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Патент USA US2411153

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Patented Nov. 19, l
‘
.
-
ash-.153
‘
2.4mm
_
MINERAL on. comosrrron AND
.
mnovmc AGENT
,
Everett W. Fuller and Henry G. Berger‘, Wood- '
bury, and Robert E. Williams, Merchantville, ‘
N. J., assignors to Socony-Vacuum Oil Com
pany, Incorporated, a corporation of New York _
No Drawing. Application February 29, 1944,
_.. . a
A
-
'
Serialflio. 524390
‘is Claims.
>
(01. eta-ism _
i
materials prepared under different conditions
and are superior to the'latter as petroleumv oil
This invention has to do with the stabilization
of petroleum products against the harmful effects
of oxidation and deterioration with use. More
speci?cally, it has to do with the improvement
additives.
.
.
'
As contemplated herein, both technically pure
5 ‘and commercial grades of oleyl alcohol may be
' or stabilization of mineral oil fractions, particu
larly viscous mineral oils, by the use of novel
reacted with P285 under the above-mentioned
reaction products, or a novel class of reaction »
reaction conditions in order to obtain‘ the desired
products, which ‘when’ admixed with a mineral
oil in minor proportions will prevent or delay un
products. Inasmuch as commercial oleyl alcohol
desirable'changes taking place in the oil. '
or "ocenol" is available in large quantities and is
ll
It is well known to those familiarwith the art
that substantiallvall of the various fractions ob
tained from mineral oils and re?ned for their
various uses are susceptible to oxidation.
relatively inexpensive it is‘ preferred herein.
‘It is well known that aliphatic alcohols will
react with P255 under moderatetemperature con
ditions to give products that consist principally of‘
the corresponding dialkyl dithiophosphoric acids.
This
susceptibility of an oil fraction to oxidation and 15 In the 'case of, oleyl alcohol this reaction may be‘
‘the manner in which oxidation manifests itself ,
ywithln the oil- varies with the type and degree of
re?nement to which the oil has been subjected .
expressed by the following equation:
4C1BH35OH+P2S5"2(C18H350)PSSH-I-HZS
The sulfur and phosphorus analysis and the acid
and with the conditions under which the oil is
used or tested. In other words, the deleterious ’20'ity (N. N. value) of the products thus formed at
50-60° 0. check fairly well with the above formula.
products formed in an oil fraction as a result of
oxidation and the degree to which they are - The dialkyl dithiophosphates have been proposed
'as addition agents for petrolum oils. However,
' .formed depends upon the extent to which the
the products prepared by reacting oleyl alcohol '
various unstable constituents, whichmay act as
oxidation catalysts, have been removed by re?n ‘25 and P285 in this way are not entirely satisfactory
for this purpose becausev of their high acidity,
ing operations, and also upon, the ‘conditions of‘
use.
- their tendency to evolve H2S, their corrosive action ‘
In recent‘y'ears a great many materials con- . with copper, and their general instability when
used in petroleum oils. ,
taining one or more characterizing chemical ele
ments have. been proposed for use as forti‘fying so Also when oleyl alcohol and P285 are reacted
at somewhat higher temperatures, that is at
crstabilizing agents for petroleum products. Ma- _
about 100° 0;, products of a somewhat'lower
acidity are obtained-although this value is still
higher than is desirable for materials that are
ments, have been credited with improving
petroleum products in certain respects. For ex 35 to be added to. petroleum oils. The stabilityof
these products prepared at about 100° C. is also
ample, various phosphorus- and sulfur-contain
terials containing sulfur, phosphorus, halogen or
metals, or combinations of one or more such ele- ’
ing'materials such as reaction products of various
organic substancesand the several phosphorus
» unsatisfactory.
We have found, however, that when‘ the above
reaction is carried out at temperatures from
> This invention relates to phosphorus- and sul 40 about 125° C. to about 150° C. the products are
much less acidic in character and are substan
fur-containing reaction . products possessed of
tially more stable than’ those described above.
the capacity to eil‘ect' improvement ofmineral oil
Although the acidity is much‘lower, these prod.
fractions. More’ speci?cally, the present inven
ucts have approximately the sameI phosphorus
‘ tion is predicated upon the discovery of an out- ’
standing and novel group of oil-soluble, phos to and sulfur contents as the dioleyl dithiophos
sul?des have been proposed for this purpose‘.
,
phorus- and sulfur-containing reaction products
phoric acids prepared at lower temperatures.
obtained by reaction of substantially one mol of
P285 and four mols of oleyl alcohol at a tempera
ture between about 125° C. and about 150° C., and
Using an oleyl alcohol with a bromine number of
43 a reaction product was obtained‘at 95° C. with
‘ preferably at about 150° C.
a bromine number of 39.6, which" checks fairly
so well with a calculated value of 38 for a dioleyl
These reaction products are particularlyv e?ec
dithiophosphoric ‘acid prepared from this oleyl
tive as additives for mineral oils. They are char-
alcohol. When this same oleyl alcohol was re
acted with P285 at 150° C6, the resulting, product
acterized by relatively low acidity. and high de
gree of heat stability. They are different in
had a bromine number of only 19.4. The above
chemical and physical properties from related 55 properties together‘with an increase in viscosity
2,411,153
.4.
A
for the material made at 125° to 150° 0. indicate
only to related products prepared at lower and
a difference in chemical structure for these new
at higher temperatures from these same react
ants but they are also superior to‘corresponding
products prepared from the long chain saturated
alcohols and P2Ss at temperatures within the
reaction products.
-
We have also found that when oleyl alcohol
' and PzS5 are reacted at temperatures much above
150° 0., further less desirable changes take- place.
range of 125-150° C. ' Thus the reaction products -
At‘ higher temperatures the product becomes‘ .
of one mol of Past with four mols of such alco
hols as stearyl alcohol and lauryl alcohol at 150°
C. are highly acidic in nature when heated for
the time speci?ed for preparing our oleyl alco
h01-P2S5 products, and if heated for a prolonged
cloudy and an insoluble sludge separates which
7‘ may contain a considerable proportion of the
phosphorus present. ‘The solubility of the reac
tion products in petroleum oils becomes less,and
in general these materials are not as satisfac
period of time decomposition sets in accompanied
tory as those prepared at_125° to '150" C. .
by the formation of insoluble sludge and an ap
preciable loss of phosphorus and sulfur. This is
,
Two other factors in?uence the quality of the
reaction product prepared at 125° to,150° C. In 15 illustrated by the results shown in Table 11. The I
products were prepared by reacting one mol of
the ?rst place, the time of reaction is important.
PzS5 with four mols of the alcohol at 150° C, for
This should be long enough to permit complete
the time indicated and then ?ltering the reaction
reaction to take place between the oleyl alcohol
mixtures through clay.
'
and the P285 and to give a product with a maxi
mum acidity (N. N. value) of about 25. How 20
Table II
_
'
ever, too long heating will result in a cloudy prod
uct or even in the deposition of an insoluble
Alcohol Time Page“ Persw‘t N. N.
sludge containing a part of the phosphorus. The
reactants should not be heated beyond the time
of incipient clouding to, obtain the most satis 25 Oleyl. _ _
2
4. 54
9.8
15
Stearyl
2
5. 55
9. 7
67
factory products. We have found that 6 hours
Do. __
6 __________________ __
49
heating at 125° C. or 2 hours heating at 150° C.,
Do __
9
2. 76
9. 4
l0
Lauryl.
3
6. 69
12. 95
91
with the quantities used in the examples pro
Do. __
7
4. 54
10.4
' l9
vided hereinbelow, gives satisfactory results. In
general, then, the reaction time may be described
as a "relatively short time.” Another factor that
should be controlled is the molar ratio of the
oleyl alcohol and the Pass. ‘We have found that
the phosphorus and sulfur containing reaction
Products prepared from substantially one mol of
P285 and four mols of oleyl alcohol, or ocenol,
are best suited for use in mineral oils. However,
» this ratio may be varied slightly without detract
Remarks
Clear product.
Do.
'
Slightly cloudy.
Resinous deposit.
Clear product.
Resinous deposit.
To summarize the above statements, we have
found that by reacting approximately one mol of
P285v with four mols of oleyl alcohol for a few
hours at temperatures from about 125° C. to about
150° C. products are formed which are exception
ably suitable as »mineral oil additives. These
" products are superior to those obtained by re
acting the same ingredients at lower or at higher
temperatures and in different mol ratios, and are _
ing from the value of the ?nal products. In gen
also superior to the reaction products of other
40
,eral, a molar excess of P285 not greater than
long chain alkyl alcohols with P285 under the
about 25 per cent of the 1 to 4 ratio may be used.
' same conditions of temperature, time and molar >
When too large an excess of P285 is used, the re
ratio.
‘action products are undesirable. For example
The effectiveness of the novel reaction products
when PzSsv and oleyl alcoho1 were reacted in a
contemplated herein in mineral oils is demon
molar ratio of 1 t0 2 at 125° to 150° C. semi-‘Solid. ‘15
mixtures having little oil solubility were obtained,
Experimental data is presented in Table I be
strated by the following test results.
Corrosion inhibition
low. to’ illustrate some of the statements made
Motor oils, especially those refinedv by certain
above. The various products shown therein were
solvent-extraction methods, tend to oxidize when
prepared by reacting substantially one mol of 50 submitted to high temperatures and to form
P255 and four mols of ocenol with stirring at the _
products that are corrosive to‘ metal bearings,
. indicated temperatures. The reaction mixtures .
such as those having the corrosion-susceptibility
thus obtained were then ?ltered through clay.
of cadmium-silver alloys; ‘and may cause their
As defined in Table I, a stable product is one
failure within a comparatively short time. The
which, when used as a 1 per cent solution in oil, 55 following test was used to determine the corrosive
does not evolve H28, corrode copper, or form a
action ofv motor oil on an automobile connecting
cloud in the oil when heated for 24 hours at
rod bearing. .
.
100° c. .
The oil used consisted of Pennsylvania neutral
Table I
and residuum stocks separately re?ned by means
60of chlorex and then blended to give an S. A. E. 20
Composition of
motor oil with a speci?c gravity of 0.872, a ?ash
Reaction
product
’
Appear‘
Temp
Time
'
Per-
Pen
cent
cent
P
S
an”
Stabilit Y
point of 435° F., and a Saybolt universal viscosity
of 318 seconds at 100° F. The oil was tested by
adding a section of a bearing containing a cad
a mium-silver
alloy surface, weighing about 6
N.N.
grams, and heating it to 175° C. for 22 hours
60-60
4.81
10.2
95
125
150
6
2% 4.68
6
4.64
.2
4.54
9.9
9.8
9.8
78
Clear ____ ._
Unstable.
150
5
3.72
9.9
8
Cloud _.-_ Fairly stable.
175
2
3.22
10.1
4
Precip tate
53 _..__do.___.
Do.
21 ..___do_____ Stable.
15 __.._do.__._
Do.
Do.
while a stream of air was bubbled against the
surface of the bearing. The loss'inweight of
the bearing during this treatment measures-the
70 amount of corrosion that has taken place. A
sample of the oil containing a stabilizing agent
was run at the same time as a sample of the
straight oil, and the loss inpweight of the bearing
‘The reaction products of oleyl‘ alcohol and
section in the inhibited oil can thus be compared
P185 prepared at 125° to 150° C. are superior not 75 directly with the loss of the ‘section in the un
9,411,153
inhibited oil. The results . obtained in thistest
are set forth in Table III below.
‘me use. The great e?e
_ rials is demonstrated by the small amounts nec
essary to stabilize mineral oils. They may be
Table in '
used in varying concentrations as upto about 5
per cent depending upon the type of oil, the con
ditions under which the blend is to be used, etc.
l
Mgms. loss
in weight
Per
cent
conc
Reaction product
‘In general, however, concentrations from about
None- -
_
.
Oley] alcohol-P181 at 150°C. for 2 hours.._.
' V2 per cent to about 2 per cent of these reaction
25
0. 10 ,
.5
products will be sumcient to eii‘ect substantial
10 improvement of the oil.
These new reaction
products may be used either in straight mineral
oils or in oils containing additives that have been
Lauson engine test
To ‘further demonstrate the e?'ectiveness of the
reaction products contemplated herein as mineral
oil addition agents a blank oil and a blend of the
231 gngaaég?m?giizc?gt. mg:‘1:121:iigts‘lbjs‘aifgg
added for other purposes, .such as detergents, pour .
point depressant, viscosity index improvers, etc.; .
15 in which case, these serve to stabilize the result
ing blends without detracting fromlthe e?ective
cylinder Lauson engine was run with an on tem-
, ness of one or more of the said additives.
_ .
perature‘ of 2906-11.. and a Jacket ‘temperature
.It is apparent from the foregoing that the reof 212° F. The oil used was an s. A. E. 10 motor
“@1311 Pmducts Prelim‘! at temperatures from '
oil solvent re?ned. The neutralization number 20 125 C' to about 150 C- are “nuke those previ'
(N. N.) and viscosity in centistokes at 210° F.
ously known in the art- Therefore, they are con
of the oil and oil blend were determined after 36,
templated herein as new °°mp°§m°ns of matter‘
mum The results are set forth in Table Iv
It is to be understood that while we have here
belom
,
-
inabove described certain typical procedures for -
Table IV
_
' Reaction product
‘ Nn‘nn
'
Olgyl alcohol-Past at 150° 0. for 2
"u""""""""""
.
"""" "
-
25 makingthe novel phosphorus- and sulfur-con
taining reaction. products contemplated herein,
Per 0km
K v @
com
gio°']_r_
N- N~
_
5.1
I0
10
‘
and have referred to certain‘ speci?c reaction
products and speci?c mineral oils the invention
is not limited to these speci?c features ‘but in-'
1.45 30 chides variations which will be apparent to-those
a. 04
skilled in the art and which come within the scope
'
of the appended claims.
_
We
Rina sticking and, sludge inhibition -
' .
'
claim:
1. An improved mineral oil composition com; I
' That the reaction, products contemplated here- 35 prising a viscous mineral oil and in admixture
in are particularly e?ective in decreasing the
therewith-a minor proportion, from about 0.1 per
tendency of petroleum lubricating oils to cause
‘ cent to about 5 per cent, of an oil-soluble, phos
ring-sticking and sludge deposition during the
phorus- and sulfur-containing reaction product
operation of internal combustion engines is
' obtained by reaction of substantially one mol of
demonstrated by the results given below in Table 40 phosphorus pentasul?de and four mols of oleyl
V._ This is clearly shown by results of the follow. ing test whichinvolves the operation of a single
cylinder 0. F. R. engine at a speed of 1200 R. P. M.
over a time‘interval of 28 hours. The tempera-
alcohol at Ya ‘temperature from about 125° C.- to
about 150° C., the reaction time-reaction tem
perature relationship being so maintained that
the acidity of said reaction product is not greater
ture of the cooling medium of the engine was 45 than about 25.
held‘at approximately 370° F., and the oil tem- '
A
,
2. An improved mineral oil composition com
perature was held at 175° F. during the test.
prising a viscous mineral oil and in admixture
The oil used was a lubricating-oil stock of 120
, therewith a minor proportion, from about 0.1 per
seconds Saybolt Universal viscosity at 210° F.,
cent to about 5 per cent, of an oil-soluble, phos
and the conditions observed at the end of the 50 phorus- and sulfur-containing reaction product
test were: (a) the exténttowhich the piston rings
obtained by reaction of substantially one mol of
were stuck, (b) the extent to which the slots in
phosphorus pentasul?de and four mols of oleyl
the oil rings were ?lled with‘ carbonaceous de-
alcohol at 150° C. for about two hours.
posits in the oil, (0) the deposits formed on the
3. An improved mineral oil composition com
piston, and (d) the acidity or neutralization num~ 55 prising a viscous mineral oil and in admixture.
ber (N. N.) of the oil. The results thus obtained _ therewith a minor proportion, from about 0.1 per
for the blank oil and a representative blend of
cent to about 5 per cent,’ of an oil-soluble, phos
the oil and a typical reaction product are set forth
phorus- and sulfur-containing reaction. product
in Table V below:
,
obtained by. reaction of substantially one mol of
Table V
'
'
Ring condition degrees
Per
Reaction product
-
NW
stuck
Slots
cent
-
Oieyl alcohol-PIS; product at 150° C.i'or2hours|_.. 1.0
1'
.
ed
cent
‘
Deposits N. N.
l
2
s
4
a
a
4
6
zoo
360
sec
360
sec
70
90
so
14.9
2.0
0
0
0
0
0
0
,0
4.5
1.1
0 _
The results given in the foregoing tables (III ‘I0 phosphorus pentasul?de and four mols of oleyl
through V) indicate that the novel reaction prod
alcohol at a temperature from about 125° C. to
ucts contemplated herein prevent thecorrosion
of hard metal bearings-inhibit the development
of acids, prevent the increase’ in viscosity and.‘
about 150° 0., the reaction time-reaction tem
perature relationship beingv so maintained as to
minimize cloud formation in said reaction prod
iormation of gummingideposits in engines mm 75, uct.
2,411,158
6. As a new composition of matter, an ~oil-sol
4. As a new composition of matter, an oil-sol
uble, phosphorus- and sulfur-containing reaction
uble, phosphorus- and sulfur-containing reaction
‘product obtained by reaction of substantially one
product obtained by reaction of substantially one
mol of phosphorus pentasul?de and four mols
of oleyl alcohol at a temperature from about 125°
mol of phosphorus pentasuliide and four mols of
oleyl alcohol at a temperature from about 125° C.
to about 150° CL, the reaction time-reaction tem
perature relationship being so maintained as to
minimize cloud formation in said reaction
C. to about 150° 0., the reaction time-reaction
temperature relationship being so maintained
that the acidity of said reaction product is not
greater than about 25.
,
5. As anew composition oi‘ matter, an oil-sol
uble, phosphorus- and sulfur-containingreaction
product obtained by reaction of substantially one
mol of phosphorus pentasul?de and ~four mols of
oleyl alcohol at 150° C. for about two hours.
product.
10
-
EVERE'I'I' W. FULLER.
HENRYG. BERGER.
ROBERT H. WILLIAMS. »
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