Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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ALKYLPHENOL DETERGENTS
TECHNICAL FIELD
[0001] The disclosed technology relates to hydrocarbyl- (e.g. alkyl-)
phenol detergents and
their salts. In particular, the disclosed technology includes a hydroxy-
aromatic carboxylic acid.
.. Such compounds and their salts are useful as lubricant additives.
BACKGROUND OF THE INVENTION
[0002] Phenol-based detergents are known. Among these are phenates based
on phenolic
monomers, linked with sulfur bridges or alkylene bridges such as methylene
linkages derived from
formaldehyde. The phenolic monomers themselves are typically substituted with
an aliphatic
.. hydrocarbyl group to provide a measure of oil solubility. The hydrocarbyl
groups may be alkyl
groups, and, historically, dodecylphenol (or propylene tetramer-substituted
phenol) has been
widely used. An early reference to basic sulfurized polyvalent metal phenates
is U.S. Patent
2,680,96, Walker et al., June 1, 1954; see also U.S. Patent 3,372, 116,
Meinhardt, March 6, 1968.
[0003] Recently, however, certain alkylphenols and products prepared
from them have come
.. under increased scrutiny due to their association as potential endocrine
disruptive materials. In
particular, alkylphenol detergents which are based on phenols alkylated with
oligomers of
propylene, specifically propylene teramer (or tetrapropenyl), may contain
residual alkyl phenol
species. There is interest, therefore, in developing alkyl-substituted phenol
detergents, for uses in
lubricants, fuels, and as industrial additives, which contain a reduced or
eliminated amount of
.. dodecylphenol component and other substituted phenols having propylene
oligomer substituents
of 10 to 15 carbon atoms. Nevertheless, it is desirable that the products
should have similar oil-
solubility parameters as phenates prepared from C10-15 propylene oligomers.
[0004] There have been several efforts to prepare phenate detergents
that do not contain alkyl
phenols derived from oligomers of propylene. U.S. Patent 7,435,709,
Stonebraker et al.,
October 14, 2008, discloses a linear alkylphenol derived detergent
substantially free of endocrine
disruptive chemicals. It comprises a salt of a reaction product of (1) an
olefin having at least 10
carbon atoms, where greater than 90 mole % of the olefin is a linear C20-C30 n-
alpha olefin, and
wherein less than 10 mole % of the olefin is a linear olefin of less than 20
carbon atoms, and less
than 5 mole % of the olefin a branched chain olefin of 18 carbons or less, and
(2) a
hydroxyaromatic compound.
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[0005] U. S . Application 201 1/0190185, Sinquin et al, August 4, 2011,
discloses an overbased
salt of an oligomerized alkylhydroxyaromatic compound. The alkyl group is
derived from an olefin
mixture comprising propylene oligomers having an initial boiling point of at
least about 195 C
and a final boiling point of greater than 325 C. The propylene oligomers may
contain a
distribution of carbon atoms that comprise at least about 50 weight percent of
C14 to C20 carbon
atoms.
[0006] U. S . Application 201 1/0124539, Sinquin et al, May 26, 2011,
discloses an overbased,
sulfurized salt of an alkylated hydroxyaromatic compound. The alkyl
substituent is a residue of at
least one isomerized olefin having from 15 to about 99 wt. % branching. The
hydroxyaromatic
.. compound may be phenol, cresols, xylenols, or mixtures thereof.
[0007] U. S . Application 201 1/01 18160, Campbell et al., May 19, 2011,
discloses an alkylated
hydroxyaromatic compound substantially free of endocrine disruptive chemicals.
An alkylated
hydroxyaromatic compound is prepared by reacting a hydroxyaromatic compound
with at least
one branched olefinic propylene oligomer having from about 20 to about 80
carbon atoms. Suitable
hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone,
pyrogallol,
cresol, and the like.
[0008] U.S. Application 2010/0029529, Campbell et al., February 4, 2010,
discloses an
overbased salt of an oligomerized alkylhydroxyaromatic compound. The alkyl
group is derived
from an olefin mixture comprising propylene oligomers having an initial boing
point of at least
about 195 C and a final boiling point of no more than about 325 C. Suitable
hydroxyaromatic
compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol,
cresol, and the like.
[0009] U.S. Application 2008/0269351, Campbell et al., October 30, 2008,
discloses an
alkylated hydroxyaromatic compound substantially free of endocrine disruptive
chemicals,
prepared by reacting a hydroxyaromatic compound with a branched olefinic
oligomer having from
about 20 to about 80 carbon atoms.
[0010] WO/PCT application 2013/059173, Cook et al., discloses discloses
an overbased salt
of an oligomerized alkylhydroxyaromatic compound. The alkyl group is a
combination of very
short hydrocarbyl group (i.e. 1 to 8 carbon atoms) and a long hydrocarbyl
group (at least about 25
carbon atoms). Suitable compounds incude those made from a mixture of para-
cresol and
polyisobutylene-substituted phenol.
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[0011] Other general technology includes that of U.S. Patent 6,310,009,
Carrick et al.,
October 30, 2001, which discloses salts of the general structure
OM
X
0
R31,
where R may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18 carbon
atoms. It is understood
that le will normally comprise a mixture of various chain lengths, so that the
foregoing numbers
will normally represent an average number of carbon atoms in the le groups
(number average).
SUMMARY OF THE INVENTION
[0012] The present invention provides an alkyl-phenol detergent
composition having
appropriate oil solubility which may also provide one or more other benefits
to a lubricating
composition including anti-wear performance, oxidation performance, and/or
viscosity
performance. In one embodiment the disclosed technology may provide a solution
to potential
problems posed by detergents containing C12 alkyl phenol moieties i.e., the
disclosed invention
may be free from or substantially free from C12 alkyl phenol moieties
typically formed from
oligomerisation or polymerisation of propylene.
[0013] The present invention provides an alkylphenol containing detergent
comprising a
polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof,
wherein the polyolefin is
derived from a branched alkene having at least 4 carbon atoms and wherein the
polyolefin has a
number average molecular weight of 150 to 800 and wherein the detergent is a
neutral or overbased
salt of a carboxylic acid. In certain embodiments, the alkylphenol detergent
of the present
invention is substantially free of (or entirely free of, or contains less than
5 percent or 3 percent or
1 percent or 0.3 percent or 0.1 percent by mole of) oligomer units containing
propylene. In certain
embodiments, the alkylphenol detergent of the present invention is
substantially free from or
substantially free from C12 alkyl phenol moieties.
[0014] In one embodiment, the alkylphenol-containing detergent may be a
polyolefin-
substituted hydroxy-aromatic carboxylic acid or salt thereof, such as a
salicylate. Detergents of
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this type are ionic detergents, i.e. they generally comprise a salt of the
detergent substrate (the
phenol-containing material) and a suitable cationic counterion. Detergents of
the disclosed
technology may be metal-containing salts, amine or ammonium containing salts,
or mixtures
thereof. In one embodiment, the detergent comprises one or more alkali metals,
one or more
alkaline earth metals, or mixtures thereof.
[0015] The present invention also includes a process to prepare an
alkylphenol-containing
detergent compound comprising (i) forming a polyolefin-substituted hydroxy-
aromatic carboxylic
acid wherein the polyolefin is derived from a branched alkene having at least
4 carbon atoms and
wherein the polyolefin has a number average molecular weight of 150 to 800 to
form a substrate
and (ii) reacting the substrate with a metal base (such as an alkalie metal or
alkaline earth metal
oxide or hydroxide) in the presence of carbon dioxide to form an alkylphenol
containing detergent.
The reaction conditions for the process are known in the art and include
alkylation of phenol in
the presence of known catalysts including BF3, A1C13, or HF. The reaction of
the substrate with a
metal base), in the presence of carbon dioxide are well known processes in the
art of preparing
detergents.
[0016] The disclosed technology also provides a lubricant comprising an
oil of lubricating
viscosity and said alkylphenol detergent, as well as a method of lubricating a
mechanical device
with said lubricant.
[0017] The disclosed technology also provides a method of lubricating a
mechanical device
comprising supplying to the mechanical device a lubricating composition
disclosed herein.
[0018] The disclosed technology also provides for the use of the
alkylphenol detergent in a
lubricating composition to provide detergency, deposit control, and/or
oxidative stability to the
lubricant.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The disclosed technology provides an alkylphenol detergent, a
lubricating composition,
a method for lubricating a mechanical device, such as an internal combustion
engine, and a use as
disclosed herein.
[0020] The alkylphenol detergent of the present invention comprises a
polyolefin-substituted
hydroxy-aromatic carboxylic acid wherein the polyolefin is derived from a
branched alkene having
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at least 4 carbon atoms and wherein the polyolefin has a number average
molecular weight of 150
to 800.
[0021] The alkylphenol-containing detergent of the present invention is
a polyolefin-
substituted hydroxy-aromatic carboxylic acid. Such a detergent may be
represented by the formula
(I):
0
HO
OH
R2-
-1
(I)
wherein RI- is an alkyl group is derived from a branched polyolefin compound
having at least 4
carbon atoms, for example, 8 to 50 carbon atoms, or at least 10 carbon atoms,
or at least 12 carbon
atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or at least
18 carbon atoms, or at
least 20 carbon atoms, or at least 24 carbon atoms, or up to 40 carbon atoms,
or up to 35 carbon
atoms, or up to 30 carbon atoms. The polyolefin group may have a number-
average molecular
weight Mn of at least 150, or at least 200, or at least 300, or up to 800, or
up to 600, or up to 500,
or up to 400, or up to 360. R2 may be a hydrogen or a hydrocarbyl group of at
least one 1 up to
about 40 carbon atoms. In one embodiment, R2 may also be an alkyl group is
derived from a
branched polyolefin compound having at least 4 carbon atoms, for example, 8 to
50 carbon atoms,
or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14
carbon atoms, or at least 16
carbon atoms, or at least 18 carbon atoms, or at least 20 carbon atoms, or at
least 24 carbon atoms,
or up to 40 carbon atoms, or up to 35 carbon atoms, or up to 30 carbon atoms.
The polyolefin
group may have a number-average molecular weight Mn of at least 150, or at
least 200, or at least
300, or up to 800, or up to 600, or up to 500, or up to 400, or up to 360.
[0022] The polyolefin-substituted hydroxy-aromatic carboxylic acid may
be selected from any
known carboxylic acid in the art for such applications. The polyolefin-
substituted hydroxy-
aromatic carboxylic acid may be a neutral or overbased metal salt of a
carboxylic acid. 4-
hydroxybenzoic acid, 2-hydroxybenzoic acid (aka salicylic acid), 3-
hydroxybenzoic acid, 1-
hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, and 6-hydroxy-2-
naphthoic acid.
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[0023] The preparation of dergents from carboxylic acids is generally
known to those skilled
in the art. For example, methods of forming such detergents are disclosed in
U.S. Patents 4,719,023
and 3,372,116. The present invention may be prepared by any methods now known
or hereafter
developed.
[0024] In one embodiment, the polyolefin-substituted hydroxy-aromatic
carboxylic acid may
be an alkylsalicylate or salicylate detergent. A salicylate detergent may be a
neutral or overbased
metal salt of alkylsalicylic acid. Alkylsalicylic acid may be represented by
the formula (II)
OH 0
401 OH
[0025] In the polyolefin-substitued hydroxy-aromatic carboxylic acids shown
in Formulas (I)
and (II) above, R or le represent the alkyl group of the alkylphenol. In the
present invention, the
alkyl group is derived from a branched polyolefin compound having at least 4
carbobn atoms, for
example, 8 to 50 carbon atoms, or at least 10 carbon atoms, or at least 12
carbon atoms, or at least
14 carbon atoms, or at least 16 carbon atoms, or at least 18 carbon atoms, or
at least 20 carbon
atoms, or at least 24 carbon atoms, or up to 40 carbon atoms, or up to 35
carbon atoms, or up to
30 carbon atoms. The polyolefin group may have a number-average molecular
weight Mn of at
least 150, or at least 200, or at least 300, or up to 800, or up to 600, or up
to 500, or up to 400, or
up to 360. A polyolefin group with Mn of less than 500, e.g., up to about 400,
for example about
300 to 400 is particularly suitable as it allows the compound to provide good
detergent properties
for deposit control and cleanliness without resulting in viscosity creep or
undesirable thickening
of the oil.
[0026] Examples of branched polyolefin groups suitable for use as the R
or le group include
polyolefin groups which are derived from a branched alkene having at least 4
carbon atoms, or up
to 12 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms, such as
a C4-C6 branched
alkene. Suitable branched alkenes include isobutylene (2-methylpropene), 2-
methylbutene, 2-
ethyl-1 -butene, 2-methyl-1-pentene, 3-methyl-1 -pentene, 4-methyl-1-pentene,
2-methyl, 3 -
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methyl-l-pentene, 2-ethyl- 1 -pentene, 3 -ethyl-l-p entene, 2-methyl- 1 -
hexene, 3 -methyl-l-hexene,
2-ethyl- 1 -hexene, 3 -ethyl-l-hexene, 4-ethyl-1 -hexene, 2-methyl-l-heptene,
3 -methyl-l-heptene,
2-methyl-l-octene, 2-methyl-l-nonene, 2-methyl-l-decene, 2-methyl-1-undecene,
and mixtures
thereof. Each polyolefin group is derived from at least two or at least three,
or at least four, or up
to twenty, or up to eighteen, or up to twelve branched alkene monomer units to
form a chain with
at least two or at least three, or at least four branches from the main chain.
In one embodiment, the
polyolefin includes a chain derived from at least four, or at least five, or
up to eighteen, or up to
eight, or up to seven, or up to six branched alkene units. The branched alkene
may be branched at
the alpha or beta position, or further along the longest chain. In one
embodiment, R is derived from
a branched alkene which is solely or at least partially isobutylene.
[0027] In one embodiment, the compound is free of C8 and higher
unbranched alkyl groups.
[0028] In one embodiment, R, le, and R2 are composed solely of carbon
and hydrogen.
[0029] The polyolefin-substituted hydroxy-aromatic carboxylic acid, such as an
alkylsalicylate, may be a neutral or nearly neutral salt of the carboxylic
acid; by nearly neutral, it
is meant that there is an excess of base of no more than 15 mol percent, i.e.
if the salt is metal-
containing, the metal ratio is 1.15 or less. In one embodiment the neutral
salt of the polyolefin-
substituted hydroxy-aromatic carboxylic acid, such as alkylsalicylic acid, may
be an amine or
ammonium salt, a metal salt, or mixtures thereof
[0030] Amines suitable for use in the preparation of the neutral amine
salted polyolefin-
substituted hydroxy-aromatic carboxylic acid, such as an alkylsalicylate are
not overly limited and
may include any alkyl amine, though generally are fatty acid amines derived
from fatty carboxylic
acids. The alkyl group present in the amine may contain from 10 to 30 carbon
atoms, or from 12
to 18 carbon atoms, and may be linear or branched. In some embodiments the
alkyl group may be
linear and unsaturated. Typical amines include pentadecylamine,
octadecylamine, cetylamine,
oleylamine, decylamine, dodecylamine, dimethyldodecylamine, tridecyl amine,
heptadecylamine,
octadecylamine, stearylamine, and any combination thereof. In some embodiments
the fatty acid
derived amine salt of an alkylsalicylic acid may be a salt of oleylamine. In
certain embodiments,
the amine may be a gamma-aminoester compound; aminoesters of this type may be
derived from
Michael addition of a primary amine to an alkyl diester of itaconic acid
represented by the formula
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0
R1 01:r
OR2
NHR3
where le and R2 are hydrocarbyl groups containing 2 to 30 carbon atoms, and le
is a hydrocarbyl
group containing 4 to 50 carbon atoms. In some embodiments, le of the
aminoester compound is
an alkyl group that has at least one hydrocarbyl group substituted at the 1-,
or 2-position of the
alkyl group. In one embodiment, the aminoester is dibutyl 2-(((2-ethylhexyl)-
amino)methyl)succinate.
[0031] In certain embodiments, the neutral salt of the polyolefin-
substituted hydroxy-aromatic
carboxylic acid, such as an alkylsalicylic acid may be a quaternary ammonium
salt, also referred
to as a quaternary nitrogen compound. Quaternary nitrogen compounds are
characterized in that
the nitrogen atom is four-coordinate; this results in a cationic species that
is not protic, i.e. an acidic
proton is not released under basic conditions. Quaternary nitrogen compounds
may be
characterized as falling into two large groups, four coordinate
tetrahydrocarbylammonium
compounds, for example tetrabutylammonium, and three coordinate aromatic
compounds, for
example N-hydrocarbylpyridinium.
[0032] In some embodiments the quaternary nitrogen salt may comprise the
reaction product
of (a) hydrocarbyl-substituted compound having a tertiary amino group and (b)
a quaternizing
agent suitable for converting the tertiary amino group of (a) to a quaternary
nitrogen, wherein the
quaternizing agent may be chosen from dialkyl sulfates, benzyl halides,
hydrocarbyl substituted
carbonates; hydrocarbyl epoxides in combination with an acid or mixtures
thereof In one
embodiment, the quaternary nitrogen salt comprises the reaction product of (i)
at least one
compound chosen from: a polyalkene-substituted amine having at least one
tertiary amino group
and/or a Mannich reaction product having a tertiary amino group; and (ii) a
quaternizing agent.
[0033] The polyolefin-substituted hydroxy-aromatic carboxylic acid
detergents of the present
invention may be metal-containing detergents. Metal-containing detergents may
be neutral, or very
nearly neutral, or overbased. An overbased detergent contains a stoichiometric
excess of a metal
base for the acidic organic substrate. This is also referred to as metal
ratio. The term "metal ratio"
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is the ratio of the total equivalents of the metal to the equivalents of the
acidic organic compound.
A neutral metal salt has a metal ratio of one. A salt having 4.5 times as much
metal as present in a
normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The
term "metal ratio" is
also explained in standard textbook entitled "Chemistry and Technology of
Lubricants", Third
Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219,
sub-heading 7.25.
[0034] In one embodiment the overbased metal-containing polyolefin-
substituted hydroxy-
aromatic carboxylic acid may be calcium or magnesium overbased detergent. In
one embodiment,
the overbased detergent may comprise a calcium alkylphenol detergent with a
metal ratio of at
least 1.5, at least 3, at least 5, or at least 7. In certain embodiments, the
overbased calcium
alkylphenol detergent may have a metal ratio of 1.5 to 25, 2.5 to 20 or 5 to
16.
[0035] Alternatively, the polyolefin-substituted hydroxy-aromatic
carboxylic acid detergent
may be described as having TBN. Overbased carboxylic acid detergents, such as
salicylates,
typically have a total base number of 120 to 600 mg KOH/g, or 150 to 550 mg
KOH/g, or 180 to
350 mg KOH/g. The amount of the alkylphenol-containing detergent present in a
lubricant
composition may be defined as the amount necessary to deliver an amount, or
range of amounts,
of TBN to the lubricant composition. In certain embodiments, the polyolefin-
substituted hydroxy-
aromatic carboxylic acid containig detergent may be present in a lubricant
composition in amount
to deliver 0.5 to 10 TBN to the composition, or 1 to 7 TBN, or 1.5 to 5 TBN to
the composition.
[0036] Overbased detergents may also be defined as the ratio of the
neutral detergent salt, also
referred to as detergent soap, and the detergent ash. The overbased detergent
may have a weight
ratio of ash to soap of 3:1 to 1:8, or 1.5:1 to 1 to 4.1, or 1.3:1 to 1:3.4.
[0037] The polyolefin-substituted hydroxy-aromatic carboxylic acid
detergent of the present
invention may beneficially be used as an additive in a lubricant. The amount
of the polyolefin-
substituted hydroxy-aromatic carboxylic acid detergent in a lubricant may be
0.1 to 8 percent by
weight, on an oil-free basis, but including the calcium carbonate and other
salts present in an
overbased composition. When present as an overbased detergent, the amount may
typically be in
the range of 0.1 to 25 weight percent, or 0.2 to 28, or 0.3 to 20, or 0.5 to
15 percent. The higher
amounts are typical of marine diesel cylinder lubricants, e.g., 1 or 3 or 5
percent up to 25, 20, or
15 percent. Amounts used in gasoline or heavy-duty diesel engines (not marine)
will typically be
in lower ranges, such as 0.1 to 10 percent or 0.5 to 5 or 1 to 3 percent by
weight. When used as a
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substantially neutral or non-overbased salt, its amount may typically be
correspondingly less for
each of the engine types, e.g., 0.1 to 10 percent or 0.2 to 8 or 0.3 to 6
percent.
[0038] In certain embodiments, the amount of the polyolefin-substituted
hydroxy-aromatic
carboxylic acid detergent in a lubricant may be measured as the amount of
alkylphenol-containing
soap that is provided to the lubricant composition, irrespective of any
overbasing. In one
embodiment, the lubricant composition may contain 0.05 weight percent to 1.5
weight percent
alkylphenol-containing soap, or 0.1 weight percent to 0.9 weight percent
alkylphenol-containing
soap. In one embodiment, the alkylphenol-containing soap provides 20 percent
by weight to
100 percent by weight of the total detergent soap in the lubricating
composition. In one
embodiment the alkylphenol-containing soap provides 30 percent by weight to 80
percent by
weight of the total detergent soap, or 40 percent by weight to 75 percent by
weight of the total
detergent soap of the lubricating composition.
[0039] A lubricant composition may contain alkylphenol-containing
detergents different from
that of the disclosed technology. In one embodiment, the lubricant composition
of the disclosed
technology comprises the polyolefin-substituted hydroxy-aromatic carboxylic
acid or salt thereof
detergent of the disclosed technology in an amount 0.1 to 25 weight percent,
or 0.2 to 28, or 0.3 to
20, or 0.5 to 15 weight percent, and is free of or substantially free of an
alkylphenol-containing
detergent derived from alkylphenol which is derived from oligomers of
propylene, especially
tetrapropenyl. "Substantially free of' in this case means no more than 0.01
weight percent or an
amount considered to arise through contamination or other unintentional means.
Oil of Lubricating Viscosity
[0040] The lubricating composition comprises of the present invention an
oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil derived from
hydrocracking,
hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or
mixtures thereof A more
detailed description of unrefined, refined and re-refined oils is provided in
International
Publication W02008/147704, paragraphs [0054] to [0056] (a similar disclosure
is provided in US
Patent Application 2010/197536, see [0072] to [0073]). A more detailed
description of natural and
synthetic lubricating oils is described in paragraphs [0058] to [0059]
respectively of
W02008/147704 (a similar disclosure is provided in US Patent Application
2010/197536, see
[0075] to [0076]). Synthetic oils may also be produced by Fischer-Tropsch
reactions and typically
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may be 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.
[0041] Oils of lubricating viscosity may also be defined as specified in
April 2008 version of
"Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car
Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories". The
API Guidelines
are also summarized in US Patent US 7,285,516 (see column 11, line 64 to
column 12, line 10).
[0042] In one embodiment the oil of lubricating viscosity may be an API
Group Ito III mineral
oil, a Group IV synthetic oil, or a Group V naphthenic or ester synthetic oil,
or mixtures thereof.
In one embodiment the oil of lubricating viscosity may be an API Group II,
Group III mineral oil,
or a Group IV synthetic oil, or mixtures thereof
[0043] The amount of the oil of lubricating viscosity present is
typically the balance remaining
after subtracting from 100 weight % the sum of the amount of the additives of
the disclosed
technology and the other performance additives.
[0044] The lubricating composition may be in the form of a concentrate
and/or a fully
formulated lubricant. If the lubricating composition of the disclosed
technology (comprising the
additives disclosed herein) is in the form of a concentrate which may be
combined with additional
oil to form, in whole or in part, a finished lubricant), the ratio of the of
these additives to the oil of
lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1
by weight, or 80:20 to
10:90 by weight. Typically the lubricating composition of the disclosed
technology comprises at
least 50 weight %, or at least 60 weight %, or at least 70 weight %, or at
least 80 weight % of an
oil of lubricating viscosity.
Engine Lubricating Compositions ¨ Other Additives
[0045] Engine lubricating compositions in accordance with the present
invention may also
contain other additives that provide particular performance benefits to the
engine lubricant. These
additional additives may include detergents, antioxidants, dispersants, anti-
wear agents, oil soluble
titanium compounds, extreme pressure agents, foam inhibitors, viscosity
modifiers, corrosion
inhibitors, metal deactivators, pour point depressants, friction modifiers,
demulsifiers, and seal
swell agents. These additional components are described in more detail below.
[0046] The lubricating composition optionally further includes at least
one detergent, other
than the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt there
of as described
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herein. Exemplary optional detergents include overbased metal-containing
detergents. The metal
of the metal-containing detergent may be zinc, sodium, calcium, barium, or
magnesium. An
overbased metal-containing detergent may be chosen from sulfonates, non-sulfur
containing
phenates, sulfur containing phenates, salixarates, salicylates, and mixtures
thereof, or borated
equivalents thereof. The overbased detergent may be borated with a borating
agent such as boric
acid.
[0047] An overbased metal-containing detergent may also include "hybrid"
detergents formed
with mixed surfactant systems including phenate and/or sulfonate components,
e.g.,
phenate/salicylates, sulfonate/phenates, sulfonate/salicylates,
sulfonates/phenates/salicylates, as
described, for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and
6,281,179. Where
a hybrid sulfonate/phenate detergent is employed, the hybrid detergent can be
considered
equivalent to amounts of distinct phenate and sulfonate detergents introducing
like amounts of
phenate and sulfonate soaps, respectively.
[0048] Example overbased metal-containing detergents include zinc,
sodium, calcium and
magnesium salts of sulfonates, phenates (including sulfur-containing and non-
sulfur containing
phenates), salixarates and salicylates. Such overbased sulfonates,
salixarates, phenates and
salicylates may have a total base number of 120 to 700, or 250 to 600, or 300
to 500 (on an oil free
basis).
[0049] Overbased metal-containing detergents may be a zinc, sodium,
calcium or magnesium
salt of a sulfonate, a phenate, sulfur containing phenate, salixarate or
salicylate. Overbased
sulfonates, salixarates, phenates and salicylates typically have a total base
number of 120 to 700
TBN. Overbased sulfonates typically have a total base number of 120 to 700, or
250 to 600, or 300
to 500 (on an oil free basis).
[0050] Example sulfonate detergents include linear and branched
alkylbenzene sulfonate
detergents, and mixtures thereof, which may have a metal ratio of at least 8,
as described, for
example, in U.S. Pub. No. 2005065045. Linear alkyl benzenes may have the
benzene ring attached
anywhere on the linear chain, usually at the 2, 3, or 4 position, or be
mixtures thereof Linear
alkylbenzene sulfonate detergents may be particularly useful for assisting in
improving fuel
economy. In one embodiment, an alkylbenzene sulfonate detergent may be a
branched
alkylbenzene sulfonate, a linear alkylbenzene sulfonate, or mixtures thereof
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[0051] In one embodiment, the lubricating composition may be free of
linear alkylbenzene
sulfonate detergent. In one embodument, a sulfonate detergent may be a metal
salt of one or more
oil-soluble alkyl toluene sulfonate compounds as disclosed in U.S. Pub. No.
20080119378.
[0052] The lubricating composition may include at least 0.01 wt. % or at
least 0.1 wt. % of a
detergent other than the polyolefin-substituted hydroxy-aromatic carboxylic
acid or salt thereof,
and in some embodiments, up to 2 wt. %, or up to 1 wt. % of another detergent.
[0053] The lubricating composition optionally further includes at least
one antioxidant.
Exemplary antioxidants useful herein include phenolic and aminic antioxidants,
such as
diarylamines, alkylated diarylamines, hindered phenols, and mixtures thereof
The diarylamine or
alkylated diarylamine may be a phenyl-a-naphthylamine (PANA), an alkylated
diphenylamine, an
alkylated phenylnapthylamine, or mixture thereof Example alkylated
diphenylamines include
dinonyl diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctyl
diphenylamine,
didecyl diphenylamine, decyl diphenylamine, and mixtures thereof. Example
alkylated
diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl and didecyl
phenylnapthylamines.
Hindered phenol antioxidants often contain a secondary butyl and/or a tertiary
butyl group as a
steric hindering group. The phenol group may be further substituted with a
hydrocarbyl group
(e.g., a linear or branched alkyl) and/or a bridging group linking to a second
aromatic group.
Examples of suitable hindered phenol antioxidants include 2,6-di-tert-
butylphenol, 4-methy1-2,6-
di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-
butylphenol, 4-butyl -2,6-
di-tert-butylphenol, and 4-dodecy1-2,6-di-tert-butylphenol. In one embodiment,
the hindered
phenol antioxidant may be an ester, such as those described in U.S. Pat. No.
6,559,105. One such
hindered phenol ester is sold as IrganoxTM L-135, obtainable from Ciba.
[0054] When present, the lubricating composition may include at least
0.1 wt. % or at least 0.5
wt. %, or at least 1 wt. % antioxidant, and in some embodiments, up to 3 wt.
%, or up to 2.75 wt.
%, or up to 2.5 wt. % antioxidant.
[0055] The lubricating composition optionally further includes at least
one dispersant.
Exemplary dispersants include succinimide dispersants, Mannich dispersants,
succinamide
dispersants, and polyolefin succinic acid esters, amides, and ester-amides,
and mixtures thereof
The succinimide dispersant, where present, may be as described above for the
succinimides
described as useful for cation M.
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[0056]
The succinimide dispersant may be derived from an aliphatic polyamine, or
mixtures
thereof The aliphatic polyamine may be an ethylenepolyamine, a
propylenepolyamine, a
butylenepolyamine, or a mixture thereof In one embodiment the aliphatic
polyamine may be an
ethylenepolyamine. In one embodiment the aliphatic polyamine may be chosen
from
ethylenediamine, diethylenetriamine, tri ethyl
enetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
[0057]
In one embodiment, the dispersant may be a polyolefin succinic acid ester,
amide, or
ester-amide. A polyolefin succinic acid ester-amide may be a polyisobutylene
succinic acid reacted
with an alcohol (such as pentaerythritol) and a polyamine as described above.
Example polyolefin
succinic acid esters include polyisobutylene succinic acid esters of
pentaerythritol and mixture
thereof
[0058]
The dispersant may be an N-substituted long chain alkenyl succinimide. An
example
of an N-substituted long chain alkenyl succinimide is polyisobutylene
succinimide. Typically the
polyisobutylene from which polyisobutylene succinic anhydride is derived has a
number average
molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide
dispersants and their
preparation are disclosed, for example, in US Pat. Nos. 3,172,892, 3,219,666,
3,316,177,
3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405,
3,542,680,
3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235, and 7,238,650 and
EP Patent
Application 0 355 895 A.
[0059] The succinimide dispersant may comprise a polyisobutylene
succinimide, wherein the
polyisobutylene from which polyisobutylene succinimide is derived has a number
average
molecular weight of 350 to 5000, or 750 to 2500.
[0060]
The exemplary dispersants may also be post-treated by conventional methods
by a
reaction with any of a variety of agents. Among these are boron compounds
(such as boric acid),
urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones,
carboxylic acids,
such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic
anhydride, nitriles,
epoxides, and phosphorus compounds. In one embodiment the post-treated
dispersant is borated.
In one embodiment the post-treated dispersant is reacted with
dimercaptothiadiazoles. In one
embodiment the post-treated dispersant is reacted with phosphoric or
phosphorous acid. In one
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embodiment the post-treated dispersant is reacted with terephthalic acid and
boric acid (as
described in U.S. Pub. No. 2009/0054278.
[0061] When present, the lubricating composition may include at least
0.01 wt. %, or at least
0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. % of other dispersant(s),
and in some embodiments,
up to 20 wt. %, or up to 15 wt. %, or up to 10 wt. %, or up to 6 wt. % or up
to 3 wt. % dispersant.
[0062] The lubricating composition optionally further includes at least
one antiwear agent.
Examples of suitable antiwear agents suitable for use herein include titanium
compounds, tartrates,
tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized
olefins, metal
dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates),
phosphites (such as dibutyl
phosphite), phosphonates, thiocarbamate-containing compounds, such as
thiocarbamate esters,
thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates,
and bis(S-
alkyldithiocarbamyl) disulfides. The antiwear agent may in one embodiment
include a tartrate, or
tartrimide as described in U.S. Pub. Nos. 2006/0079413; 2006/0183647; and
2010/0081592. The
tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon
atoms on the alkyl
groups is at least 8. The antiwear agent may, in one embodiment, include a
citrate as is disclosed
in US Pub. No. 20050198894.
[0063] The lubricating composition may in one embodiment further include
a phosphorus-
containing antiwear agent. Example phosphorus-containing antiwear agents
include zinc
dialkyldithiophosphates, phosphites, phosphates, phosphonates, and ammonium
phosphate salts,
and mixtures thereof
[0064] When present, the lubricating composition may include at least
0.01 wt. %, or at least
0.1 wt. %, or at least 0.5 wt. % antiwear agent, and in some embodiments, up
to 3 wt. %, or up to
1.5 wt. %, or up to 0.9 wt. antiwear agent.
[0065] The lubricating composition may include one or more oil-soluble
titanium compounds,
which may function as antiwear agents, friction modifiers, antioxidants,
deposit control additives,
or more than one of these functions. Example oil-soluble titanium compounds
are disclosed in U.S.
Pat. No. 7,727,943 and U.S. Pub. No. 2006/0014651. Example oil soluble
titanium compounds
include titanium (IV) alkoxides, such as titanium (IV) isopropoxide and
titanium (IV) 2
ethylhexoxide. Such alkoxides may be formed from a monohydric alcohol, a
vicinal 1,2-diol, a
polyol, or mixture thereof. The monohydric alkoxides may have 2 to 16, or 3 to
10 carbon atoms.
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In one embodiment, the titanium compound comprises the alkoxide of a vicinal
1,2-diol or polyol.
1,2-vicinal diols include fatty acid mono-esters of glycerol, where the fatty
acid may be, for
example, oleic acid. Other example oil soluble titanium compounds include
titanium carboxylates,
such as titanium neodecanoate.
[0066] When present in the lubricating composition, the amount of oil-
soluble titanium
compounds is included as part of the antiwear agent.
[0067] The lubricating composition may include an extreme pressure
agent. Example extreme
pressure agents that are soluble in the oil include sulfur- and chlorosulfur-
containing EP agents,
dimercaptothiadiazole or CS2 derivatives of dispersants (typically succinimide
dispersants),
.. derivative of chlorinated hydrocarbon EP agents and phosphorus EP agents.
Examples of such EP
agents include chlorinated wax; sulfurized olefins (such as sulfurized
isobutylene), hydrocarbyl-
substituted 2,5-dimercapto-1,3,4-thiadiazoles and oligomers thereof, organic
sulfides and
polysulfides, such as dibenzyldisulfide, bis¨(chlorobenzyl) disulfide, dibutyl
tetrasulfide,
sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized
dipentene, sulfurized
terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons
such as the reaction
product of phosphorus sulfide with turpentine or methyl oleate; phosphorus
esters, such as
dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl
phosphite,
dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite,
tridecyl phosphite,
distearyl phosphite and polypropylene substituted phenol phosphite; metal
thiocarbamates, such
.. as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts
of alkyl and
dialkylphosphoric acids or derivatives including, for example, the amine salt
of a reaction product
of a dialkyldithiophosphoric acid with propylene oxide and subsequently
followed by a further
reaction with P205; and mixtures thereof Some useful extreme pressure agents
are described in
US Pat. No. 3,197,405.
[0068] When present, the lubricating composition may include at least 0.01
wt. %, or at least
0.1 wt. %, or at least 0.5 wt. % extreme pressure agent, and in some
embodiments, up to 3 wt. %,
or up to 1.5 wt. %, or up to 0.9 wt. % of the extreme pressure agent.
[0069] The lubricating composition may include a foam inhibitor. Foam
inhibitors that may
be useful in the lubricant composition include polysiloxanes; copolymers of
ethyl acrylate and 2-
ethylhexylacrylate and optionally vinyl acetate; demulsifiers including
fluorinated polysiloxanes,
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trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene
oxides and
(ethylene oxide-propylene oxide) polymers.
[0070] The lubricating composition may include a viscosity modifier.
Viscosity modifiers
(also sometimes referred to as viscosity index improvers or viscosity
improvers) useful in the
lubricant composition are usually polymers, including polyisobutenes,
polymethacrylates (PMA)
and polymethacrylic acid esters, diene polymers, polyalkylstyrenes, esterified
styrene-maleic
anhydride copolymers, hydrogenated alkenylarene-conjugated diene copolymers
and polyolefins
also referred to as olefin copolymer or OCP. PMA's are prepared from mixtures
of methacrylate
monomers having different alkyl groups. The alkyl groups may be either
straight chain or branched
chain groups containing from 1 to 18 carbon atoms. Most PMA's are viscosity
modifiers as well
as pour point depressants. In one embodiment, the viscosity modifier is a
polyolefin comprising
ethylene and one or more higher olefin, such as propylene.
[0071] When present, the lubricating composition may include at least
0.01 wt. %, or at least
0.1 wt. %, or at least 0.3 wt. %, or at least 0.5 wt. % polymeric viscosity
modifiers, and in some
embodiments, up to 10 wt. %, or up to 5 wt. %, or up to 2.5 wt. % polymeric
viscosity modifiers.
[0072] The lubricating composition may include a corrosion inhibitor.
Corrosion
inhibitors/metal deactivators that may be useful in the exemplary lubricating
composition include
fatty amines, octylamine octanoate, condensation products of dodecenyl
succinic acid or
anhydride, and a fatty acid such as oleic acid with a polyamine, derivatives
of benzotriazoles (e.g.,
tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles
and 2-
alkyl dithi ob enz othi azol es .
[0073] The lubricating composition may include a pour point depressant.
Pour point
depressants that may be useful in the exemplary lubricating composition
include polyalphaolefins,
esters of maleic anhydride-styrene copolymers, polymethacrylates,
polyacrylates, and
polyacrylamides.
[0074] The lubricating composition may include a friction modifier.
Friction modifiers that
may be useful in the exemplary lubricating composition include fatty acid
derivatives such as
amines, esters, epoxides, fatty imidazolines, condensation products of
carboxylic acids and
polyalkylene-polyamines and amine salts of alkylphosphoric acids. The friction
modifier may be
an ash-free friction modifier. Such friction modifiers are those which
typically not produce any
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sulfated ash when subjected to the conditions of ASTM D 874. An additive is
referred to as "non-
metal containing" if it does not contribute metal content to the lubricant
composition. As used
herein the term "fatty alkyl" or "fatty" in relation to friction modifiers
means a carbon chain having
8 to 30 carbon atoms, typically a straight carbon chain.
[0075] In one embodiment, the ash-free friction modifier may be represented
by the formula:
/0\ 0
D I (pq __________________________________________ Ey_R22
/P
where, D and D' are independently selected from -0-, >NH, >NR23, an imide
group
formed by taking together both D and D' groups and forming a R21-N< group
between two >C=0
groups; E is selected from ¨R24-0-R25-, >CH2, >cHR26, >cR26R27,
>C(OH)(CO2R22),
>C(CO2R22)2, and >CHOR28; where R24 and R25 are independently selected from
>CH2, >cHR26,
>cR26.-.K27,
>C(OH)(CO2R22), and >CHOR28; q is 0 to 10, with the proviso that when q=1, E
is not
>CH2, and when n=2, both Es are not >CH2; p is 0 or 1; R21 is independently
hydrogen or a
hydrocarbyl group, typically containing 1 to 150 carbon atoms, with the
proviso that when R21 is
hydrogen, p is 0, and q is more than or equal to 1; R22 is a hydrocarbyl
group, typically containing
1 to 150 carbon atoms; R23, R24, R25, R26 and R27
are independently hydrocarbyl groups; and R28 is
hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms,
or 4 to 32 carbon
atoms, or 8 to 24 carbon atoms. In certain embodiments, the hydrocarbyl groups
R23, R24, and R25,
may be linear or predominantly linear alkyl groups.
[0076] In certain embodiments, the ash-free friction modifier is a fatty
ester, amide, or imide
of various hydroxy-carboxylic acids, such as tartaric acid, malic acid lactic
acid, glycolic acid, and
mandelic acid. Examples of suitable materials include tartaric acid di(2-
ethylhexyl) ester (i.e., di(2-
ethylhexyl)tartrate), di(C8-Cio)tartrate, di(C12-15)tartrate, di -
oleyltartrate, oleyltartrimide, and oleyl
maleimide.
[0077] In certain embodiments, the ash-free friction modifier may be
chosen from long chain
fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty
imidazolines such as
condensation products of carboxylic acids and polyalkylene-polyamines; amine
salts of
alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty
alkyl tartramides; fatty
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phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides;
glycerol esters;
borated glycerol esters; fatty amines; alkoxylated fatty amines; borated
alkoxylated fatty amines;
hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines;
hydroxy alkyl
amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty
oxazolines; fatty ethoxylated
alcohols; condensation products of carboxylic acids and polyalkylene
polyamines; or reaction
products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or
thiourea and salts
thereof.
[0078] Friction modifiers may also encompass materials such as
sulfurized fatty compounds
and olefins, sunflower oil or soybean oil monoester of a polyol and an
aliphatic carboxylic acid.
[0079] In another embodiment the friction modifier may be a long chain
fatty acid ester. In
another embodiment the long chain fatty acid ester may be a mono-ester and in
another
embodiment the long chain fatty acid ester may be a triglyceride.
[0080] The amount of the ash-free friction modifier in a lubricant may
be 0.1 to 3 percent by
weight (or 0.12 to 1.2 or 0.15 to 0.8 percent by weight). The material may
also be present in a
concentrate, alone or with other additives and with a lesser amount of oil. In
a concentrate, the
amount of material may be two to ten times the above concentration amounts.
[0081] Molybdenum compounds are also known as friction modifiers. The
exemplary
molybdenum compound does not contain dithiocarbamate moieties or ligands.
[0082] Nitrogen-containing molybdenum materials include molybdenum-amine
compounds,
as described in U.S. Pat. No. 6,329,327, and organomolybdenum compounds made
from the
reaction of a molybdenum source, fatty oil, and a diamine as described in U.S.
Pat. No. 6,914,037.
Other molybdenum compounds are disclosed in U.S. Pub. No. 20080280795.
Molybdenum amine
compounds may be obtained by reacting a compound containing a hexavalent
molybdenum atom
with a primary, secondary or tertiary amine represented by the formula
NR29R30R31, where each
of R29, R3 and R31 is independently hydrogen or a hydrocarbyl group of 1 to
32 carbon atoms and
wherein at least one of R29, R3 and R31 is a hydrocarbyl group of 4 or more
carbon atoms or
represented by the formula:
OH
R33R34
R32
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where R32 represents a chain hydrocarbyl group having 10 or more carbon atoms,
s is 0 or 1, R33
and/or R34 represents a hydrogen atom, a hydrocarbyl group, an alkanol group
or an alkyl amino
group having 2 to 4 carbon atoms, and when s = 0, both R33 and R34 are not
hydrogen atoms or
hydrocarbon groups.
[0083] Specific examples of suitable amines include monoalkyl (or alkenyl)
amines such as
tetradecylamine, stearylamine, oleylamine, beef tallow alkylamine, hardened
beef tallow
alkylamine, and soybean oil alkylamine; dialkyl(or alkenyl)amines such as N-
tetradecyl m ethyl ami ne, N-p entadecyl m ethyl amine,
N-hexadecylmethylamine, N-
stearylmethyl amine, N-ol eylmethyl amine, N-dococylmethyl amine, N-beef
tallow alkyl
methylamine, N-hardened beef tallow alkyl methylamine, N-soybean oil alkyl
methylamine,
ditetradecylamine, dipentadecyl amine, dihexadecylamine, distearylamine,
dioleyl amine,
di dococyl amine, bi s(2-hexyldecyl)amine, bi s(2-octyl dodecyl)amine, bi s(2-
decyltetradecyl)amine,
beef tallow dialkylamine, hardened beef tallow dialkylamine, and soybean oil
dialkylamine; and
tri alk(en)yl amines such as tetrade cyl di m ethyl amine,
hexadecyldimethylamine,
octadecyldimethylamine, beef tallow alkyldimethylamine, hardened beef tallow
al kyl di m ethyl ami ne, soybean oil al kyl di m ethyl ami ne, di ol eyl m
ethyl amine, tritetradecyl amine,
tristearylamine, and trioleylamine. Suitable secondary amines have two alkyl
(or alkenyl) groups
with 14 to 18 carbon atoms.
[0084]
Examples of the compound containing the hexavalent molybdenum atom include
molybdenum trioxides or hydrates thereof (MoO3nH20), molybdenum acid (H2Mo04),
alkali
metal molybdates (Q2Mo04) wherein Q represents an alkali metal such as sodium
and potassium,
ammonium molybdates {(NH4)2Mo04 or heptamolybdate (NH4)6[Mo7024].4H20},
Mo0C14,
MoO2C12, MoO2Br2, Mo203C16 and the like. Molybdenum trioxides or hydrates
thereof,
molybdenum acid, alkali metal molybdates and ammonium molybdates are often
suitable because
of their availability. In one embodiment, the lubricating composition
comprises molybdenum
amine compound.
[0085]
Other organomolybdenum compounds of the invention may be the reaction
products
of fatty oils, mono-alkylated alkylene diamines and a molybdenum source.
Materials of this sort
are generally made in two steps, a first step involving the preparation of an
aminoamide/glyceride
mixture at high temperature, and a second step involving incorporation of the
molybdenum.
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[0086] Examples of fatty oils that may be used include cottonseed oil,
groundnut oil, coconut
oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil,
rapeseed oil (low or high
erucic acids), soyabean oil, sunflower oil, herring oil, sardine oil, and
tallow. These fatty oils are
generally known as glyceryl esters of fatty acids, triacylglycerols or
triglycerides.
[0087] Examples of some mono-alkylated alkylene diamines that may be used
include
methylaminopropylamine, methylaminoethylamine, butylaminopropyl amine,
butylamino-
ethylamine, octylaminopropylamine, octylaminoethylamine,
dodecylaaminopropylaamine,
dodecylaminoethylamine, hexadecylaminopropyl amine, hexadecylaminoethylamine,
octadecyl-
aminopropylamine, octadecylaminoethylamine, isopropyloxypropy1-1,3-
diaminopropane, and
octyloxypropy1-1,3-diaminopropane. Mono-alkylated alkylene diamines derived
from fatty acids
may also be used. Examples include N-coco alkyl-1,3-propanediamine (Duomeen
C), N-tall oil
alkyl-1,3-propanediamine (Duomeen T) and N-oley1-1,3-propanediamine (Duomeen
0), all
commercially available from Akzo Nobel.
[0088] Sources of molybdenum for incorporation into the fatty
oil/diamine complex are
generally oxygen-containing molybdenum compounds include, similar to those
above, ammonium
molybdates, sodium molybdate, molybdenum oxides and mixtures thereof. One
suitable
molybdenum source comprises molybdenum trioxide (Mo03).
[0089] Nitrogen-containing molybdenum compounds which are commercially
available
include, for example, Sakuralube 710 available from Adeka which is a
molybdenum amine
compound, and Molyvang 855, available from R.T. Vanderbilt.
[0090] The nitrogen-containing molybdenum compound may be present in the
lubricant
composition at 0.005 to 2 wt. % of the composition, or 0.01 to 1.3 wt. %, or
0.02 to 1.0 wt. % of
the composition. The molybdenum compound may provide the lubricant composition
with 0 to
1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to
250 ppm of
molybdenum.
[0091] Demulsifiers useful herein include trialkyl phosphates, and
various polymers and
copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures
thereof
[0092] Seal swell agents useful herein include sulfolene derivatives
such as Exxon Necton-
37TM (FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
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[0093] A lubricating composition may be prepared by adding the product
of the process
described herein to an oil of lubricating viscosity, optionally in the
presence of other performance
additives (as described herein below).
[0094] An engine lubricant in different embodiments may have a
composition as illustrated in
Table 1. All additives are expressed on an oil-free basis.
[0095] TABLE 1: Engine Lubricating Compositions
Additive Embodiments (wt. %)
A
polyolefin-substituted hydroxy-
aromatic carboxylic acid or salt 0.1 to 20 0.5 to 10 1 to 5
thereof
Overbased Sulfonate Detergent 0 to 9 0.3 to 8 1 to 5
Phenol-based detergent 0 to 10 0.5 to 7 0.75 to 5
(Borated) Dispersant 0 to 12 0.5 to 8 1 to 5
Antioxidant 0 to 13 0.1 to 10 0.5 to 5
Antiwear Agent 0 to 15 0.1 to 10 0.3 to 5
Corrosion Inhibitor 0 to 2 0.1 to 1 0.2 to 0.5
Friction Modifier 0 to 6 0.05 to 4 0.1 to 2
Viscosity Modifier 0 to 10 0.5 to 8 1 to 6
Other Performance Additives 0 to 10 0 to 8 0 to 6
Oil of Lubricating Viscosity Balance to 100 %
[0096] Use of the Engine Lubricating Composition
[0097] The end use of the engine lubricating composition described
herein includes use as a
cylinder lubricant for an internal combustion engine, such as a 2-stroke
marine diesel engine, but
may also find use as an engine oil for a two or 4-stroke engine in a passenger
car, heavy, medium
and light duty diesel vehicles, small engines such as motorcycle and 2-stroke
oil engines, as a
driveline lubricant, including gear and automatic transmission oils, and for
other industrial oils,
such as hydraulic lubricants.
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[0098] An exemplary method of lubricating a mechanical device, such as a
cylinder of an
internal combustion engine, includes supplying the exemplary lubricating
composition to the
device.
[0099] Generally, the lubricating composition is added to the
lubricating system of an internal
combustion engine, which then delivers the lubricating composition to the
cylinder of the engine,
during its operation, where it may be combusted with the fuel.
[0100] The internal combustion engine may be a diesel-fueled engine,
such as a 2-stroke
marine diesel engine, or a gasoline fueled engine, a natural gas fueled
engine, a mixed
gasoline/alcohol fueled engine, or a biodiesel fueled engine. The internal
combustion engine may
be a 2-stroke or 4-stroke engine.
[0101] The lubricating composition may be suitable for use as a cylinder
lubricant irrespective
of the sulfur, phosphorus or sulfated ash (ASTM D-874) content of the fuel.
The sulfur content of
the lubricating composition, which is particularly suited to use as an engine
oil lubricant, may be
1 wt. % or less, or 0.8 wt. % or less, or 0.5 wt. % or less, or 0.3 wt. % or
less. In one embodiment,
the sulfur content may be in the range of 0.001 wt. % to 0.5 wt. %, or 0.01
wt. % to 0.3 wt. %. The
phosphorus content may be 0.2 wt. % or less, or 0.12 wt. % or less, or 0.1 wt.
% or less, or 0.085
wt. % or less, or 0.08 wt. % or less, or even 0.06 wt. % or less, 0.055 wt. %
or less, or 0.05 wt. %
or less. In one embodiment, the phosphorus content may be 100 ppm to 1000 ppm,
or 200 ppm to
600 ppm. The total sulfated ash content may be 2 wt. % or less, or 1.5 wt. %
or less, or 1.1 wt. %
or less, or 1 wt. % or less, or 0.8 wt. % or less, or 0.5 wt. % or less, or
0.4 wt. % or less. In one
embodiment, the sulfated ash content may be 0.05 wt. % to 0.9 wt. %, or 0.1
wt. % to 0.2 wt. %
or to 0.45 wt. %.
[0102] Other lubricating compositions may also be formulated using the
polyolefin substituted
hydroxy-aromatic carboxylic acid detergent of the present invention along with
additional
additives. Exemplary other lubricating compositions are described below.
[0103] Driveline Lubricating Compositions
[0104] In one embodiment, the lubricating composition in accordance with
the present
invention is for use in a driveline device. Lubricating compositions for
driveline devices may
include the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt
thereof or salt thereof
as described herein in an oil of lubricating viscosisty, optionally in the
presence of other
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performance additives, which may include dispersants, antiwear agents,
dispersant viscosity
modifiers, friction modifiers, viscosity modifiers, antioxidants, overbased
detergents (other than
the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof or
salt thereof as
described above), foam inhibitors, demulsifiers, or pour point depressants or
mixtures thereof. In
one embodiment the invention provides a lubricant composition comprising in
addition to the
polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, at
least one of a
polyisobutylene succinimide dispersant, an antiwear agent, a corrosion
inhibitor, a dispersant
viscosity modifier, a friction modifier, a viscosity modifier (typically a
polymethacrylate having
linear, comb or star architecture), an antioxidant (including phenolic and
aminic antioxidants), an
overbased detergent (including overbased sulphonates, phenates, and
salicylates other than the
polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof or
salt thereof described
above), or mixtures thereof.
[0105] The amount of each other performance additive and chemistry of
the other performance
additive will depend on type of driveline device being lubricated. When
present common additives
across each driveline lubricant includes viscosity modifiers, dispersants,
foam inhibitors, corrosion
inhibitors, pour point depressants, demulsifiers, and seal swell agents.
[0106] Driveline lubricating compositions are described below. All
additives are expressed on
an oil-free basis.
[0107] Manual Transmission Lubricant
[0108] In one embodiment the invention provides a manual transmission
lubricant
composition comprising:
an oil of lubricating viscosity,
a thiadiazole (typically present at 0.05 to 1 wt %, or 0.07 to 0.7 wt %, or
0.1 to 0.3 wt %,
or 0.15 to 0.25 wt %),
a dispersant (typically present at 0.1 to 5 wt %, or 0.3 to 4 wt %, or 1 to 3
wt %, or 0.1 to
3 wt %),
a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus
compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phosphorus
compound,
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from about 0.1 to about 2 wt% of a detergent, typically present in an amount
to deliver 110
to 700ppm, 130 to 600ppm, 150 to 500ppm or 160 to 400ppm calcium; and wherein
from about
0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to
about 1.5 wt% of the
detergent comprises the polyolefin-substituted hydroxy-aromatic carboxylic
acid or salt thereof or
salt thereof described herein.
[0109]
The manual transmission may have synchromesh, or in another embodiment the
manual transmission does not have a synchromesh. The synchromesh may be
composed of
aluminum, steel, bronze, molybdenum, brass (sintered or non-sintered), carbon
in the form of
fibers, graphitic material (optionally in combination with a cellulosic
material), or a cellulosic
material, or a phenolic resin.
[0110]
In one embodiment the lubricant may comprise 0.03 to 1.0 wt %, or 0.1 to
0.6 wt %, or
0.2 to 0.5 wt % of calcium.
[0111]
The lubricant may have 100 to 2000ppm, 150 to 1500ppm, 200 to 1000, or 250
to
800ppm, or 500 to 875 ppm of phosphorus delivered by an antiwear agent i.e.,
delivered by zinc
dialkyl dithiophosphate or another phosphorus-containing antiwear agent.
[0112]
In one embodiment the invention provides a method of lubricating a manual
transmission comprising supplying to the manual transmission a lubricant
composition
comprising:
an oil of lubricating viscosity,
a thiadiazole (typically present at 0.05 to 1 wt %, or 0.07 to 0.7 wt %, or
0.1 to 0.3 wt %,
or 0.15 to 0.25 wt %),
a dispersant (typically present at 0.1 to 5 wt %, or 0.3 to 4 wt %, or 1 to 3
wt %, or 0.1 to
3 wt %),
a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus
compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phosphorus
compound,
from about 0.1 to about 5 wt% of a detergent, typically present in an amount
to deliver 110
to 700ppm, 130 to 600ppm, 150 to 500ppm or 160 to 400ppm calcium; and wherein
from about
0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to
about 1.5 wt% of the
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detergent comprises the polyolefin-substituted hydroxy-aromatic carboxylic
acid or salt thereof
described herein.
[0113]
The thiadiazole compound may include mono- or di-hydrocarbyl substituted
2,5-
dimercapto-1,3,4-thiadiazole compounds. Examples of a thiadiazole include 2,5-
dimercapto-
1,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-substituted 2,5-
dimercapto-1,3,4-
thiadiazole, a hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole,
or oligomers thereof
The oligomers of hydrocarbyl -substituted 2,5-dimercapto-1,3,4-thiadiazole
typically form by
forming a sulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazole units
to form oligomers
of two or more of said thiadiazole units. These thiadiazole compounds may also
be used in the
post treatment of dispersants as mentioned below in the formation of a
dimercaptothiadiazole
derivative of a polyisobutylene succinimide.
[0114]
Examples of a suitable thiadiazole compound include at least one of a
dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole, 3,5-dimercapto-
[1,2,4]-thiadiazole,
3 ,4-dimercapto- [1,2,5]-thiadiazole, or 4-5-dimercapto-[1,2,3]-thiadiazole.
Typically readily
available materials such as 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-
substituted 2,5-
dim ercapto-1,3 ,4-thi adi az ol e or a hydrocarbylthio-sub stituted 2,5-dim
ercapto-1,3 ,4-thiadiazole
are commonly utilised.
[0115]
The other additives used in the manual transmission fluid may be selected
from those
described herein, or known to those skilled in the art, or those hereafter
developed.
Automatic Transmission Lubricants
[0116]
In one embodiment the invention provides an automatic transmission
lubricant
composition comprising:
an oil of lubricating viscosity,
a dispersant typically present at 0.01 to 5 wt %, or 0.05 to 3 wt %, or 0.1 to
3 wt %, or or
0.1 to 2 wt %,
from about 0.1 to about 1, typically present in an amount to deliver 40 to
1000ppm, 50 to
700ppm, 60 to 600ppm or 70 to 250ppm calcium; and wherein from about 0.01 to
about 0.8 wt%,
or from about 0.1 to about 0.5 wt%, or about 0.2 to about 0.15 wt% of the
detergent comprises the
polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof or
salt thereof described
herein, and
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a friction modifier typically present at 0 to 4 wt %, or 0.1 to 4 wt %, 0.2 to
3 wt %, 0.3 to
3 wt %, 0.25 to 2.5 wt%. In one embodiment the friction modifier is present,
and in an alternative
embodiment the friction modifier is not present.
[0117]
In one embodiment the invention provides a method of lubricating an
automatic
transmission comprising supplying to the automatic transmission a lubricant
composition
comprising:
an oil of lubricating viscosity,
a dispersant typically present at 0.5 to 3 wt %, or 1 to 2.5 wt %, or 1.5 to 4
wt %, or 1.5 to
3 wt %,
a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus
compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phosphorus
compound,
a thiadiazole, typically present at 0.1 to 0.5 wt %,or 0.2 to 0.4 wt %, or
0.25 to 0.35 wt
%.
from about 0.1 to about 5 wt% of a detergent, typically present in an amount
to deliver 40
to 700ppm, 50 to 600ppm, 60 to 500ppm or 70 to 250ppm calcium; and wherein
from about 0.01
to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5
wt% of the detergent
comprises the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt
thereof or salt
thereof described herein, and
a friction modifier typically present at 0 to 4 wt %, or 0.1 to 4 wt %, 0.2 to
3 wt %, 0.3 to
3 wt %, 0.25 to 2.5 wt%. In one embodiment the friction modifier is present,
and in an alternative
embodiment the friction modifier is not present.
[0118]
The automatic transmission includes continuously variable transmissions
(CVT),
infinitely variable transmissions (IVT), Toroidal transmissions, continuously
slipping torque
converted clutches (CSTCC), stepped automatic transmissions or dual clutch
transmissions (DCT).
[0119]
The other additives used in the automatic transmission fluid may be
selected from those
described herein, or known to those skilled in the art, or those hereafter
developed.
[0120]
The automatic transmission lubricant composition described herein may
contain a
calcium-containing detergent, other than the polyolefin-substituted hydroxy-
aromatic carboxylic
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acid of the present invention. The optional additional detergent may be an
overbased detergent, a
non-overbased detergent, or mixtures thereof. Typically the detergent may be
overbased.
Off-Highway Vehicle
[0121]
The polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof
or salt
thereof described herein can be employed in lubricating compositions for off-
highway vehicles,
such as, for example, farm tractors and construction vehicles. Such vehicles
often have a common
sump that lubricates not only the transmission but also the gears, axles, and
hydraulics in the
vehicle. In one embodiment the invention includes a lubricant composition
comprising:
an oil of lubricating viscosity,
a dispersant typically present at 0.1 to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to
2 wt %,
from about 0.1 to about 5 wt% of a detergent, typically present in an amount
to deliver 100
to 5000ppm, 500 to 4500ppm, 500 to 4250ppm, 650 to 4200ppm calcium; and
wherein from about
0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to
about 1.5 wt% of the
detergent comprises the polyolefin-substituted hydroxy-aromatic carboxylic
acid or salt thereof or
salt thereof described herein.
[0122]
In one embodiment the invention includes a method of lubricating an off-
highway
vehicle comprising supplying to the vehicle a lubricant composition
comprising:
an oil of lubricating viscosity,
a dispersant typically present at 0.1 to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to
2 wt %,
a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus
compound, which may be a hydrocarbyl phosphite, such as a zinc
dialkyldithiophosphate; or (ii)
an amine salt of a phosphorus compound,
from about 0.1 to about 5 wt% of a detergent, typically present in an amount
to deliver 10
to 5000ppm, 500 to 4500ppm, 500 to 4250ppm, 650 to 4200ppm calcium; and
wherein from about
0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to
about 1.5 wt% of the
detergent comprises the polyolefin-substituted hydroxy-aromatic carboxylic
acid or salt thereof or
salt thereof described herein.
[0123]
The off-highway vehicle lubricated typically has a wet-brake, a
transmission, a
hydraulic, a final drive, a power take-off system. These parts are typically
lubricated by a single
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lubricant supplied from a common sump. The transmission may be a manual
transmission or an
automatic transmission.
[0124] The other additives used in the off-highway vehicle may be
selected from those
described herein, or known to those skilled in the art, or those hereafter
developed.
Hydraulics Oil, Turbine Oil or Circulating Oil
[0125] In one embodiment, the lubricating composition in accordance with
the present
invention is for use in a hydraulic system, turbine system or a circulating
oil system. A hydraulic
system is generally a device or apparatus in which a fluid, typically an oil-
based fluid, transmits
energy to different parts of the system by hydraulic force. A turbine
lubricant is typically used to
lubricate the gears or other moving parts of a turbine (or turbine system),
such as a steam turbine
or a gas turbine. A circulating oil is typically used to distribute heat to or
through a device or
apparatus through which it is circulated.
[0126] In one embodiment the lubricant composition contains the
polyolefin-substituted
hydroxy-aromatic carboxylic acid or salt thereof or salt thereof as described
herein in an amount
from 0.001 wt % or 0.005 wt % to 5 wt %, or 0.01 wt % or 0.05 wt % to 1.5 wt
%, 0.05 wt % to 1
wt %, 0.01 wt % to 1 wt %, 0.01 wt % to 0.5 wt % of the overall composition.
[0127] The hydraulic, turbine, or circulating lubricant compositions may
also contain one or
more additional additives. In some embodiments the additional additives may
include an
antioxidant, an anti-wear agent, a corrosion inhibitor, a rust inhibitor, a
foam inhibitor, a
dispersant, a demulsifier, a metal deactivator, a friction modifier, a
detergent, other than the
polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof or
metal salt thereof of the
present invention, an emulsifier, an extreme pressure agent, a pour point
depressant, a viscosity
modifier, or any combination thereof
[0128] The lubricant may thus comprise an antioxidant, or mixtures
thereof. The anti-oxidant
may be present at 0 wt % to 4.0 wt %, or 0.02 wt % to 3.0 wt %, or 0.03 wt %
to 1.5 wt % of the
lubricant.
[0129] The lubricant compositions may also include a dispersant or
mixtures thereof Suitable
dispersants include: (i) polyetheramines; (ii) borated succinimide
dispersants; (iii) non-borated
succinimide dispersants; (iv) Mannich reaction products of a dialkylamine, an
aldehyde and a
hydrocarbyl substituted phenol; or any combination thereof In some embodiments
the dispersant
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may be present at 0 wt % or 0.01 wt % to 2.0 wt%, 0.05 wt% to 1.5 wt %, or
0.005 wt % to 1 wt
%, or 0.05 wt % to 0.5 wt % of the overall composition.
[0130] Anti-foam agents, also known as foam inhibitors, are known in the
art and include
organic silicones and non-silicon foam inhibitors. Examples of organic
silicones include dimethyl
silicone and polysiloxanes. Examples of non-silicon foam inhibitors include
copolymers of ethyl
acrylate and 2-ethylhexylacrylate, terpolymers of ethyl acrylate, 2-
ethylhexylacrylate and vinyl
acetate, polyethers, polyacrylates and mixtures thereof. In some embodiments
the anti-foam is a
polyacrylate. Antifoams may be present in the composition from 0.001 wt % to
0.012 wt % or
0.004 wt % or even 0.001 wt % to 0.003 wt %.
[0131] Demulsifiers are known in the art and include 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 is
a polyether. Demulsifiers may be present in the composition from 0.002 wt % to
0.012 wt %.
[0132] Pour point depressants are known in the art and include esters of
maleic anhydride-
styrene copolymers, polymethacrylates; polyacrylates; polyacrylamides;
condensation products of
haloparaffin 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.
[0133] The lubricant composition may also include a rust inhibitor.
Suitable rust inhibitors
include hydrocarbyl amine salts of alkylphosphoric acid, hydrocarbyl amine
salts of
dialkyldithiophosphoric acid, hydrocarbyl amine salts of hydrocarbyl aryl
sulfonic acid fatty
carboxylic acids or esters thereof, an ester of a nitrogen-containing
carboxylic acid, an ammonium
sulfonate, an imidazoline, alkylated succinic acid derivatives reacted with
alcohols or ethers, or
any combination thereof; or mixtures thereof.
[0134] The rust inhibitors may be present in the range from 0 or 0.02 wt
% to 0.2 wt %, from
0.03 wt % to 0.15 wt %, from 0.04 wt % to 0.12 wt %, or from 0.05 wt % to 0.1
wt % of the
lubricating oil composition. The rust inhibitors may be used alone or in
mixtures thereof
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[0135] The lubricant may contain a metal deactivator, or mixtures
thereof. Metal deactivators
may be chosen from a derivative of benzotriazole (typically tolyltriazole),
1,2,4-triazole,
benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole, 1-
amino-2-propanol, a
derivative of dimercaptothiadiazole, octylamine octanoate, condensation
products of dodecenyl
succinic acid or anhydride and/or a fatty acid such as oleic acid with a
polyamine. The metal
deactivators may also be described as corrosion inhibitors.
[0136] The metal deactivators may be present in the range from 0 or
0.001 wt % to 0.1 wt %,
from 0.01 wt % to 0.04 wt % or from 0.015 wt % to 0.03 wt % of the lubricating
oil composition.
Metal deactivators may also be present in the composition from 0.002 wt % or
0.004 wt % to 0.02
wt %. The metal deactivator may be used alone or mixtures thereof
[0137] In one embodiment the invention provides a lubricant composition
further comprises a
metal-containing detergent, other than the polyolefin-substituted hydroxy-
aromatic carboxylic
acid or salt thereof as described herein. The additional metal-containing
detergent may be present
at 0 wt % to 5 wt %, or 0.001 wt % to 1.5 wt %, or 0.005 wt % to 1 wt %, or
0.01 wt % to 0.5 wt
% of the hydraulic composition.
[0138] The lubricant may comprise an extreme pressure agent. The extreme
pressure agent
may be a compound containing sulfur and/or phosphorus. Examples of extreme
pressure agents
include polysulfides, sulfurized olefins, thiadiazoles, or mixtures thereof.
[0139] The extreme pressure agent may be present at 0 wt % to 3 wt %,
0.005 wt % to 2 wt %,
0.01 wt % to 1.0 wt % of the hydraulics composition.
[0140] The lubricant may further comprise a viscosity modifier, or
mixtures thereof. Viscosity
modifiers (often referred to as viscosity index improvers) suitable for use in
the invention include
polymeric materials including a styrene-butadiene rubber, an olefin copolymer,
a hydrogenated
styrene-isoprene polymer, a hydrogenated radical isoprene polymer, a
poly(meth)acrylic acid
ester, a polyalkylstyrene, an hydrogenated alkenylaryl conjugated-diene
copolymer, an ester of
maleic anhydride-styrene copolymer or mixtures thereof In some embodiments the
viscosity
modifier is a poly(meth)acrylic acid ester, an olefin copolymer or mixtures
thereof. The viscosity
modifiers may be present at 0 wt % to 10 wt %, 0.5 wt % to 8 wt %, 1 wt % to 6
wt % of the
lubricant.
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[0141] In one embodiment the lubricant disclosed herein may contain at
least one friction
modifier. The friction modifier may be present at 0 wt % to 3 wt %, or 0.02 wt
% to 2 wt %, or
0.05 wt % to 1 wt %, of the lubricant composition.
[0142] In one embodiment the lubricant composition further includes an
anti-wear agent.
Typically the anti-wear agent may be a phosphorus anti-wear agent or mixtures
thereof The anti-
wear agent may be present at 0 wt % to 5 wt %, 0.001 wt % to 2 wt %, 0.01 wt %
to 1.0 wt % of
the lubricant.
[0143] A hydraulic lubricant may thus comprise:
0.01 wt % to 2 wt % of the polyolefin-substituted hydroxy-aromatic carboxylic
acid or
salt thereof or salt thereof as described herein,
0.0001 wt % to 0.15 wt % of a corrosion inhibitor chosen from 2,5-bis(tert-
dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or mixtures thereof,
an oil of lubricating viscosity,
0.02 wt % to 3 wt % of antioxidant chosen from aminic or phenolic
antioxidants, or
mixtures thereof,
0 wt % to 1.5 wt % of a dispersant such as a borated succinimide or a non-
borated
succinimide dispersant or a substantially nitrogen free dispersants as
described herein,
0.001 wt % to 1.5 wt % of a neutral or slightly overbased calcium sulfonate
and
0.001 wt % to 2 wt %, or 0.01 wt % to 1 wt % of an anti-wear agent chosen from
zinc
dialkyldithiophosphate, zinc dialkylphosphate, amine salt of a phosphorus acid
ester, or mixtures
thereof
[0144] A hydraulic lubricant may thus comprise:
0.01 wt % to 1.5 wt % of of the polyolefin-substituted hydroxy-aromatic
carboxylic acid
or salt thereof or salt thereof as described herein,
0.0001 wt % to 0.15 wt % of a corrosion inhibitor chosen from 2,5-bis(tert-
dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or mixtures thereof,
an oil of lubricating viscosity,
0.02 wt % to 3 wt % of antioxidant chosen from aminic or phenolic
antioxidants, or
mixtures thereof,
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0.005 wt % to 1.5 wt % of a dispersant, such as a borated succinimide or a non-
borated
succinimide dispersant or a substantially nitrogen free dispersant as
described herein,
0.001 wt % to 1.5 wt % of a neutral of slightly overbased calcium sulfonate
0.001 wt % to 2 wt %, or 0.01 wt % to 1 wt % of an anti-wear agent chosen from
zinc
dialkyldithiophosphate, zinc dialkylphosphate, amine salt of a phosphorus acid
ester, or mixtures
thereof
[0145] A hydraulic lubricant may also comprise a formulation defined in
the following table:
TABLE 2: Hydraulic Lubricant Compositions
Hydraulic Lubricant compositions
Additive Embodiments (wt %)
A
Polyolefin-substituted hydroxy- 0.01 to 2.0 0.01 to 1.5 0.01 to 1.0
aromatic carboxylic acid or salt
thereof as described herein
Antioxidant 0 to 4.0 0.02 to 3.0 0.03 to 1.5
Dispersant 0 to 2.0 0.005 to 1.5 0.01 to 1.0
Detergent 0 to 5.0 0.001 to 1.5 0.005 to
1.0
Anti-wear Agent 0 to 5.0 0.001 to 2 0.1 to 1.0
Friction Modifier 0 to 3.0 0.02 to 2 0.05 to 1.0
Viscosity Modifier 0 to 10.0 0.5 to 8.0 1.0 to 6.0
Any Other Performance Additive 0 to 1.3 0.00075 to 0.5 0.001 to
0.4
(antifoam / demulsifier/pour point
depressant)
Metal Deactivator 0 to 0.1 0.01 to 0.04 0.015 to
0.03
Rust Inhibitor 0 to 0.2 0.03 to 0.15 0.04 to
0.12
Extreme Pressure Agent 0 to 3.0 0.005 to 2 0.01 to 1.0
Oil of Lubricating Viscosity Balance to Balance to 100 Balance to
100% 100%
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[0146] Specific examples of a hydraulic lubricant include those
summarized in the following
table:
Table 3: Hydraulic Lubricant Compositions
Additive Embodiments (wt %)
A
Polyol efin-sub stituted hydroxy- 0.02 0.06 0.30
aromatic carboxylic acid or salt
thereof as described herein
Antioxidant- aminic /phenolic 0.4 0.4 0.4
Calcium Sulfonate Detergent 0.02 0.1 0.2
Zinc dialkyl dithiophosphate 0.2 0.5 1.0
Any Other Performance Additive 0.2 0.6 1.0
(antifoam /demulsifier/pour point
depressant)
Triazole Metal Deactivator 0.005 0.0075 0.01
Oil of Lubricating Viscosity Balance to Balance to Balance to
100% 100% 100%
[0147] The other additives used in the hydraulic lubricant may be selected
from those
described herein, or known to those skilled in the art, or those hereafter
developed.
EXAMPLES
[0148] A detergent in accordance with the present invention was prepared
as follows:
[0149] A Pm phenol was prepared by reacting a high vinylidene 550 Mn
polyisobutylene with
phenol using BF3 as a catalyst. The P113 phenol was then reacted with KOH to
give potassium
phenate, which was then heated to 150 C and vacuum stripped (25 mmHg/5 h) to
remove water
and the mixture was then exposed to CO2 for 5 hrs. The final material was
found to have a ratio
of pib salicylate to pib phenol of 66% to 34% (determined by 13C NMR), %K =
3.31%, TBN =
56.41, 50% actives in dil oil. The potassium phenate/salicylate was then
converted to an overbased
calcium salicylate by treatment with 90 g CaCl2 in MAOL (360 g) at 60 C for 1
h. Hydrated lime
(55 g), acetic acid (50% aq. solution) and a mixture and isobutyl and amyl
alcohol (100 g) were
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added and CO2 was bubbled through the mixture at 60 C for 40 minutes (0.6
cfh) to a DBN of
11. Volatile solvents were removed by vacuum distillation (150 C, 25 mmHg, 30
minutes). The
reaction mixture was then filtered and clear brown liquid was obtained.The
final product was found
to have 115 TBN by NN 29C, %K = 4.71 by D4951, SA = 15.665% by D874
[0150] The Total Base Number (TBN) may be determined using the methodology
of ASTM
D2896.
[0151] Lubricating compositions incorporating the polyolefin-substituted
hydroxy-aromatic
carboxylic acid of the present invention may be prepared as described herein
and evaluated for
cleanliness, i.e. the ability to prevent or reduce deposit formation; sludge
handling; soot handling;
antioxidancy; and wear reduction, anti-wear performance, deposit control, and
oxidation control,
among others.
[0152] Sludge handling performance of each lubricant may be evaluated in
accordance with
ASTM D4310-10 (Standard Test Method for Determination of Sludging and
Corrosion Tendencies
of Inhibited Mineral Oils). Performance is judged by measuring the total
amount of sludge formed
during the oxidation of lubricants and mineral oil based fluids in the
presence of oxygen, water
and copper and iron metals at elevated temperatures as well as the ability of
these oils to corrode
copper catalyst metals.
[0153] Anti-wear performance is measured in a programmed temperature
high frequency
reciprocating rig (HFRR) available from PCS Instruments. HFRR conditions for
the evaluations
are 200 g load, 75 minute duration, 1000 micrometer stroke, 20 hertz
frequency, and temperature
profile of 15 minutes at 40 C followed by an increase in temperature to 160
C at a rate of 2 C
per minute. Wear scar in micrometers and film formation as percent film
thickness are then
measured with lower wear scar values and higher film formation values
indicating improved wear
performance.
[0154] Deposit control is measured by the Komatsu Hot Tube (KHT) test,
which employs
heated glass tubes through which sample lubricant is pumped, approximately 5
mL total sample,
typically at 0.31 mL/hour for an extended period of time, such as 16 hours,
with an air flow of
10 mL/minute. The glass tube is rated at the end of test for deposits on a
scale of 0 (very heavy
varnish) to 10 (no varnish).
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[0155] In the Panel Coker deposit test, the sample, at 105 C., is
splashed for 4 hours on an
aluminum panel maintained at 325 C. The aluminum plates are analyzed using
image analysis
techniques to obtain a universal rating. The rating score is based on "100"
being a clean plate and
"0" being a plate wholly covered in deposit.
[0156] Oxidation control is evaluated utilizing pressure differential
scanning calorimtery
(PDSC) which determines oxidation induction time (OTT) for lubricating
compositions. This is a
standard test procedure in the lubricating oil industry, based on CEC L-85 T-
99. In this testing the
lubricating composition is heated to an elevated temperature, typically about
25 C below the
average decomposition temperature for the sample being tested (in this case
215 C at 690 kPa),
and the time to when the composition begins to decompose is measured. The
longer the test time,
reported in minutes, the better the oxidative stability of the composition and
the additives present
within it.
[0157] Driveline lubricating compositions, such as transmission fluids
may be assessed for
friction performance and durablility using tests such as the variable speed
friction test, friction
coefficient testing based on Falex LFW-1 or JASO M358, VT20 Durability test,
JASO M349 anti-
shudder durability test, or testing using an Automax rig.
[0158] 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 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.
[0159] 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, by-products, derivatives, and other
such materials which
are normally understood to be present in the commercial grade. However, the
amount of each
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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.
[0160] 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.
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