U.S. patent application number 10/367432 was filed with the patent office on 2003-12-04 for lubricating oil additive comprising ec-treated succinimide, borated dispersant and corrosion inhibitor.
Invention is credited to Dam, Willem Van, Harrison, James J., Logan, Mark R., Menasco, Michael T..
Application Number | 20030224948 10/367432 |
Document ID | / |
Family ID | 29586669 |
Filed Date | 2003-12-04 |
United States Patent
Application |
20030224948 |
Kind Code |
A1 |
Dam, Willem Van ; et
al. |
December 4, 2003 |
Lubricating oil additive comprising EC-treated succinimide, borated
dispersant and corrosion inhibitor
Abstract
An additive formulation comprising one or more ec-treated
dispersants, borated dispersants, and a dispersed aromatic
dicarboxylic acid corrosion inhibitor; a dispersant inhibitor
package comprising one or more ec-treated dispersants, borated
dispersants, and a dispersed aromatic dicarboxylic acid corrosion
inhibitor; a lubricating oil comprising said dispersant inhibitor
package; and a method for lubricating engines.
Inventors: |
Dam, Willem Van; (Novato,
CA) ; Menasco, Michael T.; (Richmond, CA) ;
Harrison, James J.; (Novato, CA) ; Logan, Mark
R.; (San Ramon, CA) |
Correspondence
Address: |
Josetta I. Jones
ChevronTexaco Corporation
P.O. Box 6006
San Ramon
CA
94583-0806
US
|
Family ID: |
29586669 |
Appl. No.: |
10/367432 |
Filed: |
February 14, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60356699 |
Feb 14, 2002 |
|
|
|
Current U.S.
Class: |
508/192 ;
508/242; 508/291; 508/295 |
Current CPC
Class: |
C10N 2060/00 20130101;
C10N 2040/252 20200501; C10N 2040/25 20130101; C10M 141/06
20130101; C10M 2207/142 20130101; C10N 2060/14 20130101; C10M
133/56 20130101; C10N 2030/12 20130101; C10N 2070/02 20200501; C10M
133/00 20130101; C10M 2215/28 20130101 |
Class at
Publication: |
508/192 ;
508/242; 508/291; 508/295 |
International
Class: |
C10M 133/44 |
Claims
What is claimed is:
1. A lubricating oil additive composition comprising: (a) one or
more ethylene carbonate-treated succinimides; (b) one or more
borated succinimides, and (c) one or more dispersed aromatic
dicarboxylic acid corrosion inhibitors which are succinimide salts
of one or more aromatic dicarboxylic acids.
2. The lubricating oil additive composition of claim 1, wherein the
corrosion inhibitors are one of more succinimide salts of
terephthalic acid.
3. The lubricating oil additive composition of claim 2, wherein the
succinimide salts of terephthalic acid are polyisobutenyl
succinimide salts.
4. The lubricating oil additive composition of claim 1, wherein the
ethylene carbonate-treated succinimide is a polybutene succinimide
derived from the reaction product of a polyisobutenyl succinic
anhydride with a polyamine.
5. The lubricating oil additive composition of claim 4, wherein the
ethylene carbonate-treated succinimide is derived from polybutenes
having a molecular weight of from at least 1800.
6. The lubricating oil additive composition of claim 1, wherein the
borated succinimide is derived from the reaction product of a
polyisobutenyl succinic anhydride with a polyamine.
7. The lubricating oil additive composition of claim 6, wherein the
borated succinimide is derived from polybutenes having a molecular
weight of from 1200 to 1400.
8. A lubricating oil composition comprising a major amount of an
oil of lubricating viscosity and a lubricating oil additive
composition comprising: (a) one or more ethylene carbonate treated
succinimides, (b) one or more borated succinimides, and (c) one or
more dispersed aromatic dicarboxylic acid corrosion inhibitors
which are succinimide salts of one or more aromatic dicarboxylic
acids.
9. A method for lubricating an internal combustion engine
comprising contacting the engine with a lubricating oil composition
of claim 8.
10. The method of claim 9, wherein the internal combustion engine
is a heavy duty diesel engine.
11. A method for reducing bearing corrosion in a diesel engine
which comprises operating the engine with a lubricating oil
composition of claim 8.
Description
[0001] This application claims the benefit of priority from U.S.
Provisional Application No. 60/356,699, filed Feb. 14, 2002.
FIELD OF THE INVENTION
[0002] This invention includes an additive formulation comprising
one or more ethylene carbonate (EC) treated polyalkene succinimides
and one or more borated polyalkene with a specific dispersed
aromatic dicarboxylic acid corrosion inhibitor; a lubricating oil
comprising this additive formulation, an oil of lubricating
viscosity and any other additives typically used in the lubricating
oil industry.
[0003] The lubricating oil of this invention may be used in any
engine but they are particularly advantageous for lubricating
internal combustion engines, and even more particularly useful in
heavy-duty diesel engines. The lubricating oil of this invention
lowers wear in engines. It is particularly useful to lower bearing
wear and valve train wears. The lubricating oil of this invention
also prevents deposits, disperses soot, and provides excellent high
temperature performance.
BACKGROUND OF THE INVENTION
[0004] New diesel engines are equipped with Exhaust Gas
Recirculation (EGR). EGR introduces NOx in the intake stream of the
engine. In the presence of water and at lower temperature, acids
may be formed which may condensate in the intake system. These
acids lower the TBN of the crankcase lubricant and may ultimately
cause an increase in bearing corrosion. The use of the corrosion
inhibitor and the use of a borated dispersant result in improved
bearing corrosion control.
SUMMARY OF THE INVENTION
[0005] It has now been discovered that the combination of one or
more EC-treated polyalkene succinimides and one or more borated
polyalkene succinimides with a specific dispersed aromatic
dicarboxylic acid corrosion inhibitor provides decreased wear in
engines. It is particularly useful to lower bearing wear and valve
train wears. The lubricating oil of this invention also prevents
deposits, disperses soot, and provides excellent high temperature
performance.
[0006] Accordingly, the present invention comprises:
[0007] A lubricating oil additive composition comprising:
[0008] (a) one or more ethylene carbonate-treated succinimides;
[0009] (b) one or more borated succinimides, and
[0010] (c) one or more dispersed aromatic dicarboxylic acid
corrosion inhibitors which are succinimide salts of one or more
aromatic dicarboxylic acids.
[0011] The present invention further provides:
[0012] A lubricating oil composition comprising a major amount of
an oil of lubricating viscosity and a lubricating oil additive
composition comprising:
[0013] (a) one or more ethylene carbonate treated succinimides,
[0014] (b) one or more borated succinimides, and
[0015] (c) one or more dispersed aromatic dicarboxylic acid
corrosion inhibitors which are succinimide salts of one or more
aromatic dicarboxylic acids.
[0016] The present invention also provides a method for lubricating
an internal combustion engine comprising contacting the engine with
the lubricating oil composition of the present invention.
[0017] The present invention additionally provides a method for
reducing bearing corrosion in a diesel engine which comprises
operating the engine with the lubricating oil composition of the
present invention.
[0018] Among other factors, the present invention is based on the
surprising discovery that the unique combination of one or more
EC-treated polyalkene succinimides and one or more borated
polyalkene succinimides with a specific dispersed aromatic
dicarboxylic acid corrosion inhibitor provides decreased wear in
engines.
DESCRIPTION OF THE INVENTION
[0019] This invention includes an additive formulation comprising
one or more combinations of one or more ethylene carbonate (EC)
treated dispersants and one or more borated dispersants with one or
more dispersed aromatic dicarboxylic acid corrosion inhibitors, a
lubricating oil comprising this additive formulation, an oil of
lubricating viscosity and other additives typically used in the
lubricating oil industry.
[0020] I. EC-treated Dispersant and Borated Dispersant
Combination
[0021] The combination of one or more EC-treated dispersants and
one or more borated dispersants of this invention is described in
U.S. Pat. No. 5,861,363; this patent is incorporated herein by
reference in its entirety. The additive formulation of this
invention further comprises one or more dispersed aromatic
dicarboxylic acid corrosion inhibitors.
[0022] The EC-treated Dispersant and Borated Dispersant Combination
of the present invention comprises from 10% to 50% of a borated
dispersant derived from a lower molecular weight polyalkylene and
from 50% to 90% of an EC-treated dispersant derived from a higher
molecular weight polyalkylene. Unless otherwise specified, all
percents (%) are weight percents (wt. %).
[0023] Preferably, the EC-treated Dispersant and Borated Dispersant
Combination of this invention comprises from 20% to 40% borated
dispersant and from 60% to 80% EC-treated dispersant.
[0024] The individual dispersants used in the EC-treated Dispersant
and Borated Dispersant Combination of this invention may be
prepared by conventional processes, such as those disclosed in U.S.
Pat. Nos. 2,992,708; 3,018,250; 3,018,291; 3,024,237; 3,100,673;
3,172,892; 3,219,666; 3,272,746; 3,361,673; 3,381,022; 3,912,764;
4,234,435; 4,612,132; 4,747,965; 5,112,507; 5,241,003; 5,266,186;
5,286,799; 5,319,030; 5,334,321; 5,356,552; and 5,716,912, the
disclosures of which are all hereby incorporated by reference in
their entirety for all purposes.
[0025] The EC-treated Dispersant and Borated Dispersant Combination
of this invention may be prepared by physically mixing the borated
dispersant and the EC-treated dispersants. The EC-treated
Dispersant and Borated Dispersant Combination may have a slightly
different composition than the initial mixture, because the
components may interact.
[0026] I. (A). Borated Dispersant
[0027] The EC-treated Dispersant and Borated Dispersant Combination
comprises from 10% to 50%, preferably from 20% to 40%, of a borated
dispersant derived from the reaction product of a
polyisobutenylsuccinic anhydride with a polyamine. Preferably, the
borated dispersant is derived from polybutenes having a molecular
weight of from 1200 to 1400, most preferably about 1300.
[0028] The additive package of this invention may comprise greater
than 0% to about 40%, preferably from 5% to 30%, and more
preferably from 10% to 20% of a borated dispersant.
[0029] I. (B). EC-Treated Dispersant
[0030] The EC-treated Dispersant and Borated Dispersant Combination
comprises from 50% to 90%, preferably from 60% to 80%, of an
EC-treated dispersant derived from the reaction product of a
polyisobutenylsuccinic anhydride with a polyamine. The
polyisobutene has a number average molecular weight (M.sub.n) of at
least 1800. Preferably, the EC-treated dispersant is a polybutene
succinimide derived from polybutenes having a molecular weight of
from 2000 to 2400. The EC-treated succinimide of this invention is
described in U.S. Pat. Nos. 5,334,321 and 5,356,552. It is not a
mixture of a polybutene succinic acid derivative, a copolymer and a
polyamine such as taught in U.S. Pat. No. 5,716,912.
[0031] The additive package of this invention may comprise from
about 10% to about 80%, preferably from about 20% to about 60%, and
more preferably from about 30% to about 50% of an EC-treated
dispersant derived from the reaction product of a
polyisobutenylsuccinic anhydride with a polyamine.
[0032] II. Dispersed Aromatic Dicarboxylic Acid Corrosion
Inhibitor
[0033] The dispersed aromatic dicarboxylic acid corrosion
inhibitors of this invention are succinimide salts of one or more
aromatic dicarboxylic acids. Preferred aromatic dicarboxylic acids
may comprise one or more terephthalic acids.
[0034] Certain embodiments of the dispersed aromatic dicarboxylic
acid corrosion inhibitor of this invention are described in U.S.
Pat. Nos. 3,287,271; 3,692,681; and 3,374,174, all of which are
incorporated herein in their entirety. Certain embodiments of the
dispersed aromatic dicarboxylic acid corrosion inhibitors of this
invention comprise one or more succinimide salts of Terephthalic
Acid.
[0035] One embodiment of the dispersed aromatic dicarboxylic acid
corrosion inhibitor of this invention may comprise one or more
dispersed aromatic dicarboxylic acid corrosion inhibitors having
the general formula: 1
[0036] where R.sup.1 is one or more polyisobutenyl groups with a
number average molecular weight of about 1100-1500, and Z is one or
more protonated poly amino radical having from about 3 to about 7
nitrogen atoms, more preferably from about 4 to about 5 nitrogen
atoms and about 8 to about 20 carbon atoms.
[0037] The dispersed aromatic dicarboxylic acid corrosion
inhibitors of this invention inhibit lead corrosion better than
other known lead corrosion inhibitors. Another embodiment of this
invention may comprise a combination of one or more of the
dispersed aromatic dicarboxylic acid corrosion inhibitors described
herein.
[0038] III. Dispersed Aromatic Dicarboxylic Acid Corrosion
Inhibitor Synthesis
[0039] The dispersed aromatic dicarboxylic acid corrosion
inhibitors of this invention may be synthesized as described in
U.S. Pat. Nos. 3,287,271; 3,692,681; and 3,374,174, all of which
are incorporated herein in their entirety.
[0040] One embodiment of the dispersed aromatic dicarboxylic acid
corrosion inhibitor of this invention may be synthesized by
reacting about 1100 to about 1500, preferably about 1300 molecular
weight polyisobutenyl succinic anhydride (PIBSA) with one or more
polyamines, preferably one or more heavy polyamines (HPA) at an
amine/PIBSA CMR of about 0.4 to about 0.6, preferably about 0.45.
This produces a reaction product that may then be reacted with
terephthalic acid.
[0041] Another embodiment of the dispersed aromatic dicarboxylic
acid corrosion inhibitor of this invention may be synthesized by
the reaction of PIBSA with polyamine and terephthalic acid shown in
formula (2). Diethylenetriamine (DETA) may be used as the polyamine
in this reaction. Any polyamine may be used. 2
[0042] Another embodiment of the dispersed aromatic dicarboxylic
acid corrosion inhibitor of this invention may be synthesized as
follows. One or more PIBSAs may be reacted with one or more
polyamines to produce one or more succinimides by heating the
mixture, with or without diluent, at a temperature of from about
110.degree. C. to about 200.degree. C., preferably about
150.degree. C. to about 170.degree. C., for 1 to 20 hours. Heating
for about 3 to about 6 hours is preferred. Reactants may be mixed
and then heated or heating may occur while the reactants are being
mixed. During the heating period, water of the reaction may be
removed by any means known in the art. Any PIBSA may be used. This
includes thermal PIBSA made from conventional PIB or high
reactivity PIB, chlorination PIBSA, a mixture of thermal and
chlorination PIBSA, sulfonic acid catalyzed PIBSA, PolyPIBSA, or
Terpolymer PIBSA. A mixture of PIBSA and a copolymer may also be
used. An amine/PIBSA charge mole ratio (CMR) of about 0.4 to 0.6
may be used. A preferred CMR may be about 0.4 to about 0.5. After
heating, the reaction mixture may be cooled to about 110.degree. C.
to about 150.degree. C., preferably about 130.degree. C. to about
135.degree. C. Terephthalic acid may then be added. About 2% to
about 5% terephthalic acid, preferably about 2.5% to about 3.5% by
weight, based on the succinimide weight may be used. This mixture
may then be heated for about 1 to about 10 hours, preferably about
2 to about 4 hours. The mixture may then be filtered.
[0043] Another embodiment of this invention may comprise one or
more corrosion inhibitors synthesized by reacting 1000 molecular
weight polyisobutenesuccinic anhydride (PIBSA) with
tetraethylenepentamine (TEPA) using an amine/PIBSA charge mole
ratio (CMR) of 0.71. This produces a reaction product, which may
then be reacted with terephthalic acid to form a dispersed aromatic
dicarboxylic acid corrosion inhibitor.
[0044] Another embodiment of this invention may comprise combining
one or more of the dispersed aromatic dicarboxylic acid corrosion
inhibitors of this invention.
[0045] IV. The Dispersant Inhibitor Package of this Invention and
Method of Preparation
[0046] Another embodiment of this invention may comprise a
Dispersant Inhibitor Package that comprises one or more borated
dispersants comprising EC-treated dispersants, borated dispersants,
one or more corrosion inhibitors, and any other additives
traditionally used in lubricating oils. The components of the
DI-Package may be combined in any order and heated to about
80.degree. F. to about 200.degree. F., preferably to about
145.degree. F. to about 155.degree. F., with agitation until all
components are mixed. The components may either be mixed together
while heating or mixed together and then heated to these
temperatures. The DI-Package may be blended with viscosity improver
additives and added to lubricating oil or the viscosity improver
additives may be added to the oil separately or added to the
DI-Package with the other DI-Package components. The DI-Package may
comprise greater than 0% to about 30% of one or more borated
dispersants, preferably about 10% to about 20%; about 10% to about
80% EC-treated dispersants, preferably about 20% to about 60%; and
greater than 0% to about 5%, preferably about 0.5% to about 3% of
one or more dispersed aromatic dicarboxylic acid corrosion
inhibitors and any other additives traditionally used in
lubricating oils. The percentages in the previous sentence are
weight percentages of the DI-Package.
[0047] IV. Additional Additive Components
[0048] The following additive components are examples of some of
the components that may be favorably employed in some embodiments
of this invention. These examples of additives are provided to
illustrate this invention, but they are not intended to limit
it.
[0049] A. Antioxidants
[0050] Embodiments of this invention may include but are not
limited to such antioxidants as phenol type (phenolic) oxidation
inhibitors, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol),
4,4'-bis(2,6-di-tert-butylph- enol),
4,4'-bis(2-methyl-6-tert-butylphenol),
2,2'-methylene-bis(4-methyl-- 6-tert-butylphenol),
4,4'-butylidene-bis(3-methyl-6-tert-butylphenol),
4,4'-isopropylidene-bis(2,6-di-tert-butylphenol),
2,2'-methylene-bis(4-me- thyl-6-nonylphenol),
2,2'-isobutylidene-bis(4,6-dimethylphenol),
2,2'-methylene-bis(4-methyl-6-cyclohexylphenol),
2,6-di-tert-butyl4-methy- lphenol, 2,6-di-tert-butyl4-ethylphenol,
2,4-dimethyl-6-tert-butyl-phenol,
2,6-di-tert-l-dimethylamino-p-cresol,
2,6-di-tert-4-(N,N'-dimethylaminome- thylphenol),
4,4'-thiobis(2-methyl-6-tert-butylphenol),
2,2'-thiobis(4-methyl-6-tert-butylphenol),
bis(3-methyl-4-hydroxy-5-tert-- butylbenzyl )-sulfide, and
bis(3,5-di-tert-butyl-4-hydroxybenzyl). Diphenylamine-type
oxidation inhibitors include, but are not limited to, alkylated
diphenylamine, phenyl-.alpha.-naphthylamine, and
alkylated-.alpha.-naphthylamine. Other types of oxidation
inhibitors include metal dithiocarbamate (e.g., zinc
dithiocarbamate), and methylenebis (dibutyldithiocarbamate).
[0051] B. Wear Inhibitors
[0052] Embodiments of this invention may comprise traditional wear
inhibitors. As their name implies, these agents reduce wear of
moving metallic parts. Examples of such agents include, but are not
limited to, phosphates, phosphites, carbamates, esters, sulfur
containing compounds, and molybdenum complexes.
[0053] C. Rust Inhibitors (Anti-Rust Agents)
[0054] Embodiments of this invention may comprise traditional rust
inhibitors including, but not limited to:
[0055] 1. Nonionic polyoxyethylene surface active agents:
polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether,
polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl
ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl
ether, polyoxyethylene sorbitol monostearate, polyoxyethylene
sorbitol mono-oleate, and polyethylene glycol mono-oleate; and
[0056] 2. Other compounds: stearic acid and other fatty acids,
dicarboxylic acids, metal soaps, fatty acid amine salts, metal
salts of heavy sulfonic acid, partial carboxylic acid ester of
polyhydric alcohol, and phosphoric ester.
[0057] D. Demulsifiers
[0058] Embodiments of this invention may comprise traditional
demulsifiers including but not limited to addition products of
alkylphenol and ethylene oxide, polyoxyethylene alkyl ether, and
polyoxyethylene sorbitan ester.
[0059] E. Extreme Pressure Agents (EP Agents)
[0060] Embodiments of this invention may comprise traditional EP
Agents including but not limited to EP Agents that may be used
include Zinc dialkyldithiophosphate (primary alkyl, secondary
alkyl, and aryl type), sulfurized oils, diphenyl sulfide, methyl
trichlorostearate, chlorinated naphthalene,
fluoroalkylpolysiloxane, and lead naphthenate.
[0061] F. Friction Modifiers
[0062] Embodiments of this invention may comprise traditional
friction modifiers including but not limited to fatty alcohol,
fatty acid, amine, borated ester, and other esters.
[0063] G. Multifunctional Additives
[0064] Embodiments of this invention may comprise traditional
multifunctional additives including but not limited to sulfurized
oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo
phosphorodithioate, oxymolybdenum monoglyceride, oxymolybdenum
diethylate amide, amine-molybdenum complex compound, and
sulfur-containing molybdenum complex compound may be used.
[0065] H. Viscosity Index Improvers
[0066] Embodiments of this invention may comprise traditional
viscosity index improvers including but not limited to
polymethacrylate type polymers, ethylene-propylene copolymers,
styrene-isoprene copolymers, hydrated styrene-isoprene copolymers,
polyisobutylene, and dispersant type viscosity index improvers may
be used.
[0067] I. Pour Point Depressants
[0068] Embodiments of this invention may comprise traditional pour
point depressants including but not limited to polymethyl
methacrylate may be used.
[0069] J. Foam Inhibitors
[0070] Embodiments of this invention may comprise traditional foam
inhibitors including but not limited to alkyl methacrylate polymers
and dimethyl silicone polymers may be used.
[0071] V. Lubricating Oil of This Invention
[0072] One embodiment of this invention is a lubricating oil
comprising a major amount of one or more oils of lubricating
viscosity and one or more of the dispersed aromatic dicarboxylic
acid corrosion inhibitors of this invention. The corrosion
inhibitor of this invention may be added to the lubricating oil
separately or as part of the additive package of this
invention.
[0073] One embodiment of this invention is a lubricating oil
comprising a major amount of one or more oils of lubricating
viscosity and one or more of the DI-Packages of this invention. The
DI-Package this invention may be added to the lubricating oil as a
package or the components of the DI-Package of this invention may
be added separately and in any order.
[0074] The oil of lubricating viscosity used in such embodiments
may be mineral oils or synthetic oils. A base oil having a
viscosity of at least 2.5 cSt at 40.degree. C. and a pour point
below 20.degree. C., preferably at or below 0.degree. C. is
desirable. The base oils may be derived from synthetic or natural
sources. Mineral oils for use as the base oil in this invention
include, for example, paraffinic, naphthenic and other oils that
are ordinarily used in lubricating oil compositions. Synthetic oils
include, for example, both hydrocarbon synthetic oils and synthetic
esters and mixtures thereof having the desired viscosity.
Hydrocarbon synthetic oils may include, for example, oils prepared
from the polymerization of ethylene, i.e., polyalphaolefin or PAO,
or from hydrocarbon synthesis procedures using carbon monoxide and
hydrogen gases such as in a Fisher-Tropsch process. Useful
synthetic hydrocarbon oils include liquid polymers of alpha olefins
having the proper viscosity. Especially useful are the hydrogenated
liquid oligomers of C.sub.6 to C.sub.12 alpha olefins such as
1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such
as didodecyl benzene, can be used. Useful synthetic esters include
the esters of monocarboxylic acids and polycarboxylic acids, as
well as mono-hydroxy alkanols and polyols. Typical examples are
didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl
adipate, dilaurylsebacate, and the like. Complex esters prepared
from mixtures of mono and dicarboxylic acids and mono and dihydroxy
alkanols can also be used. Blends of mineral oils with synthetic
oils are also useful. The components of the lubricating oil may be
combined while heating to a temperature from about 80.degree. F. to
about 200.degree. F., preferably about 145.degree. F. to about
155.degree. F. with agitation until all components are mixed. The
components of the lubricating oil of this invention may either be
mixed together while heating or mixed together and then heated to
these temperatures.
[0075] An embodiment of this invention may comprise a lubricating
oil that comprises an oil of lubricating viscosity and the
Dispersant Inhibitor Package of this invention. The Dispersant
Inhibitor Package of this invention may be added to an oil of
lubricating viscosity in any manner and the individual components
of the Dispersant Inhibitor Package may be combined with an oil of
lubricating viscosity separately or as a Dispersant Inhibitor
Package. Additional additives generally known in the lubricating
oil industry may also be added individually or in combination with
the additive formulation of this invention.
[0076] An embodiment of this invention may comprise lubricating oil
compositions having a major amount of a base oil of lubricating
viscosity, the EC-treated Dispersant and Borated Dispersant
Combination of this invention (about 1% to about 20%, preferably
about 3% to about 10%), the dispersed aromatic dicarboxylic acid
corrosion inhibitor of this invention (greater than 0% to about 1%,
preferably about 0.05% to about 0.3%, most preferably about 0.1% to
about 0.2%).
[0077] Another embodiment of this invention may additionally
comprise one or more of the following: detergent (greater than
about 1% to about 10%, preferably about 2% to about 5%, most
preferably about 3% to about 4%), zinc dithiophosphate (greater
than 0% to about 3%, preferably about 0.5% to about 2.5%, most
preferred about 1% to about 2%), oxidation inhibitor (greater than
0% to about 3%, preferably greater than 0% to about 1%, most
preferred 0.2% to about 0.8%), foam inhibitor (greater than 0% to
about 1%), and viscosity index improver (greater than 0% to about
20%). Any zinc dithiophosphate may be used, but a preferred zinc
dithiophosphate may comprise one or more secondary zinc
dithiophosphates. The percentages in this lubricating oil section
are weight percent of the finished lubricating oil.
[0078] Another embodiment of this invention comprises one or more
Lubricating Oil Compositions, wherein the ratio of EC-treated
succinimide to one or more borated succinimide is between about 100
to about 1 and about 10 to about 1.
[0079] VI. Methods of Lubricating Engine Embodiments of This
Invention
[0080] Another embodiment of this invention may comprise a method
for reducing bearing corrosion in one or more diesel engines
equipped with exhaust gas recirculation resulting in increased
levels of nitration of the lubricating oil used to lubricate the
engine.
[0081] Another embodiment of this invention may comprise a method
for lubricating one or more engines comprising contacting the
engine with one or more lubricating oils of this invention.
[0082] Another embodiment of this invention may comprise a method
for lubricating one or more internal combustion engines comprising
contacting the engine with one or more lubricating oils of this
invention.
[0083] Another embodiment of this invention may comprise a method
for lubricating one or more heavy-duty diesel engines comprising
contacting the engine with one or more lubricating oils of this
invention.
[0084] The following examples are included to demonstrate preferred
embodiments of the invention. It should be appreciated by those of
skill in the art that the techniques disclosed in the examples that
follow may represent techniques discovered by the inventor to
function well in the practice of the invention, and thus may be
considered to constitute preferred modes for its practice. However,
those of skill in the art should, in light of the present
disclosure, appreciate that many changes may be made in the
specific embodiments that are disclosed and still obtain a like or
similar result without departing from the spirit and scope of the
invention.
EXAMPLES
[0085] The examples describe experiments performed using Corrosion
Inhibitors 1, 2 and 3 and Samples A through K. The corrosion
inhibition performance of these samples has been evaluated in a
number of bench and engine tests, which will be discussed in the
various examples. Some of the samples contain non-EC-treated
dispersant in addition to the EC-treated dispersant (a) and the
borated dispersant (c).
[0086] Corrosion Inhibitor 1 was prepared by adding 400 g of 1000
molecular weight PIBSA (saponification number 67.1 mg KOH/g sample,
0.24 mole) to an apparatus comprising a 1L three neck flask
equipped with a mechanical stirrer, Dean Stark trap, condenser and
nitrogen inlet. This was heated to 70.degree. C. and to this was
added 32.2 g tetraethylene pentamine (TEPA), 0.17 mole, as the
temperature was heated to 160.degree. C. The amine/PIBSA CMR was
0.71. This product was heated at 160.degree. C. for 3 hours. To
387.75 g of this product, we added 156.9 g diluent oil and to this
was added at 132.degree. C. 20.95 g terephthalic acid (0.126 mole).
This was stirred for3 hours at 132.degree. C. The product was then
filtered.
[0087] Corrosion Inhibitor 2 was prepared by adding 400 g of 1000
molecular weight PIBSA (saponification number 67.1 mg KOH/g sample,
0.24 mole) to an apparatus comprising a 1L three neck flask
equipped with a mechanical stirrer, Dean Stark trap, condenser and
nitrogen inlet. This was heated to 70.degree. C. and to this was
added 32.2 g of a mixture of 20% DETA and 80% HPA, 0.17 mole, as
the temperature was heated to 160.degree. C. The amine/PIBSA CMR
was 0.71. This product was heated at 160.degree. C for 3 hours. To
387.75 g of this product, we added 156.9 g diluent oil and to this
was added at 132.degree. C. 20.95 g terephthalic acid (0.126 mole).
This was stirred for 3 hours at 132.degree. C. The product was then
filtered.
[0088] Corrosion Inhibitor 3 was be prepared by following the
general procedure from corrosion inhibitor 1 and then 16834 g of a
succinimide made from 1300 molecular weight PIBSA with HPA using a
CMR of 0.45 was mixed with 4218 g diluent oil and reacted with 780
g of terephthalic acid. The product after filtration had 1.85%
nitrogen, TAN=29 mg KOH/g sample, TBN=43.7 mg KOH/g sample, and a
viscosity @100.degree. C. of 596 cSt.
[0089] Sample A was prepared by combining about 7.0% EC-treated
dispersant (a), about 2.0% borated dispersant (c), about 0.855% LOB
Sulfonate, about 2.709% Ca-Phenate, about 2.075% wear inhibitor,
1.25% anti-oxidant, about 5 mg/kg foam inhibitor, and Group 1 base
oil. Sample A was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0090] Sample B was prepared by combining about 7.0% EC-treated
dispersant (a), about 2.0% borated dispersant (c), about 0.855% LOB
Sulfonate, about 2.709% Ca-Phenate, about 2.075% wear inhibitor,
1.25% anti-oxidant, about 5 mg/kg foam inhibitor, about 0.25%
Corrosion Inhibitor 1 and Group 1 base oil. Sample B was prepared
by combining the components at 140.degree. F. with agitation until
all components were mixed.
[0091] Sample C was prepared by combining about 7.0% EC-treated
dispersant (a), about 2.0% borated dispersant (c), about 0.855% LOB
Sulfonate, about 2.709% Ca-Phenate, about 2.075% wear inhibitor,
1.25% anti-oxidant, about 5 mg/kg foam inhibitor, about 0.5%
Corrosion Inhibitor 1 and Group 1 base oil. Sample C was prepared
by combining the components at 140.degree. F. with agitation until
all components were mixed.
[0092] Sample D was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-treated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, and Group 1 base oil. Sample D was prepared
by combining the components at 140.degree. F. with agitation until
all components were mixed.
[0093] Sample E was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-treated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.10 Corrosion Inhibitor 2 and Group
1 base oil. Sample E was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0094] Sample F was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-treated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.20 Corrosion Inhibitor 2 and Group
1 base oil. Sample F was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0095] Sample G was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-reated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.40% Corrosion Inhibitor 2 and Group
1 base oil. Sample G was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0096] Sample H was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-treated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.10% Corrosion Inhibitor 3 and Group
1 base oil. Sample H was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0097] Sample I was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-treated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.20% Corrosion Inhibitor 3 and Group
1 base oil. Sample I was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0098] Sample J was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-reated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.30% Corrosion Inhibitor 3 and Group
1 base oil. Sample J was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
[0099] Sample K was prepared by combining about 6.0% EC-treated
dispersant (a), about 1.0% non-EC-treated dispersant, about 0.6%
borated dispersant (c), about 0.684% LOB Sulfonate, about 2.924%
Ca-Phenate, about 1.826% wear inhibitor, 0.57% anti-oxidant, about
5 mg/kg foam inhibitor, about 0.40% Corrosion Inhibitor 3 and Group
1 base oil. Sample K was prepared by combining the components at
140.degree. F. with agitation until all components were mixed.
Example 1
[0100] Bearing Corrosion Evaluation in Engine Test
[0101] The Mack T-10 engine test has been developed by the American
Society for Testing and Materials (ASTM). The test is part of the
API lubricant specification for diesel engines, CI-4, and measures
piston ring, cylinder liner, and bearing wear. Bearing wear in this
test is the result of corrosion of the copper-lead surface of the
bearings. The conventional approach to bearing protection is the
neutralization of acidic contaminants responsible for bearing
corrosion. Neutralization capability is provided by detergents and
the base reserve during the test is monitored by the Total Base
Number (TBN). The capability of an oil to protect the bearing
material from corrosion is evaluated by determining the amount of
lead (Pb) found in oil samples taken from the engine at regular
intervals during the test and at the end of the test. This
determination of the Pb-content is done using an ICP analysis.
Lower Pb-contents indicate better corrosion protection.
[0102] Samples A and C were tested in the Mack T-10 engine test.
Results are presented in Table 1. The results demonstrate that both
samples show TBN depletion to the point where corrosion becomes a
concern. In the case of Sample A, the Pb-content increases
gradually over the course of the test and increases exponentially
toward the end on the test indicating that the corrosion is out of
control. Sample C, which contains Corrosion Inhibitor 1, shows TBN
depletion and a gradual increase in Pb-content over the duration of
the test but did not show any exponential increase in Pb toward the
end of the test.
1TABLE 1 Bearing Corrosion Engine Test Results Sample A Sample C
Test TBN, mg/g Pb-Content, TBN, mg/g Pb-Content, Time, h KOH mg/kg
KOH mg/kg 0 8.01 1 8.08 1 50 4.43 2 4.24 2 100 2.80 4 2.28 7 150
1.93 7 1.18 17 200 1.21 13 0.51 24 250 0.51 33 0.11 34 275 0.62 65
0.25 38 300 0.05 88 0.05 43
Example 2
[0103] Bearing Corrosion Bench Test Evaluation
[0104] Samples A through C were evaluated in a bearing corrosion
bench test. This bench test has been designed to mimic the Mack
T-10 engine test where the wear phase is preceded by a lubricant
degradation phase where the oil sees significant TBN depletion as a
result of contamination with condensed acids. In the bearing
corrosion bench test, a sample of the candidate oil was
contaminated with H.sub.2SO.sub.4. The contaminated sample was
exposed to an elevated temperature for about 20 hours while
NO.sub.2 in air was pumped through the sample. Three metal coupons
(Cu, Pb and Fe) were submersed in the sample during the test. At
the end of the test, the amount of Pb in the oil sample was
determined using the ICP.
[0105] Samples A, B and C were evaluated in the bearing corrosion
bench test and the Pb-content of the oil at the end of the test was
measured. The results are shown in Table 2.
2TABLE 2 Bearing Corrosion Bench Test Results Sample A Sample B
Sample C Corrosion Inhibitor 1 Treat 0.00 0.25 0.50 Rate, % Used
Oil Pb-Content, mg/kg 217 119 51
Example 3
[0106] Bearing Corrosion Evaluation in Bench Test
[0107] Samples D through G were evaluated in the bearing corrosion
bench test. This bench test has been described in Example 2. The
results are shown in Table 3.
3TABLE 3 Bearing Corrosion Bench Test Results Sample D Sample E
Sample F Sample G Corrosion Inhibitor 2 0.00 0.10 0.20 0.40 Treat
Rate, % Used Oil Pb-Content, 164 73 77 66 mg/kg
Example 4
[0108] Bearing Corrosion Evaluation in Bench Test
[0109] Samples H through K were evaluated in the bearing corrosion
bench test, and compared with Sample D. This bench test has been
described in Example 2. The results are shown in Table 4.
4TABLE 4 Bearing Corrosion Bench Test Results Using Corrosion
Inhibitors of This Invention Sample Sample Sample Sample Sample D H
I J K Corrosion Inhibitor 3 0.00 0.10 0.20 0.30 0.40 Treat Rate, %
Used Oil Pb-Content, 164 79 73 70 42 mg/kg
* * * * *