U.S. patent application number 10/428194 was filed with the patent office on 2004-11-04 for low sulfur, low ash, low and phosphorus lubricant additive package using overbased calcium oleate.
Invention is credited to Esche, Carl K..
Application Number | 20040220059 10/428194 |
Document ID | / |
Family ID | 33097915 |
Filed Date | 2004-11-04 |
United States Patent
Application |
20040220059 |
Kind Code |
A1 |
Esche, Carl K. |
November 4, 2004 |
Low sulfur, low ash, low and phosphorus lubricant additive package
using overbased calcium oleate
Abstract
The present invention provides a low sulfur, low ash, and low
phosphorus oil soluble lubricant additive package comprising an
overbased metal carboxylate. Also included in the present invention
are lubricating oils comprising the inventive oil soluble lubricant
additive package, as well as machines lubricated by such oils.
Several methods for lubricating machinery are also disclosed.
Inventors: |
Esche, Carl K.; (Richmond,
VA) |
Correspondence
Address: |
Ethyl Corporation
330 South Fourth Street
Richmond
VA
23219
US
|
Family ID: |
33097915 |
Appl. No.: |
10/428194 |
Filed: |
May 1, 2003 |
Current U.S.
Class: |
508/291 ;
508/175; 508/460 |
Current CPC
Class: |
C10N 2030/42 20200501;
C10M 2219/046 20130101; C10M 163/00 20130101; C10M 2219/088
20130101; C10N 2030/43 20200501; C10N 2040/04 20130101; C10M
2215/064 20130101; C10N 2040/252 20200501; C10M 2207/027 20130101;
C10M 2219/087 20130101; C10N 2030/04 20130101; C10N 2030/45
20200501; C10N 2040/044 20200501; C10M 2207/262 20130101; C10M
2207/26 20130101; C10N 2040/042 20200501; C10N 2040/25 20130101;
C10M 2217/043 20130101; C10M 2219/022 20130101; C10M 2219/044
20130101; C10M 2223/045 20130101; C10M 2207/028 20130101; C10M
2219/089 20130101; C10N 2010/04 20130101; C10M 2207/026 20130101;
C10M 2215/28 20130101; C10N 2040/12 20130101 |
Class at
Publication: |
508/291 ;
508/460; 508/175 |
International
Class: |
C10M 163/00 |
Claims
What is claimed is:
1. An oil soluble lubricant additive package comprising: at least
one overbased metal carboxylate having a total base number of from
about 120 to about 360; and at least one detergent, wherein the
weight ratio of said overbased metal carboxylate to said detergent
is from about 1:1 to about 3:1.
2. The oil soluble lubricant additive package as in claim 1,
wherein said oil soluble lubricant additive package has a sulfur
content and a phosphorus content sufficient to yield a lubricating
oil having a sulfur content less than about 0.3 wt % and a
phosphorus content of less than about 0.11 wt %.
3. The oil soluble lubricant additive package as in claim 1,
wherein at least one of said at least one overbased metal
carboxylate is an overbased metal oleate.
4. The oil soluble lubricant additive package as in claim 3,
wherein said overbased metal oleate is selected from the group
consisting of: overbased calcium oleate and overbased magnesium
oleate.
5. The oil soluble lubricating additive package as in claim 1,
wherein at least one of said at least one detergent is selected
from the group consisting of calcium sulfonate, magnesium
sulfonate, sodium sulfonate, non-sulfurized phenates, sulfurized
phenates, salicylates, overbased saligenin, and combinations
thereof.
6. A lubricating oil comprising the oil soluble lubricant additive
package of claim 1, wherein said lubricating oil has a total base
number of less than about 10, and at least one property selected
from the group consisting of: a sulfur content less than about 0.3
wt %, a phosphorus content of less than about 0.11 wt %, and an ash
content less than about 1.2 wt %.
7. A machine lubricated by the lubricating oil of claim 6.
8. The machine lubricated by the lubricating oil of claim 7,
wherein said machine is selected from the group consisting of: gas
engines, diesel engines, turbine engines, automatic transmissions,
manual transmissions, hypoid axles, and gear boxes.
9. A vehicle comprising the oil soluble lubricant additive package
of claim 1.
10. A method for lubricating an engine crankcase, said method
comprising the step of: at least partially filling said crankcase
with a lubricant comprising the oil soluble lubricant additive
package of claim 1.
11. A method for lubricating moving parts of a machine, said method
comprising the step of: contacting at least one said moving part
with a lubricant comprising the oil soluble lubricant additive
package as in claim 1.
12. The method for lubricating moving parts of a machine as in
claim 11, wherein said machine is selected from the group
consisting of: gas engines, diesel engines, turbine engines,
automatic transmissions, manual transmissions, hypoid axles, and
gear boxes.
13. An oil soluble lubricant additive package comprising: an
overbased metal carboxylate having a total base number of from
about 120 to about 360; and at least one dispersant, wherein the
weight ratio of said overbased metal oleate to said dispersant is
from about 1:4 to about 1:12.
14. The oil soluble lubricant additive package as in claim 13,
wherein said oil soluble lubricant additive package has a sulfur
content and a phosphorus content sufficient to yield a lubricating
oil having a sulfur content less than about 0.3 wt % and a
phosphorus content of less than about 0.11 wt %.
15. The oil soluble lubricant additive package as in claim 13,
wherein said at least one overbased metal carboxylate is an
overbased metal oleate.
16. The oil soluble lubricant additive package as in claim 15,
wherein said overbased metal oleate is selected from the group
consisting of: overbased calcium oleate and overbased magnesium
oleate.
17. The oil soluble lubricant additive package as in claim 13
wherein said at least one dispersant has a molecular weight of from
about 1000 to about 6000.
18. The oil soluble lubricant additive package as in claim 13
wherein said at least one dispersant is a maleic anhydride
functionalized polyisobutylene polymer that has been reacted with a
polyamine.
19. The oil soluble lubricant additive package as in claim 13
wherein said at least one dispersant is a product of a Mannich
reaction.
20. The oil soluble lubricant additive package as in claim 13 where
in said at least one dispersant is an ethylene-propylene type
dispersant.
21. The oil soluble lubricant additive package as in claim 13
additionally comprising at least one component selected from the
group consisting of: viscosity index improvers and pour point
depressants.
22. A lubricating oil comprising the oil soluble lubricant additive
package of claim 13, wherein said lubricating oil has a total base
number of less than about 10, and at least one property selected
from the group consisting of: a sulfur content less than about 0.3
wt %, a phosphorus content of less than about 0.11 wt %, and an ash
content less than about 1.2 wt %.
23. A machine lubricated by a lubricating oil comprising the
additive package of claim 13.
24. The machine of claim 23, wherein said machine is selected from
the group consisting of: gas engines, diesel engines, turbine
engines, automatic transmissions, manual transmissions, hypoid
axles, and gear boxes.
25. A vehicle comprising the oil soluble lubricant additive package
of claim 13.
26. A method for lubricating an engine crankcase, said method
comprising the step of: at least partially filling said crankcase
with a lubricant comprising the oil soluble lubricant additive
package of claim 13.
27. A method for lubricating moving parts of a machine, said method
comprising the step of: contacting at least one said moving part
with a lubricant comprising the oil soluble lubricant additive
package as in claim 13.
28. The method for lubricating moving parts of a machine as in
claim 27, wherein said machine is selected from the group
consisting of: gas engines, diesel engines, turbine engines,
automatic transmissions, manual transmissions, hypoid axles, and
gear boxes.
29. An oil soluble lubricating additive package comprising: an
overbased metal carboxylate having a total base number of from
about 120 to about 360; and at least one antioxidant, wherein the
weight ratio of overbased metal carboxylate to antioxidant is from
about 10:1 to about 1:3.
30. The oil soluble lubricant additive package as in claim 29,
wherein said oil soluble lubricant additive package has a sulfur
content and a phosphorus content sufficient to yield a lubricating
oil having a sulfur content less than about 0.3 wt % and a
phosphorus content of less than about 0.11 wt %.
31. The oil soluble lubricant additive package as in claim 29,
wherein said overbased metal carboxylate is an overbased metal
oleate.
32. The oil soluble lubricant additive package as in claim 31
wherein said overbased metal oleate is selected from the group
consisting of: overbased calcium oleate and overbased magnesium
oleate.
33. The oil soluble lubricant additive package as in claim 29
wherein at least one of said at least one antioxidant is selected
from the group consisting of: zinc dithiophosphates, alkylated
diphenylamines, sulfurized olefins, phenols, hindered phenols, and
sulfurized phenols.
34. A lubricating oil comprising the oil soluble lubricant additive
package of claim 29, wherein said lubricating oil has a total base
number of less than about 10, and at least one property selected
from the group consisting of: a sulfur content less than about 0.3
wt %, a phosphorus content of less than about 0.11 wt %, and an ash
content less than about 1.2 wt %.
35. A machine lubricated by a lubricating oil comprising the
additive package of claim 29.
36. The machine of claim 35, wherein said machine is selected from
the group consisting of: gas engines, diesel engines, turbine
engines, automatic transmissions, manual transmissions, hypoid
axles, and gear boxes.
37. A vehicle comprising the oil soluble lubricant additive package
of claim 29.
38. A method for lubricating an engine crankcase, said method
comprising the step of: at least partially filling said crankcase
with a lubricant comprising the oil soluble lubricant additive
package of claim 29.
39. A method for lubricating moving parts of a machine, said method
comprising the step of: contacting at least one said moving part
with a lubricant comprising the oil soluble lubricant additive
package as in claim 29.
40. The method for lubricating moving parts of a machine as in
claim 39, wherein said machine is selected from the group
consisting of: gas engines, diesel engines, turbine engines,
automatic transmissions, manual transmissions, hypoid axles, and
gear boxes.
41. An oil soluble lubricant additive package comprising: an
overbased calcium oleate having a total base number of at least
120; and at least one component selected from the group consisting
of: detergents, dispersants, antioxidants, friction modifiers,
viscosity index improvers, and pour point depressants.
42. The oil soluble lubricant additive package as in claim 41,
wherein said oil soluble lubricant additive package has at least
one property selected from the group consisting of: a sulfur
content less than about 6 wt % and a phosphorus content less than
about 1.2 wt %.
43. The oil soluble lubricant additive package as in claim 41
wherein said oil soluble lubricant additive package is essentially
free of non-sulfurized phenate.
44. A lubricating oil comprising the oil soluble lubricant additive
package of claim 41, wherein said lubricating oil has a total base
number of less than about 10, and at least one property selected
from the group consisting of: a sulfur content less than about 0.3
wt %, a phosphorus content of less than about 0.11 wt %, and an ash
content less than about 1.2 wt %.
45. A machine lubricated by a lubricating oil comprising the
additive package of claim 41.
46. The machine of claim 45, wherein said machine is selected from
the group consisting of: gas engines, diesel engines, turbine
engines, automatic transmissions, manual transmissions, hypoid
axles, and gear boxes.
47. A vehicle comprising the oil soluble lubricating additive
package of claim 41.
48. A method for lubricating an engine crankcase, said method
comprising the step of: at least partially filling said crankcase
with a lubricant comprising the oil soluble lubricant additive
package of claim 41.
49. A method for lubricating moving parts of a machine, said method
comprising the step of: contacting at least one said moving part
with a lubricant comprising the oil soluble lubricant additive
package as in claim 41.
50. The method for lubricating moving parts of a machine as in
claim 49, wherein said machine is selected from the group
consisting of: gas engines, diesel engines, turbine engines,
automatic transmissions, manual transmissions, hypoid axles, and
gear boxes.
51. A method of achieving a low sulfur, low ash, and low phosphate
oil formulation, said method comprising: providing an oil soluble
lubricant additive package, said oil soluble lubricant additive
package comprising an overbased metal carboxylate having a total
base number of from about 120 to about 360; and admixing said oil
soluble lubricant additive package with at least a base oil so as
to form a lubricating oil having a total base number of less than
about 10, and at least one property selected from the group
consisting of: a sulfur content less than about 0.3 wt %, a
phosphorus content of less than about 0.11 wt %, and an ash content
less than about 1.2 wt %.
52. The method of achieving a low sulfur, low ash, and low
phosphorus oil formulation as in claim 51, wherein said overbased
metal carboxylate is selected from the group consisting of:
overbased calcium oleate and overbased magnesium oleate.
53. The method of achieving a low sulfur, low ash, and low
phosphorus oil formulation as in claim 51 wherein said oil soluble
lubricant additive package additionally comprises at least one
additive selected from the group consisting of: detergents,
dispersants, antioxidants, friction modifiers, viscosity index
improvers, and pour point depressants.
Description
TECHNICAL FIELD
[0001] The present invention relates to lubricating oil
compositions, their method of preparation, and use. More
specifically, this invention relates to an oil soluble lubricating
additive package to achieve low sulfur, low ash, and low phosphorus
levels in fully formulated oil.
BACKGROUND
[0002] Combustion engines generate emissions that can pollute our
environment. In response to increasing regulation and environmental
concerns, engine manufacturers have recognized the need to reduce
engine emissions. In an effort to reduce emissions in exhaust
gases, manufacturers have used particulate traps and catalytic
converters. However, the lubricating oil used in the engine is
oftentimes detrimental to devices such as catalytic converters or
particulate traps. For example, phosphorus present in the
lubricating oil is believed to interfere with catalytic efficiency.
Further, it is believed that sulfur present in the lubricating oil,
after oxidation and neutralization, may form sulfates that plug
exhaust gas traps thereby preventing them from oxidizing and
burning off trapped organic particulate matter. Accordingly, engine
manufacturers are requiring lubricating oils that have lower and
lower sulfur, ash, and phosphorus levels.
[0003] An object of the present invention is to provide an oil
soluble lubricating additive package that can be used to formulate
a low sulfur, low ash, and low phosphorus content oil for use in
either gasoline or diesel engines. Further, a second object of the
present invention is to provide lubricating oils that contain
minimal sulfur, ash, and phosphorus levels.
[0004] Additionally, another goal of the present invention is to
provide a method for lubricating the moving parts of a machine.
SUMMARY
[0005] In broadest terms, provided herein is an oil soluble
lubricant additive package comprising at least one overbased metal
carboxylate having a total base number of from about 120 to about
360 and at least one detergent, wherein the weight ratio of the
overbased metal carboxylate to the detergent is from about 1:1 to
about 3:1.
[0006] In one embodiment, at least one of the at least one
detergent(s) is selected from the group consisting of calcium
sulfonate, magnesium sulfonate, sodium sulfonate, non-sulfurized
phenates, sulfurized phenates, salicylates, overbased saligenin,
and combinations thereof. In another example, the oil soluble
lubricant additive has a sulfur content and a phosphorus content
sufficient to yield a lubricating oil having a sulfur content less
than about 0.3 wt % and a phosphorus content of less than about
0.11 wt %. In yet another example, at least one of the overbased
metal carboxylates is an overbased metal oleate, or is selected
from the group consisting of overbased calcium oleate and overbased
magnesium oleate.
[0007] In broadest terms, a method for lubricating an engine
crankcase is provided that comprises the step of: at least
partially filling the crankcase with a lubricant containing the oil
soluble lubricant additive package disclosed herein.
[0008] In broadest terms, a method for lubricating the moving parts
of a machine is provided that comprises the step of contacting at
least one moving part with the oil soluble lubricant additive
package disclosed herein.
[0009] In broadest terms, an oil soluble lubricant additive package
is provided that comprises: an overbased metal carboxylate having a
total base number of from about 120 to about 360; and at least one
dispersant, wherein the weight ratio of the overbased metal oleate
to the dispersant is from about 1:4 to about 1:12.
[0010] The oil soluble lubricant additive package herein can, for
example, utilize dispersants having a molecular weight of at least
500. However, dispersants used herein can have a molecular weight
of from about 1000 to about 6000.
[0011] Additionally, in one example at least one dispersant is a
maleic anhydride functionalized polyisobutylene polymer that has
been reacted with a polyamine. Another example provides that at
least one dispersant is the product of a Mannich reaction.
Additionally, at least one dispersant can be an ethylene-propylene
type dispersant.
[0012] Oil soluble lubricant additive package formulations herein
may additionally comprise at least one component selected from the
group consisting of: viscosity index improvers and pour point
depressants.
[0013] In broadest terms, a method for lubricating an engine
crankcase is provided that comprises the step of at least partially
filling the crankcase with the oil soluble lubricant additive
package disclosed herein.
[0014] In broadest terms, a method for lubricating moving parts of
a machine is provided that comprises the step of contacting at
least one moving part with the oil soluble lubricant additive
package disclosed herein.
[0015] In broadest terms, an oil soluble lubricating additive
package is provided that comprises: an overbased metal carboxylate
having a total base number of from about 120 to about 360; and at
least one antioxidant, wherein the weight ratio of overbased metal
carboxylate to antioxidant is from about 10:1 to about 1:3.
[0016] In an embodiment, at least one of the at least one
antioxidant is selected from the group consisting of: zinc dialkyl
dithiophosphates, alkylated diphenylamines, sulfurized olefins,
phenols, hindered phenols, and sulfurized phenols.
[0017] Also included herein are machines lubricated by the
inventive lubricating oils disclosed herein. While the machine may
be any machine that uses a lubricating oil to maintain the
operability of its moving parts, it is preferred that the machine
is selected from the group consisting of: gas engines, diesel
engines, turbine engines, automatic transmissions, manual
transmissions, hypoid axles, and gear boxes.
[0018] In broadest terms, a method for lubricating an engine
crankcase is provided that comprises the step of at least partially
filling the crankcase with the oil soluble lubricant additive
package disclosed herein.
[0019] In broadest terms, a method for lubricating moving parts of
a machine is provided that comprises the step of contacting at
least one moving part with the oil soluble lubricant additive
package disclosed herein.
[0020] In broadest terms, an oil soluble lubricant additive package
is provided that comprises: an overbased calcium oleate having a
total base number of at least 120; and at least one component
selected from the group consisting of: detergents, dispersants,
antioxidants, friction modifiers, viscosity index improvers, and
pour point depressants.
[0021] The oil soluble lubricant additive package of the present
invention has at least one property selected from the group
consisting of: a sulfur content less than about 6 wt % and a
phosphorus content less than about 1.2 wt %.
[0022] In one example, the oil soluble lubricant additive package
of the present invention is essentially free of non-sulfurized
phenates.
[0023] In broadest terms, a method for lubricating an engine
crankcase is provided that comprises the step of at least partially
filling the crankcase with a lubricant containing the oil soluble
lubricant additive package disclosed herein.
[0024] In broadest terms, a method for lubricating moving parts of
a machine is provided that comprises the step of contacting at
least one moving part with the oil soluble lubricant additive
package disclosed herein.
[0025] A method of achieving a low sulfur, low ash, and low
phosphate oil formulation is provided that comprises the steps of:
providing an oil soluble lubricant additive package comprising an
overbased metal carboxylate having a total base number of from
about 120 to about 360; and admixing the oil soluble lubricant
additive package with at least a base oil so as to form a
lubricating oil having a total base number of less than about 10,
and at least one property selected from the group consisting of: a
sulfur content less than about 0.3 wt %, a phosphorus content of
less than about 0.11 wt %, and an ash content less than about 1.2
wt %.
[0026] In one example, the overbased metal carboxylate is selected
from the group consisting of: overbased calcium oleate and
overbased magnesium oleate.
[0027] Additionally, the oil soluble lubricant additive package
provided herein can further comprise at least one additive selected
from the group consisting of: detergents, dispersants,
antioxidants, friction modifiers, viscosity index improvers, and
pour point depressants.
[0028] In another example, the oil soluble lubricant package has a
sulfur content and a phosphorus content sufficient to yield a
lubricating oil having a sulfur content less than about 0.3 wt %
and a phosphorus content of less than about 0.11 wt %.
[0029] For each of the above disclosed formulations it is useful
but not required that at least one of the at least one overbased
metal carboxylate is an overbased metal oleate. In a specific
example, the overbased metal oleate is selected from the group
consisting of: overbased calcium oleate and overbased magnesium
oleate.
[0030] The present application also includes lubricating oils
comprising the oil soluble lubricant additive packages disclosed
herein. In one embodiment, the lubricating oil has a total base
number of less than about 10, and at least one property selected
from the group consisting of: a sulfur content less than about 6.0
wt %, a phosphorus content of less than about 0.11 wt %, and an ash
content less than about 1.2 wt %.
[0031] Also included herein are machines lubricated by the
inventive lubricating oils disclosed herein. While the machine may
be any machine that uses a lubricating oil to maintain the
operability of its moving parts, it is suggested that the machine
is selected from the group consisting of: gas engines, diesel
engines, turbine engines, automatic transmissions, manual
transmissions, hypoid axles, and gear boxes.
[0032] Further, the present invention includes vehicles comprising
at least one of the oil soluble lubricant additive packages
disclosed herein.
[0033] Although any of the inventive methods disclosed herein may
be practiced on a wide variety of machines, it is suggested that
the machine is selected from the group consisting of: gas engines,
diesel engines, turbine engines, automatic transmissions, manual
transmissions, hypoid axles, and gear boxes.
[0034] In addition to the novel features and advantages mentioned
above, other objects and advantages will be readily apparent from
the following descriptions of the drawing(s) and preferred
embodiment(s).
DETAILED DESCRIPTION
[0035] In accordance with the foregoing summary, the following
presents a detailed description of the preferred embodiments that
are currently considered to be or include the best mode.
[0036] We begin with a discussion of the various components
employed in the present invention. Then we shall present an oil
formulation based upon the oil soluble additive package of the
present invention. Finally, we conclude with a comparison of the
inventive oil formulation against a control formulation in the CAT
1N engine test.
Base Oil
[0037] The base oils useful herein include natural lubricating
oils, synthetic lubricating oils and mixtures thereof. Suitable
lubricating oils also include basestocks obtained by isomerization
of synthetic wax and slack wax, as well as basestocks produced by
hydrocracking the aromatic and polar components of the crude. In
general, both the natural and synthetic lubricating oils will each
have a kinematic viscosity ranging from about 1 to about 40
mm.sup.2/s (cSt) at 100.degree. C., although typical applications
will require each of the base oils to have a viscosity ranging from
about 1 to about 12, preferably 2 to 8, mm.sup.2/s (cSt) at
100.degree. C.
[0038] Natural lubricating oils include animal oils, vegetable oils
(e.g., castor oil and lard oil), petroleum oils, mineral oils, and
oils derived from coal or shale. The preferred natural lubricating
oil is mineral oil.
[0039] The mineral oils useful herein include all common mineral
oil base stocks. This would include oils that are naphthenic or
paraffinic in chemical structure. Oils that are refined by
conventional methodology using acid, alkali, and clay or other
agents such as aluminum chloride, or be extracted oils produced,
for example, by solvent extraction with solvents such as phenol,
sulfur dioxide, furfural, dichlorodiethyl ether, etc. They may be
hydrotreated or hydrorefined, dewaxed by chilling or catalytic
dewaxing processes, or hydrocracked. The mineral oil may be
produced from natural crude sources or be composed of isomerized
wax materials or residues of other refining processes. In a
preferred embodiment, the oil of lubricating viscosity is a
hydrotreated, hydrocracked and/or iso-dewaxed mineral oil having a
Viscosity Index (VI) of greater than 80, preferably greater than
90; greater than 90 volume % saturates and less than 0.03 wt. %
sulfur.
[0040] Group II and Group III basestocks are particularly suitable
for use in the present invention, and are typically prepared from
conventional feedstocks using a severe hydrogenation step to reduce
the aromatic, sulfur and nitrogen content, followed by dewaxing,
hydrofinishing, extraction and/or distillation steps to produce the
finished base oil. Group II and III basestocks differ from
conventional solvent refined Group I basestocks in that their
sulfur, nitrogen and aromatic contents are very low. As a result,
these base oils are compositionally very different from
conventional solvent refined basestocks. The American Petroleum
Institute has categorized these different basestock types as
follows: Group I, >0.03 wt. % sulfur, and/or <90 vol %
saturates, viscosity index between 80 and 120; Group II,
.ltoreq.0.03 wt. % sulfur, and .gtoreq.90 vol % saturates,
viscosity index between 80 and 120; Group III, .ltoreq.0.03 wt. %
sulfur, and .gtoreq.90 vol % saturates, viscosity index >120;
Group IV, poly-alpha-olefins. Hydrotreated basestocks and
catalytically dewaxed basestocks, because of their low sulfur and
aromatics content, generally fall into the Group II and Group III
categories.
[0041] There is no limitation as to the chemical composition of the
various basestocks used in the present invention. For example, the
proportions of aromatics, paraffinics, and naphthenics in the
various Group I, Group II and Group III oils can vary
substantially. The degree of refining and the source of the crude
used to produce the oil generally determine this composition.
[0042] In a preferred embodiment, the base oil comprises a mineral
oil having a VI of at least 110.
[0043] The lubricating oils may be derived from refined, re-refined
oils, or mixtures thereof. Unrefined oils are obtained directly
from a natural source or synthetic source (e.g., coal, shale, or
tar sands bitumen) without further purification or treatment.
Examples of unrefined oils include shale oil obtained directly from
a retorting operation, petroleum oil obtained directly from
distillation, or an ester oil obtained directly from an
esterification process, each of which is then used without further
treatment. Refined oils are similar to the unrefined oils except
that refined oils have been treated in one or more purification
steps to improve one or more properties. Suitable purification
techniques include distillation, hydrotreating, dewaxing, solvent
extraction, acid or base extraction, filtration, and percolation,
all of which are known to those skilled in the art. Re-refined oils
are obtained by treating used oils in processes similar to those
used to obtain the refined oils. These re-refined oils are also
known as reclaimed or reprocessed oils and are often additionally
processed by techniques for removal of spent additives and oil
breakdown products.
[0044] Synthetic lubricating oils include hydrocarbon oils and
halo-substituted hydrocarbon oils such as oligomerized,
polymerized, and interpolymerized olefins; alkylbenzenes;
polyphenyls; and alkylated diphenyl ethers, alkylated diphenyl
sulfides, as well as their derivatives, analogs, and homologs
thereof, and the like. Preferred synthetic oils are oligomers of
.alpha.-olefins, particularly oligomers of 1-decene, having a
viscosity ranging from about 1 to about 12, preferably 2 to 8,
mm.sup.2/s (cSt) at 100.degree. C. These oligomers are known as
poly-.alpha.-olefins or PAOs.
[0045] Synthetic lubricating oils also include alkylene oxide
polymers, interpolymers, copolymers, and derivatives thereof where
the terminal hydroxyl groups have been modified by esterification,
etherification, etc. This class of synthetic oils is exemplified by
polyoxyalkylene polymers prepared by polymerization of ethylene
oxide or propylene oxide; the alkyl and aryl ethers of these
polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol
ether having an average molecular weight of 1000, diphenyl ether of
polypropylene glycol having a molecular weight of 100-1500); and
mono- and poly-carboxylic esters thereof (e.g., the acetic acid
esters, mixed C.sub.3--C.sub.8fatty acid esters, and C.sub.12 oxo
acid diester of tetraethylene glycol).
[0046] Another suitable class of synthetic lubricating oils
comprises the esters of dicarboxylic acids (e.g., phthalic acid,
succinic acid, alkyl succinic acids and alkenyl succinic acids,
maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid,
adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids,
alkenyl malonic acids, etc.) with a variety of alcohols (e.g.,
butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoethers, propylene
glycol, etc.). Specific examples of these esters include dibutyl
adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl
sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl
isothalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl
diester of linoleic acid dimer, and the complex ester formed by
reacting one mole of sebasic acid with two moles of tetraethylene
glycol and two moles of 2-ethyl-hexanoic acid, and the like. A
preferred type of oil from this class of synthetic oils is adipates
of C.sub.4 to C.sub.12 alcohols.
[0047] Esters useful as synthetic lubricating oils also include
those made from C.sub.5 to C.sub.12 monocarboxylic acids and
polyols and polyol ethers such as neopentyl glycol,
trimethylolpropane pentaeythritol, dipentaerythritol,
tripentaerythritol, and the like.
[0048] Silicon-based oils (such as the polyalkyl-, polyaryl-,
polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils)
comprise another useful class of synthetic lubricating oils. These
oils include tetra-ethyl silicate, tetra-isopropyl silicate,
tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)
silicate, tetra-(p-tert-butylphenyl) silicate,
hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes and
poly (methylphenyl) siloxanes, and the like. Other synthetic
lubricating oils include liquid esters of phosphorus containing
acids (e.g., tricresyl phosphate, trioctylphosphate, and diethyl
ester of decylphosphonic acid), polymeric tetra-hydrofurans,
poly-alpha-olefins, and the like.
Overbased Metal Carboxylate
[0049] The oil soluble lubricating additive package taught herein
contain at least one metal salt of an acidic organic compound.
These salts are generally referred to as overbased materials or
overbased metal salts. Overbased materials can be single phase,
homogeneous Newtonian systems characterized by a metal content in
excess of that which would be present according to the
stoichiometry of the metal and the particular acidic organic
compound reacted with the metal.
[0050] The amount of excess metal is commonly expressed in terms of
metal ratio. The term "metal ratio" is the ratio of the total
equivalents of the metal to the equivalents of the acidic organic
compound. A neutral metal salt has a metal ratio of one. A salt
having a 4.5 times as much metal as present in a normal salt will
have metal excess of 3.5 equivalents, or a ratio of 4.5.
[0051] The overbased metal salts used in one embodiment herein are
prepared by reacting an acidic material (typically an inorganic
acid or lower carboxylic acid, preferably carbon dioxide) with a
mixture comprising an acidic organic compound, a reaction medium
comprising at least one inert, organic solvent (mineral oil,
naptha, toluene, xylene, etc.) for the acidic organic compound, a
stoichiometric excess of a metal base, and a promoter.
[0052] The metals useful in making the overbased compositions
herein can include, for example, magnesium and calcium, as well as
any other suitable or desirable metal or mixture of metals.
[0053] The acidic compounds useful in making the overbased
compositions of the present invention can include, for example,
carboxylic acids. The carboxylic acids may be aliphatic or
aromatic, mono- or polycarboxylic acid, or acid-producing
compounds. These carboxylic acids can include lower molecular
weight carboxylic acids (e.g., carboxylic acids having about 22
carbon atoms such as acids having about 4 to about 22 carbon atoms
or tetrapropenyl-substituted succinic anhydride) as well as higher
molecular weight carboxylic acids.
[0054] The carboxylic acids are preferably oil soluble. Usually, in
order to provide the desired oil-solubility, the number of carbon
atoms in the carboxlyic acid should be at least about 8, more
preferably at least about 18, more preferably at least about 30,
even more preferably at least about 50. Generally, these carboxylic
acids do not contain more than about 400 carbon atoms per
molecule.
[0055] The lower molecular weight monocarboxylic acids contemplated
for use herein can include saturated and unsaturated acids.
Examples of such useful acids include dodecanoic acid, decanoic
acid, oleic acid, stearic acid, linoleic acid, tall oil acid, etc.
Mixtures of two or more such agents can also be used.
[0056] A particularly useful overbased calcium oleate for use
herein is PLASTISTAB 2265 commercially available from OMG Americas,
Inc. of Westlake, Ohio.
[0057] Representative examples of suitable carboxylic acids are
presented in U.S. patent application Publication No. 2002/0177532A1
and in International Publication No. WO 02/094925 A2. The
disclosure of the afore-mentioned reference is incorporated by
reference herein.
Detergents
[0058] A detergent is an additive that reduces the formation of
piston deposits, for example high-temperature varnish and lacquer
deposits, in engines. Detergents typically possess
acid-neutralizing properties and are capable of keeping finely
divided solids in suspension. Metal detergents are used preferably
for improving the acid-neutralizing properties, high-temperature
detergency, and anti-wear properties of the resulting lubricating
oil composition.
[0059] Detergents used in the present invention may be any
detergent used in lubricating oil formulations, and may be of the
ash-producing or ashless variety. Detergents suitable for use in
the present invention include all of the detergents customarily
used in lubricating oils, including metal detergents. Specific
examples of metal detergents are those selected from alkali metal
or alkaline earth metal sulfonates, alkali metal or alkaline earth
metal phenates, and alkali metal or alkaline earth metal
salicylates.
[0060] Representative examples of suitable detergents useful in the
present invention are found in U.S. Pat. No. 6,008,166. Additional
representative examples of suitable detergents are found in U.S.
patent application Nos. 2002/0142922A1, 2002/0004069A1, and
2002/0147115A1. The disclosures of the afore-mentioned references
are incorporated by reference herein.
Dispersants
[0061] Dispersants used in the present invention may be
ash-producing or ashless. Suitable dispersants for use herein
typically comprise amine, alcohol, amide, or ester polar moieties
attached to the polymer backbone via a bridging group. The
dispersant may be, for example, selected from oil soluble salts,
esters, amino-esters, amides, imides, and oxazolines of long chain
hydrocarbon substituted mono- and dicarboxlyic acids or their
anhydrides; thiocarboxylate derivatives of chain hydrocarbons; long
chain aliphatic hydrocarbons having a polyamine attached directly
thereto; and Mannich condensation products formed by condensing a
long chain substituted phenol with formaldehyde and polyalkylene
polyamine, and Koch reaction products.
[0062] Representative examples of dispersants suitable for use
herein are found in U.S. Pat. Nos. 5,075,383; 5,139,688; 5,238,588;
and 6,107,257. Additional representative examples are found in U.S.
patent application Publication No. 2001/0036906A1. The disclosures
of the afore-mentioned references are incorporated herein by
reference.
Antioxidants
[0063] Useful antioxidant materials include oil soluble phenolic
compounds, oil soluble sulfurized organic compounds, oil soluble
amine antioxidants, oil soluble organo borates, oil soluble organo
phosphites, oil soluble organo phosphates, oil soluble organo
dithiophosphates and mixtures thereof. Preferably such antioxidants
are metal free (that is, free of metals which are capable of
generating sulfated ash), and therefore are most preferably ashless
(having a sulfated ash value not greater than 1 wt. % SASH, as
determined by ASTM D874).
[0064] Further, zinc dialkyl dithiophosphates are well known
antioxidants. Specific examples of preferred zinc dialkyl
dithiophosphates are zinc dipropyldithiophosphate, zinc
dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc
dihexyldithiophosphate, zinc diheptyldithiophosphate, and zinc
dioctyldithiophosphate, of which alkyl groups may be straight-chain
or branched, and mixtures thereof. Furthermore, zinc
dialkyldithiophosphates having alkyl groups having different carbon
number (3 to 8 carbon atoms) or structure in one molecule are also
eligible.
[0065] Representative examples of suitable antioxidants useful
herein are found in U.S. Pat. No. 5,102,566. Additional
representative examples of suitable useful antioxidants are found
in U.S. patent application Publication No. 2001/0012821A1. The
disclosures of the afore-mentioned references are incorporated by
reference herein.
Friction Modifiers
[0066] Friction modifiers serve to impart the proper friction
characteristics to lubricating oil compositions.
[0067] Friction modifiers useful in the lubricating compositions
hereof can include such compounds as aliphatic amines or
ethoxylated aliphatic amines, aliphatic fatty acid amines,
aliphatic carboxylic acids, aliphatic carboxylic esters of polyols
such as glycerol esters of fatty acid as exemplified by glycerol
oleate, aliphatic carboxylic ester-amides, aliphatic phosphonates,
aliphatic phosphates, aliphatic thiophosphonates, aliphatic
thiophospates, etc., wherein the aliphatic group usually contains
above about eight carbon atoms so as to render the compound
suitably oil soluble. Also suitable are aliphatic substituted
succinimides formed by reacting one or more aliphatic succinic
acids or anhydrides with ammonia. Additionally suited for use
herein are friction modifiers containing molybdenum, including but
not limited to molybdenum carboxylates, cabamates,
dithiocarbamates, amides, and others. Representative examples of
molybdenum-containing friction modifiers include those found in
U.S. Pat. Nos. 5,650,381; RE37,363E; 5,628,802; 4,889,647;
5,412,130; 4,786,423; 4,812,246; 5,137,647; 5,364,545; 5,840,672;
5,925,600; 5,962,377; 5,994,277; 6,017,858; 6,150,309; 6,174,842;
6,187,723; 6,268,316; European Patent Nos. EP 222 143 B1; EP 281
992 B1; EP 719 314 B1; EP 719 315 B1; EP 874 040 A1; EP 892 037 A1;
EP 931 827A1; EP 1 041 134A1; EP 1 041 135A1; EP 1 087 008A1; EP 1
088 882 A1; EP; Japanese Patent No. JP 11035961; and International
Publication Nos. WO 95/07965; WO 00/08120; WO 00/71649.
[0068] Representative examples of suitable friction modifiers are
found in U.S. Pat. Nos. 3,933,659; 4,105,571; 3,779,928; 3,778,375;
3,852,205; 3,879,306; 3,932,290; 3,932,290; 4,028,258; 4,344,853;
5,102,566; 6,103,674; 6,174,842; 6,500,786; 6,500,786; and
6,509,303. Additional representative examples of suitable friction
modifiers are found in U.S. patent application Publication No.
2002/0137636 A1. The disclosures of the above references are
incorporated herein by reference.
Viscosity Index Improvers
[0069] Viscosity index improvers impart high and low temperature
operability to the lubricating oil and permit it to remain
relatively viscous at elevated temperatures and also exhibit
acceptable viscosity or fluidity at low temperatures. Viscosity
index improvers are generally high molecular weight hydrocarbon
polymers including polyesters. The viscosity index improvers may
also be derivatized to include other properties or functions, such
as the addition of dispersancy properties. These oil soluble
viscosity modifying polymers will generally have number average
molecular weights of from 10.sup.3 to 10.sup.6, preferably 10.sup.4
to 10.sup.6, as determined by gel permeation chromatography or
osmometry.
[0070] The viscosity index improvers useful herein can include
polymethacrylate-based ones, olefin copolymer-based ones, (e.g.,
isobutylene-based and ethylene-propylene copolymer based ones),
polyalkyl sytrene-based ones, hydrogenated styrene-butadiene
copolymer-based ones, and styrene-maleic anhydride ester
copolymer-based ones.
[0071] Representative examples of suitable viscosity index
improvers are found in U.S. Pat. Nos. 5,075,383; 5,102,566;
5,139,688; 5,238,588; and 6,107,257. The above references are
incorporated herein by reference.
Pour Point Depressants
[0072] Pour point depressants are used to improve low temperature
properties of oil-based compositions. See, for example, page 8 of
"Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith
(Lezius Hiles Co. publishers, Cleveland, Ohio, 1967). Examples of
useful pour point depressants are polymethacrylates; polyacrylates;
polyacrylamides; condensation products of haloparaffin waxes and
aromatic compounds; vinyl carboxylate polymers; and ter-polymers of
dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl
ethers. Pour point depressants are described in U.S. Pat. Nos.
2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746;
2,721,877; 2,721,878; and 3,250,715, which are herein incorporated
by reference for their relevant disclosures.
Cat 1N Engine Test Results
[0073] The CAT 1N engine test is a commonly used test for
evaluating the acceptability of heavy-duty diesel engine oils for
Caterpillar engines. The test employs a single cylinder diesel
engine with an aluminum piston. The acceptability of an oil
formulation is based upon the following parameters: average oil
consumption, piston deposits, % top groove fill, % top land heavy
carbon. Further, in order to pass the CAT 1N diesel test, no stuck
pistons, piston rings or liner distress is permitted.
[0074] To determine the efficacy of the inventive additive, a
control formulation comprising a non-sulfurized phenate prepared by
a Mannich reaction between an alkylphenol and a polyamine was
compared to a formulation wherein the non-sulfurized phenate was
replaced with overbased calcium oleate in a prototype low sulfur,
low.ash, low phosphorus 15W-40 motor oil.
1 Control Composition, wt % basis Formulation Inventive Formulation
Base Oil #1 52.00 52.00 Base Oil #2 27.00 27.00 Viscosity Index
Improver 8.50 8.50 Pour Point Depressant 0.20 0.20 Dispersant #1
3.00 3.00 Dispersant #2 5.03 5.03 Non-Sulfurized Phenate 0.95 0.00
Detergent 0.50 0.50 Overbased Calcium Oleate 0.00 0.95 Zinc
Dithiophosphate 0.25 0.25 Antioxidant #1 0.50 0.50 Antioxidant #2
0.50 0.50 Anti-foaming Agent 0.01 0.01 Friction Modifier 0.50 0.50
Process Oil 1.06 1.06 Kinematic Viscosity @ 100.degree. C. 14.31
13.66 centistoke centistoke
[0075] The following table compares the control formulation's
performance against the inventive formulation. The column marked
"Test #1" provides the pass/fail limits for the CAT 1N test for a
single trial. If a given oil formulation does not provide
satisfactory results with a single trial, multiple trials may be
averaged together and this average compared against the
corresponding pass/fail limits for the number of tests being
averaged. That is to say, if two trials of the inventive
formulation were averaged together, the averaged results would be
compared against the pass/fail limits provided in the "Test #2"
column.
2 Control Inventive Formulation Formulation Test #1 Test #2 Test #3
TLHC, % 0 0 3 4 5 TGF, % 25 9 20 23 25 WD 698.6 280.7 286.2 311.7
323 O.C., avg 0.22 0.145 0.5 max (0-252 hr) O.C. 0.23 0.189 No
scuffing E.O.T. TLHC, %--Top Land Heavy Carbon TGF, %--Top Groove
Fill WD--Weight of Deposit O.C.--Oil Consumption O.C.E.O.T.--Oil
Consumption at End of Test
[0076] As can be seen from the table above, the inventive
formulation performed well in the CAT 1N test. The inventive
formulation did not require additional trials, as single trial
performance was satisfactory. The inventive formulation exhibited a
marked reduction in top groove fill percentage. Further, the
inventive formulation exhibited a significant reduction in deposit
weight. The inventive formulation also outperformed the control
formulation in both oil consumption and oil consumption at the end
of the test. These results demonstrate the improved performance
imparted to the formulated oil by the inclusion of the overbased
calcium oleate.
[0077] While the invention has been described in connection with
what is presently considered to be the most practical and preferred
embodiments, it is to be understood that the invention is not to be
limited to the disclosed embodiment(s), but on the contrary, is
intended to cover various modifications and equivalent arrangements
included within the spirit and scope of the appended claims, which
are incorporated herein by reference.
* * * * *