, including various lubricating oil addends and
d-iiferent kinds of oil-carriers or lubricity agents. Thus,
vention.
the compounds of this invention may be incorporated in
Other examples include:
Wears-scar diameters are best interpreted by compari
any lubricating oil, cutting oil, extreme pressure lubri
cant, grease, aqueous~oil suspension, soluble oil and solid
N~t~octy1carbamylethyl N’,N"-tri-n-propylphosphoro
diamidodithioate
r lubricant. The oil-carriers may be various lubricating oil
N-hexylcarbamylethyl N',N"-tri-n~propylp-hosphoro
fractions, bright stocks, neutrals or distillates. The add
ends of this invention may be used with synthetic lubri
diamidod-ithioate
N-diethylcarbamylethyl N’,N"-tri-n‘butylphosphoro_
diamidodithioate
2~ethylhexyloxycarbonylethyl N’,N"-tri-n-butylphos
phorodiamidodithioate
N-t-octylcarbamylmethyl N’,N"~tri-n-propylphosphoro
cants. The following table gives the properties of various
solvent extracts produced through the manufacture of
‘bright stocks and ‘neutral oils, by way of illustration.
This table includes the properties of the speci?c solvent
extract, number 19, used to prepare the formulations
tested in Table I.
diamidodithioate
Exa
tract
Crude source
N0.
Solvent
API
gravity
Sp. gr.
at 60° VlsJ 100° Vls./ 130° Via/210°
F.
F.
F.
VI.
F.
Pour
° F.
° F.
Iodine
num-
percent
per
cent
?ask
fire
her
QR.
sulfur
(Wits)
East Texas..."
__.._d0 ________ __
23,319
15,000
30, 410
19, 500
32, 500
25, 000
145, 000
12, 67
11 .... ._
Pennsylvania“
4, 750
____
4, 310
4, 305
__-_
6, 400
19, 000
2, 514
282
—40
285
+39
310. 1
313
-—1
+27
372
355
616
172. 1
371
...... __
__________________ __
1,500
________
1,365
______ __
__________________ __
1,500
13 .... ..
1,500
41.7
200
509
-____do ________ __
East Texas_____
_-___do ........ __
—101
---_
12 _________ “do ________ __
Mid'ContL
+5
+27
0
50.2
341
40.7
—82
~61
25
17
—16
3,098,824.
7
The materials described in Table II are all prepared or
derived through the solvent extraction of crude lubricating
oils in the manufacture of re?ned oils, i.e., neutrals and
bright stocks, as is well known in the art. These materials
normally are considered waste products, being the extract
phases derived during the solvent extraction and contain~
8
sible to vary the characteristics of the extraction product
considerably by adjustment of the amount of water pres
ent. A lower V.I. can be obtained by using a water solu
tion of phenol during the extraction and a higher V.I. can
be obtained by using anhydrous phenol.
The mineral lubricating oil bases which may constitute
the whole or part of the carrier for the addends of this
invention are derived from any paraf?inic, naphthenic, or
the raf?nate or re?ned oil. Solvent extracts are not as re
mixed-base crude oil source as Mid-Continent, Texas, Cali—
sistant to oxidation or sludging as the corresponding raf 10 fornia or Pennsylvania crude oil. Examples of lubricat
?nates and have lower viscosity indices and higher vis
ing oil bases are given in Table 111.
ing a predominance of the aromatic~type constituents as
opposed to the para?inic~type constituents which remain in
TABLE III.——-BASE OILS
API
gravity
Mineral oil
O OO
?ash,
0 0C
?re,
° 1"
° F.
SUS at
100 ° 1“.
SUS at
210 ° F.
Vis.
index
NPA
color
Percent
carbon
Percent
sulfur
residue
Stable
pour
° F.
100 ViS. neutral__.___.._v
33. 6
405
450
103. 2
39. 7
101
+2
0.00
0. 12
+5
70 viS. neutral_.__
150 bright Stock-
_
_._
36. 6
26. 8
370
570
40,5
630
71. 3
2, 511
36. 9
156. 0
111
99
+1
6+
0. 00
0. 73
0. l8
0. 53
0
—5
170 vis. neutral ________ -_
31. 2
420
480
177. 7
45. 2
101
1+
0. 00 ........ --
0
cosities than the ra?’inates. Accordingly, in using solvent 25
Other addends may be used in the compositions of this
extracts alone to prepare compositions containing the
invention, including lubricity agents, pour depressants, V1.
addends of this invention, these changes in properties must
improvers, oxidation inhibitors and the like. Acryloid
be taken into consideration as concerns their usefulness
#618 is the trade name of an acrylic acid polymer useful
as a base oil.
as a V1. improver. This product is a well~known addend
Solvent extracts are obtained in the following manner, 30 having a molecular weight of about 3000, a speci?c grav
to give an illustration:
ity of about 0.906 (60° F./ 60° F.), a ?lash point (C.O.C.)
In a typical operation, desalted crude oil is ?rst charged
of about 400° 1F., a viscosity at 100° F. of about 8000 cs.,
to a distillation unit where straight-run gasoline, two grades
neutralization No. of 0.2, and ASTM color of 3. The
of naphtha, kerosene, and virgin distillate are taken off,
physical properties of other Acryloid lubricating oil addi~
leaving a reduced crude residue. The reduced crude is 35 tives are given in Table IV.
continuously charged to a vacuum distillation unit where
three lubricating oil distillates are taken off as side streams,
a light distillate is taken off as overhead, and a residuum
is withdrawn from the bottom of the tower. This resid~
TABLE IV
uum is charged to a propane deasphalting unit wherein
propane dissolves the desirable lubricating oil constituents
Acryloid No.
and leaves the asphaltic materials. A typical vacuum re
Property
siduum charge to the propane deasphalting unit may have
an API gravity of 129°, viscosity SUS at 210° F. of
1249, ?ash 585° F., ?re 650° F., C.R. of 13.9 weight per
cent and be black in color. The deasphalted oil may have
an API gravity of 21.5 ° to 21.8", viscosity SUS at 210°
F. of 165-175, NPA color 6-7, ?ash 575° F., ?re 640° F.,
and CR. of 1.7-2.0. The deasphalted oil and various
710
and
788
Sp. gr., 60° F./60° F ......................... -_
Lbs/gal
Flash point, 0.0.0., ° F).
ASTM, pour point, ° F.2
Viscosity, cS./l00° F_____
SUS/100° F___
lubricating oil distillates from the reduced crude are sep 50 Viscosity,
Viscosity, es./210° F-____
arately subjected to solvent extraction for the separation
Viscosity, SUS/210° F-
of non-aromatic from aromatic constituents. The re?ned
Neut. number-
Color, ASTMZ.
763
0. 906
0. 901
7. 54
400
+25
7. 50
400
+25
9, 400
3, 000
800
3, 700
7,200
33.000
800
3, 700
0. 2
0. 2
3
______________________ -_
3
oil or “ra?inate” from such processes is used per se or as
blending stock and the solvent extract, containing pre
1 When diluted with three parts ofa 400° F. ?ash mineral oil to decrease
viscosity and prevent local overheating and cracking.
dominantly aromatic constituents, is the material that may 55 the2 Viscosity
pour point.
be used as a part of the base oil.
For example, a crude oil from East Texas with an API
gravity of 33.1 was topped to remove such light fractions
as gaoline, naphtha, kerosene, and a light lubricating dis
The detergent-antioxidant that is included in the for
tillate. The vacuum residue was a reduced crude having 60
mulations tested herein is known under the trade name of
a viscosity of 1251 SUS at 210° F., 2.2 percent sulfur, and
Paranox 65. Broadly, addends of this type comprise about
an API gravity of 12.6. After propane deasphalting, the
65 % by weight of a phenol sul?de salt and an alkaline
oil had a viscosity of 174 SUS at 210° -F., and an API
earth metal sulfonate combination with about 35% min
gravity of 21.7. This deasphalted oil was treated with
eral oil carrier. The active ingredients comprise about
phenol to produce a ra?’inate from which an aviation 65 80% by weight of a phenol sul?de salt and 20% of the
lubricating oil may be produced. The extract phase from
sulfonate. As described in United States Patents 2,379,
this phenol treatment, after removal of phenol, is ready
241 and 2,761,845, these anti-oxidant-detergents are oil
for use in preparing compositions in accordance with this
soluble metal salts of an alkylated hydroxy aryl sul?de
invention.
mixed alkaline-earth metal petroleum sulfonates. The ac
Other solvents than phenol may be used to obtain the 70 tive ingredients in Paranox 65 comprise 65% of a mixture
extraction product used in accordance with this invention;
of barium salt of hydroxy diisobutyl phenyl sul?de and
for example, liquid sulfur dioxide, nitrobenzene, Chlorex,
calcium petroleum sulfonate With a mineral oil, wherein
chlorophenol, trichloroethylene, cresylic acid, pyridine,
the proportions of the sul?de salt to sulfonate are 80/20,
furfural or the Duo—Sol solution comprising liquid propane
as before stated. Paranox 65 has the following physical
and cresol may be used. When using phenol, it is pos 75 properties:
“
3,098,824
10
TABLE V.——TYPICA_L PHYSICAL PROPERTIES OF
LPARAINOX 65?
Physical characteristic:
trialkylphosphorodiamidodithioates wherein the alkyl
radicals have from 3 to 25 carbon atoms.
Value
Viscosity at 210° F, S-US _____________ __
106.5
Flash point, ° F ______________________ __
425
Pour point, "F ______________________ __
10
12. A lubricating composition comprising a major
amount of a mineral lubricating oil and about 0.1 to 5.0
weight percent of lformylethyl-N,N’-trialkyl-phosphorodi
amidodithioates wherein the alkyl radicals have from 3
Speci?c gravity, 60/60° F _____________ __ 1.0136
to 25 carbon atoms.
Weight, awg, lb./gal. at 60° F _________ __
8.5
13. A lubricating composition comprising a major
Barium, weight percent ________________ __
7.73
amount of a mineral lubricating oil and about 0.1 to
Calcium, weight percent _______________ __
0.6
10 5.0 weight percent of formylmethyl-N,N'-trialkylplros
Sulfur, weight percent _________________ __ 12.71
phorodiami-dodithioates wherein the alkyl radicals have
Ash, Weight percent __________________ __
14.9
[from 3 to 25 carbon atoms.
Sulfated ash, weight percent ____________ __
15.4
Conradson canbon residue, weight percent__
16.7
Neutralization number, ASTM __________ __
1 58
Acid number ________________________ __
2.3
14. A lubricating composition comprising a major
amount of a mineral lubricating oil and about 0.1 to
5.0 weight percent of N-t-octylcarbamylethyl-N,N'-tri
alkylphosphorodiamidodithioates wherein the alkyl radi
1 Base number.
cals have \from 3 to 25 carbon atoms.
What is claimed is:
15. A lubricating composition comprising a major
1. A lubricating composition comprising a major
amount of a mineral lubricating oil and about 0.1 to
amount of a mineral lubricating oil and about 0.1 to 20 ‘5.0 weight percent of N-t~octylcarbamylmethyl-N,N’-tri
5.0 weight percent of a carbonyl-substituted alkyl N,N'
trialkyl phosphorodiamidodithioate of the formula
alkylphosphorodiamidodithioates wherein the alkyl radi
cals have from 3 to 25 carbon atoms.
16. A lubricating composition comprising a major
amount of a mineral lubricating oil and about 0.1 to
25
5.0 weight percent of 2-ethyl-hexyloxycarbonylethyl-N,N'
tricycloalkylphosphorodiamidodithioates wherein the tri
cycloalkyl radicals have from 3 to 25 carbon atoms.
.17. A lubricating composition comprising a major
amount of a mineral lubricating oil and about 0.1 to
wherein R is an alkyl radical having 3 to 25 carbon atoms, 30 5.0 weight percent of Z-ethylhexyloxycanbonylmethyl
N,N' - tricycloalkylphosphorodiamidodith-ioaltes wherein
R’ is of the group consisting of methylene and ethylene,
and X is of the group consisting of hydrogen, acetyl,
the tricycloalkyl radicals have from 3 to 25 carbon atoms.
18. A lubricating composition comprising a major
amino, diethylamino, hexylamino, t-octylamino, dodecyl
amino, pentacosylamino, and 2-ethyl bexyloxy radicals.
amount of a mineral lubricating oil and about 0.1 to
1 in which R’ is a methylene ‘group.
n-propylphosphorodiamidodithioate.
2. A lubricating composition in accordance with claim 35 5.0 weight percent of Nat-octylcarbamylmethyl-N,N'-tri
19. A lubricating composition comprising a major
3. A lubricating composition in accordance with claim
amount of a mineral lubricating oil and about 0.1 to
1 in which R’ is an ethylene group.
4. A lubricating composition in accordance
1 in which X is hydrogen.
5. A lubricating composition in accordance
1 in which X is acetyl.
6. A lubricating composition in accordance
1 in which X is a Z-ethylhexyloxy group.
7. A lubricating composition in accordance
5.0 weight percent of 2~ethylhexyloxycarbonylethyl-N,N'
with claim
tricyclohexylphosphorodiamidodithioate.
20. A lubricating composition comprising a major
wit-h claim
amount of a mineral lubricating oil and about 0.1 to
5.0 weight percent of Z-ethylhexyloxy carbonylethyl—N,N'
with claim
tri-nbutylphosphorodiamidodithioate.
21. A lubricating composition comprising a major
with claim
amount of a mineral lubricating oil and about 0.1 to
1 in which X is an amino group.
5.0 weight percent of formylethyl-N,N’-tri-2-ethylhexyl
8. A lubricating composition in accordance with claim
phosphorodiamidodithioate.
1 in which X is a t-octylamino group.
9. A lubricating composition in accordance with claim
1 in which X is a diethylamino group.
22. A lubricating composition comprising a major
50 amount of a mineral lubricating oil and about 0.1 to
5.0 weight percent of N-t-octylcarbamylethyl—N',N"-tri
10. A lubricating composition comprising a major
n-butylphosphorodiarnidodithioate.
amount of a mineral lubricating oil and about 0.1 to 5.0
weight percent of Z-ethyl-hexyloxycarbonyl-ethyl-NN'
trialkylphosphorodiamidodithioates wherein the alkyl radi
cals have from 3 to 25 carbon atoms.
11. A lubricating composition comprising a major
amount of a mineral lubricating oil and about 0.1 to 5.0
weight percent of Z-ethylhexyloxycanbonyl-rnethyl-N,N'
55
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,146,584
2,760,957
2,881,201
Lipkin ______________ __ Feb. 7, 1939
Adelson ____________ __ Aug. 28, 1956
Schrader _____________ __ Apr. 7, 1959
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,098,824
July 23, 1963
Allen F. Millikan et a1.
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 3, line 22, for "10,596" read -— 10.5% ——; columns 5
and 6, insert as a heading for the table at the bottom of the
page:
TABLE II
SOURCES AND PHYSICAL CHARACTERISTICS OF SOLVENT EXTRACTS
column 8, line 69, after "mixed" inser t —— with ——.
Signed and sealed this 3rd day of March 1964.
(SEAL)
Attest:
ERNEST w_ SWIDER
Attesting Officer
EDWIN L. REYNOLDS
AC ti ng Commissioner of Patents
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