U.S. patent number 3,873,454 [Application Number 05/453,609] was granted by the patent office on 1975-03-25 for lubricant composition.
This patent grant is currently assigned to Mobil Oil Corporation. Invention is credited to Andrew G. Horodysky, Henry Raich.
United States Patent |
3,873,454 |
Horodysky , et al. |
March 25, 1975 |
Lubricant composition
Abstract
Lubricant compositions containing in an amount sufficient to
impart antiwear and extreme pressure properties, a compound having
the structure: ##SPC1## This compound is particularly useful as an
extreme pressure additive in lubricant compositions.
Inventors: |
Horodysky; Andrew G. (Cherry
Hill, NJ), Raich; Henry (Cherry Hill, NJ) |
Assignee: |
Mobil Oil Corporation (New
York, NY)
|
Family
ID: |
23801270 |
Appl.
No.: |
05/453,609 |
Filed: |
March 22, 1974 |
Current U.S.
Class: |
508/144; 549/11;
508/300 |
Current CPC
Class: |
C10M
1/08 (20130101); C07D 341/00 (20130101); C10M
2219/102 (20130101); C10M 2209/104 (20130101); C10N
2040/241 (20200501); C10N 2040/22 (20130101); C10M
2229/05 (20130101); C10N 2050/10 (20130101); C10M
2207/282 (20130101); C10M 2217/042 (20130101); C10M
2211/02 (20130101); C10N 2040/245 (20200501); C10M
2227/081 (20130101); C10N 2010/02 (20130101); C10M
2205/028 (20130101); C10M 2207/281 (20130101); C10M
2209/00 (20130101); C10M 2207/34 (20130101); C10M
2219/104 (20130101); C10N 2040/242 (20200501); C10M
2207/04 (20130101); C10M 2217/043 (20130101); C10N
2040/20 (20130101); C10M 2215/102 (20130101); C10N
2010/04 (20130101); C10M 2219/106 (20130101); C10M
2209/02 (20130101); C10M 2207/125 (20130101); C10M
2205/00 (20130101); C10N 2040/24 (20130101); C10M
2209/105 (20130101); C10M 2207/122 (20130101); C10M
2207/121 (20130101); C10M 2207/283 (20130101); C10N
2040/244 (20200501); C10M 2219/082 (20130101); C10N
2040/243 (20200501); C10M 2201/02 (20130101); C10M
2211/08 (20130101); C10M 2219/10 (20130101); C10M
2227/02 (20130101); C10N 2040/247 (20200501); C10M
2209/10 (20130101); C10M 2223/045 (20130101); C10M
2207/286 (20130101); C10M 2229/02 (20130101); C10N
2040/246 (20200501); C10M 2205/026 (20130101); C10M
2201/062 (20130101); C10M 2201/103 (20130101); C10M
2227/04 (20130101) |
Current International
Class: |
C07D
341/00 (20060101); C10m 001/38 () |
Field of
Search: |
;252/27,40.7,45,48.8,49.5 ;260/327R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Cannon; W.
Attorney, Agent or Firm: Huggett; Charles A. Barclay;
Raymond W. Kaufman; Benjamin I.
Claims
We claim:
1. A lubricant composition containing lubricating amounts of a
member selected from the group consisting of mineral oil of
lubricating viscosity, synthetic lubricating oils, greases and
water emulsion lubricants based on said oils containing, in an
amount sufficient to impart antiwear and extreme pressure
properties, a compound having the structure: ##SPC3##
2. A composition as defined in claim 1 wherein said composition
comprises an oil of lubricating viscosity.
3. A composition as defined in claim 1 wherein said composition
comprises an oil of lubricating viscosity within the range of 45
SSU at 100.degree.F. to about 6000 SSU at 100.degree.F.
4. A composition as defined in claim 1 wherein said composition
comprises an oil of lubricating viscosity within the range of from
about 50 SSU at 210.degree.F. to about 250 SSU at 210.degree.F.
5. A composition as defined in claim 1 wherein said composition
comprises a grease.
6. A composition as defined in claim 1 wherein said composition
comprises a grease containing, in minor proportion, lithium
hydroxystearate as a thickening agent.
7. A composition as defined in claim 1 wherein said composition
comprises a grease containing, in minor proportion, a lithium
complex as a thickening agent.
8. A composition as defined in claim 1 wherein said composition
comprises a grease containing, in minor proportion, a calcium
complex as a thickening agent.
9. A composition as defined in claim 1 wherein said composition
comprises a grease containing, in minor proportion, a clay-based
thickening agent.
10. A composition as defined in claim 1 wherein said compound is
present in minor proportion.
11. A composition as defined in claim 1 wherein said compound is
present in an amount from about 0.1 to about 50 percent, by weight,
of the total weight of said composition.
12. A composition as defined in claim 1 wherein said compound is
present in an amount of from about 0.1 to about 10 percent, by
weight, of the total weight of said composition.
13. A composition as defined in claim 1 wherein said composition
contains a chlorinated paraffin in an amount sufficient to impart
additional extreme pressure properties.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to lubricant compositions and, in one of its
aspects, relates more particularly to lubricating compositions such
as lubricating oils and greases which exhibit insufficient antiwear
and extreme pressure properties, under conditions of use.
2. Description of the Prior Art
It is known that extreme pressure properties can be incorporated in
lubricant compositions such as liquid hydrocarbons and greases by
incorporating therein sulfurized olefins as extreme pressure
additives. Such additives are capable of imparting good extreme
pressure and antiwear properties, but they contain relatively high
corrosive sulfur contents, a deficiency which limits their use.
Absence of corrosive sulfur content would be desirable. In
additives of this type it is also highly desirable, from a
commercial standpoint, that they be odorless and colorless. These
latter characteristics have also been found lacking in present
commercial sulfurized extreme pressure additives.
SUMMARY OF THE INVENTION
It has now been found that improved antiwear and extreme pressure
properties can be imparted to lubricant compositions by
incorporating therein minor amounts of a relatively high
sulfur-content additive which, in addition, does not impart odor to
the lubricant and is also colorless. As more fully hereinafter
described, this novel extreme pressure additive is obtained by
reacting isobutylene and a sulfur halide to produce the
corresponding adduct; reacting the adduct thus produced with an
alkali metal mercaptide in a non-reactive liquid medium to obtain a
product comprising a compound having the structure: ##SPC2##
And separating the compound thus produced from the aforesaid
reaction mixture. The compound thus produced is found to have a
melting point of approximately 254.degree.C.
In general, the aforementioned reactions are conducted at ambient
temperature. In most operations the reactions are conducted at a
temperature from about 0.degree. to about 150.degree.C. and
preferably at a temperature from about 20.degree. to about
60.degree.C. Insofar as the production of the adduct is concerned,
sufficient sulfur halide is employed to react with all of the
isobutylene. In general, for most operations, isobutylene and the
sulfur halide are reacted in a mole ratio of from about 0.5:1 to
about 2.5:1 and preferably in a mole ratio of from about 1:1 to
about 2:1, by weight. Insofar as the reaction between the adduct
and the alkali metal mercaptide is concerned, sufficient alkali
metal mercaptide is employed to react with all of the adduct. In
general, for most operations, the adduct and the alkali metal
mercaptide are reacted in a mole ratio of from about 1:1 to about
1:5 and preferably in a mole ratio of from about 1:1 to about 1:2.5
by weight. Any sulfur monohalide may be employed for reaction with
isobutylene and may include sulfur monochloride, or a combination
of a sulfur dihalide and elemental sulfur to produce the
corresponding sulfur monohalide may also be employed as a reagent.
Any alkali metal mercaptide may be employed for reaction with the
adduct, as hereinbefore described, and may include sodium
mercaptide, potassium mercaptide, lithium mercaptide or calcium
mercaptide.
Any non-reactive liquid medium may be employed for carrying out the
reaction between the adduct and the alkali metal mercaptide and may
include lower alcohols such as methanol, ethanol, propanol or
butanol.
The resulting antiwear extreme pressure compound, suitable for use
as an extreme pressure lubricant additive is found to have a sulfur
content of about 50 percent, by weight, and is odorless and
colorless. This compound represents about 45 percent, by weight, of
the product resulting from the reaction of the aforementioned
adduct and the alkali metal mercaptide. The remaining portion of
the aforementioned product comprises about 55 percent, by weight, a
mixture of unsaturated sulfides and polysulfides.
Of particular significance, in accordance with the present
invention, is the ability to impart improved antiwear and extreme
pressure properties to lubricants comprising liquid hydrocarbon
oils in the form of either mineral oils or synthetic oils, or in
the form of a grease in which any of the aforementioned oils are
employed as a vehicle, in conjunction with a thickening agent. In
general, mineral oils employed as the lubricant or grease vehicle,
may be of any suitable lubricating viscosity range, as for example,
from about 45 SSU at 100.degree.F. to about 6000 SSU at
100.degree.F., and preferably from about 50 SSU at 210.degree.F. to
about 250 SSU at 210.degree.F. These oils may have viscosity
indices varying from below 0 to about 100 or higher. The average
molecular weights of these oils may range from about 250 to about
800. Where the lubricant is to be employed in the form of a grease,
the lubricating oil is generally employed in an amount sufficient
to balance the total grease composition after accounting for the
desired quantity of the thickening agent and other additive
components to be included in the grease formulation. In instances
where synthetic oils, or synthetic oils employed as the vehicle for
the grease, are desired in preferance to mineral oils or in
combinations therewith, various compounds of this type may be
successfully utilized. Typical synthetic vehicles include
polyisobutylene, polybutenes, hydrogenated polydecenes,
polypropylene glycol, polyethylene glycol, trimethylol propane
esters, neopentyl and pentaerythritol esters, di (2-ethylhexyl)
sebacate, di (2-ethyl hexyl) adipate, dibutyl phthalate,
fluorocarbons, silicate esters, silanes esters of
phosphorous-containing acids, liquid ureas, ferrocene derivatives,
hydrogenated mineral oils, chain-type polyphenyls, siloxanes and
silicones (polysiloxanes), alkyl-substituted diphenyl ethers
typified by a butyl-substituted bis (p-phenoxy phenyl) ether,
phenoxy phenylethers, etc.
With respect to imparting improved antiwear and extreme pressure
properties to greases, which contain the above-described novel
extreme pressure additives, any thickening agent normally employed
in grease formulations may be successfully utilized. Particularly
preferred are greases which contain in minor properties, such
conventional thickening agents as lithium hydroxystearate, lithium
complexes, calcium complexes, clay-based thickening agents,
polyurea based thickening agents and a wide variety of other
metallic soaps and thickeners normally employed in the
grease-making art. In addition, other additives, normally employed
for imparting extreme pressure properties may also be incorporated
in the novel greases and may therefore include such extreme
pressure additives as chlorinated paraffins,
phosphorous-containing, calcium carbonate, calcium acetate or zinc
phosphorodithioate-containing additives.
The following data and examples will serve to illustrate the marked
degree in antiwear and extreme pressure improvement imparted by the
novel additives of the present invention to lubricant compositions.
It will be understood, however, that it is not intended the
invention be limited to the particular lubricant compositions
disclosed nor the particular additive for imparting extreme
pressure properties. Various modifications thereof can be employed
and will be readily apparent to those skilled in the art.
EXAMPLE 1
Sulfur monochloride (1013g, 7.5 moles) was charged into a 3-L.
4-necked reaction flask equipped with a mechanical stirrer,
condenser (drying tube attached) a thermometer, and a sub-surface
gas sparger. While keeping the temperature between
45.degree.-50.degree.C., isobutylene was passed over 60g of
methanol into the reaction flask over an 8-hour period, during
which 716g (12.8 moles) of isobutylene was consumed. The reaction
mixture was then purged at 40.degree.C. with a stream of nitrogen
for 30 minutes and then filtered to yield 1579g of a light amber
liquid.
Sodium mercaptide, (1200g) and 1250 ml of ethanol were charged into
a 5-L. reaction flask fitted with a stirrer, condenser, (drying
tube attached) thermometer and an addition funnel. After stirring
to get a good dispersion of the solids, 620g of the above,
isobutylene-sulfur monochloride adduct was added rapidly and
carefully at first to attain a temperature of 45.degree.C. and then
dropwise from the addition funnel. The addition took about 2 hours.
By carefully regulating the addition, the temperature was kept at
close to 40.degree.C. and excessive foaming (H.sub.2 S evolution)
was avoided.
Following the aforementioned addition, the reaction mixture was
heated, while stirring at 45.degree.-50.degree.C. for an additional
3 hours. After cooling to room temperature, it was filtered, the
solids washed with hexane, with water and ether and a water
insoluble white solid product was collected. The filtrate was
allowed to stay overnight under house vacuum. The solid product
which precipitated from the filtrate was collected and washed
several times with water and ether and dried. The combined solids
were further purified by stirring vigorously in water and a little
ether, collected and dried to yield 250g of white solid product,
having a sulfur content of 53 percent. This product was found to
have the structure hereinbefore described.
An SAE 90 solvent-refined Mid-Continent oil having a pour point of
25.degree.F. was next subjected to the standard Four-Ball Wear
Tests for determining improvement in antiwear properties. This test
is described in U.S. Pat. No. 3,423, 316. In general, in this test,
three steel balls of 52100 steel are held fixed in a ball cup. The
test lubricant is added to the ball cup and acts as a lubricant. A
similar fourth ball positioned on a rotatable vertical spindle is
brought into contact with the three balls and is rotated against
them for a known time. The force with which the fourth ball is
pressed against the three stationary balls may be varied to give a
desired load. The temperature of the ball cup, stationary balls and
lubricant may be brought to a desired temperature and held constant
during the test. At the end of the test, the three stationary steel
balls are examined for wear-scar diameter. The extent of scarring
represents the antiwear effectiveness of the lubricant; the smaller
the wear scar at the same load, speed, temperature and time, the
more effective the antiwear characteristics of the lubricant. In
the data of Table I, are shown the results obtained in which the
aforementioned base stock oil was subjected to Four-Ball Wear
Tests.
TABLE I ______________________________________ 4-Ball Wear
Test-Scar Diameter (mm) 1/2" Balls, 52100 Steel, 60 Kg load, 1/2
hr. Lubricant: SAE 90 Base Oil Ex- Temp. Speed ample .degree.F. 500
RPM 1000 RPM 1500 RPM 2000 RPM
______________________________________ 2 Room 0.50 0.60 0.88 2.34 3
200 0.60 1.06 1.86 2.23 ______________________________________
The above-described product of Example I was next incorporated into
the base stock lubricating oil of Table I in a concentration of 0.5
percent, by weight, and then subjected to the aforementioned
Four-Ball Wear Tests. The results obtained are shown in the
following Table II.
TABLE II ______________________________________ 4-Ball Wear
Test-Scar Diameter (mm) 1/2" Balls, 52100 Steel, 60 Kg load, 1/2
hr. Lubricant: SAE 90 Base Oil + 0.5% (Wt.) of Product of Example I
Ex- Temp Speed ample .degree.F 500 RPM 1000 RPM 1500 RPM 2000 RPM
______________________________________ 4 Room 0.46 0.50 0.60 0.80 5
200 0.50 0.63 0.75 0.90 ______________________________________
It will be apparent from the comparative data of Tables I and II
that the novel sulfur compounds of the present invention are
markedly effective as antiwear additives in lubricating oils.
In another series of experimental runs, the high sulfur solid
compound of example 1 was blended into a series of grease
formulations and extreme pressure properties were measured by a
standard Four Ball EP test, ASTM D-2596 "Measurement of Extreme
Pressure Properties of Lubricating Greases (Four Ball Method)". The
comparative results obtained are shown in the following Table
III.
TABLE III
__________________________________________________________________________
Grease Characteristics Additive of Consistency Thermal Stability
4-Ball EP Test Base Grease Example I Change With at 300.degree.F.
Load Weld Ex. Thickener Fluid Wt. % Color Odor Additive Odor
Consistency Index, Load
__________________________________________________________________________
kg 6 Baragel Clay Synthetic 0 Cream None -- None No softening 32.9
160 Hydrocarbon 7 Baragel Clay do. 3.5 Cream None Slight None No
softening 82.3 500 Thickening 8 Baragel Clay do. 0.8 Cream None --
None No softening 52.5 315 9 Calcium Complex Paraffinic 3.5 Cream
None Slight None No softening 141.7 800 Thickening 10 Calcium
Complex do. 0.8 Cream None -- None No softening 75.2 500 11 Lithium
Hydroxystearate Naphthenic/ 4 Tan None Slight None No softening
48.6 315 Bright Stock Thickening 12 Lithium do. 1 Tan None Slight
None No softening 33.7 250 Hydroxystearate Thickening 13 Lithium
Complex do. 0 Tan None -- None No softening 24.3 160 14 Lithium
Complex do. 3.5 Tan None Slight None No softening 55.1 400
Thickening
__________________________________________________________________________
In Table III, the synthetic hydrocarbon fluid of examples 6, 7 and
8 comprised 89 percent of the base grease.
The Baragel clay thickener of examples 6, 7 and 8 comprised 11
percent of the base grease, by weight.
The paraffinic mineral oil fluid of examples 9 and 10 comprised 83
percent of the base grease, by weight.
The calcium complex thickener of examples 9 and 10 comprised 17
percent of the base grease, by weight.
The naphthenic bright stock mineral oil blend of examples 11 and 12
comprised 90 percent of the base grease, by weight.
The lithium hydroxystearate thickener of examples 11 and 12
comprised 10 percent of the base grease, by weight.
The naphthenic bright stock mineral oil fluid of examples 13 and 14
comprised 90 percent of the base grease, by weight.
The lithium complex thickener of examples 13 and 14 comprised 10
percent of the base grease, by weight.
It will be apparent, also, from the comparative data of Table III
that the aforementioned novel additives of the present invention,
are markedly effective extreme pressure agents in grease
formulations, as evidenced by imparting increased Load Wear Index
and Weld Load Values.
As previously indicated, other extreme-pressure additives may be
incorporated in the novel lubricant formulations such as
chlorine-containing, phosphorous-containing, calcium-carbonate or
calcium acetate containing additives, which may tend to enhance the
extreme pressure characteristics of the lubricant formulation.
Apart from the excellent extreme pressure properties exhibited in
grease formulations, it should also be noted that superior extreme
pressure characteristics may also be imparted in the use of the
aforementioned sulfur material as a dispersion or emulsion in
fluids, oils, synthetic hydrocarbon fluid, esters, fatty oils, and
water emulsion lubricants. The novel high sulfur solid extreme
pressure additive furthermore exhibits superior extreme pressure
characteristics when employed as a finely divided powdered, solid
lubricant and as part of a dry solid film lubricant. This additive
also imparts extreme pressure characteristics when used as a
dispersion or base in such media as cutting oils, metal processing
and metal-working oils and in related applications such as
extrusion compounds.
While this invention has been described with reference to preferred
compositions and components therefore, it will be understood by
those skilled in the art, that departure from the preferred
embodiments can be effectively made and are within the scope of the
specification.
* * * * *