U.S. patent application number 15/636059 was filed with the patent office on 2018-03-01 for lubricant composition.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Mary DERY, Kevin DESANTIS, Michael HOEY, Roger KUHLMAN, Bridgett RAKESTRAW.
Application Number | 20180057767 15/636059 |
Document ID | / |
Family ID | 61241501 |
Filed Date | 2018-03-01 |
United States Patent
Application |
20180057767 |
Kind Code |
A1 |
RAKESTRAW; Bridgett ; et
al. |
March 1, 2018 |
LUBRICANT COMPOSITION
Abstract
A lubricant composition has an increased oxidation induction
time. The lubricant composition includes a base oil present in an
amount of greater than 85 parts by weight per 100 parts by weight
of the lubricant composition. The lubricant composition also
includes an antioxidant component including particular first,
second, and third antioxidants.
Inventors: |
RAKESTRAW; Bridgett;
(Tarrytown, NY) ; DERY; Mary; (Putnam Valley,
NY) ; DESANTIS; Kevin; (Upper Nyack, NY) ;
HOEY; Michael; (Maplewood, NH) ; KUHLMAN; Roger;
(Ringwood, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen am Rhein
DE
|
Family ID: |
61241501 |
Appl. No.: |
15/636059 |
Filed: |
June 28, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62379500 |
Aug 25, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2030/06 20130101;
C10M 2207/289 20130101; C10M 133/40 20130101; C10N 2040/26
20130101; C10M 2219/082 20130101; C10M 133/12 20130101; C10M 141/06
20130101; C10M 2207/026 20130101; C10M 129/76 20130101; C10M
2215/064 20130101; C10N 2030/10 20130101; C10N 2030/12 20130101;
C10M 141/08 20130101; C10N 2040/255 20200501; C10M 2203/1025
20130101; C10M 2207/284 20130101; C10M 2215/221 20130101; C10N
2040/252 20200501; C23F 1/16 20130101; C10M 2215/26 20130101 |
International
Class: |
C10M 141/06 20060101
C10M141/06; C10M 133/40 20060101 C10M133/40; C10M 133/12 20060101
C10M133/12; C10M 129/76 20060101 C10M129/76; C23F 1/16 20060101
C23F001/16 |
Claims
1. A lubricant composition having an increased oxidation induction
time determined according to ASTM D6186 and comprising: a base oil
present in an amount of greater than 85 parts by weight per 100
parts by weight of said lubricant composition; and an antioxidant
component comprising; a first antioxidant having the structure,
##STR00014## wherein R is a straight or branched alkyl group having
7 to 17 carbon atoms, and wherein n is from 6 to 18, a second
antioxidant having the structure: ##STR00015## wherein each of A,
D, E and G is carbon or nitrogen and wherein R.sup.2 and R.sup.3
are each independently chosen from hydrogen, alkyl,
N-(alkyl).sub.2, styryl, and .alpha.-alkyl styryl groups, provided
that at least one of R.sup.2 and R.sup.3 is not hydrogen, and a
third antioxidant having the structure: ##STR00016## wherein m is a
number from 1 to 10 and R.sup.4 is hydrogen or an alkyl group
having 1 to 12 carbon atoms, and wherein R.sup.5 is an alkyl group
having 1 to 20 carbon atoms and each of R.sup.6 and R.sup.7 is
independently --CH.sub.2--S-alkyl, wherein the alkyl group bonded
to the sulfur atom has 1 to 20 carbon atoms.
2. The lubricant composition of claim 1 wherein said first, second,
and third antioxidants are present in a ratio of from 0.1:0.1:0.1
to 3:5:5.
3. The lubricant composition of claim 1 wherein R is a straight or
branched alkyl group of 11 or 17 carbon atoms.
4. The lubricant composition of claim 1 wherein R is a straight or
branched alkyl group of 8 to 14 carbon atoms.
5. The lubricant composition of claim 1 wherein R is a straight or
branched alkyl group of 10 to 14 carbon atoms.
6. The lubricant composition of claim 1 wherein R is a straight or
branched alkyl group of 10 to 12 carbon atoms.
7. The lubricant composition of claim 1 wherein R is a straight or
branched alkyl group of 11 atoms.
8. The lubricant composition of claim 1 wherein said second
antioxidant has the structure: ##STR00017## wherein each of A, D,
E, and G is a carbon atom, R.sup.2 is an octyl group, and R.sup.3
is a butyl group.
9. The lubricant composition of claim 1 wherein said second
antioxidant has the structure: ##STR00018## wherein at least two of
A, D, E and G are nitrogen atoms and wherein R.sup.2 and R.sup.3
are each independently hydrogen or N-(alkyl).sub.2 wherein the
alkyl group has 1 to 20 carbon atoms.
10. The lubricant composition of claim 1 wherein said second
antioxidant has the structure: ##STR00019## wherein at least one of
A, D, E and G is a nitrogen atom and wherein R.sup.2 and R.sup.3
are each independently hydrogen or N-(alkyl).sub.2 wherein the
alkyl group has 1 to 20 carbon atoms.
11. The lubricant composition of claim 1 wherein said third
antioxidant has the structure: ##STR00020## wherein m is 1 and
R.sup.4 is: ##STR00021##
12. The lubricant composition of claim 1 wherein said third
antioxidant has the structure: ##STR00022## m is 1 and R.sup.4 is
C.sub.8H.sub.17.
13. The lubricant composition of claim 1 wherein said third
antioxidant has the structure: ##STR00023## wherein R.sup.5 is a
methyl group and each of R.sup.6 and R.sup.7 is independently
--CH.sub.2--S--C.sub.8H.sub.17.
14. The lubricant composition of claim 1 wherein said base oil is
further defined as an API Group II, Group III or Group IV oil.
15. The lubricant composition of claim 1 having an oxidation
induction time of greater than 10 minutes determined according to
ASTM D6186.
16. The lubricant composition of claim 1 having an oxidation
induction time of greater than 12 minutes determined according to
ASTM D6186.
17. The lubricant composition of claim 1 having an oxidation
induction time of greater than 12 minutes determined according to
ASTM D6186, wherein said base oil is further defined as an API
Group II oil, wherein said first antioxidant has the structure:
##STR00024## wherein R is a straight alkyl group having 11 carbon
atoms, wherein said second antioxidant having the structure:
##STR00025## wherein each of A, D, E, and G is a carbon atom,
R.sup.2 is an octyl group, and R.sup.3 is a butyl group, and
wherein said third antioxidant having the structure: ##STR00026##
wherein m is 1 and R.sup.4 is: ##STR00027## and wherein said first,
second, and third antioxidants are present in a ratio of from
0.1:0.1:0.1 to 3:5:5.
18. A method of forming the lubricant composition of claim 1
wherein the method comprises the step of combining the base oil and
the antioxidant component to form the lubricant composition.
19. A method of reducing corrosion of a steel article, said method
comprising the steps of: A. providing a base oil; B. providing an
antioxidant component comprising; a first antioxidant having the
structure, ##STR00028## wherein R is a straight or branched alkyl
group having 7 to 17 carbon atoms, and wherein n is from 6 to 18, a
second antioxidant having the structure: ##STR00029## wherein each
of A, D, E and G is carbon or nitrogen and wherein R.sup.2 and
R.sup.3 are each independently chosen from hydrogen, alkyl,
N-(alkyl).sub.2, styryl, and .alpha.-alkyl styryl groups, provided
that at least one of R.sup.2 and R.sup.3 is not hydrogen, and a
third antioxidant having the structure: ##STR00030## wherein m is a
number from 1 to 10 and R.sup.4 is hydrogen or an alkyl group
having 1 to 12 carbon atoms, and wherein R.sup.5 is an alkyl group
having 1 to 20 carbon atoms and each of R.sup.6 and R.sup.7 is
independently --CH.sub.2--S-alkyl, wherein the alkyl group bonded
to the sulfur atom has 1 to 20 carbon atoms, C. combining the base
oil and the antioxidant component to form the lubricant composition
wherein the base oil is present in an amount of greater than 85
parts by weight per 100 parts by weight of the lubricant
composition; and D. applying the lubricant composition to the steel
article; wherein the composition has an oxidation induction time of
greater than 10 minutes determined according to ASTM D6186.
20. The method of claim 19 wherein the composition has an oxidation
induction time of greater than 12 minutes determined according to
ASTM D6186, wherein the base oil is further defined as an API Group
II oil, wherein the first antioxidant has the structure:
##STR00031## wherein R is a straight alkyl group having 11 carbon
atoms, wherein the second antioxidant having the structure:
##STR00032## wherein each of A, D, E, and G is a carbon atom,
R.sup.2 is an octyl group, and R.sup.3 is a butyl group, and
wherein the third antioxidant having the structure: ##STR00033##
wherein m is 1 and R.sup.4 is: ##STR00034## and wherein the first,
second, and third antioxidants are present in a ratio of from
0.1:0.1:0.1 to 3:5:5
Description
FIELD OF THE DISCLOSURE
[0001] The present disclosure generally relates to a lubricant
composition that has an increased oxidation induction time and that
includes a base oil and an antioxidant component. More
specifically, the antioxidant component includes three particular
antioxidants.
BACKGROUND
[0002] Lubricant compositions are generally well known in the art
and are typically categorized as engine oils, driveline system
oils, gear oils, greases, 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 and most are designed to
minimize corrosion and wear, to resist thermal and physical
breakdown, and to be able to minimize the effects of common
contaminants such as oxidizing compounds and metal fragments.
[0003] Additives such as antioxidants can be utilized to improve
corrosion and wear resistance of the compositions. However, during
use, acids tend to form and accumulate in the compositions. These
acids typically break down common antioxidants which leads to the
compositions having decreased useable lifetimes. For example, as
the amount of acid builds up in the compositions, antioxidants are
typically degraded and the oxidation induction times of the
compositions typically decrease. Accordingly, there remains an
opportunity to develop an improved lubricant composition.
SUMMARY OF THE DISCLOSURE
[0004] This disclosure provides a lubricant composition having an
increased oxidation induction time determined according to ASTM
D6186. The lubricant composition includes a base oil present in an
amount of greater than 85 parts by weight per 100 parts by weight
of the lubricant composition. The lubricant composition also
includes an antioxidant component. The antioxidant component
includes a first antioxidant, a second antioxidant, and a third
antioxidant. The first antioxidant has the structure:
##STR00001##
wherein R is a straight or branched alkyl group of from 7 to 17
carbon atoms, and wherein n is from 6 to 18. The second antioxidant
has the structure:
##STR00002##
wherein each of A, D, E and G is carbon or nitrogen and wherein
R.sup.2 and R.sup.3 are each independently chosen from hydrogen,
alkyl, N-(alkyl).sub.2, styryl, and .alpha.-alkyl styryl groups,
provided that at least one of R.sup.2 and R.sup.3 is not hydrogen.
The third antioxidant has the structure:
##STR00003##
wherein m is a number from 1 to 10 and R.sup.4 is hydrogen or an
alkyl group having 1 to 12 carbon atoms, and wherein R.sup.5 is an
alkyl group having 1 to 20 carbon atoms and each of R.sup.6 and
R.sup.7 is independently --CH.sub.2--S-alkyl, wherein the alkyl
group bonded to the sulfur atom has 1 to 20 carbon atoms.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0005] The present disclosure provides a lubricant composition. 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.
[0006] The lubricant composition (hereinafter referred to as
"composition") includes a base oil and an antioxidant component,
each of which is described in greater detail below. The lubricant
composition may also include any one or more additives known to
those in the art. In various embodiments, the base oil is, consists
essentially of, or consists of the base oil, the antioxidant
component, and optionally one or more additives described herein.
The composition may be free of one or more additives described
herein or free of any one or more additives known in the art. The
language "consists essentially of" describes various embodiments
wherein the composition is free of one or more polymers, monomers,
antioxidants, and/or additives described herein or known in the
art.
Base Oil:
[0007] 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 or base 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 in one or more non-limiting embodiments. Alternatively,
the base oil may be used in or as an engine oil, driveline system
oil, gear oil, grease, automatic and manual transmission fluid or
oil, hydraulic oil, industrial gear oil, turbine oil, rust and
oxidation (R&O) inhibited oil, compressor oil, or paper machine
oil, etc.
[0008] 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.
[0009] 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.
[0010] 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.
[0011] 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
C.sub.3-C.sub.8 fatty acid esters, or the C.sub.13 oxo acid diester
of tetraethylene glycol) may also be utilized.
[0012] 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.
[0013] 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 disclosure. 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.
[0014] 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 (sulfur content >0.03 wt %, and/or <90 wt %
saturates, viscosity index 80-120); Group II (sulfur content less
than or equal to 0.03 wt %, and greater than or equal to 90 wt %
saturates, viscosity index 80-120); Group III (sulfur content less
than or equal to 0.03 wt %, and greater than or equal to 90 wt %
saturates, viscosity index greater 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 in one or more non-limiting embodiments.
[0015] The base oil is typically present in the composition in an
amount of greater than 85, e.g. from 85 to 99.9, from 90 to 99.9,
from 85 to 95, or from 85 to 90, parts by weight per 100 parts by
weight of the composition. Alternatively, the base oil may be
present in amounts of greater than 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 85 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.
Antioxidant Component:
[0016] The antioxidant component includes or is a combination of
three antioxidants, i.e., a first antioxidant, a second
antioxidant, and a third antioxidant. Combinations of one or more
first antioxidants may be used with one or more second antioxidants
and one or more third antioxidants. In other words, one or more
than one first antioxidant may be used. One or more than one second
antioxidant may be used and one or more than one third antioxidant
may be used. The antioxidant component (and the composition as a
whole) may be free of or include less than 10, 5, 1, 0.5, 0.1, or
0.05, weight percent of one or more additional antioxidants that
are not representative of the first, second, and third
antioxidants.
[0017] The first antioxidant has the structure:
##STR00004##
wherein R is a straight or branched alkyl group having 7 to 17
carbon atoms. In various embodiments, the alkyl group has 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, or 17 carbon atoms. In other
embodiments, the alkyl group has 8 to 17, 9 to 15, 10 to 14, 11 to
13, 8 to 14, 10 to 12, or 11, carbon atoms. Moreover, n is from 6
to 18. In various embodiments, n is 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, or 18. In other embodiments, n is from 7 to 17, 8 to
16, 9 to 15, 10 to 14, 11 to 13, or 11 or 12. In additional
non-limiting embodiments, all values and ranges of values including
those above, and therebetween, are hereby expressly contemplated.
Moreover, all isomers of the aforementioned compounds are hereby
expressly contemplated in various non-limiting embodiments. The
language "and/or" describes that the first antioxidant may include
molecules of the first structure above (e.g. to the exclusion of
molecules of the second structure), molecules of the second
structure above (e.g. to the exclusion of molecules of the first
structure), or a combination of molecules of both the first and
second structures above.
[0018] The second antioxidant has the structure:
##STR00005##
wherein each of A, D, E and G is carbon or nitrogen and wherein
R.sup.2 and R.sup.3 are each independently chosen from hydrogen,
alkyl, N-(alkyl).sub.2, styryl, and .alpha.-alkyl styryl groups,
provided that at least one of R.sup.2 and R.sup.3 is not hydrogen.
Each of R.sup.2 and R.sup.3 may be present at any location on their
respective rings.
[0019] In various embodiments, one or more of the alkyl groups
described immediately above has 1 to 20 carbon atoms. In various
embodiments, one or more of the alkyl groups has 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17 carbon atoms. In other
embodiments, one or more of the alkyl groups has 2 to 19, 3 to 18,
4 to 17, 5 to 16, 6 to 15, 7 to 14, 8 to 13, 9 to 12, 10, or 11,
carbon atoms. For example, one or more of the alkyl groups may be a
methyl group, ethyl group, butyl group, etc. up to and including
groups having 20 carbon atoms, and all isomers thereof. Similarly,
the .alpha.-alkyl portion of the .alpha.-alkyl styryl group may
have a number of carbon atoms as is described above. One or more of
the alkyl groups may be linear, branched, cyclic, etc. In various
embodiments A, D, E, and/or G may be carbon or nitrogen. For
example, the compound may be further described as a pyridine or
pyrimidine, e.g. and include one or two nitrogen atoms in the ring
at any position. In additional non-limiting embodiments, all values
and ranges of values including those above, and therebetween, are
hereby expressly contemplated. Moreover, all isomers of the
aforementioned compounds are hereby expressly contemplated in
various non-limiting embodiments.
[0020] In other embodiments, the second antioxidant is one or more
of the following:
##STR00006##
wherein the alkyl groups are as described above.
[0021] The third antioxidant has the structure:
##STR00007##
wherein m is a number from 1 to 10 and R.sup.4 is hydrogen or an
alkyl group having 1 to 12 carbon atoms, and wherein R.sup.5 is an
alkyl group having 1 to 20 carbon atoms and each of R.sup.6 and
R.sup.7 is independently --CH.sub.2--S--alkyl, wherein the alkyl
group bonded to the sulfur atom has 1 to 20 carbon atoms. The --OH
group, and each of R.sup.5, R.sup.6, and R.sup.7 may be located at
any location on the ring. In various embodiments, m is 1, 2, 3, 4,
5, 6, 7, 8, 9, or 10. In other embodiments, the alkyl group has 1,
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, carbon atoms. In various
embodiments, the alkyl group has 2 to 11, 3 to 10, 4 to 9, 5 to 8,
6 or 7, carbon atoms. Any one or more alkyl groups may include
heteroatom substitution (e.g. S, O, N) & bis substitution. In
additional non-limiting embodiments, all values and ranges of
values including those above, and therebetween, are hereby
expressly contemplated. Moreover, all isomers of the aforementioned
compounds are hereby expressly contemplated in various non-limiting
embodiments.
[0022] In one embodiment, the third antioxidant has the following
structure or is an isomer thereof:
##STR00008##
[0023] In another embodiment, the third antioxidant has the
following structure or is an isomer thereof:
##STR00009##
wherein the alkyl group is as described above.
[0024] In still another embodiment, the third antioxidant has the
following structure or is any isomer thereof:
##STR00010##
[0025] The individual amounts of the first, second, and third
antioxidants are not particularly limited. Similarly, the overall
total amount of the first, second, and third antioxidants is not
particularly limited. In various embodiments, the first, second,
and third antioxidants are present in a ratio of from 0.1:0.1:0.1
to 3:5:5. Each one or more of these values of the ratio may itself
be, for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5, or
any range or value of ranges therebetween, all of which are
expressly contemplated in various non-limiting embodiments. In
various embodiments the first, second, and/or third antioxidants
may each be present in the ratio of 0.1 to 2 or 0.1 to 3. In other
embodiments, the overall total amount of the first, second, and
third antioxidants, is from 0.1 to 2, 0.1 to 3, from 0.1 to 5, or
from 0.1 to 5, parts by weight per 100 parts by weight of the
composition. All values or range of values, both whole and
fractional, within those ranges and values described above are
hereby expressly contemplated in various non-limiting
embodiments.
Additives:
[0026] 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. In addition, one or more addition
antioxidants, apart from the ones described above, may be utilized
or may be excluded. In various embodiments, additives are included
such that the composition is commonly referred to as an engine oil
or as an industrial oil, such as a hydraulic fluid, a turbine oil,
an R&O (rust and oxidation inhibited) oil or a compressor
oil.
Anti-Wear Additive:
[0027] The anti-wear additive is not particularly limited and may
be any known in the art. It may be ash-containing or ash-less. In
one embodiment, the anti-wear additive is chosen from 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. In one embodiment, the anti-wear additive include
phosphorous and sulfur, e.g. in phosphorothionates and/or
dithiophosphate esters.
[0028] 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. It is
also contemplated that the antiwear additive may be present in an
amount of from 0.2 to 0.8, from 0.2 to 0.6, from 0.2 to 0.4, or
from 0.3 to 0.5, 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.
Additional Antioxidants:
[0029] The composition may include or be free of additional
antioxidants other than the aforementioned first, second, and third
antioxidants. In other words, the composition may include the
first, second, and third antioxidants and not include one or more
of any of the additional antioxidants described below. However, it
is contemplated that, in various non-limiting embodiments, one or
more of the additional antioxidants described below may be used in
conjunction with the first, second, and third antioxidants
described above.
[0030] Suitable, non-limiting, additional 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.
[0031] Other non-limiting examples of suitable additional
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.
[0032] 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.
[0033] It is also contemplated that alkylidenebisphenols, for
example 2,2'-methylenebis(6-tert-butyl-4-methyl phenol),
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-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methyl phenol,
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 additional
antioxidants.
[0034] 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.
[0035] 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-h-
ydroxybenzyl)malonate, and combinations thereof are also suitable
for use as additional antioxidants.
[0036] 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.
[0037] Additional suitable, but non-limiting examples of additional
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, dioctadecyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy 3-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.
[0038] 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.
[0039] Additional non-limiting examples of suitable additional
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-hydroxyphenylpropionyphydrazine. Other
suitable non-limiting examples of additional antioxidants 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-tetramethylpiperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethyl
piperidin-4-ol, and combinations thereof.
[0040] Even further non-limiting examples of suitable additional
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. Some of the aforementioned antioxidants may represent,
in chemical description, one or more of the first, second, and
third antioxidants. These may be utilized. In addition, any one or
more of the other antioxidants described above may also be used to
supplement one or more of the first, second, and third
antioxidants.
[0041] The one or more additional antioxidants are not particularly
limited in amount in the composition but may be 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 additional 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:
[0042] 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.
triazole) and derivatives thereof, 4,5, 6,7-tetrahydrobenzotriazole
and 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole
or triazole, e.g. 1-[bis(2-ethylhexyl)aminomethyl)triazole and
1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole,
1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl)
triazole, and combinations thereof.
[0043] 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.
[0044] 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.
[0045] 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:
[0046] In various embodiments, one or more additional rust
inhibitors and/or one or more friction modifiers can be included in
the composition. Suitable, non-limiting examples of the one or more
additional rust inhibitors and/or one or more 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
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 sulfur 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.
[0047] The one or more additional rust inhibitors and/or one or
more friction modifiers are not particularly limited in amount in
the composition but may be 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 additional rust
inhibitors and/or one or more 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:
[0048] 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. 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:
[0049] 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. 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:
[0050] 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.
[0051] 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:
[0052] 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.
[0053] 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.
[0054] 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.
Additive Concentrate Package:
[0055] The instant disclosure also provides an additive concentrate
package which includes one or more metal deactivators, one or more
anti-wear additives, and the antioxidant component. 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.
[0056] 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 disclosure 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 disclosure in its intended use, are expressly contemplated and
hereby included herein. Various embodiments of this disclosure
include one or more of the modification, reaction products, and
products formed from employing the composition, as described
above.
Oxidation Induction Time:
[0057] As is known in the art, oxidation induction time, as
determined using ASTM D6186, may be used as an indication of
oxidation stability of the lubricant composition. This test method
tends to be faster than other oil oxidation tests and requires a
very small amount of sample. This test method may be used for
research and development, quality control, and specification
purposes. This test method covers the determination of oxidation
induction time of lubricating oils subjected to oxygen at 3.5 MPa
(500 psig) and temperatures between 130 and 210.degree. C.
[0058] Typically, a small quantity of the composition is weighed
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 composition at the
specified test temperature. The oxidation induction time of various
embodiments of this disclosure is increased as compared to the
oxidation induction time of comparative examples that include the
same base oil and just one or two of the first, second, and third
antioxidants. In other words, the specific combination of the
first, second, and third antioxidants provides an unexpected
synergistic increase in oxidation induction times that is not
predicted by those of skill in the art. In various embodiments, the
oxidation induction time of the composition is greater than 10,
10.5, 11, 11.5, 12, 12.5, or even greater, minutes, as determined
using ASTM D6186. In various embodiments, the maximum oxidation
induction time is 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5,
15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, or 20, minutes.
In various non-limiting embodiments, all values and range of
values, both whole and fractional, within those ranges and values
described above, including the endpoints, are hereby expressly
contemplated. Moreover, any of the aforementioned values may vary
by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc.
[0059] Without intending to be bound by any particular theory, it
is believed that the second antioxidant has an NH bond that is
readily cleaved allowing nitrogen to pick up a free radical from
the base oil and stop a catalytic cycle. Moreover, it is believed
that the third antioxidant functions due to steric hindrance of the
--OH group thereby preventing or minimizing a nucleophilic
reaction. As a type of hindered phenol, the hydrogen atom of the
third antioxidant may be abstracted and generate its own radical
which allows the third antioxidant to pick up a radical from the
base oil.
Method of Forming the Composition:
[0060] This disclosure also provides a method of forming the
composition. The method includes the steps of providing the base
oil, providing the antioxidant component and combining the base oil
and the antioxidant component to form the composition. The method
may also include the step of combining any or more of the
aforementioned additives with the base oil and/or the antioxidant
component. The base oil, the antioxidant component, and any one or
more optional additives may be combined in any order and each
individually in one or more separate parts.
Method for Reducing Corrosion of a Steel Article:
[0061] This disclosure also provides a method for reducing
corrosion of a steel article using the composition. The method
includes the steps of providing the base oil and providing the
antioxidant component. The method also includes the steps of
combining the base oil and the antioxidant component to form the
composition and applying the composition to the steel article to
reduce corrosion.
Method for Reducing Wear of a Metal:
[0062] This disclosure also provides a method for reducing wear of
a metal, e.g. a metal article. The method may include any one or
more of the aforementioned method steps. The method of reducing
wear of the metal includes the step of providing the metal and the
step of applying the lubricant composition to the metal.
[0063] The step of providing the metal can occur before, after, or
simultaneously with, the optional steps of providing the base oil,
providing the antioxidant component, and/or combining the base oil
and the antioxidant component and any one or more optional
additives to form a lubricant composition.
EXAMPLE S
[0064] An inventive composition is formed in addition to various
comparative compositions. The comparative compositions differ from
the inventive composition in that none of the comparative
compositions include all three of the first, second, and third
antioxidants. After formation, each of the inventive composition
and the comparative compositions is evaluated to determine
oxidation induction time according to ASTM D6186. The compositions
and the results of the oxidation induction time testing are set
forth below.
TABLE-US-00001 Invent. 1 Comp. 1 Comp. 2 Comp. 3 Comp. 4 Comp. 5
Comp. 6 Base Oil 98.14% 99.5% 99.14% 99.5% 99.0% 98.64% 98.64%
Antioxidant 1 0.86% -- 0.86% -- -- 0.86% 0.86% Antioxidant 2 0.5%
0.5% -- -- 0.5% 0.5% -- Antioxidant 3 0.5% -- -- 0.5 0.5% -- 0.5%
Oxidation 12.3 4.6 1.5 3.3 8.3 5.8 8.8 Induction Time (min)
[0065] Base Oil is a Group II base oil.
[0066] Antioxidant 2 is an aminic antioxidant that has the
structure:
##STR00011##
wherein R.sup.2 is a octyl group and R.sup.3 is a butyl group.
[0067] Antioxidant 1 is a hindered amine antioxidant that has the
structure:
##STR00012##
wherein R is a straight alkyl group having 11 carbon atoms.
[0068] Antioxidant 3 is a phenolic antioxidant that has the
structure:
##STR00013##
wherein m is 1 and R.sup.4 is C.sub.8H.sub.17.
[0069] The data clearly indicates a special, superior, and
unexpected synergistic effect when all three of the aforementioned
antioxidants are combined. For example:
[0070] When Antioxidant 1 is used by itself, the oxidation
induction time is 1.5 minutes;
[0071] When Antioxidant 2 is used by itself, the oxidation
induction time 4.6 minutes;
[0072] When Antioxidant 3 is used by itself, the oxidation
induction time is 3.3 minutes;
[0073] Therefore, if Antioxidants 1, 2, and 3 were used together,
the expected outcome would be additive and would be approximately
9.4 minutes. However, the actual result is 12.3 minutes which is an
unexpected 31% higher. Clearly, this is both superior and
unexpected.
[0074] All combinations of the aforementioned embodiments
throughout the entire disclosure are hereby expressly contemplated
in one or more non-limiting embodiments even if such a disclosure
is not described verbatim in a single paragraph or section above.
In other words, an expressly contemplated embodiment may include
any one or more elements described above selected and combined from
any portion of the disclosure.
[0075] One or more of the values described above may vary by
.+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%, etc. so long as the
variance remains within the scope of the disclosure. Unexpected
results may be obtained from each member of a Markush group
independent from all other members. Each member may be relied upon
individually and or in combination and provides adequate support
for specific embodiments within the scope of the appended claims.
The subject matter of all combinations of independent and dependent
claims, both singly and multiply dependent, is herein expressly
contemplated. The disclosure is illustrative including words of
description rather than of limitation. Many modifications and
variations of the present disclosure are possible in light of the
above teachings, and the disclosure may be practiced otherwise than
as specifically described herein.
[0076] It is also to be understood that any ranges and subranges
relied upon in describing various embodiments of the present
disclosure 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
disclosure, 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.
* * * * *