Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICANT COMPOSITION
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Prov. Ser. No. 61/231,468,
filed on
August 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
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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
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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] Figure 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 Figure 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] Figure 2 is similar to Figure 1 except that the HDEO is contaminated
with 2
wt % aged rapeseed methyl ester as the biodiesel fuel.
[0010] Figure 3 is also similar to Figure 1 except that the HDEO is
contaminated with
2 wt % aged palm methyl ester as the biodiesel fuel.
[0011] Figure 4 is also similar to Figure 1 except that the HDEO is
contaminated with
2 wt % aged coconut methyl ester as the biodiesel fuel.
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[0012] Figure 5 is similar to Figure 1 except that the HDEO is contaminated
with 6
wt % aged soy methyl ester as the biodiesel fuel.
[0013] Figure 6 is similar to Figure 2 except that the HDEO is contaminated
with 6
wt % aged rapeseed methyl ester as the biodiesel fuel.
[0014] Figure 7 is also similar to Figure 3 except that the HDEO is
contaminated with
6 wt % aged palm methyl ester as the biodiesel fuel.
[0015] Figure 8 is also similar to Figure 4 except that the HDEO is
contaminated with
6 wt % aged coconut methyl ester as the biodiesel fuel.
[0016] Figure 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 Figure 9
demonstrate differing effectiveness of the various Mixtures relative to
increasing a
number of hours to increase viscosity according to SAE 040793.
[0017] Figure 10 is similar to Figure 9 except that the HDEO is contaminated
with 2
wt % aged rapeseed methyl ester as the biodiesel fuel.
[0018] Figure 11 is also similar to Figure 9 except that the HDEO is
contaminated
with 2 wt % aged palm methyl ester as the biodiesel fuel.
[0019] Figure 12 is also similar to Figure 9 except that the HDEO is
contaminated
with 2 wt % aged coconut methyl ester as the biodiesel fuel.
[0020] Figure 13 is similar to Figure 9 except that the HDEO is contaminated
with 6
wt % aged soy methyl ester as the biodiesel fuel.
[0021] Figure 14 is similar to Figure 10 except that the HDEO is contaminated
with 6
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wt % aged rapeseed methyl ester as the biodiesel fuel.
[0022] Figure 15 is also similar to Figure 11 except that the HDEO is
contaminated
with 6 wt % aged palm methyl ester as the biodiesel fuel.
[0023] Figure 16 is also similar to Figure 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 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 when the composition is measured
containing up to
about 6 wt % of the biodiesel fuel. 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.
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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 August 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
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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. Nos.
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. Serial Number
61/231,468, filed on August 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
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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
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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 C5 to C12
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,
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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
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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:
H
N
R' I R'
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
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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 CX/Cy 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. Patent 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
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least one diphenylamine antioxidant may be as described in U.S. Prov. Ser. No.
61/231,468, filed on August 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:
O O
HO (CXH2X)11 0-(CyH2y~_S-(CyH2y)-O11 (CXH2X) OH
R R
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. Patent 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
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having the formula:
Ri
HN
C
wherein Ri 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 August 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
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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
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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.
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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
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anti-wear additive may be as described in U.S. Prov. Ser. No. 61/231,468,
filed on
August 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-((x-
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
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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-((x-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-((x-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,(X-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-hydr oxy-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)-
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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-methylphenyl]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] 0-, 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)malonate, bis [4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-
di-tert-
butyl-4-hydroxybenzyl)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-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
hydroxyphenoxy) -1,3,5-triazine, 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-
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hydroxyphenylethyl)- 1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxybhenyl
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 (3-(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,
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tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-
thiaundecanol, 3-
thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-
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-l-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-l-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 (3-(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-
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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-l-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-l-
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) sebac ate, 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
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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, 1 trithiatridecane 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 August 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
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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
August 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
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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-
oleoylsarco sine, sorbitan monooleate, lead naphthenate, alkenylsuccinic
anhydrides,
for example dodecenylsuccinic anhydride, 2-carboxymethyl-l-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-l-(2-hydroxyethyl)imidazoline,
phosphorus-containing compounds, for example: Amine salts of phosphoric acid
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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
August 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
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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 August 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 August 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
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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 August 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
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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 August 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 .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
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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.
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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
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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 August 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 CI-C5 esters, in particular methyl
and ethyl
esters. Mixtures of methyl esters of saturated, monounsaturated and
polyunsaturated
C13-C22 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
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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).
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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 composition 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 when the composition is measured
containing up to
about 6 wt % of the biodiesel fuel. It is to be understood that the
composition is not
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limited to including up to about 6 wt % but is typically evaluated when it
contains this
amount of biodiesel fuel. In other words, and as described above, the amount
of
biodiesel fuel in the composition can vary and may exceed 6 wt %. 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
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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.
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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,
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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.
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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 C via
high
pressure differential scanning calorimetry.
[00100] 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 160C 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 C with soluble iron catalyst.
[00101] The biodiesel described above is a methyl ester of soy, rapeseed,
palm, or
coconut oil and is aged for 20 hours at 110 C under an air flow of 15 mL/min.
This
ageing is done to simulate oxidative degradation during combustion in diesel
engines.
[00102] 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.
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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
[00103] 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 2
Weight Percent Biodiesel Fuel Added to 15W-40 Oil
Mixture Aged Soy Aged Rapeseed Aged Palm Aged Coconut
Methyl Ester Methyl Ester Methyl Ester Methyl Ester
2wt% 6wt 2wt% 6wt% 2wt% 6wt% 2wt% 6wt%
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
[00104] The data set forth represents a summary of a larger data set that is
set forth in
the line graphs of Figures 1-16. In some of Figures 1-16, Mixture C is not
evaluated.
Some of the methyl ester contamination of the HDEO is relatively mild relative
to
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WO 2011/017555 PCT/US2010/044601
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."
[00105] 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 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 C.
Accordingly, the
data evidences that the Mixtures of this invention are superior at protection
engine oil
contaminated with biodiesel against oxidation.
[00106] 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
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WO 2011/017555 PCT/US2010/044601
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.
[00107] 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
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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.
[00108] 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.
44
