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Патент USA US3065184

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tice
latent
3,065,178
Patented Nov. 26, 1962
1
2
3,065,178
LUBRIQATIN OHL COMPOSITION
Roland C. Nunn, Grinds, Calif, and Harold Martin
Brewster, Linden, N.J., assignors to Esso Research and
Engineering Company, a corporation of Delaware
No Drawing. Filed Dec. 21, 1959, Ser. No. 860,634
1 Claim. (Cl. 252-334)
and 2,4,6 tri-tertiary butyl phenol. ‘The alkyl groups of
the orthoalkylated phenol will preferably contain about -1
to 6 carbon atoms. The 4,4’-methylene bis-(2,6 di-tertiary
butyl phenol) is particularly preferred in the preparation
of the lubricating oil compositions of this invention.
Phenyl-alpha-naphthylamine is well known in the prior
art and has been used in various lubricating oil com
positions as an anti-oxidant. Phenyl-alpha-naphthylamiue
and its preparation are disclosed in U.S. Patent 1,988,299.
This invention relates to an improved lubricating oil.
More, particularly, the present invention relates to a lubri 10
The magnesium sulfonates useful in the present inven
cating oil composition of improved stability which com
tion will be highly basic and have a total base number in
prises a major proportion of a lubricating oil, and syn
‘the range of 100 to 400. The total base number is ab
ergistic amounts of a compound selected from the group
breviated TBN and is determined by standard poten
consisting of orthoalkylated phenols and phenyl-alpha
tiometric methods in accordance with ASTM D-664 test
naphthylamines in combination with highly basic mag 15 procedure. These highly basic magnesium sulfonates are
nesium sulfonates.
available commercially and are known as Bryton 7560—B,
It has now been found and this ?nding forms the basis
9076-A, 9199-A, 9200-A, etc. This type of highly
of the present invention, that the use of highly basic mag
basic magnesium sulfonate is normally prepared by treat—
nesium sulfonates in combination With an orthoalkylated
ing a conventional magnesium sulfonate with magnesia
phenol or a phenyl-alpha-naphthylamine ‘in lubricating 20 and carbon ‘dioxide.
oils imparts surprising and unexpectedly improved oxida
The ?nished lubricating oil composition will contain in
tion stability to the lubricating oil fraction.
the range of 80 to 98 vol. percent of the lubricating oil
The lubricating oil compositions of the present inven
fraction, 2 to 20 vol. percent of the highly basic mag
tion are extremely useful as lubricants for internal com
nesium sulfonate and 0.2 to 1.0 wt. percent, based on the
bustion engines because of their outstanding oxidation sta 25 total weight of the above composition, of an ortl1o~
bility at high temperatures. While the lubricants of this
alkylated phenol or phenyl-alpha-naphthylamine.
invention may be used to lubricate any type of internal‘
Other additives such as polymeric viscosity index im
combustion engine they are particularly important as
provers, pour point depressants, and anti-foaming amounts
crankcase lubricants for railway diesel locomotives since
of silicone ?uids may be added if desired.
this particular type of diesel engine is designed to oper
EXAMPLE I
ate at rather high temperatures, especially under high
load conditions.
In order to further illustrate the present invention, a
The lubricating oil fraction employed in the practice
number of compositions were made up in accordance with
of the present invention will preferably be a mineral
the present invention in which synergistic amounts of the
lubricating oil of coastal or Mid-Continent origin. For
orthoalkylated phenol and phenyl-alpha-naphthylamines
example, the mineral lubricating oil base stock may be
were combined with the highly basic magnesium sulfo
derived from Gulf Coastal, Panhandle, Pennsylvania, or
nates. 'These compositions were compared with other
California type crude oil. The lubricating oil fraction
compositions employing the orthoalkylated phenol and
will preferably have a viscosity index in the range of
phenyl-alpha-naphthylamine in combination with various
50400 and a viscosity at 100° F. in the range of 800—
alkaline earth metal sulfonates.
1200 SSU. While the lubricating oil fraction is prefer
Table 1 illustrates the various sulfonates, A through E,
ably a mineral lubricating oil, other lubricating oils may
'used in the preparation of the lubricating oil compositions
be employed in the composition of the present invention.
of this invention and the sulfonates, F through I, used in
Thus, lubricating oils produced synthetically by polymer
the comparative formulations. The highly basic mag
izing ole?ns and/ or esters to oils of the proper molecular
nesium sulfonates of this invention were purchased from
weight and having the lubricating oil characteristics and
Bryton and the highly basic calcium sulfonates were pur
viscosity ranges indicated may be used.
chased from Lubrizol Corp.
Table I
RAILROAD DIESEL LUBRICANTS-HIGH ALKALINITY SULFONATES
Over- 'I‘ype-
Percent Percent Percent Percent
based 1 TBN 2
CO3
Ash 8
Ca
Mg
with
Sultonate of invention:
Mg sullonate 4 (30%) ______ ._
Mg
Mg sulfonate 4 (30%).Mg sulfonate 4 (30%).-
Mg
Mg
Mg sulfonate 4 (30%)"
_ Mg
Mg sulfonate 4 (30%) ______ __
Mg
Ca sultonate (45%) ________________ -l
_
Ca sulfonate (45%).-.-
-
Ca
Ca sulfouate 4 (45%) _______ __ Mg
Ca. sulfonate 5 (45%) ....... ._
0a
10. 4
2.9
______ -_
127
29
6.2
21.5
6.2
______ __
75
______ _-
3.3
14
1. 7
1. 7
275
1 By adding excess Ca or Mg oxide and treating with C02.
2 Total vase number (ASTM D-664).
B Sulfated.
4 These Ca and Mg sultonates were purchased from Bryton.
_
6 This Ca sulfonate was purchased from Lubrizol Corp. as Lubrizol 56.
The orthoalkylated phenol is preferably an orthoalkyl
Table II shows the actual formulation and results ob
ated phenol such as 2,6 di-tertiary-butyl phenol, 2,6 di 70 tained in the E.R.E. stability test as well as the wear char
tertiary-Z-dimethylamine para-cresol, 4,4’-methylene bis
acteristics obtained in the three disc silver wear test for
(2,6 di-tertiary butyl phenol), ortho-tertiary butyl phenol,
the lubricating oil formulations containing the magnesium
3,0§5,178
sulfonate-phenol combination of this invention. Table II
Large increases in torque indicate severe Wear while small
also illustrates the improved results obtained with magincreases in the torque readings indicate slight Wear.
nesium sulfonates over both neutral and high alkalinity
All the lubricants of this invention and the compara
oalcium sulfonates.
tive formulations were prepared with a hydro?ned, phenol
The several blends were subjected to an E.R.E. stabil- 5 extracted coastal distillate (boiling between 340° and
ity test which comprises heating the lubricant to 340° F.
700° F. at 10 mm. mercury pressure), having a viscosity
in the presence of a Cu-Pb bearing and a silver strip and
index of 63, as the lubricating oil fraction. The formu
measuring the viscosity increase in terms of Sayboit seclations were prepared by simple admixture of the additives
onds Universal after 19 and 23 hours. This test is used
with the above lubricating oil base.
Table II
OXIDATION STABILITY AND SILVER LUBRIOI’I‘Y
Lubricant composition ‘
ERE stability test
Vis.
SSU
Phenol 2, at 100°
weight
F.
Sulfonate
Vol.
Vis. inc. SSU/
Cu-Pb bearing
Three disc
100° F. at-
weight loss in
mg. at-
silver wear
test rating
percent
Type a percent
19 hrs.
23 hrs.
19 hrs. 23 hrs.
Lubricants of invention:
.\ V
A
A
5.0
10.0
0. a
0. 8
39
25
50
33
0
0
1
1
A
A
5.0
10.0
0. 2
0.2
34
26
55
35
3
1
8
2
Good-fair.
Good.
B
5.0
0.8
24
55
2
4
Fair.
B
B
0
0
0
0. 8
0. 8
0. 8
0. 8
0.8
0.8
0. 8
28
45
20
35
30
52
89
24
44
39
2
4
0
0
0
4
5
0
0
0
Do.
Do.
Good.
Do.
Do.
D
D
10.0
15.0
5.0
10.0
15.0
5.0
10.0
28
20
33
25
0
0
1
0
Fair.
Good.
D
15.0
0.8 ...... __
21
2e
0
0
F
5.0
0.8
75
250
G
G
H
H
I
5.0
10.0
5.0
10.0
10.0
0. 8
0. 8
0. 8
0.8
0.8
______ __
1,170
1,177
1,172
1,189
929
352
97
520
473
51
______________ __
993
296
839
947
194'
31
5
145
71
0
127
9
303
181
0
Fair-poor.
Excellent
Poor.
Very poor.
Good.
Poor.
Good.
1 Base stock——-63VI undewaxed, severely hydro?ned and phenol extracted coastal distillate.
1 The phenol is 4,4’-1nethylene bis-(2,6 (ii-tertiary butyl phenol).
3 Relates to designation given in Table I above.
to determine the stability of the lubricant to oxidation as
shown by the viscosity increase as well as the lubricant’s
Table III shows the synergistic oxidation stability ob
tained by the combination of sulfonates with an orthoal
corrosiveness to silver-steel and copper-lead bearings.
kylated phenol and particularly the unexpected improve
The three disc silver wear test is a laboratory test develment in oxidation stability obtained when the sulfonate is
oped to measure the silver wear prevention characteristics 45 a highly basic magnesium sulfonate, as illustrated by
of railroad diesel lubricants when silver is used as a bearlubricants 28 through 30.
Table III
Lubricant composition 1
Lubricant
Sull'onate
Type 3
ERE lubricating stability
test (23 hrs. at 340811.)
Vis. SSU
Phenol 3, at 100°F. Vis. inc.
weight
percent
SSU at
100° F
Vol.
Cu-Pb
Silver
Three disc
silver wear
bearing weight test rating
weight lossinmg.
lossin mg.
percent
5. 0
7.5
10. 0
0. 0
0. 0
5. 0
7.5
0.0
0.0
0. 0
0. 8
0. 25
0. 2
0. 2
920
955
995
1,151
709
931
955
1, 004
1,371
1, 055
318
313
55
7a
10. 0
0. 2
1, 004
36
189
200
110
156
144
8
1
0 5
0 5
0. 5
1. 5
a. 9
0 2
0. 4
Good.
Do.
Do.
Do.
2 ........ -_
1 Base stock-68 VI undewaxed. severely hydro?ned and phenol extracted coastal distillate.
? The phenol is 4,4'-methylene bis-(2,6 (ii-tertiary butyl phenol).
3 Relates to designation given in Table I above.
ing surface for steel. The results obtained in this test
Table IV illustrates the overall performance in aChev
are important since about 65% of all railway diesel
rolet L-4 engine test of a lubricating oil composition of
engines use a silver-on-steel surfaced bearing. The test 70 this invention as compared with similar experimental and
consists of rotating a steel ball at 600 r.p.m. on three stacommercial lubricating oil compositions. Lubricant “32”
tionaryl silver discs under a constantly applied load of 10
of Table IV is representative of the lubricating oil com
kg..in-the presence of the test lubricant at 150° C. Torque
positions of this invention while lubricants 33, 34 and 35
is measured after one minute of operation and every two
represent comparative compositions.
minutes thereafter, up to a total test time of 15 minutes. 75
The Chevrolet L-4 engine test is well known in the
‘
11 '
-
3,065,178
art and uses a standard 6~cylinder Chevrolet engine ?tted
with copper-lead bearings. Here the engine was run con
obtained in Table III ‘for the phenol-magnesium sulfo
mates of this invention.
Table V
Base Stock 1 plus
Phenyl-
Mg sulionate, vol.
alphanaph-
percent
thylarnine,
weight
percent
0.0
2 5.0
2 10.0
3 5.0
3 10.0
3 15. 0
ERE lubricant stability test
Viscosity
SSU at
100° F.
Viscosity Increase,
SSU at 100° F. at—19 hrs.
23 hrs.
Bearing
Silver
weight
loss at 23
weight
change at 23
hrs., mg.
hrs., mg.
0. 5
0.0
0.0
0. 4
0. 4
0. 4
021
920
995
917
933
946
525
765
769
73
63
71
800
1, 004
1, 066
88
74
84
279
189
110
6
1
0
——l. 6
-—0. 5
——0. 6
0.0
0.0
—0. 1
0. 4
901
800
1, 103
67
0.0
Ca sulfonate 4
vol. percent
10.0
1 63 V .I. undewaxed, severely hydro?ned and phenol extracted coastal distillate having a
viscosity at 210° F. of 60-80 SSU
2 TBN (D-664) =375.
3 TBN (D4564) =300.
4 'I‘BN (D-664) =275 (purchased as Lubrizol 56).
tinuously for 36 hours after which time the piston deposits
In summary, Table I characterizes the highly basic
and weight loss of the Cu-Pb hearings were measured and
magnesium sulfonates of this invention. Tables 11
an inspection of the used lubricant was made. The Chev
through IV illustrate the surprising oxidation stability
rolet L-4 engine test is important since it gives a good in 30 and wear resistance obtained by the combination of these
dication of the oil’s oxidation stability under actual operat
highly basic magnesium sulfonates with an orthoalkyl
ing conditions.
ate-d phenol in a lubricating oil fraction. Table V
shows that phenol-alpha-naphthylamine will also impart
an unexpectedly high oxidation stability to the lubricat
Table IV
35 ing oil fraction when combined with the highly basic
magnesium sulfonatcs of this invention.
CHEVROLET L-4 EVALUATION
Tables 11 and V are of particular importance since
they show advantage for magnesium sulfonates over cal
Piston deposit 2 merit
rating
Lubricant
Cu-Pb l
Vls. inc.
BWL, mg.
SSU/
Overall
Piston
skirt
100° F.
cium sulfonates in the same base number range. They
40 also show that a total base number in the range of 100
to 400 and preferably in the range of about 150 to 300
is preferred.
60
120
22
97. 3
96. 5
97. 3
96.
93. 9
97.
9
197
85
What is claimed is:
A lubricating oil composition consisting essentially of
45 a hydro?ned and phenol extracted mineral lubricating
oil having a viscosity index of about 50 to about 100,
and a synergistic combination with regard to oxidation
(cicmpl%te1y covered with deposits and 100 being completely free of
inhibition of about 5 to 10 volume percent of a 30 wt.
eposi s.
I Same as lubricant 2 of Table II.
percent concentrate in mineral oil of a high basic mag
I 93.75 vol. percent of base stock of Table II, 2.25 v01. percent of Ca-Ba
nonyl phenol sul?de, 4.0 vol. percent of sulfonate F of Table I and 0.4 50 nesium sulfonate having a total base number about 375,
I Represents the weight loss in mg. of the copper-lead bearing.
1 Represents piston cleanliness based on visnalrating of0 to 100, 0 beingr
weight percent phcnyl-alpha-naphthylamine.
and about 0.2 wt. percent of 4.4'-methylene bis-(2,6 di
5 95.0 vol. percent of same base stock 0! Table II but 5.0 vol. percent
tertiary butyl phenol).
of sulfonate F of Table I and 0.8 weight percent of 4,4’ methylene bis
(2,6 di-tertiary butyl phenol).
55
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,629,693
The fact that synergistically improved oxidation stabil
2,695,273
ity can be obtained by combining the highly basic mag
2,807,653
nesium sulfonates of this invention with phenyl-alpha
2,856,359
naphthylamine is shown in the following table. The im 60 2,895,913
proved oxidation stability obtained with the phenyl-alpha~
naphthylamine-magnesium sulfonate combination is com_
parable with the unexpected and surprising improvement
454,227
Barton et al ___________ __ Feb. 24, 1953
Hook et al ___________ __ Nov. 23, 1954
Filbey et al _______ __‘____ Sept. 24, 1957
Schlicht _____________ __ Oct. 14, 1958
Carlyle a a1. _________ __ July 21, 1959
FOREIGN PATENTS
Canada ______________ __ Jan. 18, 1949
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