U.S. patent application number 12/850798 was filed with the patent office on 2011-02-10 for lubricant composition.
Invention is credited to Vineet Bajpai, David Eliezer Chasan, Margaret Frances Egiziaco, Paul Fasano.
Application Number | 20110030269 12/850798 |
Document ID | / |
Family ID | 42983360 |
Filed Date | 2011-02-10 |
United States Patent
Application |
20110030269 |
Kind Code |
A1 |
Chasan; David Eliezer ; et
al. |
February 10, 2011 |
LUBRICANT COMPOSITION
Abstract
A lubricant composition is suitable for use in diesel engines
and is resistant to degradation by oxidative by-products of
biodiesel fuel. The composition includes (A) a base oil, (B) at
least one diphenylamine antioxidant, and (C) at least one
antioxidant. The antioxidant (C) is selected from the group
consisting of a sulfur containing phenolic antioxidant, a
phenyl-alpha-naphthylamine antioxidant, and combinations thereof.
The lubricant composition is formed using a method. In the method,
the (A) base oil has an initial oxidation value measured according
to ASTM D 6186. In addition in the method, the lubricant
composition includes up to about 6 wt % of the biodiesel fuel and
has a final oxidation value measured according to ASTM D 6186 that
is equal to or greater than the initial oxidation value of the (A)
base oil.
Inventors: |
Chasan; David Eliezer;
(Teaneck, NJ) ; Fasano; Paul; (Carmel, NY)
; Egiziaco; Margaret Frances; (North White Plains,
NY) ; Bajpai; Vineet; (Cos Cob, CT) |
Correspondence
Address: |
HOWARD & HOWARD ATTORNEYS PLLC;BASF SE
450 West Fourth Street
Royal Oak
MI
48067
US
|
Family ID: |
42983360 |
Appl. No.: |
12/850798 |
Filed: |
August 5, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61231468 |
Aug 5, 2009 |
|
|
|
Current U.S.
Class: |
44/388 ; 508/478;
508/563 |
Current CPC
Class: |
C10M 2219/06 20130101;
C10N 2030/10 20130101; C10M 2215/065 20130101; C10M 2207/289
20130101; C10N 2040/252 20200501; C10M 2215/064 20130101; C10M
133/12 20130101; C10M 2207/281 20130101; C10M 2219/087 20130101;
C10M 141/08 20130101; C10N 2030/78 20200501 |
Class at
Publication: |
44/388 ; 508/563;
508/478 |
International
Class: |
C10L 1/19 20060101
C10L001/19; C10M 169/04 20060101 C10M169/04 |
Claims
1. A lubricant composition suitable for use in a diesel engine and
resistant to degradation by oxidative by-products of biodiesel
fuel, said composition comprising: A. a base oil; B. at least one
diphenylamine antioxidant; and C. at least one antioxidant selected
from a sulfur containing phenolic antioxidant, a
phenyl-alpha-naphthylamine antioxidant, and combinations
thereof.
2. A lubricant composition as set forth in claim 1 wherein said (C)
at least one antioxidant comprises both said sulfur containing
phenolic antioxidant and said phenyl-alpha-naphthylamine
antioxidant.
3. A lubricant composition as set forth in claim 1 wherein said (C)
at least one antioxidant comprises said sulfur containing phenolic
antioxidant
4. A lubricant composition as set forth in claim 1 wherein said (C)
at least one antioxidant consists essentially of said sulfur
containing phenolic antioxidant.
5. A lubricant composition as set forth in claim 4 wherein said (C)
at least one antioxidant is free of said phenyl-alpha-naphthylamine
antioxidant.
6. A lubricant composition as set forth in claim 1 wherein said (C)
at least one antioxidant comprises said phenyl-alpha-naphthylamine
antioxidant.
7. A lubricant composition as set forth in claim 1 wherein said (C)
at least one antioxidant consists essentially of said
phenyl-alpha-naphthylamine antioxidant.
8. A lubricant composition as set forth in claim 7 wherein said (C)
at least one antioxidant is free of said sulfur containing phenolic
antioxidant.
9. A lubricant composition as set forth in claim 1 wherein said
phenyl-alpha-naphthylamine antioxidant is further defined as having
the formula: ##STR00004## and wherein R.sub.1 is an aryl radical
having from 6 to 12 carbon atoms or an aryl radical having from 6
to 20 carbon atoms and substituted by one, two or three straight or
branched chain alkyl radicals each having from 1 to 18 carbon
atoms.
10. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant is further defined as
having the formula: ##STR00005## wherein each R' is independently a
hydrogen atom, a straight or branched chain alkyl radical having
from 1 to 18 carbon atoms, or an aralkyl radical having 7 to 14
carbon atoms; wherein said (C) at least one antioxidant comprises
said sulfur containing phenolic antioxidant and said sulfur
containing phenolic antioxidant is further defined as having the
formula: ##STR00006## and wherein x is a number from 0 to 6, y is a
number from 2 to 20 and R is a straight or branched chain alkyl
radical having from 1 to 6 carbon atoms.
11. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant is further defined as
comprising at least one octylated/butylated diphenylamine
antioxidant and also comprising thiodiethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
12. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant is further defined as
having the formula: ##STR00007## wherein each R' is independently a
hydrogen atom, a straight or branched chain alkyl radical having
from 1 to 18 carbon atoms, or an aralkyl radical having 7 to 14
carbon atoms; wherein said (C) at least one antioxidant comprises
said phenyl-alpha-naphthylamine antioxidant and said
phenyl-alpha-naphthylamine antioxidant is further defined as having
the formula: ##STR00008## and wherein R.sub.1 is an aryl radical
having from 6 to 12 carbon atoms or an aryl radical having from 6
to 20 carbon atoms and substituted by one, two or three straight or
branched chain alkyl radicals each having from 1 to 18 carbon
atoms.
13. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant is further defined as
comprising at least one octylated/butylated diphenylamine
antioxidant, wherein said (C) at least one antioxidant comprises
said phenyl-alpha-naphthylamine antioxidant, and said
phenyl-alpha-naphthylamine antioxidant is further defined as
octylated phenyl-alpha-naphthylamine.
14. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant and said (C) at least
one antioxidant are present in a weight ratio of from about 9:1 to
about 1:9 to each other, respectively.
15. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant and said (C) at least
one antioxidant are present in a combined amount of from about 0.3
to 7 parts by weight per 100 parts by weight of said base oil.
16. A lubricant composition as set forth in claim 1 wherein said
(B) at least one diphenylamine antioxidant and said (C) at least
one antioxidant are present in a combined amount of from about 0.5
to 3 parts by weight per 100 parts by weight of said base oil.
17. A lubricant composition as set forth in claim 1 further
comprising a biodiesel fuel.
18. A lubricant composition as set forth in claim 17 wherein said
biodiesel fuel is present in said lubricant composition in an
amount of from 1 to 50 weight percent.
19. A lubricant composition as set forth in claim 17 wherein said
biodiesel fuel comprises at least one fatty acid methyl ester of a
vegetable or oleaginous seed oil.
20. A lubricant composition as set forth in claim 19 wherein fatty
acid methyl ester is further defined as a soy oil fatty acid methyl
ester, a rapeseed oil fatty acid methyl ester, a palm oil fatty
acid methyl ester, or a coconut oil fatty acid methyl ester.
21. A lubricant composition as set forth in claim 17 wherein said
biodiesel fuel is further defined as a first, second, or third
generation biodiesel fuel.
22. A lubricant composition as set forth in claim 1 wherein said
base oil is further defined as an API Group II or Group III base
oil.
23. A lubricant composition as set forth in claim 1 wherein said
base oil is further defined as an API Group II base oil, said (B)
at least one diphenylamine antioxidant is further defined as an
octylated/butylated diphenylamine, and said (C) at least one
antioxidant comprises octylated phenyl-alpha-naphthylamine, and (B)
and (C) are present in a combined amount of from about 0.5 to 3
parts by weight per 100 parts by weight of said base oil
24. A lubricant composition as set forth in claim 23 further
comprising a biodiesel fuel in an amount of from 0.5 to 6 parts by
weight per 100 parts by weight of said lubricant composition.
25. A lubricant composition as set forth in claim 1 wherein the (A)
base oil has an initial oxidation value measured according to ASTM
D 6186 and wherein said lubricant composition comprises up to about
6 wt % of the biodiesel fuel and has a final oxidation value
measured according to ASTM D 6186 that is equal to or greater than
the initial oxidation value of the (A) base oil.
26. A lubricant composition as set forth in claim 25 comprising
from 0.3 to 7 parts by weight of said (B) and (C) antioxidants per
100 parts by weight of said lubricant composition.
27. A lubricant composition as set forth in claim 25 comprising
from 0.9 to 3.5 parts by weight of said (B) and (C) antioxidants
per 100 parts by weight of said lubricant composition.
28. A lubricant composition as set forth in claim 25 comprising
less than about 2.1 parts by weight of said (B) and (C)
antioxidants per 100 parts by weight of said lubricant
composition.
29. A method of improving the performance of a lubricant
composition suitable for use in diesel engines by improving
resistance to degradation by oxidative by-products of a biodiesel
fuel, wherein the lubricant composition comprises (A) a base oil,
said method comprising the steps of: i. providing the (A) base oil;
ii. providing (B) at least one diphenylamine antioxidant; iii.
providing (C) at least one antioxidant selected from a sulfur
containing phenolic antioxidant, a phenyl-alpha-naphthylamine
antioxidant, and combinations thereof; and iv. combining (A), (B),
and (C) to form the lubricant composition; wherein the (A) base oil
has an initial oxidation value measured according to ASTM D 6186,
wherein the lubricant composition comprises up to about 6 wt % of
the biodiesel fuel and has a final oxidation value measured
according to ASTM D 6186 that is equal to or greater than the
initial oxidation value of the (A) base oil.
30. A method as set forth in claim 29 wherein the lubricant
composition comprises from 0.3 to 7 parts by weight of the (B) and
(C) antioxidants per 100 parts by weight of the lubricant
composition.
31. A method as set forth in claim 29 wherein the lubricant
composition comprises from 0.9 to 3.5 parts by weight of the (B)
and (C) antioxidants per 100 parts by weight of the lubricant
composition.
32. A method as set forth in claim 29 wherein the lubricant
composition comprises less than about 2.1 parts by weight of the
(B) and (C) antioxidants per 100 parts by weight of the lubricant
composition.
33. A method as set forth in claim 29 wherein the lubricant
composition is diluted with the biodiesel fuel in a lubricant sump
of a diesel engine.
34. A method as set forth in claim 29 wherein the (C) at least one
antioxidant comprises both the sulfur containing phenolic
antioxidant and the phenyl-alpha-naphthylamine antioxidant.
35. A method as set forth in claim 29 wherein the (C) at least one
antioxidant comprises the sulfur containing phenolic
antioxidant
36. A method as set forth in claim 29 wherein the (C) at least one
antioxidant comprises the phenyl-alpha-naphthylamine
antioxidant.
37. A method as set forth in claim 29 wherein the
phenyl-alpha-naphthylamine antioxidant is further defined as having
the formula: ##STR00009## and wherein R.sub.1 is an aryl radical
having from 6 to 12 carbon atoms or an aryl radical having from 6
to 20 carbon atoms and substituted by one, two or three straight or
branched chain alkyl radicals each having from 1 to 18 carbon
atoms.
38. A method as set forth in claim 29 wherein the (B) at least one
diphenylamine antioxidant is further defined as having the formula:
##STR00010## wherein each R' is independently a hydrogen atom, a
straight or branched chain alkyl radical having from 1 to 18 carbon
atoms, or an aralkyl radical having 7 to 14 carbon atoms; wherein
the (C) at least one antioxidant comprises the sulfur containing
phenolic antioxidant and the sulfur containing phenolic antioxidant
is further defined as having the formula: ##STR00011## and wherein
x is a number from 0 to 6, y is a number from 2 to 20 and R is a
straight or branched chain alkyl radical having from 1 to 6 carbon
atoms.
39. A method as set forth in claim 29 wherein (B) at least one
diphenylamine antioxidant is further defined as comprising at least
one octylated/butylated diphenylamine antioxidant and also
comprising thiodiethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
40. A method as set forth in claim 29 wherein the (B) at least one
diphenylamine antioxidant is further defined as having the formula:
##STR00012## wherein each R' is independently a hydrogen atom, a
straight or branched chain alkyl radical having from 1 to 18 carbon
atoms, or an aralkyl radical having 7 to 14 carbon atoms; wherein
the (C) at least one antioxidant comprises the
phenyl-alpha-naphthylamine antioxidant and the
phenyl-alpha-naphthylamine antioxidant is further defined as having
the formula: ##STR00013## and wherein R.sub.1 is an aryl radical
having from 6 to 12 carbon atoms or an aryl radical having from 6
to 20 carbon atoms and substituted by one, two or three straight or
branched chain alkyl radicals each having from 1 to 18 carbon
atoms.
41. A method as set forth in claim 29 wherein the (B) at least one
diphenylamine antioxidant is further defined as comprising at least
one octylated/butylated diphenylamine antioxidant, wherein the (C)
at least one antioxidant comprises the phenyl-alpha-naphthylamine
antioxidant, and the phenyl-alpha-naphthylamine antioxidant is
further defined as octylated phenyl-alpha-naphthylamine.
42. A method as set forth in claim 29 wherein base oil is further
defined as an API Group II base oil, the (B) at least one
diphenylamine antioxidant is further defined as an
octylated/butylated diphenylamine, and the (C) at least one
antioxidant comprises octylated phenyl-alpha-naphthylamine, and (B)
and (C) are present in a combined amount of from about 0.5 to 3
parts by weight per 100 parts by weight of the base oil.
Description
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Prov. Ser. No.
61/231,468, filed on Aug. 5, 2009, the disclosure of which is
expressly incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention generally relates to a lubricant
composition including a base oil and two antioxidants. More
specifically, the lubricant composition includes the base oil, at
least one diphenylamine antioxidant, and at least one sulfur
containing phenolic antioxidant and/or phenyl-alpha-naphthylamine
antioxidant.
DESCRIPTION OF THE RELATED ART
[0003] Lubricant compositions are generally well known in the art
and are broadly categorized as oil or water based compositions,
i.e., compositions that include large weight percentages of
non-polar compounds or large weight percentages of water. Lubricant
compositions are typically further categorized as engine oils,
driveline system oils, gear oils, automatic and manual transmission
fluids and oils, hydraulic oils, industrial gear oils, turbine
oils, rust and oxidation (R&O) inhibited oils, compressor oils,
or paper machine oils, etc. Each of these compositions has
particular specifications and design requirements. Nevertheless,
most are designed to minimize corrosion and wear, resist thermal
and physical breakdown, and be able to minimize the effects of
common contaminants such as oxidizing compounds and metal
fragments.
[0004] Stabilizers are typically added to lubricant compositions to
improve performance characteristics. In many cases, antioxidants
are utilized to reduce oxidative degradation of the compositions
and various compounds present therein. In diesel engines, for
example, high temperatures in the combustion chambers of the
engines and the presence of nitrogenous oxides tend to promote
oxidation of the compositions. In fact, the nitrogenous oxides act
as oxidation catalysts.
[0005] As is well recognized in the art, biodiesel fuel is fast
becoming an important renewable energy source. Biodiesel fuel can
be employed as a fuel itself (without dilution) or may be used in
combination with traditional petroleum diesel fuels. The physical
properties and chemical stability of biodiesel fuels depends on
fatty acid composition and content. Biodiesel fuel derived from
vegetable oil tends to include unsaturated alkyl groups which are
more prone to oxidation than saturated alkyl groups. As a result,
biodiesel fuels tend to be associated with generation and
accumulation of oxidative by-products in diesel engines.
[0006] When diesel fuel is used, certain amounts of non-consumed
(i.e., non-combusted) and/or oxidatively degraded fuel typically
passes over piston rings and seals and enters lubricant sumps. This
phenomenon is known in the art as "blow-by." Both traditional
diesel fuel and biodiesel fuels are subject to this phenomenon and,
as a result, tend to collect in lubricant sumps. Even though
traditional diesel fuel tends to collect in the sumps, it does not
usually accumulate due to evaporation. Biodiesel fuel, on the other
hand, has higher distillation and boiling temperatures than
traditional diesel fuel and, thus, tends to accumulate in the sumps
due to reduced evaporation. In some cases, biodiesel fuel becomes
concentrated in the sumps once the traditional diesel fuel
evaporates. For these reasons, oxidative by-products that are
produced as the result of the oxidation of the biodiesel fuels also
tend to accumulate and/or become concentrated in the sumps. These
oxidative by-products directly affect the performance of the
lubricant compositions that flow through the sumps. Even though
many lubricant compositions include antioxidants, these
antioxidants are traditionally insufficient and ineffective in
neutralizing the oxidative by-products of the biodiesel fuels. As a
result, performance and durability of the lubricant compositions
and the diesel engines, suffer. Accordingly, there remains an
opportunity to develop an improved lubricant composition that is
resistant to degradation by oxidative by-products of biodiesel
fuel.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0007] Other advantages of the present invention will be readily
appreciated, as the same becomes better understood by reference to
the following detailed description when considered in connection
with the accompanying drawings wherein:
[0008] FIG. 1 is a line graph illustrating results of high pressure
differential scanning calorimetry (DSC) testing of heavy duty
engine oil (HDEO) according to ASTM D 6186. The HDEO includes 2 wt
% aged soy methyl ester as biodiesel fuel and various weight
percents of antioxidant Mixtures A-E of the Examples. Minutes of
oxidation induction are plotted against a weight percent of the
Mixtures added to the HDEO. The results set forth in FIG. 1
demonstrate differing effectiveness of the various Mixtures
relative to achieving a final oxidation value of the HDEO/biodiesel
combination that is equal to or greater than an initial oxidation
value of the HDEO itself, according to ASTM D 6186.
[0009] FIG. 2 is similar to FIG. 1 except that the HDEO is
contaminated with 2 wt % aged rapeseed methyl ester as the
biodiesel fuel.
[0010] FIG. 3 is also similar to FIG. 1 except that the HDEO is
contaminated with 2 wt % aged palm methyl ester as the biodiesel
fuel.
[0011] FIG. 4 is also similar to FIG. 1 except that the HDEO is
contaminated with 2 wt % aged coconut methyl ester as the biodiesel
fuel.
[0012] FIG. 5 is similar to FIG. 1 except that the HDEO is
contaminated with 6 wt % aged soy methyl ester as the biodiesel
fuel.
[0013] FIG. 6 is similar to FIG. 2 except that the HDEO is
contaminated with 6 wt % aged rapeseed methyl ester as the
biodiesel fuel.
[0014] FIG. 7 is also similar to FIG. 3 except that the HDEO is
contaminated with 6 wt % aged palm methyl ester as the biodiesel
fuel.
[0015] FIG. 8 is also similar to FIG. 4 except that the HDEO is
contaminated with 6 wt % aged coconut methyl ester as the biodiesel
fuel.
[0016] FIG. 9 is a line graph illustrating results of viscosity
testing of heavy duty engine oil (HDEO) according to the procedure
described in SAE 040793. The HDEO includes 2 wt % aged soy methyl
ester as biodiesel fuel and various weight percents of antioxidant
Mixtures A-E of the Examples. Hours needed to reach a 375% increase
in viscosity of the HDEO/biodiesel combination are plotted against
a weight percent of the Mixtures added to the HDEO. The results set
forth in FIG. 9 demonstrate differing effectiveness of the various
Mixtures relative to increasing a number of hours to increase
viscosity according to SAE 040793.
[0017] FIG. 10 is similar to FIG. 9 except that the HDEO is
contaminated with 2 wt % aged rapeseed methyl ester as the
biodiesel fuel.
[0018] FIG. 11 is also similar to FIG. 9 except that the HDEO is
contaminated with 2 wt % aged palm methyl ester as the biodiesel
fuel.
[0019] FIG. 12 is also similar to FIG. 9 except that the HDEO is
contaminated with 2 wt % aged coconut methyl ester as the biodiesel
fuel.
[0020] FIG. 13 is similar to FIG. 9 except that the HDEO is
contaminated with 6 wt % aged soy methyl ester as the biodiesel
fuel.
[0021] FIG. 14 is similar to FIG. 10 except that the HDEO is
contaminated with 6 wt % aged rapeseed methyl ester as the
biodiesel fuel.
[0022] FIG. 15 is also similar to FIG. 11 except that the HDEO is
contaminated with 6 wt % aged palm methyl ester as the biodiesel
fuel.
[0023] FIG. 16 is also similar to FIG. 12 except that the HDEO is
contaminated with 6 wt % aged coconut methyl ester as the biodiesel
fuel.
SUMMARY OF THE INVENTION AND ADVANTAGES
[0024] The instant invention provides a lubricant composition that
is suitable for use as in diesel engines and that is resistant to
degradation by oxidative by-products of biodiesel fuel. The
lubricant composition includes (A) a base oil, (B) at least one
diphenylamine antioxidant, and (C) at least one antioxidant
selected from the group consisting of a sulfur containing phenolic
antioxidant, a phenyl-alpha-naphthylamine antioxidant, and
combinations thereof. The invention also provides a method for
improving the performance of the lubricant composition by improving
resistance to degradation by oxidative by-products of the biodiesel
fuel. The method includes the steps of providing the (A) base oil,
providing the (B) at least one diphenylamine antioxidant, and
providing the (C) at least one antioxidant. The method also
includes the step of combining (A), (B), and (C) to form the
lubricant composition. In the method, the (A) base oil has an
initial oxidation value measured according to ASTM D 6186. In
addition in the method, the lubricant composition includes up to
about 6 wt % of the biodiesel fuel and has a final oxidation value
measured according to ASTM D 6186 that is equal to or greater than
the initial oxidation value of the (A) base oil. The antioxidants
(B) and (C) supplement the (A) base oil and overall lubricant
composition and allow the lubricant composition to resist
degradation by oxidative by-products of biodiesel fuel.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention provides a lubricant composition that
is suitable for use in diesel engines and that is resistant to
degradation by oxidative by-products of biodiesel fuel. In various
embodiments, the lubricant composition can be further described as
a fully formulated lubricant or alternatively as an engine oil. In
one embodiment, the terminology "fully formulated lubricant" refers
to a total final composition that is a final commercial oil. This
final commercial oil may include, for instance, detergents,
dispersants, antioxidants, antifoam additives, pour point
depressants, viscosity index improvers, anti-wear additives,
friction modifiers, and other customary additives. In the art,
engine oils may be referred to as including a base oil as described
below and performance additives (not including (B) and (C)
described below). The lubricant composition may be as described in
U.S. Prov. Ser. No. 61/231,468, filed on Aug. 5, 2009, the
disclosure of which is also expressly incorporated herein by
reference in its entirety.
[0026] The lubricant composition (hereinafter referred to as
"composition") includes (A) a base oil in addition to (B) at least
one diphenylamine antioxidant, and (C) at least one antioxidant
selected from the group consisting of a sulfur containing phenolic
antioxidant, a phenyl-alpha-naphthylamine antioxidant, and
combinations thereof. Each of (A), (B), and (C) are described in
greater detail below.
Base Oil:
[0027] The base oil is not particularly limited and may be further
defined as including one or more oils of lubricating viscosity such
as natural and synthetic lubricating oils and mixtures thereof. In
one embodiment, the base oil is further defined as a lubricant. In
another embodiment, the base oil is further defined as an oil of
lubricating viscosity. In still another embodiment, the base oil is
further defined as a crankcase lubricating oil for spark-ignited
and compression ignited internal combustion engines, including
automobile and truck engines, two-cycle engines, aviation piston
engines, and marine and railroad diesel engines. Alternatively, the
base oil can be further defined as an oil to be used in gas
engines, stationary power engines, and turbines. The base oil may
be further defined as a heavy or light duty engine oil. In one
embodiment, the base oil is further defined as a heavy duty diesel
engine oil. Alternatively, the base oil may be described as an oil
of lubricating viscosity or lubricating oil, for instance as
disclosed in U.S. Pat. No. 6,787,663 and U.S. 2007/0197407, each of
which is expressly incorporated herein by reference. It is also
contemplated that the base oil may be as described in U.S. Ser. No.
61/231,468, filed on Aug. 5, 2009, the disclosure of which is
expressly incorporated herein by reference in its entirety.
[0028] The base oil may be further defined as a base stock oil.
Alternatively, the base oil may be further defined as a component
that is produced by a single manufacturer to the same
specifications (independent of feed source or manufacturer's
location) that meets the same manufacturer's specification and that
is identified by a unique formula, product identification number,
or both. The base oil may be manufactured or derived using a
variety of different processes including but not limited to
distillation, solvent refining, hydrogen processing,
oligomerization, esterification, and re-refining. Re-refined stock
is typically substantially free from materials introduced through
manufacturing, contamination, or previous use. In one embodiment,
the base oil is further defined as a base stock slate, as is known
in the art.
[0029] Alternatively, the base oil may be derived from
hydrocracking, hydrogenation, hydrofinishing, refined and
re-refined oils or mixtures thereof or may include one or more such
oils. In one embodiment, the base oil is further defined as an oil
of lubricating viscosity such as a natural or synthetic oil and/or
combinations thereof. Natural oils include, but are not limited to,
animal oils and vegetable oils (e.g., castor oil, lard oil) as well
as liquid petroleum oils and solvent-treated or acid-treated
mineral lubricating oils such as paraffinic, naphthenic or mixed
paraffinic-naphthenic oils.
[0030] In various other embodiments, the base oil may be further
defined as an oil derived from coal or shale. Non-limiting examples
of suitable oils include hydrocarbon oils such as polymerized and
interpolymerized olefins (e.g., polybutylenes, polypropylenes,
propylene-isobutylene copolymers, poly(1-hexenes), poly(1-octenes),
poly(1-decenes), and mixtures thereof; alkylbenzenes (e.g.,
dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, and
di(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls,
terphenyls, and alkylated polyphenyls), alkylated diphenyl ethers
and alkylated diphenyl sulfides and the derivatives, analogs, and
homologs thereof.
[0031] In still other embodiments, the base oil may be further
defined as a synthetic oil which may include one or more alkylene
oxide polymers and interpolymers and derivatives thereof wherein
terminal hydroxyl groups are modified by esterification,
etherification, or similar reactions. Typically, these synthetic
oils are prepared through polymerization of ethylene oxide or
propylene oxide to form polyoxyalkylene polymers which can be
further reacted to form the oils. For example, alkyl and aryl
ethers of these polyoxyalkylene polymers (e.g.,
methylpolyisopropylene glycol ether having an average molecular
weight of 1,000; diphenyl ether of polyethylene glycol having a
molecular weight of 500-1,000; and diethyl ether of polypropylene
glycol having a molecular weight of 1,000-1,500) and/or mono- and
polycarboxylic esters thereof (e.g. acetic acid esters, mixed C3-C8
fatty acid esters, or the C13 oxo acid diester of tetraethylene
glycol) may also be utilized.
[0032] In even further embodiments, the base oil may include esters
of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl
succinic acids and alkenyl succinic acids, maleic acid, azelaic
acid, suberic acid, sebacic acid, fumaric acid, adipic acid,
linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl
malonic acids) with a variety of alcohols (e.g., butyl alcohol,
hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene
glycol, diethylene glycol monoether, and propylene glycol).
Specific examples of these esters include, but are not limited to,
dibutyl adipate, di(2-ethylhexyl sebacate, di-n-hexyl fumarate,
dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl
phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl
diester of linoleic acid dimer, the complex ester formed by
reacting one mole of sebacic acid with two moles of tetraethylene
glycol and two moles of 2-ethylhexanoic acid, and combinations
thereof. Esters useful as the base oil or as included in the base
oil also include those formed from C.sub.5 to C.sub.12
monocarboxylic acids and polyols and polyol ethers such as
neopentyl glycol, trimethylolpropane, pentaerythritol,
dipentaerythritol, and tripentaerythritol.
[0033] The base oil may be alternatively described as a refined
and/or re-refined oil, or combinations thereof. Unrefined oils are
typically obtained from a natural or synthetic source without
further purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained
directly from distillation, or an ester oil obtained directly from
an esterification process and used without further treatment, could
all be utilized in this invention. Refined oils are similar to the
unrefined oils except that they typically have undergone
purification to improve one or more properties. Many such
purification techniques are known to those of skill in the art such
as solvent extraction, acid or base extraction, filtration,
percolation, and similar purification techniques. Re-refined oils
are also known as reclaimed or reprocessed oils and often are
additionally processed by techniques directed to removal of spent
additives and oil breakdown products.
[0034] The base oil may alternatively be described as specified in
the American Petroleum Institute (API) Base Oil Interchangeability
Guidelines. In other words, the base oil may be further described
as one or a combination of more than one of five base oil groups:
Group I (sulphur content >0.03 wt %, and/or <90 wt %
saturates, viscosity index 80-120); Group II (sulphur content less
than or equal to 0.03 wt %, and greater than or equal to 90 wt %
saturates, viscosity index 80-120); Group III (sulphur content less
than or equal to 0.03 wt %, and greater than or equal to 90 wt %
saturates, viscosity index less than or equal to 120); Group IV
(all polyalphaolefins (PAO's)); and Group V (all others not
included in Groups I, II, III, or IV). In one embodiment, the base
oil is selected from the group consisting of API Group I, II, III,
IV, V and combinations thereof. In another embodiment, the base oil
is selected from the group consisting of API Group II, III, IV, and
combinations thereof. In still another embodiment, the base oil is
further defined as an API Group II, III, or IV oil and includes a
maximum of about 49.9 wt %, typically up to a maximum of about 40
wt %, more typically up to a maximum of about 30 wt %, even more
typically up to a maximum of about 20 wt %, even more typically up
to a maximum of about 10 wt % and even more typically up to a
maximum of about 5 wt % of the lubricating oil an API Group I or V
oil. It is also contemplated that Group II and Group II basestocks
prepared by hydrotreatment, hydrofinishing, hydroisomerzation or
other hydrogenative upgrading processes may be included in the API
Group II described above. Moreover, the base oil may include Fisher
Tropsch or gas to liquid GTL oils. These are disclosed for example
in U.S. 2008/0076687, which is expressly incorporated herein by
reference.
[0035] The base oil is typically present in the composition in an
amount of from 70 to 99.9, from 80 to 99.9, from 90 to 99.9, from
75 to 95, from 80 to 90, or from 85 to 95, parts by weight per 100
parts by weight of the composition. Alternatively, the base oil may
be present in amounts of greater than 70, 75, 80, 85, 90, 91, 92,
93, 94, 95, 96, 97, 98, or 99, parts by weight per 100 parts by
weight of the composition. In various embodiments, the amount of
lubricating oil in a fully formulated lubricant (including diluent
or carrier oils presents) is from about 80 to about 99.5 percent by
weight, for example, from about 85 to about 96 percent by weight,
for instance from about 90 to about 95 percent by weight. Of
course, the weight percent of the base oil may be any value or
range of values, both whole and fractional, within those ranges and
values described above and/or may vary from the values and/or range
of values above by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%,
.+-.30%, etc.
(B) At Least One Diphenylamine Antioxidant:
[0036] Referring back to the (B) at least one diphenylamine
antioxidant, this antioxidant is not particularly limited. In one
embodiment, the diphenylamine antioxidant is further defined as
having the formula:
##STR00001##
wherein each R' is independently a hydrogen atom, a straight or
branched chain alkyl radical having from 1 to 18 carbon atoms, or
an aralkyl radical having 7 to 14 carbon atoms. In various
embodiments, the straight or branched chain alkyl radical has from
2 to 17, from 3 to 16, from 4 to 15, from 5 to 14, from 6 to 13,
from 7 to 12, from 8 to 11, or from 9 to 10, carbon atoms. The
alkyl group may be branched or unbranched and may be further
defined as, for example, a methyl, ethyl, propyl, isopropyl,
n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,
isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,
1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl,
undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or
octadecyl group. Alternatively, R' can include blends of alkyl
groups that have even numbers of carbon atoms or odd numbers of
carbon atoms, or both. For example, R' can include mixtures of
C.sub.x/C.sub.y alkyl groups wherein x and y are odd numbers or
even numbers. Alternatively, one may be an odd number and the other
may be an even number. In various embodiments, x and y are numbers
that differ from each other by two, e.g. 6 and 8, 8 and 10, 10 and
12, 12 and 14, 14 and 16, 16 and 18, 7 and 9, 9 and 11, 11 and 13,
13 and 15, or 15 and 17. R' can also include mixtures of 3 or more
alkyl groups, each of which may include even or odd numbers of
carbon atoms.
[0037] The aralkyl radical may be further defined as a benzyl,
alpha-methyl benzyl or cumyl group. In various embodiments, the
aralkyl radical has from 8 to 13, from 9 to 12, or from 10 to 11,
carbon atoms. In other embodiments, the diphenylamine antioxidant
is an alkylated diphenylamine, for instance a nonylated
diphenylamine. Alternatively, the diphenylamine antioxidant may be,
for instance, an octylated/butylated diphenylamine produced by
alkylating diphenylamine with a molar excess of diisobutylene as
described in U.S. Pat. No. 4,824,601, which is expressly
incorporated in its entirety herein by reference. In one
embodiment, the (B) at least one diphenylamine antioxidant is
further defined as including at least one octylated/butylated
diphenylamine antioxidant and also including thiodiethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. It is also
contemplated that the (B) at least one diphenylamine antioxidant
may be as described in U.S. Prov. Ser. No. 61/231,468, filed on
Aug. 5, 2009, the disclosure of which is expressly incorporated
herein by reference in its entirety.
(C) Sulfur Containing Phenolic
Antioxidant/Phenyl-Alpha-Naphthylamine Antioxidant:
[0038] The sulfur containing phenolic antioxidant is also not
particularly limited. In one embodiment, the sulfur containing
phenolic antioxidant is further defined as having the formula:
##STR00002##
wherein x is a number from 0 to 6, y is a number from 2 to 20 and R
is a straight or branched chain alkyl radical having from 1 to 6
carbon atoms. Various non-limiting examples of suitable alkyl
radicals include methyl, ethyl, propyl, isopropyl, n-butyl,
sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl groups. In various
embodiments, x is a number of from 1 to 5, from 2 to 4, or from 3
to 4. In other embodiments, y is a number of from 3 to 19, from 4
to 18, from 5 to 17, from 6 to 16, from 7 to 15, from 8 to 14, from
9 to 13, from 10 to 12, or from 11 to 12.
[0039] In one embodiment, the sulfur containing phenolic
antioxidant is further defined as an ester of
di(lower)alkylhydroxphenyl alkanoic acid containing a sulfur atom
as described in U.S. Pat. Nos. 3,441,575 and 4,228,297, which are
hereby incorporated in their entirety by reference. A specific
example is thiodiethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
[0040] The phenyl-alpha-naphthylamine antioxidant is also not
particularly limited. In one embodiment, the
phenyl-alpha-naphthylamine antioxidant is further defined as having
the formula:
##STR00003##
wherein R.sub.1 is an aryl radical having from 6 to 12 carbon atoms
or an aryl radical having from 6 to 20 carbon atoms and substituted
by one, two or three straight or branched chain alkyl radicals each
having from 1 to 18 carbon atoms. In various embodiments, aryl
radical has from 7 to 11, from 8 to 10, or from 9 to 10, carbon
atoms. Suitable non-limiting examples include phenyl, naphthyl or
biphenyl groups. Alternatively, the aryl radical may have from 7 to
19, from 8 to 18, from 9 to 17, from 10 to 16, from 11 to 15, from
12 to 14, or from 12 to 13, carbon atoms. The one, two, or three
straight or branched chain alkyl radicals can be as described above
relative to R'. Alkylated phenyl-alpha-naphthalylamine antioxidants
are described as starting materials in U.S. Pat. No. 5,160,647,
incorporated by reference. A particular example is octylated
phenyl-alpha-naphthylamine. It is also contemplated that the
phenyl-alpha-naphthalylamine antioxidant and/or sulfur containing
phenolic antioxidant may be as described in U.S. Prov. Ser. No.
61/231,468, filed on Aug. 5, 2009, the disclosure of which is
expressly incorporated herein by reference in its entirety.
[0041] In one embodiment, the (B) at least one diphenylamine
antioxidant is further defined as having the aforementioned formula
wherein each R' is independently a hydrogen atom, a straight or
branched chain alkyl radical having from 1 to 18 carbon atoms, or
an aralkyl radical having 7 to 14 carbon atoms. In this same
embodiment, the (C) at least one antioxidant includes the sulfur
containing phenolic antioxidant and the sulfur containing phenolic
antioxidant is further defined as having the aforementioned formula
wherein x is a number from 0 to 6, y is a number from 2 to 20 and R
is a straight or branched chain alkyl radical having from 1 to 6
carbon atoms.
[0042] In an alternative embodiment, the (B) at least one
diphenylamine antioxidant is further defined as having the
aforementioned formula wherein each R' is independently a hydrogen
atom, a straight or branched chain alkyl radical having from 1 to
18 carbon atoms, or an aralkyl radical having 7 to 14 carbon atoms.
In this embodiment, the (C) at least one antioxidant includes the
phenyl-alpha-naphthylamine antioxidant and the
phenyl-alpha-naphthylamine antioxidant is further defined as having
the aforementioned formula wherein R1 is an aryl radical having
from 6 to 12 carbon atoms or an aryl radical having from 6 to 20
carbon atoms and substituted by one, two or three straight or
branched chain alkyl radicals each having from 1 to 18 carbon
atoms.
[0043] In still another embodiment, the (B) at least one
diphenylamine antioxidant is further defined as including at least
one octylated/butylated diphenylamine antioxidant. In this same
embodiment, the (C) at least one antioxidant includes the
phenyl-alpha-naphthylamine antioxidant, and the
phenyl-alpha-naphthylamine antioxidant is further defined as
octylated phenyl-alpha-naphthylamine.
[0044] In various embodiments, the (B) at least one diphenylamine
antioxidant and the (C) at least one antioxidant are present in a
weight ratio of from about 9:1 to about 1:9, respectively.
Alternatively, (B) and (C) may be present in weight ratios of about
(8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1) to about (1:8, 1:7,
1:6, 1:5, 1:4, 1:3, 1:2, or 1:1). In other embodiments, the weight
ratio is from about 8:2 to about 2:8, from about 7:3 to about 3:7,
from about 6:4 to about 4:6 or about 1:1. The ratios described
above are not limiting and may be any value or range of values,
both whole and fractional, within those ranges and values described
above and/or may vary from the values and/or range of values above
by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
[0045] In still other embodiments, the combination of (B) and (C)
is present in amounts of from about 0.3 to about 7 parts by weight,
of from about 0.9 to about 3.5 parts by weight, of from about 0.5
to 2, of from about 0.5 to 3, or less than about 2.1, parts by
weight, per 100 parts by weight of the composition. In other
embodiments, the combination of (B) and (C) is present in amounts
of about 0.3, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5
or about 7 weight percent, based on a total weight of the
composition and not the combination of biodiesel fuel and the
composition. The amounts described above are not limiting and may
be any value or range of values, both whole and fractional, within
those ranges and values described above and/or may vary from the
values and/or range of values above by .+-.5%, .+-.10%, .+-.15%,
.+-.20%, .+-.25%, .+-.30%, etc.
[0046] In one embodiment, the (C) at least one antioxidant includes
both the sulfur containing phenolic antioxidant and the
phenyl-alpha-naphthylamine antioxidant. In another embodiment, the
(C) at least one antioxidant includes the sulfur containing
phenolic antioxidant. In still another embodiment, the (C) at least
one antioxidant consists essentially of the sulfur containing
phenolic antioxidant. In still a further embodiment, the (C) at
least one antioxidant is free of the phenyl-alpha-naphthylamine
antioxidant. Alternatively, the (C) at least one antioxidant can
include the phenyl-alpha-naphthylamine antioxidant. The (C) at
least one antioxidant may consist essentially of the
phenyl-alpha-naphthylamine antioxidant. The (C) at least one
antioxidant may also be free of the sulfur containing phenolic
antioxidant.
Additives:
[0047] The composition can additionally include one or more
additives to improve various chemical and/or physical properties.
Non-limiting examples of the one or more additives include
anti-wear additives, metal passivators, rust inhibitors, viscosity
index improvers, pour point depressors, dispersants, detergents,
and antifriction additives. Such composition is commonly referred
to as an engine oil.
Anti-Wear Additive:
[0048] The anti-wear additive first introduced above is not
particularly limited and may be any known in the art. In one
embodiment, the anti-wear additive is selected from the group of
ZDDP, zinc dialkyl-dithio phosphates, and combinations thereof.
Alternatively, the anti-wear additive may include sulfur- and/or
phosphorus- and/or halogen-containing compounds, e.g. sulfurised
olefins and vegetable oils, zinc dialkyldithiophosphates, alkylated
triphenyl phosphates, tritolyl phosphate, tricresyl phosphate,
chlorinated paraffins, alkyl and aryl di- and trisulfides, amine
salts of mono- and dialkyl phosphates, amine salts of
methylphosphonic acid, diethanolaminomethyltolyltriazole,
bis(2-ethylhexyl)aminomethyltolyltriazole, derivatives of
2,5-dimercapto-1,3,4-thiadiazole, ethyl
3-[(diisopropoxyphosphinothioyl)thio]propionate, triphenyl
thiophosphate (triphenylphosphorothioate),
tris(alkylphenyl)phosphorothioate and mixtures thereof (for example
tris(isononylphenyl)phosphorothioate), diphenyl monononylphenyl
phosphorothioate, isobutylphenyl diphenyl phosphorothioate, the
dodecylamine salt of 3-hydroxy-1,3-thiaphosphetane 3-oxide,
trithiophosphoric acid 5,5,5-tris[isooctyl 2-acetate], derivatives
of 2-mercaptobenzothiazole such as
1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole,
ethoxycarbonyl-5-octyldithio carbamate, and/or combinations
thereof. It is also contemplated that the anti-wear additive may be
as described in U.S. Prov. Ser. No. 61/231,468, filed on Aug. 5,
2009, the disclosure of which is expressly incorporated herein by
reference in its entirety.
[0049] The anti-wear additive is typically present in the
composition in an amount of from 0.1 to 20, from 0.5 to 15, from 1
to 10, from 5 to 10, from 5 to 15, from 5 to 20, from 0.1 to 1,
from 0.1 to 0.5, or from 0.1 to 1.5, parts by weight per 100 parts
by weight of the composition. Alternatively, the anti-wear additive
may be present in amounts of less than 20, less than 15, less than
10, less than 5, less than 1, less than 0.5, or less than 0.1,
parts by weight per 100 parts by weight of the composition. Of
course, the weight percent of the anti-wear additive may be any
value or range of values, both whole and fractional, within those
ranges and values described above and/or may vary from the values
and/or range of values above by .+-.5%, .+-.10%, .+-.15%, .+-.20%,
.+-.25%, .+-.30%, etc.
Antioxidants:
[0050] In addition to the antioxidants described above, the
composition may include other antioxidants as well. Suitable,
non-limiting, antioxidants include alkylated monophenols, for
example 2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol,
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, and combinations
thereof.
[0051] Other non-limiting examples of suitable antioxidants
includes alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof.
Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate, and combinations
thereof, may also be utilized.
[0052] Furthermore, hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis
(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis-(3,6-di-sec-amylphenol),
4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide, and combinations
thereof, may also be used.
[0053] It is also contemplated that alkylidenebisphenols, for
example 2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis
[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hyd-
roxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercapto
butane, ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane-
, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methyl phenyl)pentane,
and combinations thereof may be utilized as antioxidants.
[0054] O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol
terephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5di-tert-butyl-4-hydroxy benzylmercaptoacetate, and
combinations thereof, may also be utilized.
[0055] Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malona-
te,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy-
droxybenzyl)malonate, and combinations thereof are also suitable
for use as antioxidants.
[0056] Triazine Compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl
propionyl)-hexahydro-1,3,5-triazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and
combinations thereof, may also be used.
[0057] Additional suitable, but non-limiting examples of
antioxidants include aromatic hydroxybenzyl compounds, for example
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and
combinations thereof. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and combinations
thereof, may also be utilized. In addition, acylaminophenols, for
example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0058] Esters of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof, may also be used. It is further contemplated
that esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof, may be used. Esters of
13-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or
polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,
neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof, may also be used. Moreover, esters of
3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or
polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,
neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof, may be utilized.
[0059] Additional non-limiting examples of suitable antioxidants
include those that include nitrogen, such as amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
Other suitable non-limiting examples of antioxidant include aminic
antioxidants such as N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated
diphenylamine, for example p,p'-di-tert-octyldiphenylamine,
4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino
methylphenol, 2,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated isopropyl/isohexyldiphenylamines, mixtures of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethyl piperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethyl
piperidin-4-ol, and combinations thereof.
[0060] Even further non-limiting examples of suitable antioxidants
includes aliphatic or aromatic phosphites, esters of
thiodipropionic acid or of thiodiacetic acid, or salts of
dithiocarbamic or dithiophosphoric acid,
2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,1trithiatridecane and
2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane,
and combinations thereof. Furthermore, sulfurized fatty esters,
sulfurized fats and sulfurized olefins, and combinations thereof,
may be used. It is also contemplated that the antioxidant may be as
described in U.S. Prov. Ser. No. 61/231,468, filed on Aug. 5, 2009,
the disclosure of which is expressly incorporated herein by
reference in its entirety.
[0061] The one or more antioxidants are not particularly limited in
amount in the composition but are typically present in an amount of
from 0.1 to 2, 0.5 to 2, 1 to 2, or 1.5 to 2, parts by weight per
100 parts by weight of the composition. Alternatively, the one or
more antioxidants may be present in amounts of less than 2, less
than 1.5, less than 1, or less than 0.5, parts by weight per 100
parts by weight of the composition. Of course, the weight percent
of the one or more antioxidants may be any value or range of
values, both whole and fractional, within those ranges and values
described above and/or may be present in amounts that vary from the
values and/or range of values above by .+-.5%, .+-.10%, .+-.15%,
.+-.20%, .+-.25%, .+-.30%, etc.
Metal Deactivators:
[0062] In various embodiments, one or more metal deactivators can
be included in the composition. Suitable, non-limiting examples of
the one or more metal deactivators include benzotriazoles and
derivatives thereof, for example 4- or 5-alkylbenzotriazoles (e.g.
tolutriazole) and derivatives thereof,
4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole;
Mannich bases of benzotriazole or tolutriazole, e.g.
1-[bis(2-ethylhexyl)aminomethyl)tolutriazole and
1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole,
1-(1-butoxyethyl)benzotriazole and
1-(1-cyclohexyloxybutyl)tolutriazole, and combinations thereof.
[0063] Additional non-limiting examples of the one or more metal
deactivators include 1,2,4-triazoles and derivatives thereof, for
example 3-alkyl(or aryl)-1,2,4-triazoles, and Mannich bases of
1,2,4-triazoles, such as
1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole;
alkoxyalkyl-1,2,4-triazoles such as
1-(1-butoxyethyl)-1,2,4-triazole; and acylated
3-amino-1,2,4-triazoles, imidazole derivatives, for example
4,4'-methylenebis(2-undecyl-5-methylimidazole) and
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether, and combinations
thereof.
[0064] Further non-limiting examples of the one or more metal
deactivators include sulfur-containing heterocyclic compounds, for
example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole
and derivatives thereof; and
3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one, and
combinations thereof. Even further non-limiting examples of the one
or more metal deactivators include amino compounds, for example
salicylidenepropylenediamine, salicylaminoguanidine and salts
thereof, and combinations thereof. It is also contemplated that the
metal deactivator may be as described in U.S. Prov. Ser. No.
61/231,468, filed on Aug. 5, 2009, the disclosure of which is
expressly incorporated herein by reference in its entirety.
[0065] The one or more metal deactivators are not particularly
limited in amount in the composition but are typically present in
an amount of from 0.01 to 0.1, from 0.05 to 0.01, or from 0.07 to
0.1, parts by weight per 100 parts by weight of the composition.
Alternatively, the one or more metal deactivators may be present in
amounts of less than 0.1, of less than 0.7, or less than 0.5, parts
by weight per 100 parts by weight of the composition. The weight
percent of the one or more metal deactivators may be any value or
range of values, both whole and fractional, within those ranges and
values described above and/or may be present in amounts that vary
from the values and/or range of values above by .+-.5%, .+-.10%,
.+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
Rust Inhibitors and Friction Modifiers:
[0066] In various embodiments, one or more rust inhibitors and/or
friction modifiers can be included in the composition. Suitable,
non-limiting examples of the one or more rust inhibitors and/or
friction modifiers include organic acids, their esters, metal
salts, amine salts and anhydrides, for example alkyl- and
alkenylsuccinic acids and their partial esters with alcohols, diols
or hydroxycarboxylic acids, partial amides of alkyl- and
alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and
alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid,
dodecyloxy(ethoxy)acetic acid and the amine salts thereof, and also
N-oleoylsarcosine, sorbitan monooleate, lead naphthenate,
alkenylsuccinic anhydrides, for example dodecenylsuccinic
anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol and the amine
salts thereof, and combinations thereof. Additional suitable,
non-limiting examples of the one or more rust inhibitors and/or
friction modifiers include nitrogen-containing compounds, for
example, primary, secondary or tertiary aliphatic or cycloaliphatic
amines and amine salts of organic and inorganic acids, for example
oil-soluble alkylammonium carboxylates, and also
1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol, and
combinations thereof. Further suitable, non-limiting examples of
the one or more rust inhibitors and/or friction modifiers include
heterocyclic compounds, for example: substituted imidazolines and
oxazolines, and 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline,
phosphorus-containing compounds, for example: Amine salts of
phosphoric acid partial esters or phosphonic acid partial esters,
and zinc dialkyldithiophosphates, molybdenum-containing compounds,
such as molydbenum dithiocarbamate and other sulphur and phosphorus
containing derivatives, sulfur-containing compounds, for example:
barium dinonylnaphthalenesulfonates, calcium petroleum sulfonates,
alkylthio-substituted aliphatic carboxylic acids, esters of
aliphatic 2-sulfocarboxylic acids and salts thereof, glycerol
derivatives, for example: glycerol monooleate,
1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols,
1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols and
2-carboxyalkyl-1,3-dialkylglycerols, and combinations thereof. It
is also contemplated that the rust inhibitors and friction
modifiers may be as described in U.S. Prov. Ser. No. 61/231,468,
filed on Aug. 5, 2009, the disclosure of which is expressly
incorporated herein by reference in its entirety.
[0067] The one or more rust inhibitors and friction modifiers are
not particularly limited in amount in the composition but are
typically present in an amount of from 0.05 to 0.5, 0.01 to 0.2,
from 0.05 to 0.2, 0.1 to 0.2, 0.15 to 0.2, or 0.02 to 0.2, parts by
weight per 100 parts by weight of the composition. Alternatively,
the one or more rust inhibitors and friction modifiers may be
present in amounts of less than 0.5, less than 0.4, less than 0.3,
less than 0.2, less than 0.1, less than 0.5, or less than 0.1,
parts by weight per 100 parts by weight of the composition. The
weight percent of the one or more rust inhibitors and friction
modifiers may be any value or range of values, both whole and
fractional, within those ranges and values described above and/or
may be present in amounts that vary from the values and/or range of
values above by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%,
.+-.30%, etc.
Viscosity Index Improvers:
[0068] In various embodiments, one or more viscosity index
improvers can be included in the composition. Suitable,
non-limiting examples of the one or more viscosity index improvers
include polyacrylates, polymethacrylates,
vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones,
polybutenes, olefin copolymers, styrene/acrylate copolymers and
polyethers, and combinations thereof. It is also contemplated that
the viscosity index improvers may be as described in U.S. Prov.
Ser. No. 61/231,468, filed on Aug. 5, 2009, the disclosure of which
is expressly incorporated herein by reference in its entirety.
[0069] The one or more viscosity index improvers are not
particularly limited in amount in the composition but are typically
present in an amount of from 1 to 1, from 2 to 8, from 3 to 7, from
4 to 6, or from 4 to 5, parts by weight per 100 parts by weight of
the composition. Alternatively, the one or more viscosity index
improvers may be present in an amount of less than 10, 9, 8, 7, 6,
5, 4, 3, 2, or 1, part by weight per 100 parts b eight of the
composition. The weight percent of the one or more viscosity index
improvers may be any value or range of values, both whole and
fractional, within those ranges and values described above and/or
may be present in amounts that vary from the values and/or range of
values above by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%,
.+-.30%, etc.
Pour Point Depressants:
[0070] In various embodiments, one or more pour point depressants
can be included in the composition. Suitable, non-limiting examples
of the pour point depressants include polymethacrylate and
alkylated naphthalene derivatives, and combinations thereof. It is
also contemplated that the pour point depressants may be as
described in U.S. Prov. Ser. No. 61/231,468, filed on Aug. 5, 2009,
the disclosure of which is expressly incorporated herein by
reference in its entirety.
[0071] The one or more pour point depressants are not particularly
limited in amount in the composition but are typically present in
an amount of from 0.1 to 1, from 0.5 to 1, or from 0.7 to 1, part
by weight per 100 parts by weight of the composition.
Alternatively, the one or more pour point depressants may be
present in amounts of less than 1, less than 0.7, or less than 0.5,
parts by weight per 100 parts by weight of the composition. The
weight percent of the one or more pour point depressants may be any
value or range of values, both whole and fractional, within those
ranges and values described above and/or may be present in amounts
that vary from the values and/or range of values above by .+-.5%,
.+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
Dispersants:
[0072] In various embodiments, one or more dispersants can be
included in the composition. Suitable, non-limiting examples of the
one or more dispersants include polybutenylsuccinic amides or
-imides, polybutenylphosphonic acid derivatives and basic
magnesium, calcium and barium sulfonates and phenolates, succinate
esters and alkylphenol amines (Mannich bases), and combinations
thereof. It is also contemplated that the dispersants may be as
described in U.S. Prov. Ser. No. 61/231,468, filed on Aug. 5, 2009,
the disclosure of which is expressly incorporated herein by
reference in its entirety.
[0073] The one or more dispersants are not particularly limited in
amount in the composition but are typically present in an amount of
from 0.1 to 5, from 0.5 to 4.5, from 1 to 4, from 1.5 to 3.5, from
2 to 3, or from 2.5 to 3, parts by weight per 100 parts by weight
of the composition. Alternatively, the one or more dispersants may
be present in an amount of less than 5, 4.5, 3.5, 3, 2.5, 2, 1.5,
or 1, part by weight per 100 parts by weight of the composition.
The weight percent of the one or more dispersants may be any value
or range of values, both whole and fractional, within those ranges
and values described above and/or may be present in amounts that
vary from the values and/or range of values above by .+-.5%,
.+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
Detergents:
[0074] In various embodiments, one or more detergents can be
included in the composition. Suitable, non-limiting examples of the
one or more detergents include overbased or neutral metal
sulphonates, phenates and salicylates, and combinations thereof. It
is also contemplated that the detergents may be as described in
U.S. Prov. Ser. No. 61/231,468, filed on Aug. 5, 2009, the
disclosure of which is expressly incorporated herein by reference
in its entirety.
[0075] The one or more detergents are not particularly limited in
amount in the composition but are typically present in an amount of
from 0.1 to 5, from 0.5 to 4.5, from 1 to 4, from 1.5 to 3.5, from
2 to 3, or from 2.5 to 3, parts by weight per 100 parts by weight
of the composition. Alternatively, the one or more detergents may
be present in an amount of less than 5, 4.5, 3.5, 3, 2.5, 2, 1.5,
or 1, part by weight per 100 parts by weight of the composition.
The weight percent of the one or more detergents may be any value
or range of values, both whole and fractional, within those ranges
and values described above and/or may be present in amounts that
vary from the values and/or range of values above by .+-.5%,
.+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
[0076] In various embodiments, the composition is substantially
free of water, e.g. includes less than 5, 4, 3, 2, or 1, weight
percent of water. Alternatively, the composition may include less
than 0.5 or 0.1 weight percent of water or may be free of water. Of
course, the weight percent of the water may be any value or range
of values, both whole and fractional, within those ranges and
values described above and/or may be present in amounts that vary
from the values and/or range of values above by .+-.5%, .+-.10%,
.+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
[0077] The instant invention also provides an additive concentrate
package which includes one or more metal deactivators, one or more
antioxidants, one or more anti-wear additives, and the one or more
alkylethercarboxylic acid corrosion inhibitor of this invention. In
various embodiments, the additive concentrate package may include
one or more additional additives as described above. The additive
package may be included in the composition in amounts of from 0.1
to 1, from 0.2 to 0.9, from 0.3 to 0.8, from 0.4 to 0.7, or from
0.5 to 0.6, parts by weight per 100 parts by weight of the
composition. The weight percent of the additive concentrate package
may be any value or range of values, both whole and fractional,
within those ranges and values described above and/or may be
present in amounts that vary from the values and/or range of values
above by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%,
etc.
[0078] Some of the compounds described above may interact in the
lubricant composition, so the components of the lubricant
composition in final form may be different from those components
that are initially added or combined together. Some products formed
thereby, including products formed upon employing the composition
of this invention in its intended use, are not easily described or
describable. Nevertheless, all such modifications, reaction
products, and products formed upon employing the composition of
this invention in its intended use, are expressly contemplated and
hereby included herein. Various embodiments of this invention
include one or more of the modification, reaction products, and
products formed from employing the composition, as described
above.
Biodiesel Fuel:
[0079] The composition may include biodiesel fuel. Alternatively,
the composition may be diluted with biodiesel fuel. The terminology
"diluted with biodiesel fuel" typically described the lubricant
composition including, or being contaminated with, at least 1
weight percent of the biodiesel fuel. The composition is typically
contaminated with the biodiesel fuel as a result of "blow by"
during operation of diesel engines. Fuel dilution into engine oil
typically cannot be easily prevented. In one embodiment, the
terminology "diluted with" refers to the composition being diluted
with the biodiesel fuel during operation of a diesel engine.
[0080] The composition is protected against dilution with the
biodiesel in that the components (i.e., the antioxidants (B) and
(C)) minimize the negative effects that typically result from
dilution of engine oils with biodiesel fuel. Typically, the
terminology "dilution" refers to contamination of the composition
with biodiesel fuel. Dilution or contamination typically occurs at
about 1 weight percent of biodiesel fuel in the composition. In
various embodiments, composition is diluted or contaminated with
from about 1 to 50, from about 5 to 50, from about 10 to 40, from
about 10 to 30, from about 20 to 30, from about 5 to 30, from about
5 to 10, from about 5 to 15, from about 5 to 20, from about 5 to
25, from about 5 to 35, from about 5 to 40, or from about 5 to 50,
weight percent of biodiesel fuel. The weight percent of the
biodiesel fuel may be any value or range of values, both whole and
fractional, within those ranges and values described above and/or
may be present in amounts that vary from the values and/or range of
values above by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%,
.+-.30%, etc.
[0081] Biodiesel fuel typically includes lower alkyl fatty acid
esters, prepared, for example, by transesterifying trigycerides
with lower alcohols, e.g. methanol or ethanol. A typical biodiesel
fuel is the fatty acid methyl ester of rapeseed oil or of soy oil.
Sources for biodiesel fuel include vegetable and animal sources.
Recycled cooking oil may be a source of biodiesel fuel. Various
types of biodiesel fuel and their preparation are taught, for
example, in U.S. Pat. Nos. 5,578,090, 5,713,965, 5,891,203,
6,015,440, 6,174,501 and 6,398,707, each of which is hereby
incorporated by reference. It is also contemplated that the
biodiesel fuel may be as described in U.S. Prov. Ser. No.
61/231,468, filed on Aug. 5, 2009, the disclosure of which is
expressly incorporated herein by reference in its entirety.
[0082] Typically, the biodiesel fuel includes lower alkyl esters of
a mixture of saturated and unsaturated straight chain fatty acids
of from 12 to 22 carbon atoms, derived from vegetable or oleaginous
seeds. In various embodiments, the terminology "lower alkyl ester"
describes C.sub.1-C.sub.5 esters, in particular methyl and ethyl
esters. Mixtures of methyl esters of saturated, monounsaturated and
polyunsaturated C.sub.13-C.sub.22 fatty acids are typically
referred to as "biodiesel" or "fatty acid methyl esters"
(FAME).
[0083] Biodiesel derived from vegetable sources such as soy,
rapeseed, corn, palm, coconut or sunflower oils are typically
referred to in the art as First Generation biodiesel fuels. Second
Generation biodiesel fuels are typically derived from non-food
sources such as jatropha, algae, yeast, used cooking oil, animal
fat (tallow) or castor oil. Third Generation biodiesel fuels are
typically derived from further sources such as wood/lignocelluloses
or biomass. The biodiesel fuel of this invention may include one or
more of the aforementioned types. In one embodiment, the biodiesel
fuel includes at least one fatty acid methyl ester of a vegetable
or oleaginous seed oil.
[0084] In one embodiment, the biodiesel fuel includes 100 wt % of
lower alkyl fatty acid esters or a combination of lower alkyl fatty
acid esters combined with traditional petroleum diesel fuel. In
various alternative embodiments, the biodiesel fuel includes from
about 2 to about 98 weight percent fatty acid ester and from about
98 to about 2 weight percent petroleum diesel fuel. In one example,
the biodiesel fuel includes from about 10 to about 90 weight
percent fatty acid ester and from about 90 to about 10 weight
percent diesel. In another example, the biodiesel fuel includes
from about 25 to about 75 weight percent fatty acid ester and from
about 75 to about 25 weight percent diesel fuel. The invention is
not limited to those amounts described above. The weight percent of
the lower alkyl fatty acid esters and/or diesel fuel may be any
value or range of values, both whole and fractional, within those
ranges and values described above and/or may be present in amounts
that vary from the values and/or range of values above by .+-.5%,
.+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
[0085] In one embodiment, the base oil is further defined as an API
Group II base oil, said (B) at least one diphenylamine antioxidant
is further defined as an octylated/butylated diphenylamine, and
said (C) at least one antioxidant comprises octylated
phenyl-alpha-naphthylamine, and (B) and (C) are present in a
combined amount of from about 0.5 to 3 parts by weight per 100
parts by weight of said base oil.
Method of Forming the Lubricant Composition:
[0086] This invention also provides a method of improving the
performance of the composition. The method includes the steps of
providing the (A) base oil, providing the (B) at least one
diphenylamine antioxidant, providing the (C) at least one
antioxidant, and combining (A), (B), and (C) to form the lubricant
composition.
Evaluation according to ASTM D 6186:
[0087] In the method, the base oil has an initial oxidation value
measured according to ASTM D 6186. Typically, this value is
measured in the absence of (B) and (C). More specifically, the base
oil is evaluated according to ASTM D 6186 to determine an initial
oxidation value that represents a pristine condition of the base
oil as originally designed and commercially sold (typically without
any of the antioxidants (B) and (C) or any other extraneous
additives not already present in the base oil as commercially
sold). In other embodiments, the base oil can be evaluated
according to SAE 940793 in conjunction with, or instead of, ASTM D
6186. The test procedure for SAE 940793 is described in the SAE
paper of the same title. After the initial oxidation value is
determined, an intermediate oxidation value can be determined, if
desired, using one or both methods described above. The
intermediate oxidation value can be determined if the composition
is diluted with, or includes, biodiesel fuel. The intermediate
oxidation value is typically only measured for analytical purposes.
The amount of biodiesel fuel added to the composition is not
particularly limited. Due to the tendency of the biodiesel fuel to
oxidize and form oxidative by-products, the intermediate oxidation
values are lower than the initial oxidation values and represent a
degraded condition that is harmful to the diesel engines in which
such base oils could be used. Of course, intermediate oxidation
values are not typically measured in working diesel engines and
conditions that would give rise to such intermediate oxidation
values are preferably avoided all together in working engines
because if the base oil was degraded to such a degree in a working
engine, failure of the oil, and damage to the engine could result.
To avoid this situation, premature replacement of the oil would be
needed.
[0088] In addition in the method, the lubricant composition is
evaluated when it includes up to about 6 wt % of the biodiesel fuel
and has a final oxidation value measured according to ASTM D 6186
that is equal to or greater than the initial oxidation value of the
base oil. It is to be understood that the composition is not
limited to including up to about 6 wt % but is merely evaluated at
this amount in one embodiment. In other words, and as described
above, the amount of biodiesel fuel in the composition can vary.
Typically, the amount is from 0.5 to 6, from 1 to 5.5, from 1.5 to
5, from 2 to 4.5, from 2.5 to 4, or from 3 to 3.5, parts by weight
per 100 parts by weight of the composition. In alternative
embodiments, and as also described above, the biodiesel may be
present in an amount from about 1 to 50, from about 5 to 50, from
about 10 to 40, from about 10 to 30, from about 20 to 30, from
about 5 to 30, from about 5 to 10, from about 5 to 15, from about 5
to 20, from about 5 to 25, from about 5 to 35, from about 5 to 40,
or from about 5 to 50, parts by weight of the biodiesel fuel per
100 parts by weight of the composition. Of course, any value or
range of values, both whole and fractional, within those ranges and
values described above may be utilized. Alternatively, the
biodiesel fuel may be present in amounts that vary from the values
and/or range of values above by .+-.5%, .+-.10%, .+-.15%, .+-.20%,
.+-.25%, .+-.30%, etc. Varying the amount of biodiesel fuel in the
composition changes the intermediate oxidation value. Typically,
increased amounts of biodiesel fuel decrease the intermediate
oxidation value. In one embodiment, the composition is diluted with
the biodiesel fuel in a lubricant sump of a diesel engine.
[0089] After the initial oxidation value is determined, the final
oxidation value, as first introduced above, can then be measured
using one or both methods also described above. The final oxidation
value can be measured using the same amount of the biodiesel fuel
in the composition as described above. In other words, even if the
intermediate value is not determined, the same amounts of biodiesel
fuels can be used to determine the final oxidation value. In one
embodiment, the final oxidation value is determined when up to
about 6 wt % of the biodiesel fuel is present in the composition in
addition to (A), (B), and (C). When the antioxidants (B) and (C) of
this invention are utilized, the final oxidation value of the
composition tends to be equal to or greater than the initial
oxidation value of the (A) base oil. This indicates that the
antioxidants (B) and (C) of this invention at least restore the
pristine quality of the base oil to at least its original condition
even after degradation/dilution with/addition of the biodiesel fuel
and oxidative by-products formed therefrom. If the final oxidation
value is greater than the initial oxidation value, then such data
indicated that the antioxidants (B) and (C) of this invention
improve the quality of the base oil (even after
degradation/dilution with/addition of the biodiesel fuel and
oxidative by-products formed therefrom) to a level that is even
better and more preferred than its original quality. In various
embodiments, it is contemplated that the final oxidation value may
be within (i.e., .+-.) about, 5, 4, 3, 2, or 1, percent of the
initial oxidation value.
[0090] In one embodiment, the (A) base oil has an initial oxidation
value measured in the absence of (B) and (C) and measured according
to ASTM D 6186, wherein the lubricant composition has a final
oxidation value measured when comprising (A), (B) and (C) and up to
about 6 wt % of a biodiesel fuel and measured according to ASTM D
6186, and wherein the final oxidation value of the lubricant
composition is equal to or greater than the initial oxidation value
of the (A) base oil. In a related embodiment, the composition
includes from 0.3 to 7 parts by weight of the (B) and (C)
antioxidants per 100 parts by weight of the lubricant composition.
In alternative related embodiments, the composition includes from
0.9 to 3.5 parts by weight of the (B) and (C) antioxidants per 100
parts by weight of the lubricant composition. In another related
embodiment, the composition includes less than about 2.1 parts by
weight of the (B) and (C) antioxidants per 100 parts by weight of
the lubricant composition.
Examples
[0091] Two mixtures of antioxidants (Mixtures A and B) are formed
according to this invention. Three comparative mixtures
(Comparative Mixtures C, D, and E) are also formed but do not
represent this invention.
[0092] More specifically, Mixture A is an 80/20 weight ratio of a
mixture of octylated/butylated diphenylamine and thiodiethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
[0093] Mixture B is an 80/20 weight ratio of a mixture of
octylated/butylated diphenylamine and octylated
phenyl-alpha-naphthylamine.
[0094] Comparative Mixture C is a diisobutylene reaction product of
a mixture of diphenylamine and phenothiazine as prepared according
to Example 1 of U.S. Pat. No. 5,503,759.
[0095] Comparative Mixture D is a 1/1 weight ratio of a mixture of
octylated/butylated diphenylamine and
3-(3,5-di-tetrabutyl-4-hydroxyphenyl)propionic acid isooctyl
ester.
[0096] Comparative Mixture E is a 1/1 weight ratio of a mixture of
octylated/butylated diphenylamine and
4,4-methylene-bis(2,6-di-tert-butylphenol).
General Procedure:
[0097] A 15W-40 oil (i.e., heavy duty diesel engine oil; HDEO) is
independently evaluated according to ASTM D 6186 and SAE 940793 to
determine an initial oxidation value that represents a pristine
condition of the oil as originally designed and commercially sold.
It is to be understood that the 15W-40 oil, in this instance, can
alternatively be described as one embodiment of a generic "base
oil" introduced above. Subsequently, samples the 15W-40 oil are
contaminated with 2 or 6 wt % of varying types of aged biodiesel
fuels (i.e., soy methyl ester, rapeseed methyl ester, palm methyl
ester, or coconut methyl ester). After contamination, the samples
are again independently evaluated according to ASTM D 6186 and SAE
940793 to determine intermediate oxidation values. Due to the
tendency of the aged biodiesel fuels to oxidize and form oxidative
by-products, the intermediate oxidation values are lower than the
initial oxidation values and represent a degraded condition that is
harmful to the diesel engines in which such 15W-40 oils could be
used.
[0098] Subsequently, various amounts of the Mixtures A and B and
the Comparative Mixtures C-E are combined with the samples of the
15W-40 oils/biodiesel fuels to form Compositions A and B (of this
invention) and Comparative Compositions C-E, each of which includes
various amounts of the respective Mixtures. After formation, these
Compositions are then independently evaluated according to ASTM D
6186 and SAE 940793 to determine final oxidation values. In other
words, the various amounts of the Mixtures A and B and the
Comparative Mixtures C-E are added to the samples of the 15W-40
oils/biodiesel fuels to increase the intermediate oxidation values
up to at least pristine condition. Said differently, ASTM D 6186
and SAE 940793 are utilized to determine a quantity of the Mixtures
needed to be used such that the final oxidation values of the
Compositions are equal to or even greater than the initial
oxidation values of the oil itself. Said even a different way,
these tests are used to determine how much of the Mixtures are
needed to return the 15W-40 oil to its pristine condition or to a
condition that is even better than the pristine/original condition.
A condition that is even better than the pristine/original
condition is represented by a final oxidation value that is higher
than the initial oxidation value.
[0099] ASTM D 6186 is a Standard Test Method for Oxidation
Induction Time of Lubricating Oils by Pressure Differential
Scanning calorimetry (PDSC). In this method, a small quantity of
oil is weighted into a sample pan and placed in a test cell. The
cell is heated to a specified temperature and then pressurized with
oxygen. The cell is held at a regulated temperature and pressure
until an exothermic reaction occurs. The extrapolated onset time is
measured and reported as the oxidation induction time for the
15W-40 oil at the specified test temperature. More specifically,
ASTM D 6186 is conducted at 150 psi and used to evaluate thin film
oxidation. Oxidation induction time is measured at isothermal
conditions at 200.degree. C. via high pressure differential
scanning calorimetry.
[0100] SAE 940793 is also described as a Viscosity Increase Test
(VIT) and is described in SAE Paper #940793. In this method, iron
(III) acetylacetonate degradation catalyst is added to 30 grams of
the 15W-40 oil in a glass oxidation tube. The tube is heated to 160
C in an oil bath and oxygen is bubbled through the 15W-40 oil.
Samples are withdrawn periodically to determine the increase in
kinematic viscosity of the 15W-40 oil. These measurements are
plotted and the time to 375% viscosity increase is determined by
graphic interpolation. More specifically, SAE 940793 is conducted
to determine viscosity increase and bulk oxidation test 160.degree.
C. with soluble iron catalyst.
[0101] The biodiesel described above is a methyl ester of soy,
rapeseed, palm, or coconut oil and is aged for 20 hours at
110.degree. C. under an air flow of 15 mL/min. This ageing is done
to simulate oxidative degradation during combustion in diesel
engines.
[0102] Table 1 below sets forth the weight percent of the Mixtures
needed to restore the original ASTM D 6186 value of the 15W-40 oil
when the various biodiesel fuels are added to the 15W-40 oil at 2
or 6 weight percent.
TABLE-US-00001 TABLE 1 Weight Percent Biodiesel Fuel Added to
15W-40 Oil Aged Soy Aged Rapeseed Aged Palm Aged Coconut Methyl
Ester Methyl Ester Methyl Ester Methyl Ester 2 wt % 6 wt % 2 wt % 6
wt % 2 wt % 6 wt % 2 wt % 6 wt % Mixture A 1.35 1.85 1.3 1.6 1.2
2.0 1.0 2.1 Mixture B 0.90 1.50 <1 1.3 <1 2.0 <1 <1
Comp. 1.25 1.60 N/A N/A N/A N/A N/A N/A Mixture C Comp. 3.00 3.6
2.9 >3 ~2 >3 3.0 >3 Mixture D Comp. 2.65 3.5 2.8 >3
>3 >3 2.7 2.9 Mixture E * Mixtures A and B are utilized at
80/20 weight ratios and not at 1:1 ratios because these Mixtures
are not liquid at 1:1 ratios and thus cannot be evaluated
[0103] Table 2 below sets forth the weight percent of the Mixtures
needed to restore the original viscosity (VIT; SAE 0407930) of the
15W-40 oil when the various biodiesel fuels are added to the 15W-40
oil at 2 or 6 weight percent.
TABLE-US-00002 TABLE 2 Weight Percent Biodiesel Fuel Added to
15W-40 Oil Aged Soy Aged Rapeseed Aged Palm Aged Coconut Methyl
Ester Methyl Ester Methyl Ester Methyl Ester Mixture 2 wt % 6 wt %
2 wt % 6 wt % 2 wt % 6 wt % 2 wt % 6 wt % Mixture A 3.0 >3 <1
3.3 <1 <1 <1 <1 Mixture B 1.85 >3 <1 3.4 <1
1.4 1.4 <1 Comp. >3 >3 N/A N/A N/A N/A N/A N/A Mixture C
Comp. >3 >3 <1 >3 <1 <1 <1 <1 Mixture D
Comp. >3 >3 <1 >3 <1 <1 <1 <1 Mixture E
[0104] The data set forth represents a summary of a larger data set
that is set forth in the line graphs of FIGS. 1-16. In some of
FIGS. 1-16, Mixture C is not evaluated. Some of the methyl ester
contamination of the HDEO is relatively mild relative to oxidative
impact. The methyl esters associated with the mild impact tend to
be more oxidatively stable due to the decreased unsaturation of
their compositions. As a result, these methyl esters present less
of a practical problem relative to contamination. The 15W-40 oils
including these methyl esters are returned to their original
conditions using less than 1 wt % of the Mixtures. Such results are
indicated in the above tables as "<1."
[0105] The data set forth above generally indicates that the impact
of adding 6 weight percent of the biodiesel fuels to the 15W-40 oil
and Mixtures of this invention results in a reduction of about 45
minutes of the oxidation induction time. The data set forth above
also indicates that the impact of adding 2 weight percent of the
biodiesel fuels to the 15W-40 oil and Mixtures results in a
reduction of about 24 minutes of the oxidation induction time. The
data also indicates the impact of adding 6 weight percent of the
biodiesel fuels to the 15W-40 oil and Mixtures of this invention
results in a reduction of 81 hours to reach a 375% viscosity
increase at 160.degree. C. Even further, the data indicates that
the impact of adding 2 weight percent of the biodiesel fuels to the
15W-40 oil and Mixtures of this invention results in a reduction of
70 hours to reach a 375% viscosity increase at 160.degree. C.
Accordingly, the data evidences that the Mixtures of this invention
are superior at protection engine oil contaminated with biodiesel
against oxidation.
[0106] It is to be understood that the appended claims are not
limited to express and particular compounds, compositions, or
methods described in the detailed description, which may vary
between particular embodiments which fall within the scope of the
appended claims. With respect to any Markush groups relied upon
herein for describing particular features or aspects of various
embodiments, it is to be appreciated that different, special,
and/or unexpected results may be obtained from each member of the
respective Markush group independent from all other Markush
members. Each member of a Markush group may be relied upon
individually and or in combination and provides adequate support
for specific embodiments within the scope of the appended
claims.
[0107] It is also to be understood that any ranges and subranges
relied upon in describing various embodiments of the present
invention independently and collectively fall within the scope of
the appended claims, and are understood to describe and contemplate
all ranges including whole and/or fractional values therein, even
if such values are not expressly written herein. One of skill in
the art readily recognizes that the enumerated ranges and subranges
sufficiently describe and enable various embodiments of the present
invention, and such ranges and subranges may be further delineated
into relevant halves, thirds, quarters, fifths, and so on. As just
one example, a range "of from 0.1 to 0.9" may be further delineated
into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e.,
from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which
individually and collectively are within the scope of the appended
claims, and may be relied upon individually and/or collectively and
provide adequate support for specific embodiments within the scope
of the appended claims. In addition, with respect to the language
which defines or modifies a range, such as "at least," "greater
than," "less than," "no more than," and the like, it is to be
understood that such language includes subranges and/or an upper or
lower limit. As another example, a range of "at least 10"
inherently includes a subrange of from at least 10 to 35, a
subrange of from at least 10 to 25, a subrange of from 25 to 35,
and so on, and each subrange may be relied upon individually and/or
collectively and provides adequate support for specific embodiments
within the scope of the appended claims. Finally, an individual
number within a disclosed range may be relied upon and provides
adequate support for specific embodiments within the scope of the
appended claims. For example, a range "of from 1 to 9" includes
various individual integers, such as 3, as well as individual
numbers including a decimal point (or fraction), such as 4.1, which
may be relied upon and provide adequate support for specific
embodiments within the scope of the appended claims.
[0108] The invention has been described in an illustrative manner,
and it is to be understood that the terminology which has been used
is intended to be in the nature of words of description rather than
of limitation. Many modifications and variations of the present
invention are possible in light of the above teachings, and the
invention may be practiced otherwise than as specifically
described.
* * * * *