Note: Descriptions are shown in the official language in which they were submitted.
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1
TITLE
LUBRICATING OIL COMPOSITION HAVING IMPROVED AIR RELEASE
FIELD OF INVENTION
[0001] The present invention relates to a lubricating oil composition
which has
improved air release properties. The invention also provides a method of
improving air
release of a functional fluid, such as a lubricating oil.
BACKGROUND OF THE INVENTION
[0002] In order to reduce the friction and wear of moving parts,
lubricants must have
sufficient viscosity at the normal operating temperature of the moving parts.
When
lubricating films are too thin, parts are not adequately protected leading to
reduced
operable lifespan. Further, low viscosity at maximum operating temperatures
can cause
equipment to seize or wear unacceptably. Sufficient viscosity is also
necessary to protect
hydraulic pumps and keep them operating efficiently by preventing leakage or
internal
pump recycling.
[0003] Air release properties of functional fluids or lubricants affect the
maximum
fluid viscosity of the lubricant. As functional fluids or lubricants move
through a system
or moving parts, air becomes trapped in the fluid. Often systems are designed
with
additional fluid reservoirs to allow functional fluids or lubricants to rest
and release
trapped air. Sometimes the inclusions of these reservoirs are impractical due
to sizing
constraints for the equipment or the amount of additional fluid or lubricant
necessary to
keep the system operating continuously.
[0004] In general, for thicker (higher viscosity) functional fluids,
air bubbles are
released more slowly from the fluid. If the amount of air trapped in the fluid
is too high,
the fluid may not form a complete film in required contact zones of equipment
or may not
be able to sufficiently maintain system pressure. Compression of air bubbles
in a fluid may
lead to ignition of the vapor inside the bubble, also known as the micro-
diesel effect. These
micro explosions accelerate fluid degradation and lead to structural damage of
metal parts.
Other issues caused by trapped air include cavitation, erosion, and high noise
levels.
[0005] Certain fluid and lubricant additives are known to negatively
impact air release
from the fluid. Typically, air release is improved by reducing the viscosity
of the fluid. It
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would be desirable to have an additive that can improve the air release of a
functional fluid
while maintaining desired viscosity grades.
SUMMARY OF THE INVENTION
[0006] One objective of the present invention is to improve the air
release of a
functional fluid or lubricating oil by mixing a base oil with an ethylene/a-
olefin
copolymer. Another objective of the present invention is to provide a
lubricating
composition having a desired lubricating viscosity with improved air release
over the base
oil alone.
[0007] In one embodiment of the invention, the objectives are
achieved by a
lubricating oil composition which comprises (a) a base oil of lubricating
viscosity; and
(b) an ethylene/a-olefin copolymer. In another embodiment, a lubricating oil
composition
of the present invention comprises (a) a base oil of lubricating viscosity,
(b) an ethylene/a-
olefin copolymer composition, and (c) an additive comprising an amine salt of
a
hydrocarbyl thiophosphoric acid ester.
[0008] In one embodiment of the invention, the objectives are achieved by a
lubricating oil composition which comprises (a) a base oil of lubricating
viscosity; and
(b) an ethylene/a-olefin copolymer. In another embodiment, a lubricating oil
composition
of the present invention comprises (a) a base oil of lubricating viscosity,
(b) an ethylene/a-
olefin copolymer composition, and (c) an additive comprising an amine salt of
a
hydrocarbyl thiophosphoric acid ester wherein the additive is obtained by
reacting a
phosphorous sulfide with one or more alcohols having about 3 to about 13
carbon atoms
to form a thiophosphoric acid ester, further reacting the thiophosphoric acid
ester with an
alkylene oxide to form a hydroxyl-substituted ester of thiophosphoric acid,
and further
reacting said hydroxyl-substituted ester of thiophosphoric acid with a
phosphorous oxide
to form a an acidic phosphoric acid intermediate, and salting said acidic
phosphoric acid
intermediate with one or more amines wherein said amines contain one or more
hydrocarbyl groups having from 2 to 30 carbon atoms.
[0009] In another embodiment, a lubricating oil composition of the
present invention
comprises (a) a base oil of lubricating viscosity, (b) 2% to 17% by weight of
an ethylene/a-
olefin copolymer composition, and (c) 0.04% to 0.20% of (c) an additive
comprising an
amine salt of a hydrocarbyl thiophosphoric acid ester.
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[0010] The present invention also provides a method of improving the
air release of a
functional fluid, such as a lubricating oil, the method comprising (i)
providing (a) a base
oil of lubricating viscosity and (b) an ethylene/a-olefin copolymer; (ii)
mixing the base oil
of lubricating viscosity with the ethylene/a-olefin copolymer to obtain a
functional fluid.
[0011] In another embodiment, the present invention also provides a method
of
improving the air release of a functional fluid, such as a lubricating oil,
the method
comprising (i) providing (a) a base oil of lubricating viscosity, (b)
providing an ethylene/a-
olefin copolymer, and (c) providing an additive comprising an amine salt of a
hydrocarbyl
thiophosphoric acid ester and (ii) mixing (a), (b), and (c) to obtain a
functional fluid.
[0012] In another embodiment, the present invention also provides a method
of
improving the air release of a functional fluid, such as a lubricating oil,
the method
comprising (i) providing (a) a base oil of lubricating viscosity, (b)
providing an ethylene/a-
olefin copolymer, and (c) providing an additive comprising an amine salt of a
hydrocarbyl
thiophosphoric acid ester and (ii) mixing (a), (b), and (c) to obtain a
functional fluid,
wherein said functional fluid comprises 2% to 17% by weight of the ethylene/a-
olefin
copolymer and 0.04% to 0.20% by weight of the additive comprising the reaction
product
of a hydroxy-substituted triester of a phosphorothioic acid with an inorganic
phosphorus
reagent selected from the class consisting of phosphorous acids, phosphorus
oxides, and
phosphorus halides and neutralizing a substantial portion of said acidic
intermediate with
an amine.
[0013] In one embodiment, the invention provides a method of
lubricating an
industrial gear comprising supplying to the industrial gear a lubricant
composition as
disclosed herein. In another embodiment, the invention provides a method of
improving
air release in an industrial gear lubricating oil.
[0014] As used herein, the transitional term "comprising", which is
synonymous with
"including", "containing", or "characterized by", is inclusive or open-ended
and does not
exclude additional, un-recited elements or method steps. However, in each
recitation of
"comprising" herein, it is intended that the term also encompass, as
alternative
embodiments, the phrases "consisting essentially of' and "consisting of',
where
"consisting of' excludes any element or step not specified and "consisting
essentially of'
permits the inclusion of additional un-recited elements or steps that do not
materially affect
the basic and novel characteristics of the composition or method under
consideration.
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[0015] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is
used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it
refers to a group having a carbon atom directly attached to the remainder of
the molecule
and having predominantly hydrocarbon character. Examples of hydrocarbyl groups
include: hydrocarbon substituents, including aliphatic, alicyclic, and
aromatic substituents;
substituted hydrocarbon substituents, that is, substituents containing non-
hydrocarbon
groups which, in the context of this invention, do not alter the predominantly
hydrocarbon
nature of the substituent; and hetero substituents, that is, substituents
which similarly have
a predominantly hydrocarbon character but contain other than carbon in a ring
or chain. A
more detailed definition of the term "hydrocarbyl substituent" or "hydrocarbyl
group" is
described in paragraphs [0118] to [0119] of International Publication
W02008147704, or
a similar definition in paragraphs [0137] to [0141] of published application
US 2010-
0197536.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The present invention provides a lubricating oil composition, a
method of
improving air release in a functional fluid, such as a lubricating oil, and a
method of
lubricating a mechanical device using the lubricating oil composition as
disclosed herein.
Various preferred features and embodiments will be described below by way of
non-
limiting illustrations.
Oils of Lubricating Viscosity
[0017] One component (a) of the disclosed technology is an oil of
lubricating
viscosity, also referred to as a base oil. The base oil may be selected from
any of the base
oils in Groups I-V of the American Petroleum Institute (API) Base Oil
Interchangeability
Guidelines, namely
Base Oil Category Sulfur (%) Saturates (%) Viscosity Index
Group I >0.03 and/or <90 80 to 120
Group II <0.03 and >90 80 to 120
Group III <0.03 and >90 >120
Group IV All polyalphaolefins (PA0s)
Group V All others not included in Groups I, II, III or IV
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Groups I, II and III are mineral oil base stocks. The oil of lubricating
viscosity can include
natural or synthetic oils and mixtures thereof Mixture of mineral oil and
synthetic oils,
e.g., polyalphaolefin oils and/or polyester oils, may be used.
[0018] Natural oils include animal oils and vegetable oils (e.g.
vegetable acid esters)
as well as mineral lubricating oils such as liquid petroleum oils and solvent-
treated or acid
treated mineral lubricating oils of the paraffinic, naphthenic, or mixed
paraffinic-
naphthenic types. Hydrotreated or hydrocracked oils are also useful oils of
lubricating
viscosity. Oils of lubricating viscosity derived from coal or shale are also
useful.
[0019] Synthetic oils include hydrocarbon oils and halosubstituted
hydrocarbon oils
such as polymerized and interpolymerized olefins and mixtures thereof,
alkylbenzenes,
polyphenyl, alkylated diphenyl ethers, and alkylated diphenyl sulfides and
their
derivatives, analogs and homologues thereof Alkylene oxide polymers and
interpolymers
and derivatives thereof, and those where terminal hydroxyl groups have been
modified by,
e.g., esterification or etherification, are other classes of synthetic
lubricating oils. Other
suitable synthetic lubricating oils comprise esters of dicarboxylic acids and
those made
from C5 to C12 monocarboxylic acids and polyols or polyol ethers. Other
synthetic
lubricating oils include liquid esters of phosphorus-containing acids,
polymeric
tetrahydrofurans, silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy-
, or polyaryl-
oxy-siloxane oils, and silicate oils.
[0020] Other synthetic oils include those produced by Fischer-Tropsch
reactions,
typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one
embodiment
oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as
well as
other gas-to-liquid oils.
[0021] Unrefined, refined and rerefined oils, either natural or
synthetic (as well as
mixtures thereof) of the types disclosed hereinabove can be used. Unrefined
oils are those
obtained directly from a natural or synthetic source without further
purification treatment.
Refined oils are similar to the unrefined oils except they have been further
treated in one
or more purification steps to improve one or more properties. Rerefined oils
are obtained
by processes similar to those used to obtain refined oils applied to refined
oils which have
been already used in service. Rerefined oils often are additionally processed
to remove
spent additives and oil breakdown products.
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[0022] In some embodiments the industrial lubricant composition may
also include a
minor amount of one or more non-synthetic base oils. Examples of these non-
synthetic
base oils include any of those described herein, including API Group I, Group
II, or Group
III base oils.
[0023] The amount of the oil of lubricating viscosity present is typically
the balance
remaining after subtracting from 100 wt % the sum of the amount of the
compounds of the
invention and the other performance additives. In one embodiment, the amount
of the oil
of lubricating viscosity present is typically the balance remaining after
subtracting from
100% by weight the sum of the amount of the ethylene/a-olefin copolymer and/or
the
additive comprising the reaction product of a hydroxy-substituted triester of
a
phosphorothioic acid with an inorganic phosphorus reagent selected from the
class
consisting of phosphorous acids, phosphorus oxides, and phosphorus halides and
neutralizing a substantial portion of said acidic intermediate with an amine
and any other
optional performance additives in the composition.
[0024] The oil of lubricating viscosity can be present in a major amount,
for a lubricant
composition, or in a concentrate forming amount, for a concentrate and/or
additive
composition. The industrial lubricant composition of the invention may be
either lubricant
compositions or concentrate and/or additive compositions.
[0025] In a fully formulated lubricating oil composition in
accordance with the present
invention, the oil of lubricating viscosity is generally present in a major
amount (i.e. an
amount greater than 50 percent by weight). Typically, the oil of lubricating
viscosity is
present in an amount of 75 to 98 percent by weight, and often greater than 80
percent by
weight of the overall composition.
[0026] The various described oils of lubricating viscosity may be
used alone or in
combinations. The oil of lubricating viscosity (considering all oil present)
may be used in
the described industrial lubricant compositions in the range of about 40 or 50
percent by
weight to about 99 percent by weight, or from a minimum of 49.8, 70, 85, 93,
93.5 or even
97 up to a maximum of 99.8, 99, 98.5, 98 or even 97 percent by weight.
[0027] In still other embodiments the oil of lubricating viscosity
may be used from 60
to 97, or from 80 to 97, or even from 85 to 97 percent by weight. Put another
way, the
compositions described herein may contain at least 60, 80, or even 85 percent
by weight
oil of lubricating viscosity.
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[0028] In concentrate compositions, typically the amount of additives
and other
components remains the same, but the amount of oil of lubricating viscosity is
reduced, in
order to make the composition more concentrated and more efficient to store
and/or
transport. A person skilled in the art would be able to easily adjust the
amount of oil of
lubricating viscosity present in order to provide a concentrate and/or
additive composition.
The Ethylene/a-Olefin Copolymer
[0029] One component in the lubricating oil composition of the
present invention is
an ethylene a-olefin copolymer. The ethylene a-olefin copolymer includes those
with a
backbone containing 1 to 3 different a-olefin monomers (beside the ethylene
monomer),
in one embodiment 1 to 3 different a-olefin monomers and in yet another
embodiment 1
a-olefin monomer in addition to the ethylene monomer. The a¨olefin monomers
include
3 to 20, and in other embodiments 3 to 12, or 3 to 10, or 3 to 6, or 3 to 4
carbon atoms, and
in another embodiment 3 carbon atoms (i.e., propylene). The olefin may be an
alpha olefin
of the above listed number of carbon atoms.
[0030] The ethylene a-olefin copolymer will have greater than 5 percent by
weight
ethylene monomer units, and in some embodiments at least 10 percent and up to
90
percent, or 15 to 85, or 20 to 80, or 30 to 50 percent by weight ethylene
monomer units.
In certain embodiments the amount of ethylene monomer will be 30-50 weight
percent; in
other embodiments the amount of ethylene monomer will be 75 to 85, or 79 to
81, weight
percent. Otherwise expressed, the amount of ethylene monomer may be 15 to 90
or 25 to
85 or 40 to 60 or 45 to 55 mole percent.
[0031] The ethylene olefin copolymer thus includes an ethylene
monomer and at least
one other co-monomer derived from an alpha-olefin having the formula 1-
1.2C=CHR3,
wherein R3 is a hydrocarbyl group, in one embodiment an alkyl radical
containing 1 to 18,
1 to 12, 1 to 10, 1 to 6 or 1 to 3 carbon atoms. The hydrocarbyl group
includes an alkyl
radical that has a straight chain, a branched chain, or mixtures thereof
[0032] Examples of suitable co-monomers include propylene, 1-butene,
1-hexene, 1-
octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-tri decene, 1-tetradecene,
1 -penta-
decene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene or mixtures
thereof.
The co-monomer may be 1-butene, propylene or mixtures thereof. Examples of a-
olefin
copolymers include ethylene-propylene copolymers and ethylene-1 -butene
copolymers
and mixtures thereof
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[0033] The polymer (c) may have a kinematic viscosity at 100 C of at
least 35 or at
least 50 or at least 100 or at least 500 mm2/s at 100 C. In certain
embodiments the polymer
(c) may have a kinematic viscosity at 100 C of at least about 500 or at least
about 1000
mm2/s or 1500 mm2/s or 2000 mm2/s, which feature will distinguish it from
similar
materials of much lower viscosity that might be used as base oils. The polymer
may have
a number average molecular weight of 1000 to 8000, or 1000 to 5000, or 1300 to
8000, or
1500 to 3000, or 1800 to 2500, or about 2000, or 2500 to 5000, or 3500 to
4500, or about
4000. Its polydispersity (Mw/Mn) may be in the range of 1.3 to 4 or 1.4 to 3
or 1.4 to 2. It
may be prepared by known methods by polymerization of (typically) ethylene and
an alpha
olefin such as propylene using an A1C13 or BF3 catalyst or by other known
methods.
[0034] The lubricating composition of the present invention also
includes an additive
comprising an amine salt of a hydrocarbyl thiophosphoric acid ester.
[0035] The thiophosphoric acid ester is also known as thiophosphoric
acid (needed to
link to previous patents) and has one or more sulfur to phosphorus bonds. The
thiophosphoric acid ester has one or more ester groups. Inorganic phosphorus
agents
include phosphorus acids, phosphorus oxides or phosphorus halides. The
hydroxyl-
substituted ester of thiophosphoric acid may be derived from mono- or
dithiophosphoric
acid esters containing one or more ester groups. The amine salt of a
hydrocarbyl
thiophosphoric acid ester has one or more sulfur to phosphorus bonds. The
amine salt of a
hydrocarbyl thiophosphoric acid ester may contain one or more ester groups. In
one
embodiment, the sulfur-containing phosphorus acid ester is referred to as a
thiophosphorus
acid salt thereof The thiophosphoric acid or salt may be prepared by reacting
one or more
phosphorus sulfides with alcohols, such as those described above. Useful
phosphorus
sulfide-containing sources include phosphorus pentasulfide, phosphorus sesqui
sulfide,
phosphorus heptasulfide and the like. Dithiophosphoric acid esters are also
referred to
generally as dithiophosphates.
[0036] The thiophosphoric acid ester may be prepared by reacting one
or more
phosphorus sulfide sources with alcohols. Useful phosphorus sulfides sources
include
phosphorus sulfide, phosphorus sesquisulfide, phosphorus heptasulfide and the
like. The
alcohols generally contain from one to about 30, or from two to about 24, or
from about 3
to about 12, or up to about 8 carbon atoms. Alcohols used to prepare the
thiophosphoric
acid esters include butyl, amyl, 2-ethylhexyl, hexyl, octyl, oleyl, and cresol
alcohols.
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Examples of commercially available alcohols include Alfol 810 (a mixture of
primarily
straight chain, primary alcohols having from 8 to 10 carbon atoms); Alfol 1218
(a mixture
of synthetic, primary, straight-chain alcohols containing 12 to 18 carbon
atoms); Alfol 20+
alcohols (mixtures of C18-C28 primary alcohols having mostly C20 alcohols as
determined by GLC (gas-liquid-chromatography); and Alfol 22+ alcohols (C18-C28
primary alcohols containing primarily C22 alcohols). Alfol alcohols are
available from
Continental Oil Company. Another example of a commercially available alcohol
mixtures
are Adol 60 (about 75% by weight of a straight chain C22 primary alcohol,
about 15% of
a C20 primary alcohol and about 8% of C18 and C24 alcohols) and Adol 320
(oleyl
alcohol). The Adol alcohols are marketed by Ashland Chemical.
[0037] A variety of mixtures of monohydric fatty alcohols derived
from naturally
occurring triglycerides and ranging in chain length of from C8 to C18 are
available from
Procter & Gamble Company. These mixtures contain various amounts of fatty
alcohols
containing mainly 12, 14, 16 or 18 carbon atoms. For example, CO-1214 is a
fatty alcohol
mixture containing 0.5% of C10 alcohol, 66.0% of C12 alcohol, 26.0% of C14
alcohol and
6.5% of C16 alcohol.
[0038] Another group of commercially available mixtures include the
"Neodol"
products available from Shell Chemical Co. For example, Neodol 23 is a mixture
of C12
and C13 alcohols; Neodol 25 is a mixture of C12 and C15 alcohols; and Neodol
45 is a
mixture of C14 to C15 linear alcohols. Neodol 91 is a mixture of C9, C10 and
C11
alcohols.
[0039] Fatty vicinal diols also are useful and these include those
available from
Ashland Oil under the general trade designation Adol 114 and Adol 158. The
former is
derived from a straight chain alpha-olefin fraction of C11-C14, and the latter
is derived
from a C15-C18 alpha-olefin fraction.
[0040] In one embodiment, the thiophosphoric acid is a
monothiophosphoric acid.
Monothiophosphoric acids may be prepared by the reaction of a sulfur source
with a
dihydrocarbyl phosphite. The sulfur source may for instance be elemental
sulfur, or a
sulfide, such as a sulfur-coupled olefin or a sulfur-coupled dithiophosphate.
Elemental
sulfur is a good sulfur source. The preparation of monothiophosphoric acids is
disclosed
in U.S. Patent 4,755,311 and PCT Publication WO 87/07638, incorporated herein
by
reference for their disclosure of monothiophosphoric acids, sulfur sources,
and the process
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for making monothiophosphoric acids. Monothiophosphoric acids may also be
formed in
the lubricant blend by adding a dihydrocarbyl phosphite to a lubricating
composition
containing a sulfur source, such as a sulfurized olefin. The phosphite may
react with the
sulfur source under blending conditions (i.e., temperatures from about 30 C to
about
100 C, or higher) to form the monothiophosphoric acid.
[0041] In another embodiment, the hydroxyl-substituted ester of
thiophosphoric acid
is a dithiophosphoric acid or phosphorodithioic acid. The dithiophosphoric
acid may be
represented by the formula (R70)2PSSH, wherein each R7 is independently a
hydrocarbyl
group containing from about 3 to about 30, or from about 3 up to about 18, or
from about
4 up to about 12, or up to about 8 carbon atoms. Examples of R7 include
isopropyl,
isobutyl, n-butyl, sec-butyl, amyl, n-hexyl, methylisobutyl carbinyl, heptyl,
2-ethylhexyl,
isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, alkylphenyl groups, or
mixtures thereof.
Illustrative lower alkylphenyl R7 groups include butylphenyl, amylphenyl, and
heptylphenyl and mixtures thereof Examples of mixtures of R7 groups include: 1-
butyl
and 1-octyl ; 1-p entyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl
and isoamyl; 2-
propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl and
isooctyl.
[0042] In one embodiment, the hydroxyl-substituted ester of
thiophosphoric acid is a
phosphorus ester prepared by reacting one or more dithiophosphoric acid esters
with an
epoxide or a glycol. This reaction product may be used alone, or further
reacted with a
phosphorus acid, anhydride, or lower ester. The epoxide is generally an
aliphatic epoxide
or a styrene oxide. Examples of useful epoxides include ethylene oxide,
propylene oxide,
butene oxide, octene oxide, dodecene oxide, styrene oxide, etc. Propylene
oxide is
particularly useful. The glycols may be aliphatic glycols, having from 1 to
about 12, or
from about 2 to about 6, or from about 2 to about 3 carbon atoms, or aromatic
glycols.
Glycols include ethylene glycol, propylene glycol, catechol, resorcinol, and
the like.
[0043] The inorganic phosphorus reagent useful in the reaction with
the hydroxyl-
substituted ester of thiophosphoric acid is preferably phosphorus pentoxide.
Other
phosphorus oxides such as phosphorus trioxide and phosphorus tetroxide
likewise are
useful. Also useful are phosphorus acids, and phosphorus halides. They are
exemplified
by phosphoric acid, pyrophosphoric acid, metaphosphoric acid, hypophosphoric
acid,
phosphorous acid, pyrophosphorous acid, metaphosphorous acid, hypophosphorous
acid,
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phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride,
monobromophosphorus tetrachloride, phosphorus oxychloride, and phosphorus
triiodide.
[0044] The reaction of the hydroxyl-substituted ester of
thiophosphoric acid with the
inorganic phosphorus reagent results in an acidic phosphoric acid
intermediate. The
chemical constitution of the acidic phosphoric acid intermediate depends to a
large
measure on the nature of the inorganic phosphorus reagent used.
[0045] The dithiophosphoric acids, glycols, epoxides, inorganic
phosphorus reagents
and methods of reacting the same are described in U.S. Patents 3,197,405 and
3,544,465,
incorporated herein by reference for their disclosure to these.
[0046] The amine salt of a hydrocarbyl thiophosphoric acid ester is
prepared by
reacting the acidic phosphoric acid intermediate with ammonia or a basic
nitrogen
compound, such as an amine or a nitrogen containing dispersant. The salts may
be formed
separately, and then the salt of the hydrocarbyl thiophosphoric acid ester may
be added to
the lubricating composition. Alternatively, the salts may also be formed in
situ when the
acidic phosphorus acid ester is blended with other components to form a fully
formulated
lubricating composition.
[0047] The ammonium salts of the hydrocarbyl thiophosphoric acid
esters may be
formed from ammonia, or an amine, or mixtures thereof These amines may be
monoamines or polyamines. Useful amines include those disclosed in U.S. Pat.
4,234,435
at Col. 21, line 4 to Col. 27, line 50, incorporated herein by reference.
[0048] The monoamines generally contain from 1 to about 24, or from 1
to about 12,
or from 1 to about 6 carbon atoms. Examples of monoamines include methylamine,
ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and
dodecylamine.
Examples of secondary amines include dimethylamine, diethylamine,
dipropylamine,
dibutylamine, methylbutylamine, ethylhexylamine, etc. Tertiary amines include
trimethylamine, tributylamine, methyldiethylamine, ethyldibutylamine, etc.
[0049] In one embodiment, the amine is a fatty (C8-30) amine such as
n-octylamine,
n-decylamine, n-dodecylamine, n-hexadecylamine, n-octadecylamine, oleyamine,
etc.
Also fatty amines include "Armeen" amines (products available from Akzo
Chemicals,
Chicago, Illinois), such Armeen C, Armeen 0, Armeen T, and Armeen S, wherein
the
letter designates the fatty group, such as coco, oleyl, tallow, or stearyl
groups.
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[0050] Other useful amines include primary ether amines, such as
those represented
by the formula, R"(ORN)xNH2, wherein RN is a divalent alkylene group having
about 2
to about 6 carbon atoms; x is a number from 1 to about 150, or from about 1 to
about 5, or
1; and R" is a hydrocarbyl group of about 5 to about 150 carbon atoms. An
example of an
ether amine is available under the name SURFAM amines produced and marketed
by
Mars Chemical Company, Atlanta, Georgia. Useful etheramines are exemplified by
those
identified as SURFAM P 14B (decyloxypropylamine), SURFAM P 16A (linear C16),
SURFAM Pl7B (tridecyloxypropylamine). The carbon chain lengths (i.e., C14,
etc.) of
the SURFAMS described above and used hereinafter are approximate and include
the
oxygen ether linkage.
[0051] In one embodiment, the amine is a tertiary-aliphatic primary
amine. Generally,
the aliphatic group, generally an alkyl group, contains from about 4 to about
30, or from
about 6 to about 24, or from about 8 to about 22 carbon atoms. Such amines are
illustrated
by t-butylamine, t-hexylamine, 1-methyl-1-amino-cyclohexane, t-octylamine, t-
decylamine, t-dodecylamine, t-tetradecylamine, t-hexadecylamine, t-
octadecylamine, t-
tetracosanylamine, and t-octacosanylamine.
[0052] The amine may be mixtures of tertiary aliphatic amines such as
"Primene 81R"
(a mixture of Cl 1-C14 tertiary alkyl primary amines) and "Primene JMT" (a
mixture of
C18-C22 tertiary alkyl primary amines). These amines are available from Rohm
and Haas
Company. The tertiary aliphatic primary amine useful for the purposes of this
invention
and methods for their preparation are described in U.S. Pat. 2,945,749,
incorporated by
reference for its teaching in this regard.
[0053] In one embodiment, the amine may be a hydroxyamine. Typically,
the
hydroxyamines are primary, secondary, or tertiary alkanol amines or mixtures
thereof
Such amines can be represented by the formulae: H2)N)R')OH, H(R'1)N)R')OH, and
(R'1)2)N)R')OH, wherein each R'l is independently a hydrocarbyl group having
from 1 to
about 8 carbon atoms or hydroxyhydrocarbyl group having from one to about
eight carbon
atoms, or from one to about four, and R' is a divalent hydrocarbyl group of
about 2 to about
18 carbon atoms, or from 2 to about 4. The group -R'-OH in such formulae
represents the
hydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group.
Typically, R'
is an acyclic straight or branched alkylene group, such as an ethylene, 1,2-
propylene, 1,2-
butylene, and 1,2-octadecylene groups. Where two RI groups are present in the
same
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molecule they can be joined by a direct carbon-to-carbon bond or through a
heteroatom
(e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring
structure.
Typically, however, each R'1 is independently a methyl, ethyl, propyl, butyl,
pentyl or
hexyl group. Examples of these alkanolamines include mono-, di-, and
triethanolamine,
diethylethanol amine, ethyl ethanolamine, butyldiethanolamine, etc.
[0054] The hydroxyamines may also be an ether N-
(hydroxyhydrocarbyl)amine.
These are hydroxypoly(hydrocarbyloxy) analogs of the above-described
hydroxyamines
(these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N-
(hydroxyhydrocarbyl) amines can be conveniently prepared by reaction of one or
more of
the epoxides described herein with afore-described amines and may be
represented by the
formulae: H2N)(R'0)x)H, H(R'1))N)(R'0)x)H, and (R'1)2)N)(R'0)x)H, wherein x is
a
number from about 2 to about 15 and R'l and R' are as described above. R'l may
also be
a hydroxypoly(hydrocarbyloxy) group. Useful hydroxyhydrocarbyl amines include
2-
hydroxyethylhexylamine; 2-hydroxyethyloctylamine; 2-
hydroxyethylpentadecylamine;
2-hydroxyethyl ol eyl amine; 2-hydroxyethylsoyamine; b i s(2-
hydroxyethyl)hexyl amine;
bis(2-hydroxyethyl)oleylamine; and mixtures thereof.
[0055] In one embodiment, the amine may be a hydroxyhydrocarbyl
amine. These
hydroxyhydrocarbyl amines are available from the Akzo Chemical Division of
Akzona,
Inc., Chicago, Illinois, under the general trade designations "Ethomeen" and
"Propomeen."
Specific examples of such products include: Ethomeen C/15; Ethomeen C/20 and
C/25;
Ethomeen 0/12; Ethomeen 5/15 and S/20; Ethomeen T/12, T/15 and T/25; and
Propomeen
0/12.
[0056] The amine may also be a polyamine. The polyamines include
alkoxylated
diamines, fatty polyamine diamines, alkylenepolyamines, hydroxy containing
polyamines,
condensed polyamines, arylpolyamines, and heterocyclic polyamines.
Commercially
available examples of alkoxylated diamines include Ethoduomeen T/13 and T/20,
which
are ethylene oxide condensation products of N-tallowtrimethylenediamine
containing 3
and 10 moles of ethylene oxide per mole of diamine, respectively.
[0057] In another embodiment, the polyamine is a fatty diamine. The
fatty diamines
include mono- or dialkyl, symmetrical or asymmetrical ethylenediamines,
propanediamines (1,2 or 1,3), and polyamine analogs of the above. Suitable
commercial
fatty polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S (N-soya-
1,3-
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diaminopropane), Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen 0 (N-
oleyl-
1,3-diaminopropane). "Duomeens" are commercially available from Armak Chemical
Co., Chicago, Illinois.
[0058] In another embodiment, the amine is an alkylenepolyamine.
Alkylenepolyamines are represented by the formula HR4N-(Alkylene-N)n-(R4)2,
wherein
each R4 is independently hydrogen; or an aliphatic or hydroxy-substituted
aliphatic group
of up to about 30 carbon atoms; n is a number from 1 to about 10, or from
about 2 to about
7, or from about 2 to about 5; and the "Alkylene" group has from 1 to about 10
carbon
atoms, or from about 2 to about 6, or from about 2 to about 4. In another
embodiment, R4
is defined the same as R'l above. Such alkylenepolyamines include
methylenepolyamines,
ethylenepolyamines, butylenepolyamines, propylenepolyamines,
pentylenepolyamines,
etc. Specific examples of such polyamines are ethylenediamine,
triethylenetetramine, tris-
(2-aminoethyl)amine, propylenediamine, trimethylenediamine,
tripropylenetetramine,
triethylenetetriamine, tetraethyl enep entamine,
hexaethyleneheptamine,
pentaethylenehexamine, etc. Higher homologs obtained by condensing two or more
of the
above-noted alkyleneamines are similarly useful as are mixtures of two or more
of the
aforedescribed polyamines.
[0059]
In one embodiment, the polyamine is an ethylenepolyamine. Such polyamines
are described in detail under the heading Ethylene Amines in Kirk Othmer's
"Encyclopedia
of Chemical Technology," 2d Edition, Vol. 7, pages 22-37, Interscience
Publishers, New
York (1965). Ethylenepolyamines are often a complex mixture of
polyalkylenepolyamines
including cyclic condensation products. Other useful types of polyamine
mixtures are
those resulting from stripping of the above-described polyamine mixtures to
leave, as
residue, what is often termed "polyamine bottoms". In general,
alkylenepolyamine
bottoms can be characterized as having less than 2%, usually less than 1% (by
weight)
material boiling below about 200 C. A typical sample of such ethylenepolyamine
bottoms
obtained from the Dow Chemical Company of Freeport, Texas designated "E-100"
has a
specific gravity at 15.6 C of 1.0168, a percent nitrogen by weight of 33.15
and a viscosity
at 40 C of 121 centistokes. Gas chromatography analysis of such a sample
contains about
0.93% "Light Ends" (most probably diethyl enetriamine), 0.72%
triethylenetetriamine,
21.74% tetraethyl enepentamine and 76.61% pentaethylenehexamine and higher
analogs.
These alkylenepolyamine bottoms include cyclic condensation products such as
piperazine
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and higher analogs of diethylenetriamine, triethylenetetramine and the like.
These
alkylenepolyamine bottoms may be reacted solely with the acylating agent or
they may be
used with other amines, polyamines, or mixtures thereof
[0060]
Another useful polyamine is a condensation reaction between at least one
hydroxy compound with at least one polyamine reactant containing at least one
primary or
secondary amino group. The hydroxy compounds include polyhydric alcohols and
amines.
The polyhydric alcohols are described below. In one embodiment, the hydroxy
compounds
are polyhydric amines. Polyhydric amines include any of the above-described
monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene
oxide,
butylene oxide, etc.) having from two to about 20 carbon atoms, or from 2 to
about 4.
Examples of polyhydric amines include tri-(hydroxypropyl)amine, tris-
(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol, N,N,N',N'-
tetrakis
(2-hydroxypropyl) ethyl enediamine, and N,N,N',N'-tetrakis
(2-hydroxyethyl)
ethylenediamine. Tris(hydroxymethyl) aminomethane (THAM) is particularly
useful.
[0061]
Polyamines that may react with the polyhydric alcohol or amine to form the
condensation products or condensed amines, are described above. Preferred
polyamines
include tri ethyl enetetramine (TETA),
tetraethyl enep entamine (TEPA),
pentaethylenehexamine (PEHA), and mixtures of polyamines such as the above-
described
"amine bottoms." The condensation reaction of the polyamine reactant with the
hydroxy
compound is conducted at an elevated temperature, usually from about 60 C to
about
265 C, or from about 220 C to about 250 C in the presence of an acid catalyst.
[0062]
The amine condensates and methods of making the same are described in PCT
publication WO 86/05501 and U.S. Pat. 5,230,714 (Steckel), incorporated by
reference for
its disclosure to the condensates and methods of making. A particularly useful
amine
condensate is prepared from HPA Taft Amines (amine bottoms available
commercially
from Union Carbide Co. with typically 34.1% by weight nitrogen and a nitrogen
distribution of 12.3% by weight primary amine, 14.4% by weight secondary amine
and
7.4% by weight tertiary amine), and tris(hydroxymethyl)aminomethane (THAM).
[0063]
In another embodiment, the polyamines are polyoxyalkylene polyamines, e.g.
polyoxyalkylene diamines and polyoxyalkylene triamines, having average
molecular
weights ranging from about 200 to about 4000, or from about 400 to about 2000.
The
polyoxyalkylene polyamines are commercially available and may be obtained, for
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example, from the Jefferson Chemical Company, Inc. under the trade name
"Jeffamines
D-230, D-400, D-1000, D-2000, T-403, etc." U.S. Patents 3,804,763 and
3,948,800 are
expressly incorporated herein by reference for their disclosure of such
polyoxyalkylene
polyamines and acylated products made therefrom.
[0064] In another embodiment, the polyamines are hydroxy-containing
polyamines.
Hydroxy-containing polyamine analogs of hydroxy monoamines, particularly
alkoxylated
alkylenepolyamines, e.g., N,N-(diethanol)ethylene diamines can also be used.
Such
polyamines can be made by reacting the above-described alkylene amines with
one or
more of the alkylene oxides described herein. Similar alkylene oxide-alkanol
amine
reaction products may also be used such as the products made by reacting the
above
described primary, secondary or tertiary alkanol amines with ethylene,
propylene or higher
epoxides in a 1.1 to 1.2 molar ratio. Specific examples of hydroxy-containing
polyamines
include N-(2-hydroxyethyl) ethyl enediamine, N,N'-bis(2-hydroxyethyl)-
ethylenediamine,
1-(2-hydroxyethyl)piperazine, mono(hydroxypropy1)-sub stituted tetraethyl
enepentamine,
N-(3-hydroxybuty1)-tetramethylene diamine, etc.
[0065] In another embodiment, the polyamine is a heterocyclic
polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines, tetra- and
dihydropyridines, pyrroles, indoles, piperidines, imidazoles, di- and
tetrahydroimidazoles,
piperazines, isoindoles, purines, morpholines,
thiomorpholines, N-
aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,
N,N'-
diaminoalkylpiperazines, azepines, azocines, azonines, azecines and tetra-, di-
and
perhydro derivatives of each of the above and mixtures of two or more of these
heterocyclic amines.
[0066] The following examples relate to amine salts of hydrocarbyl
thiophosphoric
acid esters. Unless the context indicates otherwise, temperatures are in
degrees Celsius,
pressure is atmospheric, and the parts and percentages are by weight
[0067] The additive may be referred to as an anti-wear additive.
[0068] Viscosity grades are used to describe the various categories
of fluid viscosity
as summarized in Table 1 below:
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Viscosity Limits of ISO VG Categories According to ISO 3448
Iso 3448 Typical Minimum Maximum
Viscosity Viscosity Viscosity Viscosity
Grades cSt @ 40 C cSt @ 40 C cSt @ 40 C
ISO VG 15 15.0 13.5 16.5
ISO VG 22 22.0 19.8 24.2
ISO VG 32 32.0 28.8 35.2
ISO VG 46 46.0 41.4 50.6
ISO VG 68 68.0 61.2 74.8
ISO VG 100 100.0 90.0 110.0
ISO VG 150 150.0 135.0 165.0
ISO VG 220 220.0 198.0 242.0
ISO VG 320 320.0 288.0 352.0
[0069] Air release performance may be measured by a number of tests,
for example
ASTM D3427, which measures air release from a lubricating oil at 50 C.
Viscosity may
be measured by a number of tests including ASTM D445 and DIN EN ISO 3104.
[0070] It has been observed that the lubricating oil compositions
comprising an oil of
lubricating viscosity, an ethylene/a-olefin copolymer, as described herein,
and an additive
comprising an amine salt of a hydrocarbyl thiophosphoric acid ester, in
particular wherein
the additive is obtained by reacting a phosphorous sulfide with one or more
alcohols
having about 3 to about 13 carbon atoms to form a thiophosphoric acid ester,
further
reacting the thiophosphoric acid ester with an alkylene oxide to form a
hydroxyl-
substituted ester of thiophosphoric acid, and further reacting said hydroxyl-
substituted
ester of thiophosphoric acid with a phosphorous oxide to form a an acidic
phosphoric acid
intermediate, and salting said acidic phosphoric acid intermediate with one or
more amines
wherein said amines contain one or more hydrocarbyl groups having from 2 to 30
carbon
atoms unexpectedly show improved air release properties while maintaining the
viscosity
grade of the lubricating oil, indicating a synergistic effect between the
ethylene/a-olefin
copolymer and the additive.
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Other Additives
[0071] The compositions of the invention may include other
performance additives or
an industrial additive package, which may also be referred to as an industrial
lubricant
additive package. In other words, the compositions of the invention are
designed to be
industrial lubricants, or additive packages for making the same. The present
invention does
not relate to automotive gear lubricants or other lubricating compositions.
[0072] In some embodiments the industrial lubricant additive package
includes a
demulsifier, a dispersant, and a metal deactivator. Any combination of
conventional
additive packages designed for industrial application may be used. The
invention in some
embodiments specifies the additive package is essentially free, if not
completely free of,
the compatibiliser described herein, or at least do not contain the type of
compatibiliser
specified by the invention in the amounts specified.
[0073] The additives which may be present in the industrial additive
package include
a foam inhibitor, a demulsifier, a pour point depressant, an antioxidant, a
dispersant, a
metal deactivator (such as a copper deactivator), an antiwear agent, an
extreme pressure
agent, a viscosity modifier, or some mixture thereof The additives may each be
present in
the range from 50, 75, 100 or even 150 ppm up to 5, 4, 3, 2 or even 1.5
percent by weight,
or from 75 ppm to 0.5 percent by weight, from 100 ppm to 0.4 percent by
weight, or from
150 ppm to 0.3 percent by weight, where the percent by weight values are with
regards to
the overall lubricant composition. In other embodiments the overall industrial
additive
package is present from 1 to 20, or from 1 to 10 percent by weight of the
overall lubricant
composition. However it is noted that some additives, including viscosity
modifying
polymers, which may alternatively be considered as part of the base fluid, may
be present
in higher amounts including up to 30, 40, or even 50% by weight when
considered separate
from the base fluid. The additives may be used alone or as mixtures thereof.
[0074] The compositions of the invention may also include antifoams,
also known as
foam inhibitors, which include but are not limited to organic silicones and
non-silicon
foam inhibitors. Examples of organic silicones include dimethyl silicone and
polysiloxanes. Examples of non-silicon foam inhibitors include but are not
limited to
polyethers, polyacrylates and mixtures thereof as well as copolymers of ethyl
acrylate, 2-
ethylhexylacrylate, and optionally vinyl acetate. In some embodiments the
antifoam is a
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polyacrylate. Antifoams may be present in the composition from 0.001 to 0.012
or 0.004
pbw or even 0.001 to 0.003 pbw.
[0075] The compositions of the invention may also include
demulsifiers, which
include but are not limited to derivatives of propylene oxide, ethylene oxide,
polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines or polyamines
reacted
sequentially with ethylene oxide or substituted ethylene oxides or mixtures
thereof
Examples of demulsifiers include polyethylene glycols, polyethylene oxides,
polypropylene oxides, (ethylene oxide-propylene oxide) polymers and mixtures
thereof
In some embodiments the demulsifiers are polyethers. Demulsifiers may be
present in the
composition from 0.002 to 0. 2 pbw.
[0076] The compositions of the invention may also include pour point
depressants,
which include but are not limited to esters of maleic anhydride-styrene
copolymers,
polymethacrylates; polyacrylates; polyacryl amides; condensation products of
hal paraffin
waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of
dialkyl
fumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers,
alkyl phenol
formaldehyde condensation resins, alkyl vinyl ethers and mixtures thereof.
[0077] The compositions of the invention may also include a rust
inhibitor, other than
some of the additives described above. Suitable rust inhibitors include
hydrocarbyl amine
salts of dialkyldithiophosphoric acid, hydrocarbyl amine salts of hydrocarbyl
arenesulphonic acid, fatty carboxylic acids or esters thereof, an ester of a
nitrogen-
containing carboxylic acid, an ammonium sulfonate, an imidazoline, mono-thio
phosphate
salts or esters, or any combination thereof; or mixtures thereof Examples of
hydrocarbyl
amine salts of dialkyldithiophosphoric acid of the invention include but are
not limited to
those described above, as well as the reaction product(s) of diheptyl or
dioctyl or dinonyl
dithiophosphoric acids with ethylenediamine, morpholine or PrimeneTM 81R or
mixtures
thereof Suitable hydrocarbyl amine salts of hydrocarbyl arenesulphonic acids
used in the
rust inhibitor package of the invention are represented by the formula:
I43
(R1)E -CY-15C)0- \NI*144
(V)
I
R2
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wherein Cy is a benzene or naphthalene ring. Rl is a hydrocarbyl group with
about 4 to
about 30, preferably about 6 to about 25, more preferably about 8 to about 20
carbon atoms.
z is independently 1, 2, 3, or 4 and most preferably z is 1 or 2. R2, R3 and
R4 are the same
as described above. Examples of hydrocarbyl amine salts of hydrocarbyl
arenesulphonic
acid of the invention include but are not limited to the ethylenediamine salt
of
dinonylnaphthalene sulfonic acid. Examples of suitable fatty carboxylic acids
or esters
thereof include glycerol monooleate and oleic acid. An example of a suitable
ester of a
nitrogen-containing carboxylic acid includes oleyl sarcosine. The rust
inhibitors may be
present in the range from 0.02 to 0.2, from 0.03 to 0.15, from 0.04 to 0.12,
or from 0.05 to
0.1 percent by weight of the lubricating oil composition. The rust inhibitors
of the
invention may be used alone or in mixtures thereof.
[0078]
The compositions of the invention may also include a metal deactivator. Metal
deactivators are used to neutralise the catalytic effect of metal for
promoting oxidation in
lubricating oil. Suitable metal deactivators include but are not limited to
triazoles,
tolyltriazoles, a thiadiazole, or combinations thereof, as well as derivatives
thereof
Examples include derivatives of benzotriazoles other than those described
above,
benzimidazole, 2-alkyldithiobenzimidazoles, 2-alkyldithiobenzothiazoles, 2-
(N,N'-
dialkyldithio-carbamoyl)benzothiazoles, 2,5-bis(alkyl-dithio)-1,3,4-
thiadiazoles, 2,5-
bi s(N,N' -dialkyldithiocarbamoy1)-1,3,4-thiadiazoles,
2-alkyldithio-5-mercapto
thiadiazoles or mixtures thereof. These additives may be used from 0.01 to
0.25 percent
by weight in the overall composition. In some embodiments the metal
deactivator is a
hydrocarbyl substituted benzotriazole compound. The benzotriazole compounds
with
hydrocarbyl substitutions include at least one of the following ring positions
1- or 2- or 4-
or 5- or 6- or 7- benzotriazoles. The hydrocarbyl groups contain about 1 to
about 30,
preferably about 1 to about 15, more preferably about 1 to about 7 carbon
atoms, and most
preferably the metal deactivator is 5-methylbenzotriazole used alone or
mixtures thereof
The metal deactivators may be present in the range from 0.001 to 0.5, from
0.01 to 0.04 or
from 0.015 to 0.03 pbw of the lubricating oil composition. Metal deactivators
may also be
present in the composition from 0.002 or 0.004 to 0.02 pbw. The metal
deactivator may
be used alone or mixtures thereof
[0079]
The compositions of the invention may also include antioxidants, including (i)
an alkylated diphenylamine, and (ii) a substituted hydrocarbyl mono-sulfide.
In some
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embodiments the alkylated diphenylamines of the invention are bis-nonylated
diphenylamine and bis-octylated diphenylamine. In some embodiments the
substituted
hydrocarbyl monosulfides include n-dodecy1-2-hydroxyethyl sulfide, 1-(tert-
dodecylthio)-
2-propanol, or combinations thereof In some embodiments the substituted
hydrocarbyl
monosulfide is 1-(tert-dodecylthio)-2-propanol. The antioxidant package may
also include
sterically hindered phenols. Examples of suitable hydrocarbyl groups for the
sterically
hindered phenols include but are not limited to 2-ethylhexyl or n-butyl ester,
dodecyl or
mixtures thereof Examples of methylene-bridged sterically hindered phenols
include but
are not limited to 4,4"-methylene-bis(6-tert-butyl o-cresol), 4,4"-methyl ene-
bis(2-tert-
amyl-o-cresol), 2,2"-methylene-bis(4-methy1-6-tert-butylphenol), 4,4"-
methylene-bis(2,6-
di-tertbutylphenol) or mixtures thereof
[0080] The compositions of the invention may also include nitrogen-
containing
dispersants, for example a hydrocarbyl substituted nitrogen containing
additive. Suitable
hydrocarbyl substituted nitrogen containing additives include ashless
dispersants and
polymeric dispersants. Ashless dispersants are so-named because, as supplied,
they do not
contain metal and thus do not normally contribute to sulfated ash when added
to a
lubricant. However they may, of course, interact with ambient metals once they
are added
to a lubricant which includes metal-containing species. Ashless dispersants
are
characterized by a polar group attached to a relatively high molecular weight
hydrocarbon
chain. Examples of such materials include succinimide dispersants, Mannich
dispersants,
and borated derivatives thereof.
[0081] The compositions of the invention may also include sulfur-
containing
compounds. Suitable sulfur-containing compounds include sulfurized olefins and
polysulfides. The sulfurized olefin or polysulfides may be derived from
isobutylene,
butylene, propylene, ethylene, or some combination thereof In some examples
the sulfur-
containing compound is a sulfurized olefin derived from any of the natural
oils or synthetic
oils described above, or even some combination thereof. For example the
sulfurized olefin
may be derived from vegetable oil.
[0082] The compositions of the invention may also include phosphorus
containing
compound, such as a fatty phosphite. The phosphorus containing compound can
include a
hydrocarbyl phosphite, a phosphoric acid ester, an amine salt of a phosphoric
acid ester,
or any combination thereof. In some embodiments the phosphorus containing
compound
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includes a hydrocarbyl phosphite, an ester thereof, or a combination thereof.
In some
embodiments the phosphorus containing compound includes a hydrocarbyl
phosphite. In
some embodiments the hydrocarbyl phosphite is an alkyl phosphite. By alkyl it
is meant
an alkyl group containing only carbon and hydrogen atoms, however either
saturated or
unsaturated alkyl groups are contemplated or mixtures thereof In some
embodiments the
phosphorus containing compound includes an alkyl phosphite that has a fully
saturated
alkyl group. In some embodiments the phosphorus containing compound includes
an alkyl
phosphite that has an alkyl group with some unsaturation, for example, one
double bond
between carbon atoms. Such unsaturated alkyl groups may also be referred to as
alkenyl
groups, but are included within the term "alkyl group" as used herein unless
otherwise
noted. In some embodiments the phosphorus containing compound includes an
alkyl
phosphite, a phosphoric acid ester, an amine salt of a phosphoric acid ester,
or any
combination thereof. In some embodiments the phosphorus containing compound
includes
an alkyl phosphite, an ester thereof, or a combination thereof. In some
embodiments the
phosphorus containing compound includes an alkyl phosphite. In some
embodiments the
phosphorus containing compound includes an alkenyl phosphite, a phosphoric
acid ester,
an amine salt of a phosphoric acid ester, or any combination thereof. In some
embodiments
the phosphorus containing compound includes an alkenyl phosphite, an ester
thereof, or a
combination thereof. In some embodiments the phosphorus containing compound
includes
an alkenyl phosphite. In some embodiments the phosphorus containing compound
includes dialkyl hydrogen phosphites. In some embodiments the phosphorus-
containing
compound is essentially free of, or even completely free of, phosphoric acid
esters and/or
amine salts thereof. In some embodiments the phosphorus-containing compound
may be
described as a fatty phosphite. Suitable phosphites include those having at
least one
hydrocarbyl group with 4 or more, or 8 or more, or 12 or more, carbon atoms.
Typical
ranges for the number of carbon atoms on the hydrocarbyl group include 8 to
30, or 10 to
24, or 12 to 22, or 14 to 20, or 16 to 18. The phosphite may be a mono-
hydrocarbyl
substituted phosphite, a di-hydrocarbyl substituted phosphite, or a tri-
hydrocarbyl
substituted phosphite. In one embodiment the phosphite is sulphur-free i.e.,
the phosphite
is not a thiophosphite. The phosphite having at least one hydrocarbyl group
with 4 or more
carbon atoms may be represented by the formulae:
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R7
R6-0 H ()
R7-CV
0 R6 Oor
wherein at least one of R6, IC and le may be a hydrocarbyl group containing at
least 4
carbon atoms and the other may be hydrogen or a hydrocarbyl group. In one
embodiment
R6, IC and le are all hydrocarbyl groups. The hydrocarbyl groups may be alkyl,
cycloalkyl,
aryl, acyclic or mixtures thereof In the formula with all three groups R6, R7
and le, the
compound may be a tri-hydrocarbyl substituted phosphite i.e., R6, IC and le
are all
hydrocarbyl groups and in some embodiments may be alkyl groups. The alkyl
groups may
be linear or branched, typically linear, and saturated or unsaturated,
typically saturated.
Examples of alkyl groups for R6, IC and le include octyl, 2-ethylhexyl, nonyl,
decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl,
octadecenyl, nonadecyl, eicosyl or mixtures thereof. In some embodiments the
fatty
phosphite component of the invention, and/or the composition overall is
essentially free
of, or even completely free of phosphoric acid ester and/or amine salts
thereof. In some
embodiments the fatty phosphite comprises an alkenyl phosphite or esters
thereof, for
example esters of dimethyl hydrogen phosphite. The dimethyl hydrogen phosphite
may be
esterified, and in some embodiments transesterified, by reaction with an
alcohol, for
example oleyl alcohol.
[0083] The compositions of the invention may also include one or more
phosphorous
amine salts, but in amounts such that the additive package, or in other
embodiments the
resulting industrial lubricant compositions, contains no more than 1.0 percent
by weight
of such materials, or even no more than 0.75 or 0.6 percent by weight. In
other
embodiments the industrial lubricant additive packages, or the resulting
industrial
lubricant compositions, are essentially free of or even completely free of
phosphorous
amine salts.
[0084] The compositions of the invention may also include one or more
antiwear
additives and/or extreme pressure agents, one or more rust and/or corrosion
inhibitors, one
or more foam inhibitors, one or more demulsifiers, or any combination thereof
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[0085] In some embodiments the industrial gear lubricant additive
packages, or the
resulting industrial gear lubricant compositions, are essentially free of or
even completely
free of phosphorous amine salts, dispersants, or both.
[0086] In some embodiments the industrial lubricant additive
packages, or the
resulting industrial lubricant compositions, include a demulsifier, a
corrosion inhibitor, a
friction modifier, or combination of two or more thereof. In some embodiments
the
corrosion inhibitor includes a tolyltriazole. In still other embodiments the
industrial
additive packages, or the resulting industrial lubricant compositions, include
one or more
sulfurized olefins or polysulfides; one or more phosphorus amine salts; one or
more
thiophosphate esters, one or more thiadiazoles, tolyltriazoles, polyethers,
and/or alkenyl
amines; one or more ester copolymers; one or more carboxylic esters; one or
more
succinimide dispersants, or any combination thereof
[0087] The industrial lubricant additive package may be present in
the overall
industrial lubricant from 1 to 5 percent by weight, or in other embodiments
from 1, 1.5, or
even 2 percent by weight up to 2, 3, 4, 5, 7 or even 10 percent by weight.
Amounts of the
industrial gear additive package that may be present in the industrial gear
concentrate
compositions of the invention are the corresponding amounts to the weight
percent above,
where the values are considered without the oil present (i.e. they may be
treated as pbw
values along with the actual amount of oil present).
[0088] The compositions of the invention may also include a derivative of a
hydroxy-
carboxylic acid. Suitable acids may include from 1 to 5 or 2 carboxy groups or
from 1 to
5 or 2 hydroxy groups. In some embodiments the friction modifier is derivable
from a
hydroxy-carboxylic acid represented by the formula:
0 \
%
Ja __________________________________________ X -E0R2
y \RI-
wherein: a and b may be independently integers of 1 to 5, or 1 to 2; X may be
an aliphatic
or alicyclic group, or an aliphatic or alicyclic group containing an oxygen
atom in the
carbon chain, or a substituted group of the foregoing types, said group
containing up to 6
carbon atoms and having a+b available points of attachment; each Y may be
independently
¨0¨, >NH, or >NR3 or two Y's together representing the nitrogen of an imide
structure
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R4-N< formed between two carbonyl groups; and each R3 and le may be
independently
hydrogen or a hydrocarbyl group, provided that at least one le and R3 group
may be a
hydrocarbyl group; each R2 may be independently hydrogen, a hydrocarbyl group
or an
acyl group, further provided that at least one -0R2 group is located on a
carbon atom within
X that is a or 0 to at least one of the -C(0)-Y-le groups, and further
provided that at least
on R2 is hydrogen. The hydroxy-carboxylic acid is reacted with an alcohol
and/or an
amine, via a condensation reaction, forming the derivative of a hydroxy-
carboxylic acid,
which may also be referred to herein as a friction modifier additive. In one
embodiment
the hydroxy-carboxylic acid used in the preparation of the derivative of a
hydroxy-
1 0 carboxylic acid is represented by the formula:
0
R5C)
0 H
R50 0 H
wherein each R5 is independently H or a hydrocarbyl group, or wherein the R5
groups
together form a ring. In one embodiment, where R5 is H, the condensation
product is
optionally further functionalized by acylation or reaction with a boron
compound. In
another embodiment the friction modifier is not borated. In any of the
embodiments above,
the hydroxy-carboxylic acid may be tartaric acid, citric acid, or combinations
thereof, and
may also be a reactive equivalent of such acids (including esters, acid
halides, or
anhydrides). The resulting friction modifiers may include imide, di-ester, di-
amide, or
ester-amide derivatives of tartaric acid, citric acid, or mixtures thereof In
one embodiment
the derivative of hydroxycarboxylic acid includes an imide, a di-ester, a di-
amide, an imide
amide, an imide ester or an ester-amide derivative of tartaric acid or citric
acid. In one
embodiment the derivative of hydroxycarboxylic acid includes an imide, a di-
ester, a di-
amide, an imide amide, an imide ester or an ester-amide derivative of tartaric
acid. In one
embodiment the derivative of hydroxycarboxylic acid includes an ester
derivative of
tartaric acid. In one embodiment the derivative of hydroxycarboxylic acid
includes an
imide and/or amide derivative of tartaric acid. The amines used in the
preparation of the
friction modifier may have the formula RR'NH wherein R and R' each
independently
represent H, a hydrocarbon-based radical of 1 or 8 to 30 or 150 carbon atoms,
that is, 1 to
150 or 8 to 30 or 1 to 30 or 8 to 150 atoms. Amines having a range of carbon
atoms with
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a lower limit of 2, 3, 4, 6, 10, or 12 carbon atoms and an upper limit of 120,
80, 48, 24, 20,
18, or 16 carbon atoms may also be used. In one embodiment, each of the groups
R and
R' has 8 or 6 to 30 or 12 carbon atoms. In one embodiment, the sum of carbon
atoms in R
and R' is at least 8. R and R' may be linear or branched. The alcohols useful
for preparing
the friction modifier will similarly contain 1 or 8 to 30 or 150 carbon atoms.
Alcohols
having a range of carbon atoms from a lower limit of 2, 3, 4, 6, 10, or 12
carbon atoms and
an upper limit of 120, 80, 48, 24, 20, 18, or 16 carbon atoms may also be
used. In certain
embodiments the number of carbon atoms in the alcohol-derived group may be 8
to 24, 10
to 18, 12 to 16, or 13 carbon atoms. The alcohols and amines may be linear or
branched,
and, if branched, the branching may occur at any point in the chain and the
branching may
be of any length. In some embodiments the alcohols and/or amines used include
branched
compounds, and in still other embodiments, the alcohols and amines used are at
least 50%,
75% or even 80% branched. In other embodiments the alcohols are linear. In
some
embodiments, the alcohol and/or amine have at least 6 carbon atoms.
Accordingly, certain
embodiments of the invention employ the product prepared from branched
alcohols and/or
amines of at least 6 carbon atoms, for instance, branched C6-18 or C8-18
alcohols or branched
C12-16 alcohols, either as single materials or as mixtures. Specific examples
include 2-
ethylhexanol and isotridecyl alcohol, the latter of which may represent a
commercial grade
mixture of various isomers. Also, certain embodiments of the invention employ
the
product prepared from linear alcohols of at least 6 carbon atoms, for
instance, linear C6-18
or C8-18 alcohols or linear C12-16 alcohols, either as single materials or as
mixtures. The
tartaric acid used for preparing the tartrates, tartrimides, or tartramides of
the invention
can be the commercially available type (obtained from Sargent Welch), and it
exists in one
or more isomeric forms such as d-tartaric acid, /-tartaric acid, d,/-tartaric
acid or meso-
tartaric acid, often depending on the source (natural) or method of synthesis
(e.g. from
maleic acid). These derivatives can also be prepared from functional
equivalents to the
diacid readily apparent to those skilled in the art, such as esters, acid
chlorides, anhydrides,
etc. In other embodiments the friction modifier includes glycerol monooleate.
[0089] In some embodiments the additive package includes one or more
corrosion
inhibitors, one or more dispersants, one or more antiwear and/or extreme
pressure
additives, one or more extreme pressure agents, one or more antifoam agents,
one or more
detergents, and optionally some amount of base oil or similar solvent as a
diluent. In some
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PCT/US2017/018587
embodiments the additive package includes at least one friction modified and
at least one
demulsifier, and optionally one or more additional additives present as well.
[0090] The additional additives may be present in the overall
industrial gear lubricant
composition from 0.1 to 30 percent by weight, or from a minimum level of 0.1,
1 or even
2 percent by weight up to a maximum of 30, 20, 10, 5, or even 2 percent by
weight, or
from 0.1 to 30, from 0.1 to 20, from 1 to 20, from 1 to 10, from 1 to 5, or
even about 2
percent by weight. These ranges and limits may be applied to each individual
additional
additive present in the composition, or to all of the additional additives
present.
[0091] In one embodiment, a lubricant composition may be prepared by
adding the
ethylene/a-olefin copolymer as described herein to an oil of lubricating
viscosity,
optionally in the presence of an industrial additive package (as described
herein). In
another embodiment, a lubricant composition may be prepared by adding the
ethylene/a-
olefin copolymer and/or the additive comprising an amine salt of a hydrocarbyl
thiophosphoric acid ester to an oil of lubricating viscosity, optionally in
the presence of an
industrial additive package (as described herein).
[0092] In one embodiment, the an additive comprising an amine salt of
a hydrocarbyl
thiophosphoric acid ester, for example, an additive obtained by reacting a
phosphorous
sulfide with one or more alcohols having about 3 to about 13 carbon atoms to
form a
thiophosphoric acid ester, further reacting the thiophosphoric acid ester with
an alkylene
oxide to form a hydroxyl-substituted ester of thiophosphoric acid, and further
reacting said
hydroxyl-substituted ester of thiophosphoric acid with a phosphorous oxide to
form a an
acidic phosphoric acid intermediate, and salting said acidic phosphoric acid
intermediate
with one or more amines wherein said amines contain one or more hydrocarbyl
groups
having from 2 to 30 carbon atoms acts as the antiwear agent in the lubricating
oil
composition. In one embodiment, the lubricating oil composition comprises an
addive
comprising an amine salt of a hydrocarbyl thiophosphoric acid ester and is
substantially
free of other antiwear performance additives.
Industrial Application
[0093] The invention includes both industrial gear lubricant
compositions and
methods for improving air release in industrial gear lubricant compositions.
In some
embodiments the industrial lubricant compositions of the invention are
industrial gear
lubricant compositions.
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PCT/US2017/018587
[0094] The various ranges for the components described above can be
applied to
concentrate compositions by maintaining the same relative ratios between
components (b)
and (c), while adjustment the amount of (a), (that is the amount of (a) will
be much lower
in a concentrate composition compared to a lubricant composition). In such
embodiments
the percent by weight values for components (b) and (c) may be treated as
parts by weight
(pbw), with oil making up the balance of the concentrate composition,
including anywhere
from 0 or 0.1 or 0.5 or even 1 pbw up to 10, 20, 30 or even 40 or 50 pbw oil
and/or base
fluid.
[0095] The amount of each chemical component described is presented
exclusive of
any solvent or diluent oil, which may be customarily present in the commercial
material,
that is, on an active chemical basis, unless otherwise indicated. However,
unless otherwise
indicated, each chemical or composition referred to herein should be
interpreted as being
a commercial grade material which may contain the isomers, by-products,
derivatives, and
other such materials which are normally understood to be present in the
commercial grade.
[0096] In one embodiment the lubricant composition is an industrial gear
oil. In some
embodiments the industrial gear oil may be a Group I, Group II or Group III
basestock as
defined by the American Petroleum Institute. In some embodiments, the metal
working oil
may be mixed with Group IV or Group V basestock. In one embodiment the
lubricating
oil composition contains about 2% to about 17% by weight, for example, about
5% to
about 17% or about 5% to about 11% by weight, based on the total weight of the
lubricating oil composition of a ethylene/a-olefin copolymer and about 0.04%
to about
0.20%, for example, about 0.04 to about 0.15% or even about 0.10% to about
0.15% by
weight, based on the total weight of the lubricating oil composition of an
additive
comprising an an amine salt of a hydrocarbyl thiophosphoric acid ester.
[0097] In one embodiment, the lubricating composition of the present
invention
releases all entrapped air in about 25 minutes or less as measured by ASTM
D3427 at
50 C. In another embodiment, the lubricating composition of the present
invention
releases all entrapped air from the lubricating composition in about 18
minutes or less as
measured by ASTM D3427 at 50 C.
[0098] The following examples provide illustrations of the invention. These
examples
are non-exhaustive and are not intended to limit the scope of the invention.
CA 03016139 2018-08-29
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PCT/US2017/018587
EXAMPLES
[0099] Industrial Gear lubricating oil compositions were prepared as
shown in the
following Tables I (Comparative) and II (Inventive). Viscosity measurements
for each
base oil of lubricating viscosity were measured before and after the addition
of additives
using ASTM D445. Air release was measured for each lubricating oil composition
according to ASTM D3427 at 50 C.
TABLE I
Comparative Examples
Additive (wt %)
Cl C2 C3 C4 C5 C6 C7 C8
Ethylene
a-Olefin 11 11
Copolymer
Brightstock 50 50 50
Viscosity
12 12 14
Modifier'
Borated
0.04 0.04 0.11 0.11 0.11
0.04
dispersant
Anti-Foam 0.02 0.02 0.02
Anti-Wear' 0.1 0.1 0.1
Anti-Wear2 0.61 0.61 0.61
Corrosion
0.5 0.5 0.15 0.15 0.15
0.5
Inhibitor
Yellow metal
0.02 0.02 0.02 0.02 0.02
0.02
Inhibitor
Demulsifier 0.006 0.006 0.006 0.006 0.006 0.01
Sulfurized
1.2 1.2 1.2 1.2 1.2 1.2
Olefin
Oil of
Balance Balance Balance Balance Balance Balance Balance Balance
Lubricating to to to to to to to to
Viscosity
100% 100% 100% 100% 100% 100% 100% 100%
ISO VG 220 220 220 220 220 220 220 220
API BO Grp I
Air Release 36.8 39.3 43.4 36.4 34.2 25.9 41.9
27.1
Anti-Wear Additive comprises an amine salt of a hydrocarbyl thiophosphoric
acid ester
obtained by reacting a phosphorous sulfide with one or more alcohols having
about 3 to
about 13 carbon atoms to form a thiophosphoric acid ester, further reacting
the
thiophosphoric acid ester with an alkylene oxide to form a hydroxyl-
substituted ester of
thiophosphoric acid, and further reacting said hydroxyl-substituted ester of
thiophosphoric
acid with a phosphorous oxide to form a an acidic phosphoric acid
intermediate, and
salting said acidic phosphoric acid intermediate with one or more amines
wherein said
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PCT/US2017/018587
amines contain one or more hydrocarbyl groups having from 2 to 30 carbon atoms
as
described herein.
2 Anti-Wear Additive comprises an alkenyl phosphite based anti-wear additive.
3 Viscosity Modifier comprises a polyisobutylene based viscosity modifier with
an
embedded pour point depressant.
TAME II
CoLow-a-th,,E Ex.amplo,
Adtatica
Ex. A Ex. E C Ex. D Ex. E
Ex. F Ex. G 'Ex. 11 EI Ex. 3: Ex.
Etkyleue
Mem 5 2 fl 11
Cos.µo15.ins.t,
flra
0.04
0..04
EoratEsi S..04
0.04 a 0.04 G.314 0..=1.4 0.04 IN
nts,:mrsont
A:o.'&Foara 0.02 O. 0.k,2
:Ant-Ws:1E' 0;1 1.1 0.1 0.1 0.1 0.1 0.1
0.15 0.15
Cartosiott .0 5
0.05 0..05
0.5 0.5 0..5 0.5 as as --
Inhibitor
Yellow maul
0.02. 0.02 0.02 C.:332 0.02: 0,.02 0,02
0.0,2
Inhibitor 0.02 0.02 0.02.
Dermila45er c,...fM O. 0.0d. 0. 006 0,01. 0,01
CJX Q.GI 5
Ant.caidant 0...1.g
0,19
Stift.u.irred 11 0.65
0_65
1.2 1:2 L. 1..2 1..2 .2
plea
Gia a Ellar :e E qt1:1w.e EalaiKe Saisms E21.221ca
Balance: Esti.:921C.S BalmicE Balmo.e Balance
1.xibricatiris t tu
iSCSSky AO% 00% IX& 0t3% 10,0% 103% 1C-411% 100% 100%
ISOVG 150 $5.1 220 :22.i3 220 .220 220 :320
2:20 .220
API BO Grp 17 1 11Li t 1 t Ii fl 11
Air Fiklezie 17.5 22.2 5.S 215 17.1 13.4 10.5
16,1 17.2 1. ..g 13.9
1 001 It
is known that some of the materials described above may interact in the final
formulation, so that the components of the final formulation may be different
from those
that are initially added. The products formed thereby, including the products
formed upon
10 employing lubricant composition of the present invention in its intended
use, may not be
susceptible of easy description. Nevertheless, all such modifications and
reaction products
are included within the scope of the present invention; the present invention
encompasses
lubricant composition prepared by admixing the components described above.
[0101]
Each of the documents referred to above is incorporated herein by reference.
Except in the Examples, or where otherwise explicitly indicated, all numerical
quantities
in this description specifying amounts of materials, reaction conditions,
molecular
weights, number of carbon atoms, and the like, are to be understood as
modified by the
word "about". Unless otherwise indicated, each chemical or composition
referred to herein
should be interpreted as being a commercial grade material which may contain
the isomers,
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PCT/US2017/018587
by-products, derivatives, and other such materials which are normally
understood to be
present in the commercial grade. However, the amount of each chemical
component is
presented exclusive of any solvent or diluent oil, which may be customarily
present in the
commercial material, unless otherwise indicated. It is to be understood that
the upper and
lower amount, range, and ratio limits set forth herein may be independently
combined.
Similarly, the ranges and amounts for each element of the invention may be
used together
with ranges or amounts for any of the other elements.
[0102] While the invention has been explained in relation to its
preferred
embodiments, it is to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the specification.
Therefore, it is to be
understood that the invention disclosed herein is intended to cover such
modifications as
fall within the scope of the appended claims.
