U.S. patent application number 15/756405 was filed with the patent office on 2018-09-20 for lubricant composition.
The applicant listed for this patent is BASF SE, University of Ottawa. Invention is credited to Mary Elizabeth Dery, Evan Antony Haidasz, Paul Angelo Odorisio, Derek Andrew Pratt, Philippe Rabbat, Bridgett Rakestraw, Sai P. Shum.
Application Number | 20180265800 15/756405 |
Document ID | / |
Family ID | 56920945 |
Filed Date | 2018-09-20 |
United States Patent
Application |
20180265800 |
Kind Code |
A1 |
Rabbat; Philippe ; et
al. |
September 20, 2018 |
Lubricant Composition
Abstract
A lubricant composition includes a base oil present in an amount
of greater than 70 parts by weight per 100 parts by weight of the
lubricant composition and an antioxidant. The antioxidant has the
structure: wherein each X is independently CH or N, so long as at
least one X is N, wherein Y is CRR', NR'', PR'', S, or O, each R,
R' and R'' is independently H, alkyl or aryl, and R'' is alkyl,
aryl, alkoxy or aryloxy. Each A is independently an electron
donating group. The electron donating group (1) has an atom having
at least one lone pair of electrons that is bonded directly to the
aromatic ring, (2) is an aryl or alkyl group, or (3) is a hydrogen
atom. ##STR00001##
Inventors: |
Rabbat; Philippe;
(Maplewood, NJ) ; Dery; Mary Elizabeth; (Putnam
Valley, NY) ; Rakestraw; Bridgett; (Tarrytown,
NY) ; Shum; Sai P.; (Pleasantville, NY) ;
Odorisio; Paul Angelo; (Leonia, NJ) ; Pratt; Derek
Andrew; (Ottawa, CA) ; Haidasz; Evan Antony;
(Ottawa, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE
University of Ottawa |
Ludwigshafen
Ottawa |
|
DE
CA |
|
|
Family ID: |
56920945 |
Appl. No.: |
15/756405 |
Filed: |
September 2, 2016 |
PCT Filed: |
September 2, 2016 |
PCT NO: |
PCT/US2016/050155 |
371 Date: |
February 28, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62213245 |
Sep 2, 2015 |
|
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|
62347907 |
Jun 9, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 15/20 20130101;
C07D 498/04 20130101; C10N 2070/02 20200501; C10M 135/36 20130101;
C10M 2215/225 20130101; C07D 513/04 20130101; C10M 137/12 20130101;
C10M 133/40 20130101; C10M 2215/221 20130101; C10N 2030/10
20130101; C10M 133/48 20130101 |
International
Class: |
C10M 133/48 20060101
C10M133/48; C10M 135/36 20060101 C10M135/36 |
Claims
1. A lubricant composition comprising: a base oil present in an
amount of greater than 70 parts by weight per 100 parts by weight
of said lubricant composition; and an antioxidant having the
structure; ##STR00039## wherein each X is independently CH or N, so
long as at least one X is N; wherein Y is CRR', NR'', PR''', S, or
O; wherein each R, R' and R'' is independently H, alkyl or aryl,
and R''' is alkyl, aryl, alkoxy or aryloxy; and wherein each A is
independently an electron donating group that: (1) has an atom
having at least one lone pair of electrons that is bonded directly
to the aromatic ring; (2) is an aryl or alkyl group; or (3) is a
hydrogen atom.
2. The lubricant composition of claim 1 wherein each A is an
electron donating group that has an oxygen atom or nitrogen atom
that is bonded directly to the aromatic ring.
3. The lubricant composition of claim 1 wherein each of said
electron donating groups is chosen from --NR.sup.4.sub.2,
--NH.sub.2, --OH, --OR.sup.4, --NHCOR.sup.4, and --OCOR.sup.4,
wherein R.sup.4 is an alkyl group having 1 to 10 carbon atoms.
4.-9. (canceled)
10. The lubricant composition of claim 1 wherein at least one of
said electron donating groups is an alkyl group having 1 to 20
carbon atoms.
11. The lubricant composition of claim 1 wherein at least one of
said electron donating groups is an aryl group.
12. The lubricant composition of claim 1 wherein at least one of
said electron donating groups is a hydrogen atom.
13. The lubricant composition of claim 1 wherein each X is N.
14. The lubricant composition of claim 1 wherein at least two of X
are N.
15. The lubricant composition of claim 1 wherein at least three of
X are N.
16. The lubricant composition of claim 1 wherein Y is CRR' and each
R and R' is independently H, alkyl or aryl.
17. The lubricant composition of claim 1 wherein Y is NR'' and R''
is H, alkyl or aryl.
18. The lubricant composition of claim 1 wherein Y is S.
19. The lubricant composition of claim 1 wherein Y is O.
20. The lubricant composition of claim 1 wherein Y is PR''' and
R''' is alkyl, aryl, alkoxy or aryloxy.
21. The lubricant composition of claim 1 wherein said antioxidant
is present in an amount of from 0.1 to 2 parts by weight per 100
parts by weight of said lubricant composition.
22. The lubricant composition of claim 1 wherein said base oil is
further defined as an API Group I, Group II or Group III oil.
23. (canceled)
24. A method of forming the lubricant composition of claim 1
comprising the steps of providing the base oil, providing the
antioxidant, and combining the base oil and the antioxidant to form
the lubricant composition.
25. An antioxidant having the structure: ##STR00040## wherein each
X is independently CH or N, so long as at least one X is N; wherein
Y is CRR', NR'', PR''', S, or O; wherein each R, R' and R'' is
independently H, alkyl or aryl, and R''' is alkyl, aryl, alkoxy or
aryloxy; and wherein each A is independently an electron donating
group that: (1) has an atom having at least one lone pair of
electrons that is bonded directly to the aromatic ring; (2) is an
aryl or alkyl group; or (3) is a hydrogen atom.
26. A method of forming the antioxidant of claim 25 comprising the
following steps: I. reacting Compound A and Compound B to form
Compound C according to the following reaction: ##STR00041## II.
reacting Compound C to form Compound D according to the following
reaction: ##STR00042## III. reacting Compound D to form Compound E
according to the following reaction: and ##STR00043## IV. reacting
Compound E to form the antioxidant according to the following
reaction: ##STR00044## wherein R is an n-heptyl group.
27. An additive concentrate package comprising said antioxidant of
claim 25 and one or more metal deactivators, one or more anti-wear
additives, and/or one or more additional antioxidants.
Description
FIELD OF THE DISCLOSURE
[0001] This disclosure generally relates to a lubricant
composition. More specifically, the lubricant composition includes
a particular antioxidant that includes an electron donating
group.
BACKGROUND
[0002] 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 (such as (base) oils) or large weight
percentages of water, respectively. Lubricant compositions are
typically further 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] Antioxidants are compounds that can retard oxidation, and
thus are useful as additives in such lubricant compositions.
Antioxidants are commonly utilized in lubricant compositions to
assist in reducing unwanted oxidation and increasing performance
standards. Combustion engine lubricants oxidize readily at the high
operating temperatures of an engine, and in turn, have diminished
lubricating capacity as the viscosity of the lubricant increases.
Oxidation products also tend to accumulate to form deposits, which
in turn leads to greater wear on engine parts. For example, peroxyl
radicals can lead to formation of radical chains and ultimately
oxidative degradation. Antioxidants are used to react with such
radicals, shorten radical chains, and reduce degradation.
Unfortunately, many antioxidants do not react as fast as would be
desired. Therefore, remains an opportunity for development of
improved antioxidants.
SUMMARY OF THE DISCLOSURE
[0004] This disclosure provides a lubricant composition that
includes a base oil present in an amount of greater than 70 parts
by weight per 100 parts by weight of the lubricant composition and
also includes an antioxidant. The antioxidant has the
structure:
##STR00002##
wherein each X is independently CH or N, so long as at least one X
is N, wherein Y is CRR', NR'', PR''', S, or O, each R, R' and R''
is independently H, alkyl or aryl, and R''' is alkyl, aryl, alkoxy
or aryloxy. Each A is independently an electron donating group. The
electron donating group (1) has an atom having at least one lone
pair of electrons that is bonded directly to the aromatic ring, (2)
is an aryl or alkyl group, or (3) is a hydrogen atom.
BRIEF DESCRIPTION OF THE FIGURES
[0005] Other advantages of the present disclosure 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:
[0006] FIG. 1 is a graph that shows co-autoxidation of 4.3 M
styrene and 10 .mu.M PBD-BODIPY in PhCl at 37.degree. C., initiated
by 6.0 mM AIBN and inhibited by 2 .mu.M of the antioxidants shown
(k.sub.inh>>10.sup.7).
[0007] FIG. 2A is a graph that shows co-autoxidation of 2.8M
n-Hexadecene and 10 .mu.M PBD-BODIPY in PhCl at 70.degree. C.,
initiated by 87 mM tBu.sub.2O.sub.2, and inhibited by 0.6 .mu.M of
the various antioxidants shown.
[0008] FIG. 2B is a graph that shows co-autoxidation of 2.8M
n-Hexadecene and 10 .mu.M PBD-BODIPY in PhCl at 100.degree. C.,
initiated by 87 mM tBu.sub.2O.sub.2, and inhibited by 0.6 .mu.M of
the various antioxidants shown.
[0009] FIG. 3 is a graph that shows co-autoxidation of 0.96M
squalane and 10 .mu.M PBD-BODIPY in 1,2-dichlorobenzene at
100.degree. C., initiated by 500 .mu.M dicumyl peroxide, and
inhibited by 4 .mu.M of the antioxidants shown.
[0010] FIG. 4 is a graph that shows hydroperoxide formation in
n-hexadecane at 160.degree. C. including uninhibited autoxidation
and inhibited autoxidation with 100 .mu.M of the antioxidants
shown.
[0011] FIG. 5 is a graph that shows hydroperoxide formation in
n-hexadecane at 160.degree. C. including uninhibited and inhibited
autoxidation with 100 .mu.M of the antioxidants shown.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0012] 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, a driveline system oil, a gear oil, a grease, an
automatic and/or manual transmission fluid and/or oil, a hydraulic
oil, an industrial gear oil, a turbine oil, a rust and oxidation
(R&O) inhibited oil, a compressor oil, a paper machine oil,
and/or combinations thereof.
[0013] 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, depending on the formulation application. In the art,
engine oils may be referred to as including a base oil as described
below and performance additives. The lubricant composition of this
disclosure includes a base oil and a particular antioxidant and may
include any one or more of the aforementioned additives.
Base Oil:
[0014] 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.
[0015] 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.
[0016] 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.
[0017] 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.
[0018] 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 a weight average weight
average molecular weight of 1,000; diphenyl ether of polyethylene
glycol having a weight average molecular weight of 500-1,000; and
diethyl ether of polypropylene glycol having a weight average
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.
[0019] 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.
[0020] 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.
[0021] 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 chosen from API Group I, II, III, IV, V and combinations
thereof. In another embodiment, the base oil is chosen from 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.
[0022] 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.
Antioxidant:
[0023] The lubricant composition also includes an antioxidant. One
or more of such antioxidants can be used. The antioxidant has the
structure:
##STR00003##
[0024] In various embodiments, each X is independently CH or N, so
long as at least one X is N, Y is CRR', NR'', PR''', S, or O, each
A is independently an electron donating group, and each R, R' and
R'' is independently H, alkyl or aryl, and R''' is alkyl, aryl,
alkoxy or aryloxy. The electron donating group (1) has an atom
having at least one lone pair of electrons that is bonded directly
to the aromatic ring, (2) is an aryl or alkyl group, or (3) is a
hydrogen atom. In one embodiment, Y is PR''' and R''' is alkyl,
aryl, alkoxy or aryloxy.
[0025] In other embodiments, each X is independently CH or N, so
long as at least one X is N, Y is CH.sub.2, NH, S, or O, and each A
is independently an electron donating group. In one embodiment,
each X is N (i.e., a nitrogen atom). In other embodiments, two,
three, at least two, or at least three, of X is N. In another
embodiment, all four X are N. Examples of such embodiments are as
follows:
##STR00004## ##STR00005##
[0026] The terminology "aryl" group describes any functional group
or substituent derived from an aromatic ring, e.g. phenyl,
naphthyl, thienyl, indolyl, etc. The terminology "aryloxy" is known
in the art and in this disclosure may be based on any one or more
of the aforementioned aryl groups. The alkyl group may be linear,
branched, or cyclic and typically includes 1 to 20 carbon atoms.
Although, the alkyl group may include more than 20 carbon atoms. In
various embodiments, the alkyl group includes 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms or
any range thereof. The alkyl group may be further defined as an
alkane, an alkene, or an alkyne. The alkyl group may be
alternatively described using the formula G.sub.nH.sub.2n+1 wherein
n is 1 to 20, as described above. In various embodiments, the alkyl
group may be described as methyl, ethyl propyl, butyl, t-butyl,
pentyl, hexyl, octyl, nonyl, or any isomer thereof. The terminology
"alkoxy" is known in the art and in this disclosure may be based on
any one or more of the aforementioned alkyl groups.
[0027] When one or more carbon atoms within the aromatic ring of
the antioxidant is replaced with nitrogen, the resulting compounds
may have improved estimated activation enthalpies (.DELTA.H*) for
reactions with peroxyl radicals, while also maintaining a
relatively high estimated ionization enthalpy
(.DELTA.H<o.eta.>) which reflects their stability in air, as
compared to the same compounds without the substitution of the
nitrogen for carbon. Substitution of nitrogen atoms may produce an
increase in the ionization enthalpy (.DELTA.H'.sub.o.eta.), thus
stabilizing the compound to one-electron oxidation (such as by
reaction with O.sub.2 in air or hydroperoxides arising from
hydrocarbon oxidation). This stability may permit substitution with
electron-donating groups to increase reactivities as
radical-trapping antioxidants by lowering the activation enthalpy
(.DELTA.H*) for reactions with peroxyl radicals.
[0028] Each A is independently an electron donating group. Each
electron donating group independently (1) has an atom having at
least one lone pair of electrons that is bonded directly to the
aromatic ring of the antioxidant, (2) is an aryl or alkyl group, or
(3) is a hydrogen atom. Each electron donating group can be
alternatively described as an "EDG", as is appreciated in the art.
Alternatively, the terminology "group" may be the individual
hydrogen atom even though a singular atom is not typically
considered to be a "group." In other words, relative to this
disclosure, it is contemplated that a single hydrogen atom can be
an electron donating "group." In various embodiments, each electron
donating group independently has an atom, such a nitrogen atom, a
phosphorous atom, an oxygen atom or a sulfur atom, that has at
least one lone pair of electrons. For example, oxygen and sulfur
each typically have two lone pairs of electrons while nitrogen and
phosphorous each typically have only one lone pair of electrons.
The terminology "lone pair" describes a pair of valence electrons
that are not shared with other atoms and/or are not used in
chemical bonding. These electrons may also be described as a
non-bonding pair of electrons. Lone pair electrons are found in the
outermost electron shell of atoms. The number of lone pair
electrons plus the number of bonding electrons equals the total
number of valence electrons around an atom. Non-limiting examples
of antioxidants wherein there are atoms having at least one lone
pair of electrons that are bonded directly to the aromatic ring of
the antioxidant are as follows:
##STR00006##
[0029] In these examples, the "A" on the right side of the
structures can be O, N, S, or P. Moreover, all combinations of
compounds wherein one or both A's are O, N, S, and/or P, are also
hereby expressly contemplated even if not drawn above. It is also
contemplated that any of the aforementioned may alternatively be a
hydrogen atom, including all combinations even if not drawn
above.
[0030] Each of the electron donating groups can alternatively and
independently be an aryl or alkyl group. The terminology "aryl"
group describes any functional group or substituent derived from an
aromatic ring, e.g. phenyl, naphthyl, thienyl, indolyl, etc. The
alkyl group may be linear, branched, or cyclic and typically
includes 1 to 20 carbon atoms. Although, the alkyl group may
include more than 20 carbon atoms. In various embodiments, the
alkyl group includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, 19, or 20 carbon atoms or any range thereof. The
alkyl group may be further defined as an alkane, an alkene, or an
alkyne. The alkyl group may be alternatively described using the
formula C.sub.nH.sub.2n+1 wherein n is 1 to 20, as described above.
In various embodiments, the alkyl group may be described as methyl,
ethyl propyl, butyl, t-butyl, pentyl, hexyl, octyl, nonyl, or any
isomer thereof.
[0031] In other embodiments, each of the electron donating groups
is independently --NR.sup.4.sub.2, --NH.sub.2, --OH, --OR.sup.4,
--NHCOR.sup.4, or --OCOR.sup.4, wherein R.sup.4 is independently an
alkyl group having 1 to 10 carbon atoms, as described above. For
example, one or both of, or at least one of, the electron donating
groups may be --NR.sup.4.sub.2, wherein each R.sup.4 is
independently an alkyl group having 1 to 10 carbon atoms, as
described above. In another embodiment, one or both of, or at least
one of, the electron donating groups is --NH.sub.2. In another
embodiment, one or both of, or at least one of, the electron
donating groups is --OH. In a further embodiment, one or both of,
or at least one of, the electron donating groups is --OR.sup.4,
wherein R.sup.4 is an alkyl group having 1 to 10 carbon atoms, as
described above. In another embodiment, one or both of, or at least
one of, the electron donating groups is --H. In a further
embodiment, one or both of, or at least one of, the electron
donating groups is --NHCOR.sup.4, wherein R.sup.4 is an alkyl group
having 1 to 10 carbon atoms, as described above. In another
embodiment, one or both of, or at least one of, the electron
donating groups is --OCOR.sup.4, wherein R.sup.4 is an alkyl group
having 1 to 10 carbon atoms, as described above. Non-limiting
examples of structures corresponding to such embodiments are set
forth below:
##STR00007##
[0032] In other embodiments, each of the electron donating groups
may be independently described as aromatic or aliphatic. In still
other embodiments, one or both of, or at least one of, the electron
donating groups includes or is a hydrocarbon group, an alkoxy group
(OR.sup.5), an amine group, a monosubstituted amine group
(NHR.sup.5), or a disubstituted amine group (NR.sup.5.sub.2). In
other embodiments, one or both of, or at least one of, the electron
donating group is a diallyl amine group. The electron-donating
strength of the alkoxy or amine group comes largely from the lone
pairs of electrons on the O and N atoms, respectively, such that
each of R.sup.5 groups can be a hydrogen or a saturated or
unsaturated branched or straight chain hydrocarbon moiety and/or
may include one or more cycloaliphatic groups and/or one or more
aromatic hydrocarbons, or a combination thereof, while not
detracting from the electron donating characteristic of the alkoxy
or amine group. In such embodiments, the term "cycloaliphatic"
describes a saturated or unsaturated carbocyclic moiety comprising
mono- or bicyclic rings. Cycloaliphatic groups typically include a
3- to 7-membered saturated carbocyclic moiety. Examples of
cycloaliphatic moieties include, but are not limited to,
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and
the like, including partially unsaturated derivatives thereof such
as cyclohexenyl, cyclopentenyl, and the like. Alternatively, the
term "hydrocarbon group" may describe a hydrocarbon including from
1 to 20 carbon atoms, e.g. as described above, and includes
saturated or unsaturated, branched or straight chain hydrocarbon
moieties, including aliphatic moieties and/or one or more
cycloaliphatic groups and/or one or more aromatic hydrocarbons, or
a combination thereof.
[0033] One or both of, or at least one of, the electron donating
groups may alternatively be a thiol, sulfide, thioether, or
thioester (e.g. wherein the sulfur atom of the group is adjacent to
the group being donated into). Alternatively, one or both of, or at
least one of, the electron donating groups may be a phosphane. It
is to be understood that one or both of, or at least one of, the
electron withdrawing groups may be chosen from any of the above
options such that both electron donating groups may be the same or
they may be different from each other.
[0034] In other embodiments, one or both of the electron donating
groups is a hydrogen atom. For the purpose of this disclosure, the
hydrogen "atom" may be considered to be an electron donating
"group." Two non-limiting structural examples of such embodiments
set forth below:
##STR00008##
[0035] In still further embodiments, the antioxidant is chosen from
one or more of those structures 1-7 set forth below, and
combinations thereof:
##STR00009##
[0036] The antioxidant is typically present in an amount of, or
less than, 30, 25, 20, 15, 10, 5, 2, 1.5, 1, or 0.5, parts by
weight per 100 parts by weight of the lubricant composition. In
various embodiments, the antioxidant is present in an amount of
from 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 lubricant composition. Of
course, the weight percent of the antioxidant 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.
[0037] The Table below illustrates the effect of ring structure and
nitrogen incorporation on the N--H bond dissociation energy and
ionization potential of various antioxidants, and their
derivatives, calculated at the CBS-QB3 level of theory.
TABLE-US-00001 BDE IP Structure (kcal/mol) (kcal/mol) ##STR00010##
86.4 168.3 ##STR00011## 86.6 174.7 ##STR00012## 86.4 179.3
##STR00013## 78.7 154.0 ##STR00014## 75.1 164.9 ##STR00015## 75.7
167.1 ##STR00016## 74.7 164.2 ##STR00017## 75.5 171.8
Additives:
[0038] 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. One or more of the additives may be
ash-including or ash-less.
Anti-Wear Additive:
[0039] The anti-wear additive 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-including
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.
[0040] 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:
[0041] The lubricant composition may include one or more additional
antioxidants in addition to the antioxidant described above.
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.
[0042] 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.
[0043] 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.
[0044] It is also contemplated that alkylidenebisphenols, for
example 2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis
(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis [6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hyd-
r 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)-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.
[0045] 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.
[0046] 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.
[0047] 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.
[0048] 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 may be used.
[0049] 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.
[0050] Additional non-limiting examples of suitable additional
antioxidants include those that include nitrogen, such as amides of
j3-(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 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-tetramethyl piperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethyl
piperidin-4-ol, and combinations thereof.
[0051] 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, itrithiatridecane 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.
[0052] The one or more additional antioxidants are not particularly
limited in amount in the composition but may be present such that a
total amount of antioxidants in the composition is about, or less
than, 30, 25, 20, 15, 10, 5, 2, 1.5, 1, or 0.5, 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 total amount of
antioxidants in the composition may be 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 additional 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:
[0053] 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.
[0054] 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.
[0055] Further non-limiting examples of the one or more metal
deactivators include sulfur-including 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.
[0056] 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:
[0057] 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-including 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-including
compounds, for example: Amine salts of phosphoric acid partial
esters or phosphonic acid partial esters, and zinc
dialkyldithiophosphates, molybdenum-including compounds, such as
molybdenum dithiocarbamate and other sulfur and phosphorus
including derivatives, sulfur-including 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.
[0058] 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:
[0059] 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%, 2%, .+-.25%, .+-.30%, etc.
Pour Point Depressants:
[0060] 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:
[0061] 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.
[0062] 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:
[0063] 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.
[0064] 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%, 2%, .+-.25%, .+-.30%, etc.
[0065] 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, less than 500, 100, 50,
20, 15, 10, or 5, parts by weight of water per one million parts by
weight (ppm) of the composition, 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.
[0066] The lubricant composition may be further defined as
ash-including or ash-less, according to ASTM D 874 and known in the
art. Typically, the terminology "ash-less" refers to the absence of
(significant) amounts of metals such as sodium, potassium, calcium,
and the like. Of course, it is to be understood that the lubricant
composition is not particularly limited to being defined as either
ash-including or ash-less.
Additive Concentrate Package:
[0067] The instant disclosure also provides an additive concentrate
package which includes the antioxidant of this disclosure and also
includes one or more metal deactivators, one or more anti-wear
additives, one or more additional antioxidants, and/or one or more
of the aforementioned additives. The additive concentrate package
may include the antioxidant of this disclosure and be free of any
additional antioxidants. In one embodiment, the additive
concentrate package is further defined as a hydraulic additive
concentrate package. In another embodiment, the additive
concentrate package is further defined as an engine oil additive
concentrate package. In a further embodiment, the additive
concentrate package is further defined as a driveline system oil
additive concentrate package. In an additional embodiment, the
additive concentrate package is further defined as a gear oil
additive concentrate package. In still another embodiment, the
additive concentrate package is further defined as a grease
additive concentrate package. In a further embodiment, the additive
concentrate package is further defined as an automatic and/or
manual transmission fluid and/or oil additive concentrate package.
In another embodiment, the additive concentrate package is further
defined as an industrial gear oil additive concentrate package. In
another embodiment, the additive concentrate package is further
defined as a turbine oil additive concentrate package. In another
embodiment, the additive concentrate package is further defined as
a rust and oxidation inhibited oil additive concentrate package. In
another embodiment, the additive concentrate package is further
defined as a compressor oil additive concentrate package. In
another embodiment, the additive concentrate package is further
defined as a paper machine oil additive concentrate package. In
another embodiment, the additive concentrate package is further
defined as an additive concentrate package for combinations of two
or more of the aforementioned oils.
[0068] In another embodiment, the additive concentrate package
includes 10-40 weight percent of the antioxidant, 0-15 weight
percent of a metal deactivator (e.g. a yellow metal corrosion
inhibitor), 0-15 weight percent of a corrosion inhibitor (e.g. the
corrosion inhibitor of this disclosure and a ferrous metal
corrosion inhibitor), 0-10 weight percent of a friction modifier
(e.g. glycerol mono-oleate), 20-35 weight percent of an anti-wear
additive, and 0-1 weight percent of an anti-foam additive.
Additionally, 0-25 weight percent of a dispersant may also be
included. Viscosity modifiers and pour point depressants may also
be included but typically are not part of such packages.
[0069] 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 in various non-limiting embodiments. Various
embodiments of this disclosure include one or more of the
modification, reaction products, and products formed from employing
the composition, as described above.
Method of Forming the Composition:
[0070] This disclosure also provides a method of forming the
composition. The method includes the steps of providing the base
oil, providing the antioxidant of this disclosure and combining the
base oil and the antioxidant. The method may also include one or
more steps of providing any one or more of the aforementioned
additives and combining the one or more aforementioned additives
with the base oil and/or antioxidant of this disclosure in any
order and in any amounts.
Antioxidant Independent from Composition:
[0071] This disclosure also provides the antioxidant itself
independent from any lubricant composition. The antioxidant may be
any as described herein.
Method of Making the Antioxidant:
[0072] This disclosure also provides a method of making the
antioxidant. In various embodiments, the method includes the steps
of providing an N.sup.2,
N.sup.2-dialkyl-N.sup.5-phenyl-2,5-pyrimidinediamine, providing
elemental sulfur, providing sulfur dioxide, providing iodine, and
providing a solvent. The method may also include the step of
combining the pyrimidinediamine, sulfur, sulfur dioxide, and iodine
in the solvent such as sulfolane, to form the antioxidant.
[0073] In other embodiments, the method may include one or more
steps as outlined below. One of skill in the art may change the
starting materials as needed. For example, any suitable second
amine may be utilized in place of the bis-2-ethylhexylamine. In
still other embodiments, the method includes one or more steps as
described in U.S. Pat. No. 5,026,846, which is expressly
incorporated herein in its entirety in various non-limiting
embodiments. For example, one of skill in the art may select one or
more synthetic steps from U.S. Pat. No. 5,026,846 to form the
antioxidant of the instant disclosure.
##STR00018##
[0074] In various embodiments, the pyrimidinediamine has an alkyl
group. The alkyl group may be linear, branched, or cyclic and
typically includes 1 to 20 carbon atoms. The alkyl group may
include more than 20 carbon atoms. In various embodiments, the
alkyl group includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, 19, or 20 carbon atoms or any range thereof. The
alkyl group may be further defined as an alkane, an alkene, or an
alkyne. The alkyl group may be alternatively described using the
formula C.sub.nH.sub.2n+1 wherein n is 1 to 20, as described above.
In various embodiments, the alkyl group may be described as methyl,
ethyl propyl, butyl, t-butyl, pentyl, hexyl, octyl, nonyl, or any
isomer thereof.
[0075] In various embodiments, the antioxidant is synthesized using
nucleophilic substitution (e.g. of 5-Halopyrimidones) and
dehydration. For example, a synthetic scheme such as the one set
forth below may be utilized:
##STR00019##
[0076] In other embodiments, the antioxidant is synthesized using
cross-coupling and substitution, e.g., of 5-aminopyrimidones. For
example, a synthetic scheme such as the one set forth below may be
utilized:
##STR00020##
[0077] It is contemplated that protected 5-amino-4-pyrimidones can
be prepared in two steps from commercially available N-acetyl
glycine. Cross coupling or substitution with this intermediate can
yield azaphenoxazines in a few as three steps.
##STR00021##
[0078] It is contemplated that 5-amino-4-pyrimidones may be
unreactive under general conditions for Cu, Pd, or Ni, cross
coupling reactions, such as those set forth below. However,
alternative similar reactions may be utilized. The reactions set
forth immediately below are simply representative of some types of
reactions that might be used to form the antioxidants of this
disclosure, as modified by those of skill in the art.
##STR00022##
[0079] In other embodiments, the antioxidant is synthesized using
direct condensation, e.g. on substituted 3-dicarbonyl compounds.
For example, a synthetic scheme such as the one set forth below may
be utilized:
##STR00023##
[0080] For example, the tautomer of substituted 1,4-benzoxazinones
may or may not provide an appropriate 1,3-dielectrophile for a
condensation reaction. The reactions set forth immediately below
are simply representative of some types of reactions that might be
used to form the antioxidants of this disclosure, as modified by
those of skill in the art.
##STR00024##
[0081] In addition, direct reaction on
3-bromomethyl-1,4-benzoxazinone may yield a complex mixture of
products. Attempts to replace the halide with a less reactive
leaving group can lead to a rearrangement reaction. The reactions
set forth immediately below are simply representative of some types
of reactions that might be used to form the antioxidants of this
disclosure, as modified by those of skill in the art.
##STR00025##
[0082] Moreover, substituted, protected 1,4-benzoxizinones can be
prepared from N-tosyl 2-aminophenols.
[0083] In still other embodiments, the antioxidant is chosen from
those set forth below and may be synthesized by one or more methods
as set forth below.
[0084] Synthesis of
##STR00026##
[0085] Synthesis of
##STR00027##
[0086] Synthesis of
##STR00028##
[0087] Synthesis of
##STR00029##
[0088] Synthesis of
##STR00030##
[0089] Synthesis of
##STR00031##
[0090] Synthesis of
##STR00032##
[0091] In addition, these antioxidants can be characterized as
follows in various non-limiting embodiments:
[0092] 4-Azaphenoxazine (1): 1H-NMR (500 MHz; DMSO-d6): .delta.
8.47 (s, 1H), 7.36 (dd, J=4.8, 1.8 Hz, 1H), 6.78-6.72 (m, 3H), 6.68
(dd, J=7.9, 1.4 Hz, 1H), 6.61 (td, J=7.7, 1.4 Hz, 1H), 6.47 (dd,
J=7.7, 1.4 Hz, 1H). 13-C NMR (126 MHz; DMSO): .delta. 150.8, 143.2,
137.6, 131.7, 128.6, 124.9, 121.33, 121.17, 119.8, 116.0, 113.7
[0093] 4-Azaphenothiazine (2): 1H-NMR (400 MHz; DMSO-d6): .delta.
8.61 (s, 1H), 7.75 (dd, J=4.7, 1.5 Hz, 1H), 6.99-6.91 (m, 2H), 6.88
(dd, J=7.7, 1.4 Hz, 1H), 6.83 (dd, J=8.0, 1.5 Hz, 1H), 6.74 (td,
J=7.5, 1.3 Hz, 1H), 6.62 (dd, J=7.9, 1.1 Hz, 1H). 13-C NMR (76 MHz;
DMSO): .delta. 141.5, 140.2, 139.7, 137.5, 127.6, 126.3, 122.5,
121.8, 119.4, 116.2, 114.3
[0094] 3-Diethylamino-2,4-Diazaphenoxazine (3): 1H-NMR (500 MHz;
DMSO-d6): .delta. 8.01 (s, 1H), 7.47 (s, 1H), 6.80-6.74 (m, 2H),
6.56 (td, J=7.7, 1.3 Hz, 1H), 6.47 (dd, J=7.8, 1.3 Hz, 1H), 3.43
(q, J=7.0 Hz, 4H), 1.06 (t, J=7.0 Hz, 6H). 13-C NMR (126 MHz;
DMSO): .delta. 158.0, 156.3, 141.7, 140.8, 132.6, 125.5, 119.9,
116.4, 115.8, 114.0, 41.7, 13.6
[0095] 3-Diethylamino-2,4-Diazaphenothiazine (4): 1H-NMR (500 MHz;
DMSO-d6): .delta. 8.21 (s, 1H), 7.54 (s, 1H), 6.95 (td, J=7.6, 1.4
Hz, 1H), 6.86 (dd, J=7.7, 1.3 Hz, 1H), 6.67 (td, J=7.5, 1.2 Hz,
1H), 6.58 (dd, J=8.0, 1.2 Hz, 1H), 3.44 (q, J=7.0 Hz, 4H), 1.05 (t,
J=7.0 Hz, 6H). 13-C NMR (126 MHz; DMSO): .delta. 156.8, 152.6,
141.17, 140.99, 128.5, 127.0, 125.7, 121.2, 114.8, 114.5, 41.7,
13.5
[0096] 3-Heptyl-2,4-Diazaphenoxazine (5): .sup.1H-NMR (400 MHz;
DMSO-d.sub.6): .delta. 7.84 (s, 1H), 6.83-6.79 (m, 1H), 6.69 (td,
J=8.1, 1.5 Hz, 2H), 6.63 (ddd, J=7.8, 7.4, 1.6 Hz, 1H), 2.50-2.47
(m, 2H), 2.18 (s, 3H), 1.60 (quintet, J=7.3 Hz, 2H), 1.26 (t, J=4.6
Hz, 8H), 0.86 (t, J=6.7 Hz, 3H). .sup.13C-NMR (76 MHz; DMSO):
.delta. 161.0, 156.6, 147.9, 142.5, 132.0, 125.5, 121.6, 121.3,
116.3, 114.9, 37.8, 31.6, 29.06, 28.96, 28.3, 22.5, 19.5, 14.4
HRMS: Calc for C.sub.18H.sub.23N.sub.3O, 297.18411; Found:
297.18398
[0097] 7-tert-Butyl-3-Heptyl-1-Methyl-2,4-Diazaphenoxazine (6):
1H-NMR (300 MHz; DMSO-d6): .delta. 7.76 (s, 1H), 6.82 (dd, J=8.2,
2.1 Hz, 1H), 6.72 (d, J=2.1 Hz, 1H), 6.60 (d, J=8.2 Hz, 1H),
2.49-2.46 (m, 2H), 2.16 (s, 3H), 1.59 (t, J=7.8 Hz, 2H), 1.25 (s,
8H), 1.19 (s, 9H), 0.85 (t, J=6.7 Hz, 3H). 13-C NMR (76 MHz; DMSO):
.delta. 160.8, 156.6, 147.8, 144.3, 142.1, 129.3, 121.81, 121.70,
114.4, 113.5, 37.8, 34.2, 31.6, 31.4, 29.04, 28.97, 28.3, 22.5,
19.5, 14.4
[0098] 3-Heptyl-2,4-Diazaphenothiazine (7): 1H-NMR (300 MHz;
DMSO-d6): .delta. 8.64 (s, 1H), 7.65 (s, 1H), 7.00-6.94 (m, 1H),
6.87 (dd, J=7.7, 1.4 Hz, 1H), 6.74 (dd, J=7.5, 1.2 Hz, 1H), 6.58
(dd, J=8.0, 1.2 Hz, 1H), 2.56 (t, J=7.6 Hz, 2H), 1.60 (m, 2H), 1.24
(m, 8H), 0.85 (t, J=6.7 Hz, 3H). 13-C NMR (76 MHz; DMSO): .delta.
163.1, 151.4, 139.7, 138.7, 133.7, 128.8, 127.2, 122.5, 115.3,
114.9, 37.7, 31.6, 28.97, 28.91, 28.3, 22.5, 14.4
[0099] In other embodiments, the antioxidant is synthesized as
described using a method including the steps of:
I. reacting Compound A and Compound B to form Compound C according
to the following reaction:
##STR00033##
II. reacting Compound C to form Compound D according to the
following reaction:
##STR00034##
III. reacting Compound D to form Compound E according to the
following reaction:
##STR00035##
IV. reacting Compound E to form the antioxidant according to the
following reaction:
##STR00036##
wherein R is an n-heptyl group. In related non-limiting
embodiments, it is expressly contemplated that any one or more
reactants, intermediates, solvents, catalysts, additives, salts,
temperatures, times of reaction, and/or any other method steps
described above, or known by those of skill in the art as being
related to the above, may be substituted, altered or otherwise
modified using any other suitable reactants, intermediates,
solvents, catalysts, additives, salts, temperatures, times of
reaction, and/or any other method steps suitable to form the
antioxidant described above. In other words, all derivations of the
aforementioned reactions that would be known by those of skill in
the art as being suitable substitutes or alternatives for producing
the same reactants, compounds, or the final antioxidants, e.g.
using similar reactants, catalysts, times, solvents, temperatures,
etc., are hereby expressly contemplated in various non-limiting
embodiments.
[0100] In various non-limiting embodiments, one or more of the
antioxidants of the instant disclosure may be utilized in
combination with one or more antioxidants described in provisional
application Ser. No. 62/213,245, provisional application Ser. No.
62/213,241, provisional application Ser. No. 62/213,239,
provisional application Ser. No. 62/347,907, a PCT application
filed concurrently herewith having the BASF Docket Number:
PF76496WO01, and/or a PCT application filed concurrently herewith
having the BASF Docket Number: PF76497WO01, each of which is
expressly incorporated herein by reference in its entirety in
various non-limiting embodiments.
EXAMPLES
[0101] An example of the antioxidant of this disclosure is formed
as set forth in the reaction schematic below.
##STR00037##
Example
##STR00038##
[0102] Additional Examples
[0103] Various antioxidants are evaluated to determine how they
affect oxidation of various compounds. For example, in a first
series of experiments, Styrene/PBD-BODIPY Autoxidation is evaluated
at 37.degree. C. The results of this evaluation is set forth in
FIG. 1 which shows co-autoxidation of 4.3 M styrene and 10 .mu.M
PBD-BODIPY in PhCl at 37.degree. C., initiated by 6.0 mM AIBN and
inhibited by 2 .mu.M of the antioxidants shown
(k.sub.inh>>10.sup.7). Under these conditions, the
antioxidant that is representative of this disclosure completely
suppresses autoxidation of the PBD-BODIPY exhibiting inhibition
rate constants, k inh, above the measurable limit of the
autoxidation experiments (k.sub.inh>>10.sup.7
M.sup.-1s.sup.-1).
[0104] In a second series of experiments, Hexadecene/PBD-BODIPY
autoxidation is evaluated at 70.degree. C. and 100.degree. C. The
results of these evaluations are set forth in FIGS. 2A and 2B which
show co-autoxidation of 2.8M n-Hexadecene and 10 M PBD-BODIPY in
PhCl at 70.degree. C., initiated by 87 mM tBu.sub.2O.sub.2, and
inhibited by 0.6 .mu.M of the various antioxidants shown.
[0105] In a third series of experiments, Squalane/PBD-BODIPY
autoxidation is evaluated at 100.degree. C. The results of this
evaluation is set forth in FIG. 3 which shows co-autoxidation of
0.96M squalane and 10 M PBD-BODIPY in 1,2-dichlorobenzene at
100.degree. C., initiated by 500 M dicumyl peroxide, and inhibited
by 4 .mu.M of the antioxidants shown. In a fourth series of
experiments, Hexadecane autoxidation is evaluated at 160.degree. C.
Hydroperoxide formation in n-hexadecane at 160.degree. C. is set
forth in FIG. 4 showing uninhibited autoxidation and inhibited
autoxidation with 100 .mu.M of the antioxidants shown.
[0106] In a fifth series of experiments, hydroperoxide formation in
n-hexadecane at 160.degree. C. is evaluated and set forth in FIG. 5
which shows uninhibited and inhibited autoxidation with 100 .mu.M
of the antioxidants shown.
[0107] The data described above and set forth in the Figures
demonstrates the enhanced antioxidant performance of the molecules
of this disclosure compared to traditional alkylated diphenylamine
antioxidants.
[0108] 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.
[0109] 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.
[0110] 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.
* * * * *