Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
TOXICOLOGICALLY ACCEPTABLE ALKYLPHENOL DETERGENTS AS
FRICTION MODIFIERS IN AUTOMOTIVE LUBRICATING OILS
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to the use of toxicologically
acceptable
hydrocarbyl- (e.g. alkyl-) phenol detergents and their salts in automotive
lubricating
oils, such as, for example, automatic or manual transmissions.
[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 typi-
cally substituted with an aliphatic hydrocarbyl group to provide a measure of
oil sol-
ubility. The hydrocarbyl groups may be alkyl groups, and, historically,
dodecylphe-
nol (or propylene tetramer-substituted phenol) has been widely used. An early
refer-
ence to basic sulfurized polyvalent metal phenates is U.S. Patent 2,680,096,
Walker
et al., June 1, 1954; see also U.S. Patent 3,372,116, Meinhardt, March 5,
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 tetramer (or
tetrap-
ropenyl), 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
to 15 carbon atoms. Nevertheless, it is desirable that the products should
have
similar oil-solubility parameters as phenates prepared from C10-15 propylene
oligo-
mers.
[0004] There have been several efforts to prepare phenate detergents that
do not
contain Cn alkyl phenols derived from oligomers of propylene. U.S. Patent
7,435,709, Stonebraker et al., October 14, 2008, discloses a linear
alkylphenol de-
rived 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
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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.
[0005] U.S. Application 2011/0190185, 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 2011/0124539, Sinquin et al, May 26, 2011,
discloses an
overbased, sulfurized salt of an alkylated hydroxyaromatic compound. The alkyl
sub-
stituent 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
mix-
tures 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 hy-
droxyaromatic compound with at least one branched olefinic propylene oligomer
hav-
ing 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,
dis-
closes 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,
dis-
closes an alkylated hydroxyaromatic compound substantially free of endocrine
dis-
ruptive chemicals, prepared by reacting a hydroxyaromatic compound with a
branched olefinic oligomer having from about 20 to about 80 carbon atoms.
WO/PCT application 2013/059173, Cook et al., discloses an overbased salt of an
ol-
igomerized alkylhydroxyaromatic compound. The alkyl group is a combination of
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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
mix-
ture of para-cresol and polyisobutylene-substituted phenol.
Other general technology includes that of U.S. Patent 6,310,009, Carrick et
al., Oc-
tober 30, 2001, which discloses salts of the general structure
om Om
X Y
cDcD ........................................... X
R
[0010] where R may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18
carbon
atoms. It is understood that It' 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 It' groups (number average).
[0011] There is also co-pending application PCT/U52015/031939 to Walker et
al.
which discloses an alternative alkyl phenol for use as a detergent in internal
combus-
tion engines.
[0012] None of the art teaches the use of an alternative alkyl phenol in
driveline
devices.
SUMMARY OF THE INVENTION
[0013] The disclosed technology, therefore, solves the problem of providing
a tox-
icologically acceptable alkylphenol detergent in a driveline device by
supplying to the
device an alkyl phenol as described herein.
[0014] One aspect of the disclosed technology is directed to a transmission
lubri-
cant composition. In an embodiment, the transmission lubricant can include an
oil of
lubricating viscosity, from about 0.1 to about 5 wt% of a dispersant, and from
about
0.1 to about 5 wt% of a detergent. The detergent in the transmission lubricant
can
include from about 0.01 to about 2 wt% of an alkylphenol detergent that has at
least
one unit of an alkyl-substituted phenol wherein the alkyl group is derived
from oli-
gomers of an olefin compound containing 3 to 8 carbon atoms, wherein the
olefin-
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derived alkyl group comprises at least 30 mol percent of an olefin with 4 or
more
carbon atoms.
[0015] In an embodiment, the alkylphenol detergent can be a sulfur-bridged
phen-
ate, a sulfur-free alkylene-bridged phenate, a salicylate, or mixtures
thereof.
[0016] In another embodiment, alkylphenol detergent can include one or more
alkali metals, one or more alkaline earth metals, or mixtures thereof.
[0017] In a further embodiment, the alkylphenol detergent can be overbased,
and
in an even further embodiment the overbased alkylphenol detergent can have a
metal
ratio of at least 1.5, at least 5, or at least 7.
[0018] In an embodiment, the alkyl group of the alkylphenol detergent can
include
oligomers of n-butene, where the alkyl group can be a hydrocarbyl group of 12
to 48
carbon atoms.
[0019] In some embodiments, the alkylphenol detergent can be an overbased
sul-
fur-coupled alkylphenol detergent with a metal ratio of at least 1.5.
[0020] In further embodiments, the alkylphenol detergent can include a
sulfur-
bridged phenate represented by the structure
OH OH OH
11111
(I)
wherein each R can be an aliphatic hydrocarbyl group derived from oligomers of
n-bu-
tene, higher alphaolefins, or mixtures thereof, that contains 8 to 48 carbon
atoms; and n =
0 to 8, or 1 to 6, or 1 to 4, or 2 to 4.
[0021] In embodiments, the alkylphenol detergent can be a neutral or
overbased
salt of alkylsalicylic acid. In some instances, the alkylphenol detergent can
be an
alkyl salicylate represented by the structure
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OH 0
1401 OH
where R can be an aliphatic hydrocarbyl group derived from oligomers of n-
butene, higher
alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group contains
8 to 48 car-
bon atoms.
[0022] In an embodiment, the oil of lubricating viscosity in the lubricant
can in-
clude comprises at least one API Group I, II, III ,IV, or V, lubricant or
mixtures thereof.
[0023] In some embodiments, the lubricant can additionally include at least
one of
a phosphorus-containing antiwear agent comprising a non-ionic phosphorus com-
pound; an amine salt of a phosphorus compound; a calcium-containing detergent;
an-
other friction modifier; a sulphur-containing extreme pressure agent; a
sulphur-con-
taining corrosion inhibitor; or combinations thereof. In further embodiments,
the lubri-
cant can further include from about 0.05 to about 3 wt% of a C2-C18 di- or tri-
hydro-
carbyl phosphite, based on the total weight of said lubricant. In still
further embodi-
ments, the lubricant can include less than 2000 ppm zinc based on the total
weight of
said lubricant. In some embodiments, the lubricant can be substantially free
of, to free
of, a phenol alkylated with oligomers of propylene.
[0024] In another aspect of the technology, there is provided a method of
lubricat-
ing a manual transmission by supplying the lubricant composition described
herein to
said manual transmission. In some embodiments, the lubricant composition can
in-
clude the oil of lubricating viscosity; a thiadiazole; a phosphorous
containing antiwear
agent; the dispersant; the detergent; and the alkylphenol detergent.
[0025] In another aspect of the technology, there is provided a method of
lubricating
an automatic transmission by supplying the lubricant composition described
herein to said
automatic transmission. In some embodiments, the lubricant composition can
include
the oil of lubricating viscosity; a thiadiazole; a phosphorous containing
antiwear agent;
the dispersant; the detergent; and the alkylphenol detergent.
[0026] In another aspect of the technology, there is provided a method of
lubricating
an off-highway vehicle by supplying the lubricant composition described herein
to said
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off-highway vehicle. In some embodiments, the lubricant composition can
include the
oil of lubricating viscosity; a zinc dialkyl dithiophosphate antiwear agent;
the dispersant;
the detergent and the alkylphenol detergent. In an embodiment, the off-highway
vehicle
can be a farm-tractor vehicle or a construction vehicle.
[0027] In another aspect of the technology, there is provided a method of
lubricating
a highway vehicle by supplying the lubricant composition described herein to
said high-
way vehicle. In some embodiments, the lubricant composition can include the
oil of
lubricating viscosity; the dispersant; the detergent (including the
alkylphenol detergent); a
sulfurized olefin; a thiadiazole; and a phosphorous containing antiwear agent.
DETAILED DESCRIPTION OF THE INVENTION
[0028] Various preferred features and embodiments will be described below
by way
of non-limiting illustration. When used herein, the shorthand "wt%" refers to
the
weight percent of the material referred to based on a total weight of the
composition
within which the material is included.
[0029] The disclosed technology provides a lubricating composition for
automo-
tive gears, such as transmissions, including an alkylphenol detergent, as well
as meth-
ods for lubricating automotive gears and a use as disclosed herein.
[0030] One of the materials of the presently disclosed technology may be a
bridged alkylphenol compound. Such materials in general, their methods of
prepara-
tion, and use in lubricants are well known from, for instance, the above-
referenced
U.S. Patent 2,680,096, Walker et al. They may be prepared starting from alkyl
phenol
such as alkylphenols derived from oligomers of n-butene, or mixtures thereof,
any of
which are readily available as starting materials. The alkylation of phenol
and its
homologues is well known, typically by catalyzed reaction of an olefin, often
an
a-olefm, with phenol (or with salicylic acid or another homologue, as the case
may
be). Alkylation of phenol is described in greater detail in the Kirk-Othmer
Encyclo-
pedia of Chemical Technology, third edition (1978) vol. 2, pages 82-86, John
Wiley
and Sons, New York.
[0031] Linking of alkyl (or more generally, hydrocarbyl) phenols to form
oligo-
meric species, is also well known. They may be condensed, for instance, with
for-
maldehyde or with other aldehydes or ketones such as acetone to form methylene
(or
alkylene) bridged structures, as described on pages 76-77 of the above cited
Kirk-
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Othmer reference. If condensation with an aldehyde or ketone is intended, it
is desir-
able that the aldehyde or ketone not be a C12 species, to avoid the formation
of any
C12 substituted phenolic materials. In certain embodiments the material may be
an
aldehyde of 8 or fewer carbon atoms, such as 1 to 4, or 1 or 2, or a single
carbon atom
(formaldehyde). The length of the resulting oligomeric chain of phenolic and
alkylene
units will depend to some extent on the molar ratio of the reactants, as is
well known.
Thus an equimolar amount of phenol and formaldehyde provides a condensate with
a relatively longer oligomeric chain than that obtained when there is a
stoichiometric
excess of one species or the other. Under certain conditions, carbon- and
oxygen-
containing linkages may also be formed, such as those of the general structure
-CH2-
O-CH2- or homologues in which the hydrogens are replaced by alkyl groups.
These
may be formed by the condensation of more than a single aldehyde or ketone
group.
Such structures are known, for example, from U.S. Patent 6,310,009, see col. 2
lines
14-17 and col. 6 lines 1-45. Thus the linking groups prepared form aldehydes
or ke-
tones may be generally described as "carbon-containing" bridging groups, e.g.,
an
alkylene bridge or an ether bridge.
[0032] Substituted phenols may also be linked together to make sulfur
bridged
species, which may include bridges of single sulfur atoms ( -S-) or multiple
sulfur
atoms (e.g., -Sr- where x may be 2 to 8, typically 2 or 3). Sulfurized phenols
may be
prepared by reaction with active sulfur species such as sulfur monochloride or
sulfur
dichloride as described on pages 79-80 of the Kirk-Othmer reference or with
ele-
mental sulfur, as described, for instance, in US 2,680,096. Sulfurization
(with sulfur)
may be conducted in the presence of a basic metal compound such as calcium hy-
droxide or calcium oxide, thus preparing a metal salt, as described in greater
detail,
below. Basic sulfurized phenates and a method for their preparation are also
disclosed
in U.S. Patent 3,410,798, Cohen, November 12, 1968. The examples and claim 1
thereof disclose a method, comprising reacting at a temperature above about
150 C,
(A) a phenol, (B) sulfur, and (C) an alkaline earth base, in the presence of a
promoter
comprising (D) about 5-20 mole percent, based on the amount of component A, of
a
carboxylic acid or alkali metal, alkaline earth metal, zinc, or lead salt
thereof and
(E) as a solvent, a compound of the formula R(OR').0H, e.g., a polyalkylene
glycol.
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The phenol (A), in turn, may be a hydrocarbyl-substituted phenol which may be
pre-
pared by mixing a hydrocarbon and a phenol at a temperature of about 50-200 C
in
the presence of a suitable catalyst such as aluminum trichloride (col. 2 line
51 of
US 3,410,798, and following text).
Alkylphenol
[0033] In the present technology, the alkyl group is derived from a
polyolefin
compound comprising n-butene (also referred to as 1-butene) monomers, higher
al-
pha-olefins, or mixtures thereof. In addition to n-butene, suitable alpha-
olefins in-
clude isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-
decene,
and mixtures thereof. In one embodiment, the alkyl group of the alkylphenol is
a
polyolefin compound comprising at least 25 mol % 1-butene, at least 50 mol % 1-
bu-
tene, or at least 75 mol % 1-butene. In one embodiment, the alkyl group of the
al-
kylphenol consists of oligomers or polymers of 1-butene.
[0034] Suitable polyolefins include oligomers or polymers of n-butene. A
butene
polymer or oligomer containing 8 to 48 carbon atoms would contain 2 to 12
butene
monomer units. An n-butene polymer or oligomer containing 12 to 32 carbon
atoms
would contain 3 or 8 n-butene monomer units. Further details of alkylation are
dis-
closed in the above-cited Kirk-Othmer reference.
[0035] The alkylphenol from which the detergent may be derived may be
charac-
terized as a phenol substituted with one or more alkyl groups derived from a
polyole-
fin or oligomerized olefin as described above. The alkylphenol may contain one
or
more alkyl groups derived from an oligomer (or polymer) of n-butene. In one
embod-
iment, the alkylphenol may be C8 to C48 alkylphenol, a C12 to C32 alkylphenol,
a C16
to C24 alkylphenol, or mixtures thereof, wherein the alkyl groups are
oligomers of
n-butene.
Bridged Phenol Detergents
[0036] In certain embodiments, the alkylphenol-containing detergent may be
a
sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenate
detergent,
or mixtures thereof. Detergents of this type are ionic (usually metal) salts
of bridged
phenolic compounds. The bridged phenolic compound material may be represented
by the structure
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OH OH OH
Sy 10 Sy 10
(I)
or more generally
OH OH OH
X X
( )
?7
or isomers thereof, wherein each y may be, in the case of formula I, 1 but
more generally
from 1 to 4, especially 1 or 2, and each R may be an aliphatic hydrocarbyl
group derived
from oligomers of n-butene, higher alphaolefins, or mixtures thereof, and
wherein the hy-
drocarbyl group contains 8 to 48 carbon atoms. The average number of carbon
atoms in
all the R groups, combined, may be 16 to 320 (or 20 to 220, or 24 to 120). The
average
number of carbon atoms in all R groups, combined, may also be from about 16 to
about
100 (or 20 to 50, or 24 to 36, or 14 to 20 or 18 to 36). Where the bridging
group may be
listed as "X", each X may be, independently, a carbon-containing bridge, or an
alkylene
group, or a methylene group, or a bridge of 1 or more sulfur atoms represented
by Sy,
where y may be 1 to 4, especially 1 or 2. In these structures, n may, in
certain embodiments,
be 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4. That is, the bridged material may,
in these embod-
iments, contain 2 to 10 bridged phenolic groups, or 3 to 7, or 3 to 5, or 4
such groups.
Since n may be zero, it may be evident that throughout this specification, the
expression
"oligomeric" may be interpreted to include dimeric species. Accordingly,
sometimes the
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expression "dimeric or oligomeric" may be used to express this concept, which
may in-
clude, as above, as an example, 0 to 8 interior units bracketed by [ ]. or 2
to 10 units
overall. In certain embodiments, in the above structure, one or two of the R
groups are
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms and
the re-
mainder of the R groups are methyl groups.
[0037] In one embodiment, the sulfur-bridged alkylphenol-containing
detergent
may be an oligomer of p-(tetrabutenyl)phenol. A sulfur-bridged oligomer of
oligobu-
tenylphenol may be represented by the structure (III)
OH OH OH
(III)
where n = 0 to 4, and m = 0 to 7, or for example, from 1 to 3 or 4.
[0038] In certain embodiments, the alkylene-bridged phenate detergent may
be a
saligenin detergent. A saligenin detergent contains a bridged-alkyl phenol
compound
that may be an alkylene coupled alkylphenol represented by the structure
(IV)
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OH OH
X
(IV)
where each R may be an aliphatic hydrocarbyl group derived from oligomers of n-
bu-
tene, higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl
group
contains 8 to 48 carbon atoms; where the each bridging group (X) may be inde-
pendently a carbon-containing bridge, or a hydrocarbylether linkage (such as
¨CH2-
0-CH2-), or an alkylene group, or a methylene group; each Y may be
independently
-CHO or -CH2OH; wherein the -CHO groups comprise at least about 10 mole
percent
of the X and Y groups; and n may be an integer from 1 to 10.
[0039] In certain embodiments, the alkylene-bridged phenate detergent may
be a
salixarate detergent. A salixarate detergent contains a bridged-alkyl phenol
com-
pound that may be an alkylene coupled alkylphenol that may be further bridged
or
coupled to salicylic acid. The bridged phenol of a salixarate may be
represented by
the structure (V)
OH 0
00
X
OH OH
(V)
where R may be an aliphatic hydrocarbyl group derived from oligomers of n-
butene,
higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group
contains 8 to
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48 carbon atoms; where the each bridging group (X) may be independently a
carbon-con-
taining bridge, or an alkylene group, or a methylene group; and n may be an
integer from
1 to 10
[0040] The bridged alkylphenol detergents may be neutral or overbased or
super-
based. Such overbased detergents are generally single phase, homogeneous Newto-
nian systems characterized by a metal and/or ammonium content in excess of
that
which would be present for neutralization according to the stoichiometry of
the metal
or ammonium and the particular acidic organic compound reacted with the metal
or
ammonium compound. The overbased materials are typically prepared by reacting
an
acidic material (typically an inorganic acid or lower carboxylic acid such as
carbon
dioxide) with a mixture of bridged alkylphenol compounds (referred to as a sub-
strate), a stoichiometric excess of a metal base, typically in a reaction
medium of an
one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for
the acidic
organic substrate. Typically also a small amount of promoter such as a phenol
or
alcohol is present, and in some cases a small amount of water. The acidic
organic
substrate will normally have a sufficient number of carbon atoms to provide a
degree
of solubility in oil.
[0041] In certain embodiments, the overbased bridged-phenol detergent may
be a
metal-containing detergent, an amine or ammonium containing detergent, or
mixtures
thereof. In one embodiment the overbased metal-containing detergent may be
zinc,
sodium, calcium or magnesium salts of a phenate, sulfur containing phenate,
salixa-
rate or saligenin. In one embodiment, the overbased detergent comprises a salt
of an
alkylamine or quaternary ammonium compound. Overbased salixarates, phenates
and
saligenins typically have a total base number (TBN) (by ASTM D2896) of 50 to
600 mg KOH/g, or for example, 70 or 115 to 500 mg KOH/g.
Salicylates
[0042] In certain embodiments, the alkylphenol-containing detergent may be
an
alkylsalicylate or salicylate detergent. A salicylate detergent may be a
neutral or over-
based metal salt of alkylsalicylic acid. Alkyl salicylic acid may be
represented by the
formula (VI)
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OH 0
=OH
(VI)
where R may be an aliphatic hydrocarbyl group derived from oligomers of n-
butene,
higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group
contains
8 to 48 carbon atoms.
[0043] The alkylsalicylate may be a neutral or nearly neutral salt of
alkylsalicylic
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 alkylsalicylic acid may be an amine or
ammo-
nium salt, a metal salt, or mixtures thereof.
[0044] Amines suitable for use in the preparation of the neutral amine
salted al-
kylsalicylate are not overly limited and may include any alkyl amine, though
gener-
ally 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, octadecyl amine,
cetyla-
mine, oleylamine, decylamine, dodecylamine, dimethyldodecylamine,
tridecylamine,
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
pri-
mary amine to an alkyl diester of itaconic acid represented by the formula
oR2
NHR3
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where le and R2 are hydrocarbyl groups containing 2 to 30 carbon atoms, and R3
is a
hydrocarbyl group containing 4 to 50 carbon atoms. In some embodiments, R3 of
the ami-
noester 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.
[0045] In certain embodiments, the neutral salt of the 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
charac-
terized as falling into two large groups, four coordinate
tetrahydrocarbylammonium
compounds, for example tetrabutylammonium, and three coordinate aromatic com-
pounds, for example N-hydrocarbylpyridinium.
[0046] In some embodiments the quaternary nitrogen salt may comprise the
reac-
tion 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.
[0047] The alkylphenol-containing detergents, be they phenates, saligenins,
sa-
lixrates, or salicylates, may be metal-containing detergents. Metal-containing
deter-
gents 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" is the ratio of the
total equiv-
alents 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
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"metal ratio" is also explained in standard textbook entitled "Chemistry and
Tech-
nology of Lubricants", Third Edition, Edited by R. M. Mortier and S. T.
Orszulik,
Copyright 2010, page 219, sub-heading 7.25.
[0048] In one embodiment the overbased metal-containing alkylphenol
detergent
may be calcium or magnesium overbased detergent. In one embodiment, the over-
based 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.
[0049] Alternatively, the alkylphenol detergent may be described as having
TBN.
Overbased phenates and 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
de-
fined as the amount necessary to deliver an amount, or range of amounts, of
TBN to
the lubricant composition. In certain embodiments, the alkylphenol-containing
deter-
gent 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.
[0050] Overbased detergents may also be defined as the ratio of the neutral
deter-
gent 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
1:4.1, or
1.3:1 to 1:3.4.
[0051] The product of the disclosed technology may beneficially be used as
an
additive in a lubricant. The amount of the alkylphenol detergent in a
transmission
lubricant may be 0.01 to 2 percent by weight, on an oil-free basis, but
including the
calcium carbonate and other salts present in an overbased composition, or from
about
0.1 to about 1.75 wt%, or about 0.2 to about 1.5.
[0052] A lubricant composition may contain alkylphenol-containing
detergents
different from that of the disclosed technology in an amount of from about 0.1
to 1.5
weight percent, or 0.2 to 1.25, or 0.3 to 1 weight percent, and is free of or
substan-
tially free of an alkylphenol-containing detergent derived from alkylphenol
which is
derived from oligomers of propylene, especially tetrapropenyl. "Substantially
free
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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
[0053] The lubricating composition comprises an oil of lubricating
viscosity.
Such oils include natural and synthetic oils, oil derived from hydrocracking,
hydro-
genation, 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 may be
hydroisom-
erized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be
pre-
pared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other
gas-to-
liquid oils.
[0054] 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).
[0055] In one embodiment the oil of lubricating viscosity may be an API
Group I
to 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.
Group II+ refers to Group II base oils, to a generally recognized (but not
officially
identified by the API) as having a Viscosity Index of 110-119 and lower
volatility
than other Group II oils. Additionally, the oil of lubricating viscosity may
be a Group
III+ base oil, a term which refers to a Group III base oil having a Viscosity
Index
greater than or equal to 130. Group III+ base oils are generally known in the
art and
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17
are described in an article published in Tube Report' (see "SK Sees Group III
Short-
fall", by Nancy DeMarco. The
article may be obtained from
ittt :t/www.aseubeconu/inedia/i) 191 Olsk sees (i.ou ) iii shortfall. =df
[0056] The
amount of the oil of lubricating viscosity present is typically the bal-
ance remaining after subtracting from 100 weight % the sum of the amount of
the
additives of the disclosed technology and the other performance additives.
[0057] 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.
Other Performance Additives
[0058] A
lubricant composition may be prepared by adding the alkylphenol detergent
described herein above to an oil of lubricating viscosity, optionally in the
presence of other
performance additives (as described herein below).
[0059] The
lubricant composition may further include other additives. In one em-
bodiment the invention provides a lubricant composition further comprising at
least
one of a dispersant, an antiwear agent, a dispersant viscosity modifier, a
friction mod-
ifier, a viscosity modifier, an antioxidant, an overbased detergent (other
than the al-
kylphenol detergent described above), a foam inhibitor, a demulsifier, a pour
point
depressant or mixtures thereof. In one embodiment the invention provides a
lubricant
composition further comprising at least one of a polyisobutylene succinimide
disper-
sant, an antiwear agent, a corrosion inhibitor, a dispersant viscosity
modifier, a fric-
tion 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 alkylphenol detergent described above), or mixtures thereof.
[0060] The
amount of each other performance additive and chemistry of the other
performance additive will depend on type of driveline device being lubricated.
When
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present common additives across each driveline lubricant includes viscosity
modifi-
ers, dispersants, foam inhibitors, corrosion inhibitors, pour point
depressants, demul-
sifiers, and seal swell agents.
[0061] Viscosity modifiers may be included in the lubricant composition.
Viscos-
ity modifiers are usually polymers, including polyisobutenes, polymethacrylic
acid es-
ters, diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride
copoly-
mers, alkenylarene-conjugated diene copolymers, and polyolefins.
Multifunctional
viscosity improvers, which also have dispersant and/or antioxidancy properties
are
known and may optionally be used. The amount of viscosity modifier may range
from
0.1 to 70 wt %, or 1 to 50 wt %, or 2 to 40 wt %. Typically the viscosity
modifier may
be a polymethacrylate, or mixtures thereof.
[0062] The lubricant may comprise a dispersant, which may be a nitrogen-
contain-
ing dispersants, for example a hydrocarbyl substituted nitrogen containing
additive.
Suitable hydrocarbyl substituted nitrogen containing additives include ashless
dis-
persants 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 succin-
imide dispersants, Mannich dispersants.
[0063] The dispersant may be post-treated with other reagents, or not post-
treated.
The dispersant may be post-treated with urea, thiourea,
dimercaptothiadiazoles, car-
bon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted
suc-
cinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus
compounds.
Typically a succinimide dispersant may optionally be post-treated by
conventional
methods by a reaction with any of a variety of other agents.
[0064] The polyamine may be an alkylenepolyamine. The alkylenepolyamine
may include an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine,
or
mixtures thereof. Examples of propylenepolyamine include propylenediamine, di-
propylenetriamine and mixtures thereof.
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19
[0065] In one embodiment the polyamine is chosen from ethylenediamine,
dieth-
yl enetri amine, tri ethyl enetetramine, tetraethyl enepentamine, pentaethyl
enehexa-
mine, polyamine still bottoms and mixtures thereof.
[0066] In another embodiment, the lubricating composition may have an
antiwear
additive comprising a phosphate amine salt. The C2-C18 (or C2 to C8 or C16-
C18) di-
or tri-hydrocarbyl phosphite, or mixtures thereof may be represented by the
formula:
R7
R6-0 H Co
J) Re
P\
Fe¨CV
or R6 _O
wherein at least one of R6, R7 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 em-
bodiment R6, R7 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, R7 and le are all hydrocarbyl groups and in some embodiments may be
alkyl
groups. Typically the di- or tri-hydrocarbyl phosphite comprises dibutyl
phosphite or
oleyl phosphite.
[0067] Foam inhibitors that may be useful in the compositions include
polysilox-
anes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally
vinyl ace-
tate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates,
polyeth-
ylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-
propyl-
ene oxide) polymers.
[0068] Pour point depressants that may be useful in the compositions
include
polyalphaolefins, esters of maleic anhydride-styrene copolymers,
poly(meth)acry-
lates, polyacrylates or polyacrylamides.
[0069] Demulsifiers include trialkyl phosphates, and various polymers and
copol-
ymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof.
[0070] Seal swell agents include sulpholene derivatives Exxon Necton37TM
(FN
1380) and Exxon Mineral Seal Oi1TM (FN 3200).
Manual Transmission Lubricant
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[0071] In one embodiment the invention provides a lubricant composition
compris-
ing:
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 phospho-
rus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phos-
phorus compound,
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 alkylphenol detergent
de-
scribed herein.
[0072] The manual transmission may have synchromesh, or in another embodi-
ment the manual transmission does not have a synchromesh. The synchromesh may
be composed of aluminum, steel, bronze, molybdenum, brass (sintered or non-sin-
tered), carbon in the form of fibers, graphitic material (optionally in
combination with
a cellulosic material), or a cellulosic material, or a phenolic resin.
[0073] 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.
[0074] The detergent may be calcium or magnesium based, and the detergent
may
have at least 200 TBN, or 250 to 1000, or 450 to 900 or 650 to 800 mg KOH/g on
an
oil free basis. Typically the detergent is a calcium based detergent.
[0075] 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.
[0076] In one embodiment the invention provides a method of lubricating a
man-
ual transmission comprising supplying to the manual transmission a lubricant
com-
position comprising:
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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 phospho-
rus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phos-
phorus 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 detergent comprises alkylphenol detergent
de-
scribed herein.
[0077] The thiadiazole compound may include mono- or di-hydrocarbyl substi-
tuted 2,5-dimercapto-1,3,4-thiadiazole compounds. Examples of a thiadiazole in-
clude 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-
substi-
tuted 2,5-dimercapto-1,3,4-thiadiazole, a hydrocarbylthio-substituted 2,5-
dimer-
capto-1,3,4-thiadiazole, or oligomers thereof. The oligomers of hydrocarbyl-
substi-
tuted 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
dimercapto-
thiadiazole derivative of a polyisobutylene succinimide.
[0078] Examples of a suitable thiadiazole compound include at least one of
a di-
mercaptothiadiazole, 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]-
thiadia-
zole. Typically readily available materials such as 2,5-dimercapto-1,3,4-
thiadiazole
or a hydrocarbyl -substituted 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbylthio-
substituted 2,5-dimercapto-1,3,4-thiadiazole are commonly utilised.
[0079] The lubricant may contain a detergent aside from the aklylphenol
detergent
described above. The detergent may be neutral or overbased, typically
overbased. The
detergent may be calcium or magnesium containing, typically calcium
containing.
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[0080] Another component of the disclosed lubricant can be an overbased,
car-
bonated calcium or magnesium arylsulphonate detergent having a total base
number
(TBN) of at least 640 as calculated on an oil-free basis, or a mixture of such
detergents.
Detergents in general are typically overbased materials, otherwise referred to
as over-
based or superbased salts, which are generally homogeneous Newtonian systems
hav-
ing by a metal content in excess of that which would be present for
neutralization ac-
cording to the stoichiometry of the metal and the detergent anion. The amount
of ex-
cess metal is commonly expressed in terms of metal ratio, that is, the ratio
of the total
equivalents of the metal to the equivalents of the acidic organic compound.
Overbased
materials are prepared by reacting an acidic material (such as carbon dioxide)
with an
acidic organic compound, an inert reaction medium (e.g., mineral oil), a
stoichiometric
excess of a metal base, and a promoter such as a phenol or alcohol. The acidic
organic
material will normally have a sufficient number of carbon atoms, to provide
oil-solu-
bility.
[0081] Overbased detergents may be characterized by Total Base Number
(TBN),
the amount of strong acid needed to neutralize all of the material's basicity,
expressed
as mg KOH per gram of sample. TBN is a very well-known parameter that is
described
in ASTM D 4739. Since overbased detergents are commonly provided in a form
which
contains diluent oil, for the purpose of this document, TBN is to be
recalculated to an
oil-free basis. Various detergents may have a TBN of 100 to 1000, or 150 to
800, or,
400 to 700. The detergents may have a TBN of at least 640, for instance, 650
to 1000,
or even 680 to 800. In each case, the units are mg KOH/g.
[0082] Typically the detergent is an overbased calcium sulphonate
detergent, but
other metals may also be present, whether in a sulphonate detergent (for
example, an
overbased magnesium arylsulphonate detergent) or a different detergent
substrate (for
example, an overbased calcium phenate detergent). The metal compounds
generally
useful in making the basic metal salts are generally any Group 1 or Group 2
metal
compounds (CAS version of the Periodic Table of the Elements). Examples
include
alkali metals such as sodium, potassium, lithium, copper, magnesium, calcium,
barium,
zinc, and cadmium. In one embodiment the metals are sodium, magnesium, or
calcium.
The anionic portion of the salt may be hydroxide, oxide, carbonate, borate, or
nitrate.
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The detergents may be calcium or magnesium detergents, typically prepared
using cal-
cium or magnesium oxide or calcium or magnesium hydroxide. Since the
detergents
of particular interest are carbonated detergents, they will be materials that
have been
treated with carbon dioxide. Such treatment leads to more efficient
incorporation of
basic metal into the composition. Formation of high TBN detergents involving
reac-
tion with carbon dioxide is disclosed, for instance, in US 7,238,651, Kocsis
et al., July
3, 2007, see, for instance, examples 10-13 and the claims. Other detergents,
however,
may also optionally be present, which need not be carbonated or need not be so
highly
overbased (i.e., of lower TBN). However, if multiple detergents are present,
it is de-
sirable that the overbased calcium or magnesium arylsulphonate detergent is
present
as the predominant amount by weight of the metal detergents, that is, at least
50 weight
percent or at least 60 or 70 or 80 or 90 weight percent of the metal-
containing deter-
gents, on an oil free basis.
[0083] The lubricants may contain an overbased sulphonate detergent.
Suitable
sulphonic acids include sulphonic and thiosulphonic acids, including mono- or
poly-
nuclear aromatic or cycloaliphatic compounds. Certain oil-soluble sulphonates
may
be represented by R2-T-(503")a or R3-(503-)b, where a and b are each at least
one; T is
a cyclic nucleus such as benzene or toluene; R2 is an aliphatic group such as
alkyl,
alkenyl, alkoxy, or alkoxyalkyl; (R2)-T typically contains a total of at least
15 carbon
atoms; and R3 is an aliphatic hydrocarbyl group typically containing at least
15 carbon
atoms. The groups T, R2, and R3 may also contain other inorganic or organic
substit-
uents; they may also be described as hydrocarbyl groups. In one embodiment the
sul-
phonate detergent may be a predominantly linear alkylbenzenesulphonate
detergent as
described in paragraphs [0026] to [0037] of US Patent Application 2005-065045.
In
some embodiments the linear alkyl (or hydrocarbyl) group may be attached to
the ben-
zene ring anywhere along the linear chain of the alkyl group, but often in the
2, 3, or 4
position of the linear chain, and in some instances predominantly in the 2
position. In
other embodiments, the alkyl (or hydrocarbyl) group may be branched, that is,
formed
from a branched olefin such as propylene or 1-butene or isobutene. Sulphonate
deter-
gents having a mixture of linear and branched alkyl groups may also be used.
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[0084] In certain embodiments the carbonated calcium or magnesium
arylsulpho-
nate detergent may be based on an alkylated and sulphonated benzene; in
another em-
bodiment, it may be based on an alkylated and sulphonated toluene. In either
case
there may be one or two or three, and in certain embodiments one, alkyl (or
hydro-
carbyl) group attached to the aromatic ring, in addition to the methyl group
if toluene
is used as the starting aromatic compound. In one embodiment, the detergent is
a mon-
oalkylbenzenemonosulphonate, and in another embodiment it is a monoalkyltolu-
enemonosulphonate. If there is one alkyl group, it may contain a sufficient
number of
carbon atoms to impart oil-solubility to the detergent, such as at least 8
carbon atoms,
or 10 to 100 carbon atoms, or 10 to 50 carbon atoms, or 12 to 36 carbon atoms,
or 14
to 24 or 16 to 20 or alternatively about 18 carbon atoms. If more than one
alkyl group
(other than methyl) is present, each alkyl group may have the afore-described
number
of carbon atoms, or all the alkyl groups together may have in total the afore-
described
number of carbon atoms, (e.g., two C12 alkyl groups for a total of 24 carbon
atoms in
the alkyl groups). Another type of overbased material that may additionally be
present
(that is, in addition to the alkylphenol detergent described above) in certain
embodi-
ments of the present invention is an overbased phenate detergent. Certain
commercial
grades of calcium or magnesium sulphonate detergents contain minor amounts of
cal-
cium or magnesium phenate detergents to aid in their processing or for other
reasons
and may contain, for instance, 4% phenate substrate content and 96% sulphonate
sub-
strate content. The phenols useful in making phenate detergents may be
represented
by (R1)a-Ar-(OH)b, where 10 is an aliphatic hydrocarbyl group of 4 to 400 or 6
to 80
or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms; Ar is an aromatic group such as
benzene,
toluene or naphthalene; a and b are each at least one, the sum of a and b
being up to
the number of displaceable hydrogens on the aromatic nucleus of Ar, such as 1
to 4 or
1 to 2. There is typically an average of at least 7 or 8 aliphatic carbon
atoms provided
by the le groups for each phenol compound, and in some instances about 12
carbon
atoms. Phenate detergents are also sometimes provided as sulphur-bridged
species or
as methylene-bridged species. Sulphur-bridged species may be prepared by
reacting a
hydrocarbyl phenol with sulphur. Methylene-bridged species may be prepared by
re-
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acting a hydrocarbyl phenol with formaldehyde (or a reactive equivalent such
as para-
formaldehyde). Examples include sulphur-bridged dodecylphenol (overbased Ca
salt)
and methylene-coupled heptylphenol.
[0085] In another embodiment, an optional, additional overbased material is
an
overbased saligenin detergent. Overbased saligenin detergents are commonly
over-
based magnesium salts which are based on saligenin derivatives. A general
example
of such a saligenin derivative may be represented by the formula:
OM OM
xY ______________________________________________
0 0 X
_ m
Rlp
where X is -CHO or -CH2OH, Y is -CH2- or -CH2OCH2-, and the -CHO groups typi-
cally comprise at least 10 mole percent of the X and Y groups; M is hydrogen,
ammo-
nium, or a valence of a metal ion (that is, if M is multivalent, one of the
valences is
satisfied by the illustrated structure and other valences are satisfied by
other species
such as anions or by another instance of the same structure), Ri is a
hydrocarbyl group
of 1 to 60 carbon atoms, m is 0 to typically 10, and each p is independently
0, 1, 2, or
3, provided that at least one aromatic ring contains an le substituent and
that the total
number of carbon atoms in all 10 groups is at least 7. When m is 1 or greater,
one of
the X groups may be hydrogen. In one embodiment, M is a valence (or
equivalent) of
a Mg ion or a mixture of Mg and hydrogen. Saligenin detergents are disclosed
in
greater detail in U.S. Patent 6,310,009, with special reference to their
methods of syn-
thesis (Column 8 and Example 1) and preferred amounts of the various species
of X
and Y (Column 6).
[0086] Other optional detergents include salixarate detergents. Salixarate
deter-
gents are overbased materials that may be represented by a compound comprising
at
least one unit of formula (I) or formula (II):
R4
7 5
HO
COOR3 R6
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26
(I) (II)
each end of the compound having a terminal group of formula (III) or (IV):
(R2),
R7
COOR3 R6
(III) (Iv)
such groups being linked by divalent bridging groups A, which may be the same
or
different. In formulas (I)-(IV) R3 is hydrogen, a hydrocarbyl group, or a
valence of a
metal ion; R2 is hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2; R6 is
hydrogen, a
hydrocarbyl group, or a hetero-substituted hydrocarbyl group; either le is
hydroxyl
and R5 and R7 are independently either hydrogen, a hydrocarbyl group, or
hetero-sub-
stituted hydrocarbyl group, or else R5 and R7 are both hydroxyl and le is
hydrogen, a
hydrocarbyl group, or a hetero-substituted hydrocarbyl group; provided that at
least
one of le, R5, R6 and R7 is hydrocarbyl containing at least 8 carbon atoms;
and wherein
the molecules on average contain at least one of unit (I) or (III) and at
least one of unit
(II) or (IV) and the ratio of the total number of units (I) and (III) to the
total number of
units of (II) and (IV) in the composition is 0.1:1 to 2:1. The divalent
bridging group
"A," which may be the same or different in each occurrence, includes -CH2- and
-
CH2OCH2- , either of which may be derived from formaldehyde or a formaldehyde
equivalent (e.g., paraform, formalin).
[0087] Salixarate derivatives and methods of their preparation are
described in
greater detail in U.S. patent number 6,200,936 and PCT Publication WO
01/56968. It
is believed that the salixarate derivatives have a predominantly linear,
rather than mac-
rocyclic, structure, although both structures are intended to be encompassed
by the
term "salixarate." In one embodiment, a salixarate detergent may contain a
portion of
molecules represented (prior to neutralization) by the structure:
UH UH UH UH
HO OH
I I
HO OH
R8
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where the le groups are independently hydrocarbyl groups containing at least 8
carbon
atoms.
[0088] Glyoxylate detergents are also optional overbased materials. They
are based
on an anionic group which, in one embodiment, may have the structure:
C(0)0-
= H OH
CF0)
0
wherein each R is independently an alkyl group containing at least 4 or 8
carbon atoms,
provided that the total number of carbon atoms in all such R groups is at
least 12 or 16
or 24. Alternatively, each R may be an olefin polymer substituent. The acidic
material
upon from which the overbased glyoxylate detergent is prepared is the
condensation
product of a hydroxyaromatic material such as a hydrocarbyl-substituted phenol
with
a carboxylic reactant such as glyoxylic acid or another omega-oxoalkanoic
acid. Over-
based glyoxylic detergents and their methods of preparation are disclosed in
greater
detail in U.S. Patent 6,310,011 and references cited therein.
[0089] Another optional overbased detergent is an overbased salicylate,
e,g., an
alkali metal or alkaline earth metal salt of a substituted salicylic acid. The
salicylic
acids may be hydrocarbyl-substituted wherein each substituent contains an
average of
at least 8 carbon atoms per substituent and 1 to 3 substituents per molecule.
The sub-
stituents may be polyalkene substituents. In one embodiment, the hydrocarbyl
substit-
uent group contains 7 to 300 carbon atoms and may be an alkyl group having a
molec-
ular weight of 150 to 2000. Overbased salicylate detergents and their methods
of prep-
aration are disclosed in U.S. Patents 4,719,023 and 3,372,116.
[0090] Other optional overbased detergents may include overbased detergents
hav-
ing a Mannich base structure, as disclosed in U.S. Patent 6,569,818.
[0091] In certain embodiments, the hydrocarbyl substituents on hydroxy-
substi-
tuted aromatic rings in the above detergents (e.g., phenate, saligenin,
salixarate, gly-
oxylate, or salicylate) are free of or substantially free of C12 aliphatic
hydrocarbyl
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groups (e.g., less than 1%, 0.1%, or 0.01% by weight of the substituents are
C12 ali-
phatic hydrocarbyl groups). In some embodiments such hydrocarbyl substituents
con-
tain at least 14 or at least 18 carbon atoms.
[0092] Optionally the lubricant may further include an additional
phosphorus con-
taining material and may include a metal salt of a phosphorus acid. Metal
salts may
have the formula:
[(R80)(R90)P(=S)-S].-M
where le and R9 are independently hydrocarbyl groups containing 3 to 30 carbon
at-
oms, are readily obtainable by heating phosphorus pentasulfide (P2S5) and an
alcohol
or phenol to form an 0,0-dihydrocarbyl phosphorodithioic acid. The alcohol
which
reacts to provide the le and R9 groups may be a mixture of alcohols, for
instance, a
mixture of isopropanol and 4-methyl-2-pentanol, and in some embodiments a
mixture
of a secondary alcohol and a primary alcohol, such as isopropanol and 2-
ethylhexanol.
The resulting acid may be reacted with a basic metal compound to form the
salt. The
metal M, having a valence n, generally is aluminum, tin, manganese, cobalt,
nickel,
zinc, or copper, and in many cases, zinc, to form zinc
dialkyldithiophosphates. Such
materials are well known and readily available to those skilled in the art of
lubricant
formulation. Suitable variations to provide low phosphorus volatility are
disclosed, for
instance, in US published application 2008-0015129, see, e.g., claims.
[0093] Mixtures of amines may also be used in the invention. In one
embodiment
a useful mixture of amines is "Primene 81R" and "Primene JMT." Primene 81R
and Primene JMT (both produced and sold by Rohm & Haas) are mixtures of C11
to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary
amines
respectively.
[0094] In one embodiment the hydrocarbyl amine salt of an alkylphosphoric
acid
ester is the reaction product of a C14 to C18 alkylated phosphoric acid with
Primene
81RTM (produced and sold by Rohm & Haas) which is a mixture of C11 to C14
tertiary
alkyl primary amines.
[0095] Examples of hydrocarbyl amine salts of dialkyldithiophosphoric acid
es-
ters include the reaction product(s) of isopropyl, methyl-amyl (4-methyl-2-
pentyl or
mixtures thereof), 2-ethylhexyl, heptyl, octyl or nonyl dithiophosphoric acids
with
ethylene diamine, morpholine, or Primene 81RTM, and mixtures thereof.
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[0096] In one embodiment the dithiophosphoric acid may be reacted with an
epox-
ide or a glycol. This reaction product is further reacted with a phosphorus
acid, an-
hydride, or lower ester. The epoxide includes an aliphatic epoxide or a
styrene oxide.
Examples of useful epoxides include ethylene oxide, propylene oxide, butene
oxide,
octene oxide, dodecene oxide, styrene oxide and the like. In one embodiment
the
epoxide is Propylene oxide. The glycols may be aliphatic glycols having from 1
to
about 12, or from about 2 to about 6, or about 2 to about 3 carbon atoms. The
dithi-
phosphoric acids, glycols, epoxides, inorganic phosphorus reagents and methods
of
reacting the same are described in U.S. Patent numbers 3,197,405 and
3,544,465.
The resulting acids may then be salted with amines. An example of suitable
dithiophos-
phoric acid is prepared by adding phosphorus pentoxide (about 64 grams) at
about 58
C over a period of about 45 minutes to about 514 grams of hydroxypropyl 0,0-
di(4-
methy1-2-pentyl)phosphorodithioate (prepared by reacting di(4-methy1-2-penty1)-
phosphorodithioic acid with about 1.3 moles of propylene oxide at about 25
C). The
mixture is heated at about 75 C for about 2.5 hours, mixed with a
diatomaceous earth
and filtered at about 70 C. The filtrate contains about 11.8% by weight
phosphorus,
about 15.2% by weight sulfur, and an acid number of 87 (bromophenol blue).
[0097] If the additional phosphorus containing material is present it may
provide 1
% to 90 %, or 10 to 80 %, or 20 to 70 % of the total amount of phosphorus to
the
lubricant. In one embodiment the additional phosphorus containing material is
present,
and in one embodiment the additional phosphorus containing material is present
is ab-
sent.
[0098] The lubricant may further include an antioxidant, or mixtures
thereof. The
Antioxidant may include molybdenum compounds such as molybdenum dithiocarba-
mates, sulphurised olefins, hindered phenols, aminic compounds such as
alkylated
diphenyl amines (typically di-nonyl diphenylamine, octyl diphenylamine, or di-
octyl
diphenylamine). When present, the antioxidant may be present at 0 to 3 wt %,
or 0.1
to 2.5 wt %, or 0.2 to 1.5 wt %.
Automatic Transmission Lubricants
[0099] In one embodiment the invention provides a lubricant composition com-
prising:
an oil of lubricating viscosity,
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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 alkylphenol detergent 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.
[0100] In one embodiment the invention provides a method of lubricating an
au-
tomatic 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 phospho-
rus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phos-
phorus 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 alkylphenol detergent de-
scribed 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.
[0101] The automatic transmission includes continuously variable
transmissions
(CVT), infinitely variable transmissions (IVT), Toroidal transmissions,
continuously
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slipping torque converted clutches (CSTCC), stepped automatic transmissions or
dual
clutch transmissions (DCT).
[0102] The calcium-containing detergent may be an overbased detergent, a
non-
overbased detergent, or mixtures thereof. Typically the detergent may be
overbased.
[0103] The preparation of the calcium-containing detergent is known in the
art.
Patents describing the preparation of overbased calcium-containing detergents
in-
clude U.S. patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874;
3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and
3,629,109.
[0104] As used herein the TBN values quoted and associated range of TBN is
on "an
as is basis," i.e., containing conventional amounts of diluent oil.
Conventional amounts
of diluent oil typically range from 30 wt % to 60 wt % (often 40 wt % to 55 wt
%) of the
detergent component.
[0105] A more detailed description of the expressions "metal ratio", TBN
and
"soap content" are known to a person skilled in the art and explained in
standard
textbook entitled "Chemistry and Technology of Lubricants", Third Edition,
Edited
by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219 to 220 under
the
sub-heading 7.2.5. Detergent Classification.
[0106] The calcium-containing detergent may be a non-overbased detergent
(may
also be referred to as a neutral detergent). The TBN of a non-overbased may be
20
to less than 200, or 30 to 100, or 35 to 50 mg KOH/g. The TBN of a non-
overbased
calcium-containing detergent may also be 20 to 175, or 30 to 100 mg KOH/g.
When
a non-overbased calcium-containing detergent is prepared from a strong acid
such as
a hydrocarbyl-substituted sulphonic acid, the TBN may be lower (for example 0
to
50 mg KOH/g, or 10 to 20 mg KOH/g).
[0107] The calcium-containing detergent may be an overbased detergent,
which
may have a TBN of greater than 200 mg KOH/g (typically 250 to 600, or 300 to
500
mg KOH/g).
[0108] The calcium-containing detergent may be formed by the reaction of a
basic
calcium compound and an acidic detergent substrate. The acidic detergent
substrate
may include an alkyl phenol, an aldehyde-coupled alkyl phenol, a sulphurised
alkyl phe-
nol, an alkyl aromatic sulphonic acid (such as, alkyl naphthalene sulphonic
acid, alkyl
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toluene sulphonic acid or alkyl benzene sulphonic acid), an aliphatic
carboxylic acid, a
calixarene, a salixarene, an alkyl salicylic acid, or mixtures thereof.
[0109] The metal basic compound is used to supply basicity to the
detergent. The
basic calcium compound is a compound of a hydroxide or oxide of the metal.
[0110] The oxides and/or hydroxides may be used alone or in combination.
The
oxides or hydroxides may be hydrated or dehydrated, although hydrated is
typical.
In one embodiment the basic calcium compound may be calcium hydroxide, which
may be used alone or mixtures thereof with other metal basic compounds.
Calcium
hydroxide is often referred to as lime. In one embodiment the metal basic
compound
may be calcium oxide which may be used alone or mixtures thereof with other
metal
basic compounds.
[0111] Collectively, when the alkyl phenol, the aldehyde-coupled alkyl
phenol, and
the sulphurised alkyl phenol are used to prepare a calcium-containing
detergent, the deter-
gent may be referred to as a calcium phenate. The calcium phenate may be an
alkyl
phenate, an aldehyde-coupled alkyl phenate, a sulphurised alkyl phenate, or
mixtures
thereof.
[0112] The TBN of a calcium phenate may vary from less 200, or 30 to 175
typically
150 to 175) mg KOH/g for a neutral phenate to 200 or more to 500, or 210 to
400 (typically
230 to 270) mg KOH/g for an overbased phenate.
[0113] The alkyl group of a phenate (i.e., an alkyl phenate) may contain 4
to 80, or 6
to 45, or 8 to 20, or 9 to 15 carbon atoms.
[0114] In one embodiment the calcium-containing detergent may be a
sulphonate,
or mixtures thereof. The sulphonate may be prepared from a mono- or di- hydro-
carbyl-sub stituted benzene (or naphthalene, indenyl, indanyl, or
bicyclopentadienyl)
sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35
or 9 to
30 carbon atoms.
[0115] The hydrocarbyl group may be derived from polypropylene or a linear
or
branched alkyl group containing at least 10 carbon atoms. Examples of a
suitable
alkyl group include branched and/or linear decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl,
nonodecyl,
eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl,
hexa-eicosyl
or mixtures thereof.
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[0116] In one embodiment the hydrocarbyl-substituted sulphonic acid may in-
clude polypropene benzenesulphonic acid and/or C16-C24 alkyl benzenesulphonic
acid, or mixtures thereof.
[0117] In one embodiment a calcium sulphonate detergent may be a
predominantly
linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 as
is described
in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and
granted as US
7,407,919). In some embodiments the linear alkyl group may be attached to the
benzene
ring anywhere along the linear chain of the alkyl group, but often in the 2, 3
or 4 position
of the linear chain, and in some instances predominantly in the 2 position.
[0118] When neutral or slightly basic, a calcium sulphonate detergent may
have
TBN of less than 100, or less than 75, typically 20 to 50 mg KOH/g, or 0 to 20
mg
KOH/g.
[0119] When overbased, a calcium sulphonate detergent may have a TBN
greater
than 200, or 300 to 550, or 350 to 450 mg KOH/g.
[0120] The detergent may be borated or non-borated.
[0121] Chemical structures for sulphonates, and phenates detergents are
known to
a person skilled in the art. The standard textbook entitled "Chemistry and
Technology
of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik,
Copyright
2010, pages 220 to 223 under the sub-heading 7.2.6 provide general disclosures
of
said detergents and their structures.
[0122] In one embodiment the calcium-containing detergent may be an
overbased
calcium sulphonate, an overbased calcium phenate, or mixtures thereof.
Typically
the detergent may be an overbased calcium sulphonate.
[0123] In one embodiment the calcium-containing detergent may be in a
mixture
with a having zinc-, barium-, sodium-, or magnesium- containing detergent. The
zinc-, barium-, sodium-, or magnesium- containing detergent is also well known
in
the art and described in the same references describing a calcium-containing
deter-
gent. The TBN and metal ratios may however, differ slightly. The zinc-, barium-
,
sodium-, or magnesium- containing detergent may be a phenate, a sulphur-
containing
phenate, sulphonate, salixarate or salicylate. Typically a zinc-, barium-,
sodium-, or
magnesium- containing detergent may be a magnesium phenate, a magnesium sul-
phur-containing phenate, or a magnesium sulphonate.
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[0124] The dispersant is described above.
[0125] The lubricant composition may include a friction modifier, typically
at
least two friction modifiers. Useful friction modifiers are described below.
[0126] In one embodiment the friction modifier may be formed by the
condensa-
tion of the hydroxyalkyl compound with an acylating agent or an amine. A more
detailed description of the hydroxyalkyl compound is described in US Patent
Appli-
cation 60/725360 (filed on October 11, 2005, inventors Bartley, Lahiri, Baker
and
Tipton) in paragraphs 8, 19-21. The friction modifier disclosed in US Patent
Appli-
cation 60/725360 may be an amide represented by the formula R1R2N-C(0)R3,
wherein R1 and R2 are each independently hydrocarbyl groups of at least 6
carbon
atoms and R3 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed
by
the condensation of said hydroxyalkyl group, through a hydroxyl group thereof,
with
an acylating agent. Preparative Examples are disclosed in Examples 1 and 2
(para-
graphs 68 and 69). In one embodiment the amide of a hydroxylalkyl compound is
prepared by reacting glycolic acid, that is, hydroxyacetic acid, HO-CH2-COOH
with
an amine.
[0127] In one embodiment the friction modifier may be a secondary or
tertiary
amine being represented by the formula R4R5NR6, wherein R4 and R5 are each
inde-
pendently an alkyl group of at least 6 carbon atoms and R6 is hydrogen, a
hydrocarbyl
group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group.
A
more detailed description of the friction modifier is described in US Patent
Applica-
tion 05/037897 in paragraphs 8 and 19 to 22.
[0128] In one embodiment the friction modifier may be derived from the
reaction
of a carboxylic acid or a reactive equivalent thereof with an aminoalcohol,
wherein
the friction modifier contains at least two hydrocarbyl groups, each
containing at least
6 carbon atoms. An example of such a friction modifier includes the reaction
product
of isostearic acid or an alkyl succinic anhydride with tris-hydroxymethylamino-
methane. A more detailed description of such a friction modifier is disclosed
in In-
ternational Publication W004/007652) in paragraphs 8 and 9 to 14.
[0129] The friction modifier includes fatty amines, borated glycerol
esters, fatty
acid amides, non-borated fatty epoxides, borated fatty epoxides, alkoxylated
fatty
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amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty
imidaz-
olines, metal salts of alkyl salicylates (may also be referred to as a
detergent), metal
salts of sulphonates (may also be referred to as a detergent), condensation
products
of carboxylic acids or polyalkylene-polyamines, or amides of hydroxyalkyl com-
pounds.
[0130] In one
embodiment the friction modifier includes a fatty acid ester of glyc-
erol. The final product may be in the form of a metal salt, an amide, an
imidazoline,
or mixtures thereof. The fatty acids may contain 6 to 24, or 8 to 18 carbon
atoms.
The fatty acids may branched or straight-chain, saturated or unsaturated.
Suitable
acids include 2-ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic,
myristic,
palmitoleic, linoleic, lauric, and linolenic acids, and the acids from the
natural prod-
ucts tallow, palm oil, olive oil, peanut oil, corn oil, and Neat's foot oil.
In one em-
bodiment the fatty acid is oleic acid. When in the form of a metal salt,
typically the
metal includes zinc or calcium; and the products include overbased and non-
over-
based products. Examples are overbased calcium salts and basic oleic acid-zinc
salt
complexes which may be represented by the general formula Zn4Oleate60. When in
the form of an amide, the condensation product includes those prepared with
ammo-
nia, or with primary or secondary amines such as diethylamine and
diethanolamine.
When in the form of an imidazoline, the condensation product of an acid with a
dia-
mine or polyamine such as a polyethylenepolyamine. In one embodiment the
friction
modifier is the condensation product of a fatty acid with C8 to C24 atoms, and
a
polyalkylene polyamine, and in particular, the product of isostearic acid with
tetra-
ethyl enep entamine.
[0131] In one
embodiment the friction modifier includes those formed by the con-
densation of the hydroxyalkyl compound with an acylating agent or an amine. A
more detailed description of the hydroxyalkyl compound is described in WO
2007/0044820 paragraphs 9, and 20-22. The
friction modifier disclosed in
W02007/044820 includes an amide represented by the formula R12R13N-C(0)R14,
wherein 102 and 103 are each independently hydrocarbyl groups of at least 6
carbon
atoms and 104 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed
by
the condensation of said hydroxyalkyl group, through a hydroxyl group thereof,
with
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an acylating agent. Preparative Examples are disclosed in Examples 1 and 2
(para-
graphs 72 and 73 of W02007/044820). In one embodiment the amide of a hydrox-
ylalkyl compound is prepared by reacting glycolic acid, that is, hydroxyacetic
acid,
HO-CH2-COOH with an amine.
[0132] In one embodiment the friction modifier includes a reaction product
of a
di-cocoalkyl amine (or di-cocoamine) with glycolic acid. The friction modifier
in-
cludes compounds prepared in Preparative Examples 1 and 2 of WO 2008/014319.
[0133] In one embodiment the friction modifier includes an alkoxylated
alcohol.
A detailed description of suitable alkoxylated alcohols is described in
paragraphs 19
and 20 of US Patent Application 2005/0101497. The alkoxylated amines are also
described in US Patent 5,641,732 in column 7, line 15 to column 9, line 25.
[0134] In one embodiment the friction modifier includes a hydroxyl amine
com-
pound as defined in column 37, line 19, to column 39, line 38 of US Patent
5,534,170.
Optionally the hydroxyl amine includes borated as such products are described
in
column 39, line 39 to column 40 line 8 of US Patent 5,534,170.
[0135] In one embodiment the friction modifier includes an alkoxylated
amine
e.g., an ethoxylated amine derived from 1.8 % EthomeenTM T-12 and 0.90 %
TomahTm PA-1 as described in Example E of US Patent 5,703,023, column 28,
lines
30 to 46. Other suitable alkoxylated amine compounds include commercial alkox-
ylated fatty amines known by the trademark "ETHOMEEN" and available from Akzo
Nobel. Representative examples of these ETHOMEENTm materials is
ETHOMEENTm C/12 (bis[2-hydroxyethy1]-coco-amine); ETHOMEENTm C/20 (pol-
yoxyethylene[10]cocoamine); ETHOMEENTm S/12 (bis[2-hydroxyethyl]soyamine);
ETHOMEENTm T/12 (bis[2-hydroxyethyl] -tallow-amine); ETHOMEENTm T/15
(polyoxyethylene-[5]tallowamine); ETHOMEENTm 0/12 (bis[2-hydroxyethyl]oleyl-
amine); ETHOMEENTm 18/12 (bis[2¨hydroxyethyl]octadecylamine); and
ETHOMEENTm 18/25 (polyoxyethylene[15]octadecylamine). Fatty amines and eth-
oxylated fatty amines are also described in U.S. Patent 4,741,848.
[0136] In one embodiment the friction modifier includes a polyol ester as
de-
scribed in US Patent 5,750,476 column 8, line 40 to column 9, line 28.
[0137] In one embodiment the friction modifier includes a low potency
friction
modifier as described in US Patent 5,840,662 in column 2, line 28 to column 3,
line
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26. US Patent 5,840,662 further discloses in column 3, line 48 to column 6,
line 25
specific materials and methods of preparing the low potency friction modifier.
[0138] In one embodiment the friction modifier includes a reaction product
of an
isomerised alkenyl substituted succinic anhydride and a polyamine as described
in
US Patent 5,840,663 in column 2, lines 18 to 43. Specific embodiments of the
friction
modifier described in US Patent 5,840,663 are further disclosed in column 3,
line 23
to column 4, line 35. Preparative examples are further disclosed in column 4,
line 45
to column 5, line 37 of US Patent 5,840,663.
[0139] In one embodiment the friction modifier includes an alkylphosphonate
mono- or di- ester sold commercially by Rhodia under the trademark Duraphos
DMODP.
[0140] The condensation of a fatty acid and a polyamine typically result in
the
formation of at least one compound chosen from hydrocarbyl amides, hydrocarbyl
imidazolines and mixtures thereof. In one embodiment the condensation products
are hydrocarbyl imidazolines. In one embodiment the condensation products are
hy-
drocarbyl amides. In one embodiment the condensation products are mixtures of
hydrocarbyl imidazolines and hydrocarbyl amides. Typically the condensation
prod-
uct is a mixture of hydrocarbyl imidazolines and hydrocarbyl amides.
[0141] The fatty acid may be derived from a hydrocarbyl carboxylic acid.
The
hydrocarbyl group may be alkyl, cycloalkyl, or aryl, although alkyl is
typical, and the
hydrocarbyl groups may be linear or branched. Typically the fatty acid
contains 8 or
more, 10 or more, more 13 or 14 or more carbon atoms (including the carbon of
the
carboxy group). Typically the fatty acid contains 8 to 30, 12 to 24, or 16 to
18 carbon
atoms. Other suitable carboxylic acids may include the polycarboxylic acids or
car-
boxylic acids or anhydrides having from 2 to 4 carbonyl groups, typically 2.
The
polycarboxylic acids may include succinic acids and anhydrides and Diels-Alder
re-
action products of unsaturated monocarboxylic acids with unsaturated
carboxylic ac-
ids (such as acrylic, methacrylic, maleic, fumaric, crotonic and itaconic
acids). The
fatty carboxylic acids include fatty monocarboxylic acids containing 8 to 30,
10 to
26, or 12 to 24 carbon atoms.
[0142] Examples of suitable fatty acids may include caprylic acid, capric
acid,
lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acid and,
tall oil acids.
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In one embodiment the fatty acid is stearic acid, which may be used alone or
in com-
bination with other fatty acids.
[0143] One or both friction modifiers may in one embodiment be nitrogen-con-
taining compounds, typically both friction modifiers are nitrogen-containing.
[0144] In one embodiment one of friction modifiers is the condensation
product
of a fatty acid with C8 to C24 atoms, and a polyalkylene polyamine, and in
particular,
the product of isostearic acid with tetraethylenepentamine.
[0145] The phosphorus-containing compound may be a non-ionic phosphorus
compound.
[0146] In one embodiment the phosphorus-containing compounds comprise two
or more (possibly up to four) non-ionic phosphorus compounds. Typically the
non-
ionic phosphorus compound may have an oxidation of +3 or +5. The different em-
bodiments comprise phosphite ester, phosphate esters, or mixtures thereof.
[0147] In one embodiment the phosphorus-containing compound comprises a
non-ionic phosphorus compound (a C4-6 hydrocarbyl phosphite) and an amine salt
of
a phosphorus acid or ester.
[0148] The phosphorus-containing compound comprises a non-ionic phosphorus
compound that is a C4-6 hydrocarbyl phosphite, or mixtures thereof. The C4-6
hydro-
carbyl phosphite includes those represented by the formula:
0
wherein each R" ' may be independently hydrogen or a hydrocarbyl group having
4 to 6
carbon atoms, typically 4 carbon atoms, with the proviso that at least one of
the R" ' groups
is hydrocarbyl. Typically the C4-6 hydrocarbyl phosphite comprises dibutyl
phosphite.
[0149] The C4-6 hydrocarbyl phosphite may deliver at least 175 ppm, or at
least
200 ppm of the total amount of phosphorus delivered by the phosphorus-
containing
compounds.
[0150] The C4-6 hydrocarbyl phosphite may deliver at least 45 wt %, or 50
wt %
to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the total amount
of
phosphorus from the phosphorus-containing compound.
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[0151] The phosphorus-containing compounds may comprise a second phosphite
whose formula is similar to that disclosed above, except R" may contain 2 to
40, 8
to 24 or 11 to 20 carbon atoms, with the proviso that the second phosphite is
not a
C4-6 hydrocarbyl phosphite. Examples of suitable hydrocarbyl groups include
propyl,
dodecyl, butadecyl, hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl,
hexa-
deencyl, or octadecenylgroups.
[0152] As used herein the term "alk(en)yl" is intended to include moieties
that
have an alkyl and/or alkenyl group.
[0153] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C12-
18
alk(en)yl hydrogen phosphite and optionally phosphoric acid. In different
embodi-
ments the phosphoric acid is present or absent.
[0154] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C16-
18
alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite be may an alkyl
hy-
drogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl
hydrogen
phosphite and alkyl hydrogen phosphite. In one embodiment the alk(en)yl
hydrogen
phosphite be may a mixture of alkenyl hydrogen phosphite and alkyl hydrogen
phos-
phite and optionally phosphoric acid. The phosphoric acid may be present or
absent.
[0155] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C11-
14
alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite be may an alkyl
hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl
hydro-
gen phosphite and alkyl hydrogen phosphite. In one embodiment the alk(en)yl hy-
drogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl
hydro-
gen phosphite and optionally phosphoric acid.
[0156] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and
phosphoric
acid.
[0157] The lubricant composition in one embodiment includes a package that
comprises a phosphorus-containing compound and a non-ionic phosphorus com-
pound that is a hydrocarbyl phosphite.
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[0158] In one embodiment the lubricant composition further comprises a C8-
20 hy-
drocarbyl phosphite, or a C12-18 hydrocarbyl phosphite, or C16-18 hydrocarbyl
phosphite.
[0159] In one embodiment the lubricant composition includes an amine
antioxi-
dant. The amine antioxidant may be a phenyl-a-naphthylamine (PANA) or a hydro-
carbyl substituted diphenylamine, or mixtures thereof. The hydrocarbyl
substituted
diphenylamine may include mono- or di- C4 to C16-, or C6 to C12-, or C9- alkyl
diphe-
nylamine. For example the hydrocarbyl substituted diphenylamine may be octyl
di-
phenylamine, or di-octyl diphenylamine, dinonyl diphenylamine, typically
dinonyl
diphenylamine.
[0160] When present the amine antioxidant may be present at 0.2 wt % to 1.2
wt
%, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt % or 0.5 wt % to 0.8 wt %,
of the
lubricant composition.
[0161] The lubricant composition be optionally include at least one other
antix-
odiant that is known and includes sulphurised olefins, hindered phenols,
molybdenum
dithiocarbamates, and mixtures thereof.
[0162] The hindered phenol antioxidant often contains a secondary butyl
and/or a
tertiary butyl group as a sterically hindering group. The phenol group is
often further
substituted with a hydrocarbyl group and/or a bridging group linking to a
second
aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-
di-
tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-
butylphenol,
4-propy1-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-
dodecy1-
2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant may
be
an ester and may include, e.g., IrganoxTM L-135 from Ciba, or butyl 3-(3,5-di-
tert-
buty1-4-hydroxyphenyl)propanoate.
[0163] If present, the secondary antioxidant may be present at 0.1 wt % to
1 wt
%, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt % to 1.0 wt %,
of the
lubricant composition.
Off-Highway Vehicle
[0164] The alkylphenol detergents described herein can be employed in off-
high-
way 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
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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 10 to 2600ppm, 100 to 2300ppm, 200 to 2000ppm 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 alkylphenol detergent described herein.
[0165] In one embodiment the invention includes a method of lubricating an
off-
highway vehicle comprising supplying to the vehicle a lubricant composition
com-
prising:
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 phospho-
rus compound, which may be a hydrocarbyl phosphite, such as a zinc
dialkyldithio-
phosphate; 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 2600ppm, 100 to 2300ppm, 200 to 2000ppm 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 alkylphenol detergent described herein.
[0166] The off-highway vehicle lubricated typically has a wet-brake, a
transmis-
sion, a hydraulic, a final drive, a power take-off system. These parts are
typically
lubricated by a single lubricant supplied from a common sump. The transmission
may be a manual transmission or an automatic transmission.
[0167] The calcium-containing detergent may be an overbased detergent, a
non-
overbased detergent, or mixtures thereof. Typically the detergent may be
overbased.
[0168] The preparation of the calcium-containing detergent is known in the
art.
Patents describing the preparation of overbased calcium-containing detergents
in-
clude U.S. patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874;
3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and
3,629,109.
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[0169] The other detergent (other than the alkylphenol) and dispersant is
described
above.
[0170] The phosphorus-containing antiwear agent may include zinc
dialkyldithi-
ophosphate, a non-ionic phosphorus compound, which may be a hydrocarbyl phos-
phite; (i) a non-ionic phosphorus compound, which may be a hydrocarbyl
phosphite;
or (ii) an amine salt of a phosphorus compound, or mixtures thereof.
[0171] In one embodiment the lubricant composition disclosed herein
contains no
zinc di alkyldithi ophosphate.
[0172] In one embodiment the lubricant composition disclosed herein
contains
zinc di alkyldithi ophosphate.
[0173] The phosphorus-containing compound may be a non-ionic phosphorus
compound.
[0174] In one embodiment the phosphorus-containing compounds comprise two
or more (possibly up to four) non-ionic phosphorus compounds. Typically the
non-
ionic phosphorus compound may have an oxidation of +3 or +5. The different em-
bodiments comprise phosphite ester, phosphate esters, or mixtures thereof.
[0175] In one embodiment the phosphorus-containing compound comprises a
non-ionic phosphorus compound (a C4-6 hydrocarbyl phosphite) and an amine salt
of
a phosphorus acid or ester.
[0176] The phosphorus-containing compound comprises a non-ionic phosphorus
compound that is a C4-6 hydrocarbyl phosphite, or mixtures thereof. The C4-6
hydro-
carbyl phosphite includes those represented by the formula:
0
wherein each R" may be independently hydrogen or a hydrocarbyl group having 4
to 6
carbon atoms, typically 4 carbon atoms, with the proviso that at least one of
the R" groups
is hydrocarbyl. Typically the C4-6 hydrocarbyl phosphite comprises dibutyl
phosphite.
[0177] The C4-6 hydrocarbyl phosphite may deliver at least 175 ppm, or at
least
200 ppm of the total amount of phosphorus delivered by the phosphorus-
containing
compounds.
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[0178] The C4-6 hydrocarbyl phosphite may deliver at least 45 wt %, or 50
wt %
to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the total amount
of
phosphorus from the phosphorus-containing compound.
[0179] The phosphorus-containing compounds may comprise a second phosphite
whose formula is similar to that disclosed above, except R" may contain 2 to
40, 8
to 24 or 11 to 20 carbon atoms, with the proviso that the second phosphite is
not a
C4-6 hydrocarbyl phosphite. Examples of suitable hydrocarbyl groups include
propyl,
dodecyl, butadecyl, hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl,
hexa-
deencyl, or octadecenylgroups.
[0180] As used herein the term "alk(en)yl" is intended to include moieties
that
have an alkyl and/or alkenyl group.
[0181] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C12-
18
alk(en)yl hydrogen phosphite and optionally phosphoric acid.In different
embodi-
ments the phosphoric acid is present or absent.
[0182] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C16-
18
alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite be may an alkyl
hy-
drogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl
hydrogen
phosphite and alkyl hydrogen phosphite. In one embodiment the alk(en)yl
hydrogen
phosphite be may a mixture of alkenyl hydrogen phosphite and alkyl hydrogen
phos-
phite and optionally phosphoric acid. The phosphoric acid may be present or
absent.
[0183] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C11-
14
alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite be may an alkyl
hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl
hydro-
gen phosphite and alkyl hydrogen phosphite. In one embodiment the alk(en)yl hy-
drogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl
hydro-
gen phosphite and optionally phosphoric acid.
[0184] In one embodiment the phosphorus-containing compounds include a mix-
ture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and
phosphoric
acid.
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[0185] The lubricant composition in one embodiment includes a package that
comprises a phosphorus-containing compound and a non-ionic phosphorus com-
pound that is a hydrocarbyl phosphite.
[0186] In one embodiment the lubricant composition further comprises a C8-
20 hy-
drocarbyl phosphite, or a C12-18 hydrocarbyl phosphite, or C16-18 hydrocarbyl
phosphite,
as described above.
[0187] In on embodiment the amine salt of a phosphorus acid may be derived
from
an amine salt of a phosphate. The amine salt of the phosphorus acidmay be
repre-
sented by the formula:
0 R5
R4-0/p-o- N\
\R7
R8
wherein
R3 and R4 may be independently hydrogen or hydrocarbon typically containing 4
to
40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms, with the proviso that at
least one
is a hydrocarbon group; and
R5, R6, R7 and le may be independently hydrogen or a hydrocarbyl group, with
the
proviso that at least one is a hydrocarbyl group.
[0188] The hydrocarbon groups of R3 and/or R4 may be linear, branched, or
cy-
clic.
[0189] Examples of a hydrocarbon group for R3 and/or R4 include straight-
chain
or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl,
heptadecyl and octadecyl.
[0190] Examples of a cyclic hydrocarbon group for R3 and/or R4 include
cyclo-
pentyl, cycl ohexyl, cycloheptyl, methyl cyclopentyl, dimethylcyclopentyl,
methyl cy-
cl opentyl, dimethyl cycl opentyl, methyl ethyl cycl op entyl, di ethyl cycl
op entyl, methyl -
cycl ohexyl, dimethyl cycl ohexyl, methyl ethyl cycl ohexyl, di ethyl cycl
ohexyl, methyl -
cycl oheptyl, dimethyl cycl oheptyl, methyl ethyl cycl oheptyl, and di ethyl
cycl oheptyl.
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[0191] In one
embodiment the phosphate may be an amine salt of a mixture of
monoalkyl and dialkyl phosphoric acid esters. The monoalkyl and dialkyl groups
may be linear or branched.
[0192] The
amine salt of a phosphorus acid may be derived from an amine such
as a primary amine, a secondary amine, a tertiary amine, or mixtures thereof.
The
amine may be aliphatic, or cyclic, aromatic or non-aromatic, typically
aliphatic. In
one embodiment the amine includes an aliphatic amine such as a tertiary-
aliphatic
primary amine.
[0193]
Examples of suitable primary amines include ethylamine, propylamine,
butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, and
dodecyla-
mine, as well as such fatty amines as n-octylamine, n-decylamine, n-
dodecylamine,
n-tetradecylamine, n-hexadecylamine, n-octadecyl amine and oleyamine. Other
use-
ful fatty amines include commercially available fatty amines such as "Armeen "
amines (products available from Akzo Chemicals, Chicago, Illinois), such as
Armeen
C, Armeen 0, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD,
wherein the letter designation relates to the fatty group, such as coco,
oleyl, tallow,
or stearyl groups.
[0194]
Examples of suitable secondary amines include dimethylamine, diethyla-
mine, dipropylamine, dibutyl amine, diamyl amine, dihexylamine, diheptyl
amine,
methyl ethylamine, ethylbutyl amine, N-methyl-l-amino-cyclohexane, Armeen 2C
and ethylamylamine. The secondary amines may be cyclic amines such as
piperidine,
piperazine and morpholine.
[0195]
Examples of tertiary amines include tri-n-butylamine, tri-n-octylamine,
tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine
(Armeen DMOD).
[0196] In one
embodiment the amines are in the form of a mixture. Examples of
suitable mixtures of amines include (i) a tertiary alkyl primary amine with 11
to 14
carbon atoms, (ii) a tertiary alkyl primary amine with 14 to 18 carbon atoms,
or (iii)
a tertiary alkyl primary amine with 18 to 22 carbon atoms. Other examples of
tertiary
alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octyl
amine (such
as 1,1-
dimethylhexylamine), tert-decyl amine (such as 1,1-dimethyloctylamine),
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tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-
octadecylamine,
tert-tetracosanylamine, and tert-octacosanylamine.
[0197] In one embodiment a useful mixture of amines is "Primeneg 81R" or
"Primeneg JMT." Primeneg 81R and Primeneg JMT (both produced and sold by
Rohm & Haas) are mixtures of C11 to C14 tertiary alkyl primary amines and C18
to
C22 tertiary alkyl primary amines respectively.
[0198] The amine salt of a phosphorus acid may be prepared as is described
in US
Patent 6,468,946. Column 10, lines 15 to 63 describes phosphoric acid esters
formed
by reaction of phosphorus compounds, followed by reaction with an amine to
form
an amine salt of a phosphate hydrocarbon ester. Column 10, line 64, to column
12,
line 23, describes preparative examples of reactions between phosphorus
pentoxide
with an alcohol (having 4 to 13 carbon atoms), followed by a reaction with an
amine
(typically Primeneg81-R) to form an amine salt of a phosphate hydrocarbon
ester.
[0199] The sulphur-containing extreme pressure agent may be an olefin
sulphide,
or mixtures thereof. The olefin sulphide may include a polysulphide or a
sulphurised
olefin such as sulphurised isobutylene, or mixtures thereof.
[0200] In one embodiment the olefin sulphide includes a polysulphide.
[0201] In one embodiment the olefin sulphide includes sulphurized
isobutylene.
[0202] In one embodiment the olefin sulphide includes a mixture of a
sulphurised
isobutylene and a polysulphide.
[0203] In one embodiment at least 50 wt % of the polysulphide molecules are
a
mixture of tri- or tetra- sulphides. In other embodiments at least 55 wt %, or
at least
60 wt % of the polysulphide molecules are a mixture of tri- or tetra-
sulphides.
[0204] The polysulphide includes a sulphurised organic polysulphide from
oils, fatty
acids or ester, olefins or polyolefins.
[0205] Oils which may be sulfurized include natural or synthetic oils such
as min-
eral oils, lard oil, carboxylate esters derived from aliphatic alcohols and
fatty acids
or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and
synthetic
unsaturated esters or glycerides.
[0206] Fatty acids include those that contain 8 to 30, or 12 to 24 carbon
atoms.
Examples of fatty acids include oleic, linoleic, linolenic, and tall oil.
Sulphurised
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fatty acid esters prepared from mixed unsaturated fatty acid esters such as
are ob-
tained from animal fats and vegetable oils, including tall oil, linseed oil,
soybean oil,
rapeseed oil, and fish oil.
[0207] The
polysulphide includes olefins derived from a wide range of alkenes.
The alkenes typically have one or more double bonds. The olefins in one
embodiment
contain 3 to 30 carbon atoms. In other embodiments, olefins contain 3 to 16,
or 3 to
9 carbon atoms. In one embodiment the sulphurised olefin includes an olefin
derived
from propylene, isobutylene, pentene or mixtures thereof.
[0208] In one
embodiment the polysulphide comprises a polyolefin derived from
polymerising by known techniques, an olefin as described above.
[0209] In one
embodiment the polysulphide includes dibutyl tetrasulphide, sul-
phurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised
dipentene,
sulphurised dicyclopentadiene, sulphurised terpene, and sulphurised Diels-
Alder ad-
ducts.
[0210] The
lubricant may also include a sulphur-containing corrosion inhibitor.
The sulphur-containing corrosion inhibitor may be a thiadiazole compound, or
mix-
tures thereof. The thiadiazole compound may include mono- or di-hydrocarbyl
sub-
stituted 2,5-dimercapto-1,3,4-thiadiazole compounds. Examples of a thiadiazole
in-
clude 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-
substi-
tuted 2,5-dimercapto-1,3,4-thiadiazole, a hydrocarbylthio-substituted 2,5-
dimer-
capto-1,3,4-thiadiazole, or oligomers thereof. The oligomers of hydrocarbyl-
substi-
tuted 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
dimercapto-
thiadiazole derivative of a polyisobutylene succinimide.
[0211]
Examples of a suitable thiadiazole compound include at least one of a di-
mercaptothi adi azol e, 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]-
thiadia-
zole. Typically readily available materials such as 2,5-dimercapto-1,3,4-
thiadiazole
or a hydrocarbyl -substituted 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbylthio-
substituted 2,5-dimercapto-1,3,4-thiadiazole are commonly utilised.
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[0212] As used herein, the term "condensation product" is intended to
encompass
esters, amides, imides and other such materials that may be prepared by a
condensation
reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide,
anhydride,
or ester) with an alcohol or amine, irrespective of whether a condensation
reaction is
actually performed to lead directly to the product. Thus, for example, a
particular ester
may be prepared by a transesterification reaction rather than directly by a
condensation
reaction. The resulting product is still considered a condensation product.
[0213] The amount of each chemical component described is presented
exclusive
of any solvent or diluent oil, which may be customarily present in the
commercial ma-
terial, that is, on an active chemical basis, unless otherwise indicated.
However, unless
otherwise indicated, each chemical or composition referred to herein should be
inter-
preted as being a commercial grade material which may contain the isomers, by-
prod-
ucts, derivatives, and other such materials which are normally understood to
be present
in the commercial grade.
[0214] 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. Specifi-
cally, it refers to a group having a carbon atom directly attached to the
remainder of
the molecule and having predominantly hydrocarbon character. Examples of hydro-
carbyl groups include:
[0215] hydrocarbon substituents, that is, aliphatic (e.g., alkyl or
alkenyl), alicyclic
(e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and
alicyclic-
substituted aromatic substituents, as well as cyclic substituents wherein the
ring is com-
pleted through another portion of the molecule (e.g., two substituents
together form a
ring);
[0216] substituted hydrocarbon substituents, that is, substituents
containing non-
hydrocarbon groups which, in the context of this invention, do not alter the
predomi-
nantly hydrocarbon nature of the substituent (e.g., halo (especially chloro
and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
[0217] hetero substituents, that is, substituents which, while having a
predomi-
nantly hydrocarbon character, in the context of this invention, contain other
than car-
bon in a ring or chain otherwise composed of carbon atoms and encompass
substituents
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49
as pyridyl, fury!, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen,
and ni-
trogen. In general, no more than two, or no more than one, non-hydrocarbon
substitu-
ent will be present for every ten carbon atoms in the hydrocarbyl group;
alternatively,
there may be no non-hydrocarbon substituents in the hydrocarbyl group.
[0218] 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. For instance, metal ions (of, e.g., a
detergent) can
migrate to other acidic or anionic sites of other molecules. The products
formed
thereby, including the products formed upon employing the 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 pre-
sent invention; the present invention encompasses the composition prepared by
admix-
ing the components described above.
[0219] As used herein, the term "about" means that a value of a given
quantity is
within 20% of the stated value. In other embodiments, the value is within
15% of
the stated value. In other embodiments, the value is within 10% of the stated
value. In other embodiments, the value is within 5% of the stated value. In
other
embodiments, the value is within 2.5% of the stated value. In other
embodiments,
the value is within 1% of the stated value.
[0220] Additionally, as used herein, the term "substantially" means that a
value
of a given quantity is within 10% of the stated value. In other embodiments,
the
value is within 5% of the stated value. In other embodiments, the value is
within
2.5% of the stated value. In other embodiments, the value is within 1% of the
stated value.
[0221] Each of the documents referred to above is incorporated herein by
reference,
including any prior applications, whether or not specifically listed above,
from which
priority is claimed. The mention of any document is not an admission that such
docu-
ment qualifies as prior art or constitutes the general knowledge of the
skilled person in
any jurisdiction. Except in the Examples, or where otherwise explicitly
indicated, all
numerical quantities in this description specifying amounts of materials,
reaction con-
ditions, molecular weights, number of carbon atoms, and the like, are to be
understood
as modified by the word "about." It is to be understood that the upper and
lower
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amount, range, and ratio limits set forth herein may be independently
combined. Sim-
ilarly, the ranges and amounts for each element of the invention can be used
together
with ranges or amounts for any of the other elements.
[0222] 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 alter-
native 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 materi-
ally affect the essential or basic and novel characteristics of the
composition or method
under consideration.
[0223] While certain representative embodiments and details have been shown
for
the purpose of illustrating the subject invention, it will be apparent to
those skilled
in this art that various changes and modifications can be made therein without
de-
parting from the scope of the subject invention. In this regard, the scope of
the in-
vention is to be limited only by the following claims.
