Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE
Alkylphenol Detergents
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to hydrocarbyl- (e.g. alkyl-)
phenol
detergents and their salts having oligomers of branched olefins, including
branched
polyenes, such as terpenes. Such compounds and their salts are useful as
lubricant
additives.
[0002] Phenol-based detergents are known. Among these are phenates
based
on phenolic monomers, linked with sulfur bridges or alkylene bridges such as
meth-
ylene linkages derived from formaldehyde. The phenolic monomers themselves are
typically substituted with an aliphatic hydrocarbyl group to provide a measure
of oil
solubility. The hydrocarbyl groups may be alkyl groups, and, historically, do-
decylphenol (or propylene tetramer-substituted phenol) has been widely used.
An
early reference to basic sulfurized polyvalent metal phenates is U.S. Patent
2,680,96,
Walker et al., June 1, 1954; see also U.S. Patent 3,372, 1 16, Meinhardt,
March 6,
1968.
[0003] Recently, however, certain alkylphenols and products prepared
from
them have come under increased scrutiny due to their association as potential
endo-
crine disruptive materials. In particular, alkylphenol detergents which are
based on
phenols alkylated with oligomers of propylene, specifically propylene tetramer
(or
tetrapropenyl), may contain residual alkyl phenol species. There is interest,
therefore,
in developing alkyl-substituted phenol detergents, for uses in lubricants,
fuels, and
as industrial additives, which contain a reduced or eliminated amount of
dodecylphe-
nol component and other substituted phenols having propylene oligomer
substituents
of 10 to 15 carbon atoms. Nevertheless, it is desirable that the products
should have
similar oil-solubility parameters as phenates prepared from C10-15 propylene
oligo-
mers.
[0004] There have been several efforts to prepare phenate detergents
that do
not contain C. 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
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salt of a reaction product of (1) an olefin having at least 10 carbon atoms,
where
greater than 90 mole % of the olefin is a linear C20-C30 n-alpha olefin, and
wherein
less than 10 mole % of the olefin is a linear olefin of less than 20 carbon
atoms, and
less than 5 mole %of the olefin a branched chain olefin of 18 carbons or less,
and (2)
a hydroxyaromatic compound
[0005] U.S. Application 2011/0190185, Sinquin et al, August 4, 2011,
dis-
closes an overbased salt of an oligomerized alkylhydroxyaromatic compound. The
alkyl group is derived form 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 C 14 to C20 carbon atoms.
[0006] U.S. Application 201 1/0124539, Sinquin et al, May 26, 2011,
dis-
closes an overbased, sulfurized salt of an alkylated hydroxyaromatic compound.
The
alkyl substituent is a residue of at least one isomerized a-olefin having from
15 to
about 99 wt. % branching. The hydroxyaromatic compound may be phenol, cresols,
xylenols, or mixtures thereof.
[0007] U.S. Application 2011/0118160, Campbell et al., May 19, 2011,
dis-
closes an alkylated hydroxyaromatic compound substantially free of endocrine
dis-
ruptive chemicals. An alkylated hydroxyaromatic compound is prepared by
reacting
a hydroxyaromatic compound with at least one branched olefinic propylene
oligomer
having from about 20 to about 80 carbon atoms. Suitable hydroxyaromatic com-
pounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol,
and
the like.
[0008] U.S. Application 2010/0029529, Campbell et al., February 4,
2010,
discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound.
The
alkyl group is derived from an olefin mixture comprising propylene oligomers
having
an initial boing point of at least about 195 C and a final boiling point of
no more
than about 325 C. Suitable hydroxyaromatic compounds include phenol,
catechol,
resorcinol, hydroquinone, pyrogallol, cresol, and the like.
[0009] U.S. Application 2008/0269351, Campbell et al., October 30, 2008,
discloses an alkylated hydroxyaromatic compound substantially free of
endocrine
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disruptive chemicals, prepared by reacting a hydroxyaromatic compound with a
branched olefinic oligomer having from about 20 to about 80 carbon atoms.
[0010] U.S. Application 2017/0211008, Walker et al., July 27, 2017,
discloses
metal salts and overbased metal salts of an oligomerized alkylphenol compound.
The
alkyl group is derived from oligomers of an olefin compound containing 3 to 8
carbon
atoms, and wherein the polyolefin-derived alkyl group comprises at least 30
mol per-
cent of an olefin with 4 or more carbon atoms, especially n-butene.
[0011] WO/PCT application 2013/059173, Cook et al., discloses
discloses an
overbased salt of an oligomerized alkylhydroxyaromatic compound. The alkyl
group
is a combination of very short hydrocarbyl group (i.e. 1 to 8 carbon atoms)
and a long
hydrocarbyl group (at least about 25 carbon atoms). Suitable compounds incude
those
made from a mixture of para-cresol and polyisobutylene-substituted phenol.
[0012] Other general technology includes that of U.S. Patent
6,310,009, Car-
rick et al., October 30, 2001 , which discloses salts of the general structure
om Om
X Y
X
p
where R1 may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18 carbon
atoms.
It is understood that R1 will normally comprise a mixture of various chain
lengths, so
that the foregoing numbers will normally represent an average number of carbon
at-
oms in the R1 groups (number average).
SUMMARY OF THE INVENTION
[0013] The disclosed technology, may solve at least one problem of
providing
a phenolic material with appropriate oil solubility, providing anti-wear
performance,
frictional performance, providing oxidation performance, viscosity
performance, and
detergency (characteristic of moderate chain length alkyl groups). In one
embodi-
ment the disclosed technology may also solve the problem of containing C12
alkyl
phenol moieties i.e., the disclosed technology may be free from or
substantially free
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from C12 alkyl phenol moieties typically formed from oligomerisation or
polymeri-
sation of propylene.
[0014]
One aspect of the disclosed technology relates to an alkylphenol deter-
gent composition comprising at least one phenol moiety having a hydrocarbyl
group
attached thereto. The hydrocarbyl group can include at least one oligomer
having
monomers equivalent, in some embodiments, to 5 to 10 carbon atom branched
olefins,
and in some embodiments, more particularly to 5 to 10 carbon atom branched
poly-
enes. In embodiments, the monomers making up the oligomers can be equivalent
to
isoprene. The oligomer itself can be equivalent to a terpene, and more
particularly
can be equivalent to any of (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tet-
raene; (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene; (E)-2,9-dim ethy1-
5 -
(prop-l-ene-2 -yl)deca-1,3,8-triene;
(3E,6E, 10E)-2,6, 10-trim ethyldodeca-1,3,6, 10-
tetraene; (E)-7,11 -di methyl-3 -methyl enedodeca-1,6,10-tri ene; (6E,10E)-
7,11,15-tri-
methy1-3 -methylenehexadeca-1,6, 10,14 -tetraene;
(3E,6E, 10E)-3,7, 11,15-tetra-
methyl hexadeca-1,3 ,6,10, 1-pentaene; (6E,10E,14E)-7, 11,14-trim ethy1-3-
methyl ene-
hexadeca-1,6, 10,14 -tetraene; (3E,9E,13E)-2, 10,13 -trimethy1-6-(prop-1-en-2-
yl)pen-
tadeca- 1,3,9,13 -tetraene.
[0015]
The oligomer can also be equivalent to a hydrogenated (partial or com-
plete) form of a terpene, such as, for example, any of 3,7,11-trimethyldodec-1-
ene;
2,6, 10-trim ethyl dodec-2-ene; (E)-3,7, 11 -trimethyl dodec-2 -ene; 2,6-dim
ethyl-10-
methyl enedodecane; (E)-2,6,10-trimethyldodec-6-ene; (E)-3,7,11-trimethyldodec-
3-
ene; (E)-2,6,10-trimethyldodec-5-ene; 3,7, 11 -trimethyl dodeca-1, 10-diene
[0016]
In embodiments, the hydrocarbyl unit of the alkylphenol detergent can
contain from 15 to 60 carbon atoms.
[0017] The alkylphenol detergent can include alkylphenol moiety equivalent
to any of 4-(3,7, 11 -trimethyldodecan-2 -yl)phenol ; 4 -(2,6,10-trimethyl
dodecan-2 -
yl)phenol ; 4-(3,7, 11 -trimethyl dodec-10-en-2-yl)phenol ; 4-(2,6,10-
trimethyldodec-
11 -en-2-yl)phenol .
[0018]
The alkylphenol detergent can be a sulfur-bridged phenate detergent, a
sulfur-free alkylene-bridged phenate detergent, a salicylate detergent, or
mixtures
thereof. The alkylphenol detergent can include one or more alkali metals, one
or
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more alkaline earth metals, or mixtures thereof. The alkylphenol detergent
compo-
sition can be overbased, and in embodiments, have a metal ratio of at least
1.5, at
least 5, or at least 7.
[0019] In an embodiment, the alklylphenol detergent can be an
overbased sul-
5 fur-coupled phenate detergent with a metal ratio of at least 1.5.
[0020] In an embodiment, the alkylphenol detergent composition can
be a sul-
fur-bridged phenate represented by the structure
OH OH OH
Sy Sy
1401
wherein each R is an aliphatic hydrocarbyl group equivalent to an oligomer of
iso-
prene, higher branched olefins, or mixtures thereof, that contains 15 to 60
carbon
atoms; each y can be 1 to 4; and n = 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4.
[0021] In an embodiment, the alkylphenol detergent can be a neutral
or over-
based salt of alkylsalicylic acid.
[0022] In an embodiment, the alkylphenol detergent can be an
alkylsalicylate
represented by the structure
OH 0
1401 OH
where R is an aliphatic hydrocarbyl group equivalent to an oligomer of
isoprene,
higher branched olefins, or mixtures thereof, and wherein the hydrocarbyl
group con-
tains 15 to 60 carbon atoms.
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[0023] Another aspect of the technology relates to a lubricating
composition
having (a) an oil of lubricating viscosity and (b) the alkylphenol detergent
composi-
tion as described herein. In embodiments, lubricating composition can be
substan-
tially free to free of an alkylphenol-containing detergent wherein the
alkylphenol is
derived from oligomers of propene. The lubricating composition can also
include
other additives, such as, for example, other detergents besides the instant
alkylphenol
detergent, zinc dialkyldithiophosphate, dispersants, antiwear agents, extreme
pres-
sure agents, corrosion inhibitors, etc.
[0024] A further aspect of the technology relates to methods of
lubricating a
mechanical device, for example, by supplying to the device the lubricating
composi-
tion described herein containing the alkylphenol detergent. The mechanical
device
can be, for example, an internal combustion engine, an automotive driveline
device,
such as a transmission or an axle, or an off-highway vehicle. The technology
could
also be employed in industrial applications, such as industrial hydraulics.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Various preferred features and embodiments will be described
below by
way of non-limiting illustration.
[0026] The disclosed technology includes an alkylphenol detergent
composi-
tion (or just alkylphenol for short), a lubricating composition containing the
alkylphe-
nol, a method for lubricating a mechanical device with a lubricating
composition
containing the alkylphenol, and a use of the alkylphenol, all of which will be
more
particularly described herein.
[0027] One aspect of the disclosed technology is an alkylphenol
detergent
composition. The alkylphenol detergent will include at least one phenol moiety
with
.. at least one hydrocarbyl group attached thereto. Those of ordinary skill in
the art can
observe a chemical composition and readily imagine the moieties to which the
com-
position may be derived from. As used herein, reference to the phenol moiety
means
that moiety of the alkylphenol detergent composition one of ordinary skill in
the art
could imagine would be derived from a phenol, i.e., of Formula I.
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Formula I
OH
101
[0028] The alkylphenol will also include a hydrocarbyl group. As
used herein,
the term "hydrocarbyl group" is used in its ordinary sense, which is well-
known to
those skilled in the art. Specifically, it refers to a group having a carbon
atom directly
attached to the remainder of the molecule and having predominantly hydrocarbon
char-
acter. Examples of hydrocarbyl groups include, for example: hydrocarbon
substituents,
including aliphatic, alicyclic, and aromatic substituents; substituted
hydrocarbon sub-
stituents, that is, substituents containing non-hydrocarbon groups which, in
the context
of this invention, do not alter the predominantly hydrocarbon nature of the
substituent;
and hetero substituents, that is, substituents which similarly have a
predominantly hy-
drocarbon character but contain other than carbon in a ring or chain.
[0029] While the hydrocarbyl group can include elements of non-
hydrocarbyl
character (i.e., nitrogen, halogens, etc.), in many embodiments the
hydrocarbyl group
can be of substantially, or even completely, hydrocarbon character. In some
embodi-
ments, the hydrocarbyl group can be of substantially or completely aliphatic
character.
[0030] The hydrocarbyl group can comprise, consist essentially of,
or consist
of at least one oligomer, and the at least one oligomer itself can comprise,
consist
essentially of, or consist of monomers equivalent to 5 to 10 carbon atom
branched
olefins. By employing the terminology "equivalent to," it is recognized that
the ref-
erenced compound, in this case the monomers of the oligomer, are slightly
altered in
their final state from their original state; for example, an oligomerized
monomer ver-
sus the lone monomer. In other words, the hydrocarbyl group, when looked at in
discreet units, contains identifiable oligomer units, and the identifiable
oligomer units
can be further broken down into identifiable alkyl units that, as a monomer
would be
considered a 5 to 10 carbon atom branched olefin.
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[0031] A branched olefin, as used herein, refers to an alkyl chain
having at
least one double bond and at least one tertiary carbon atom. Without limiting
the
branched olefin, examples of such branched olefins can be represented by the
follow-
ing example branched olefin formulas.
Ra Rb Ra Rb Ra Rb
CRc
'`ICH2)11 41Rc CRc
H2 n H n
Ra Rb Ra Rb
Rc CRc
H n
where Ra, Rb, and Rc can be H or a lower Ci to C5 alkyl group; n and m can be,
independently, integers of 0 to 6, with the proviso that n+m is from 1 to 6;
and the
olefin has from 5 to 10 carbon atoms. An oligomer of such a branched olefin
could
be, for example, oligomers of the following formula.
Ra Rb
CT(111'11R)
H2 n
where Ra, Rb, Rc, m and n are as above, and y is an integer of 2 to 18, or 2
to 15, or
2 to 12.
[0032] The branched olefin can also be polyenes. That is, the
hydrocarbyl
group can comprise, consist essentially of, or consist of at least one
oligomer, and
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the at least one oligomer itself can comprise, consist essentially of, or
consist of mon-
omers equivalent to 5 to 10 carbon atom branched polyene compounds. As used
herein a polyene is a poly-unsaturated alkylene compound having at least 2
double
bonds (also known as a diene), and in some cases 3, 4, or 5 double bonds.
[0033] Branched polyene compounds can be described as alkyl chains having
at least two double bonds in the chain, and at least one tertiary carbon atom.
Although
the polyene compound may include more than 2 double bonds, an example branched
polyene compound may be a branched conjugated diene represented by the
following
formula,
R3
)T p
2 ..4
where R1, R2, R3, and R4 are independently H, or lower Ci to C5 alkyl groups;
with
the proviso that at least one of R1, R2, R3, and R4 is an alkyl group and that
taken
together the conjugated diene has a total of from 5 to 10 carbon atoms.
[0034] The at least one oligomer in the hydrocarbyl group can be
oligomerized
from 5 to 10 carbon atom branched olefin/polyenes, or the oligomer may be
prepared
in some other manner. For example, the oligomer may be formed by 1,2-monomer
addition or 1,4-monomer addition. In one embodiment, oligomers of 5 to 10
carbon
atom branched polyenes may formed by 1,4-addition of the monomers, followed by
partial hydrogenation of the resulting material to form a mono-olefinic
alkylating
agent, which could then react with phenol to form the oligomeric alkyl phenol.
The
hydrocarbyl group may also be derived from an alkylating agent containing a
het-
eroatom, such as phytol or farnesol, which may be prepared from reacting
monomers
of a mono or polyene containing a heteroatom. For instance, Tetrahedron Vol
43. No.
19. pp. 4481 to 4486, 1987 describes the synthesis of phytol from two C10
units
derived from geraniol.
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In another example, the oligomer may also be produced via biological activity,
such
as through the fermentation of a cell culture system that is capable of
producing the
desired branched olefin/polyene or a composition having the appearance of an
oli-
gomer containing monomers equivalent to 5 to 10 carbon atom branched
olefin/pol-
5 yene compounds. For instance, WO 2011/160081 provides a biological
pathway for
the production of isoprene, and the use of the so-produced isoprene to produce
oli-
gomers (also called terpenes, i.e., having a formula of (C5H8), where n is 2,
3,4, 5
or higher). The hydrocarbyl group may also be derived from an alkylating agent
produced from a biological pathway, including, for instance, a biological
pathway
10 for the production of natural phytol from the crude extraction of
silkworm excre-
ment, Moms alba leaf, bamboo leaf, pine needle and Ginkgo biloba leaf, for
exam-
ple as taught in CN 102807471 A Dec 05, 2012. Other biological pathways are
known to produce the oligomers (e.g., terpenes) themselves.
[0035] An oligomer containing monomers equivalent to 5 to 10 carbon
atom
branched olefins could be, for example, oligomers of the following formula
R1 R3
R4)7
2
where R1, R2, R3, and R4 and y are the same as defined above.
[0036] The branched polyene compound containing 5 to 10 carbon atoms
may
include isoprene monomers of Formula IV.
Formula IV
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In addition to isoprene, suitable branched olefins 2-methyl-l-butene, 3-methyl-
l-bu-
tene, 4-methyl-l-pentene, 2-m ethyl-l-pentene, 3 -methyl-l-pentene, 2-methyl-l-
hex-
ene, 3 -methyl -1-hexene, 5 -methyl -1-hexene, 4-methyl -1-hexene, 2-methyl -1-
hep-
tene, 2.3 -dim ethyl -1,3 -butadiene, 2,4-dimethyl -1,3 -pentadi ene, 3 -
methyl -1,3-penta-
diene, and mixtures thereof.
[0037] In an embodiment, the oligomer contains units equivalent to
isoprene.
An isoprene oligomer containing 15 to 60 carbon atoms would contain 3 to 12
iso-
prene monomer units. An isoprene polymer or oligomer containing 15 to 30
carbon
atoms would contain 3 or 6 isoprene monomer units.
[0038] In an embodiment, the oligomer can be a trimer of isoprene, which
can
be envisioned in the following forms
(2E,5E,7E,1oE)-3,6,10-trimethyldodeca-2,5,7,10-tetraene
(3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene
(E)-2,9-dimethy1-5-(prop-1-en-2-y1)deca4,3,84riene
(3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-tetraene
(E)-7,11-dimethy1-3-methylenedodeca-1,6,10-triene
[0039] Tetramers of isoprene may also be employed in the oligomer,
and can
be envisioned in the following forms
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(6E,10E)-7,11,15-trimethy1-3-methylenehexadeca-1,6,10,14-tetraene
(3E,6E,10E)-3,7,11,15-tetramethylhexadeca-1,3,6,10,14-pentaene
(6E,10E,14E)-7,11,14-trimethy1-3-methylenehexadeca-1,6,10,14-tetraene
(3E,9E,13E)-2,10,13-trimethy1-6-(prop-1-en-2-yl)pentadeca-1,3,9,13-tetraene
[0040] In one embodiment, the hydrocarbyl group of the alkylphenol
detergent
can comprise, consist essentially of, or consist of oligomer compounds
comprising,
consisting essentially of, or consisting of at least 50 mol% monomers
equivalent to
isoprene, at least 75 mol% monomers equivalent to isoprene, or at least 90
mol%
monomers equivalent to isoprene. In one embodiment, the hydrocarbyl group in
the
alkylphenol detergent consists of oligomers of isoprene.
[0041] In some embodiments, the oligomer can be hydrogenated forms,
either
partial or complete, of what the oligomer of the alkylene units would
otherwise ap-
.. pear as. Hydrogenation may be performed, for example, by any hydrogenating
agent
known to a skilled artisan. For example, a saturated oligomer of polyene
compounds
can be prepared by hydrogenating at least a portion of the double bonds in the
oligo-
mer in the presence of a hydrogenation reagent, such as hydrogen in the
presence of
a catalyst, or by treatment with hydrazine in the presence of a catalyst.
[0042] In some embodiments, at least a portion of the C=C bonds of the oli-
gomer is reduced to the corresponding C¨C bonds by hydrogenation. In some em-
bodiments, all of the C=C bonds of the oligomer are reduced to the
corresponding C-
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C bonds by hydrogenation. In an embodiment, the oligomer can include a
hydrogen-
ated form of oligomer in the form of any of the following structures:
[0043] Whether prepared from the oligomerization of discreet units or
other-
wise, one of ordinary skill in the art will recognize the presence of the
oligomers and
monomers therein equivalent to 5 to 10 carbon atom branched polyenes within
the
hydrocarbyl group.
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[0044] The hydrocarbyl group can contain from 10 to 200 carbon atoms,
or in
some examples 12 to 100 carbon atoms, or even 15 to 80 carbon atoms. In some
em-
bodiments, the hydrocarbyl group can have 15 to 60 carbon atoms, or in some
cases
15 to 30 or 45 carbon atoms, or 20 to 30 carbon atoms.
[0045] The alkylphenol detergent, including the phenol moiety and the
hydro-
carbyl group, may include the structure represented by the following formula.
OH
where R represents the hydrocarbyl group described above. For example, the al-
kylphenol can include the structure shown in the following formulas.
OH OH
OH OH
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[0046] 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
5 by the structure:
OH OH OH
Sy Sy
401
or more generally
OH OH OH
Xy, Xy
401
or isomers thereof, wherein each R represents the hydrocarbyl group described
above
10 having substantially or completely aliphatic character and 15 to 60, or
in some cases
15 to 30 carbon atoms; aliphatic hydrocarbyl groups containing 30 to 200 or 35
to 80
carbon atoms; methyl groups; and mixtures thereof, each y can be 1 to 4.
[0047] The average number of carbon atoms in all the R groups,
combined,
may be 15 to 100 (or 20 to 50, or 24 to 36 or 14 to 20 or 18 to 36). Where the
bridging
15 group may be listed as "X", each X may 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
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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 embodiments, 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 in-
clude dimeric species. Accordingly, sometimes the expression "dimeric or oligo-
meric" may be used to express this concept, which may include, as above, as an
ex-
ample, 0 to 8 interior units bracketed by [ ]. or 2 to 10 units overall.
[0048] In one embodiment, the sulfur-bridged alkylphenol-containing
deter-
gent may be an oligomer of p-(isoprene)phenol. A sulfur-bridged oligomer of ol-
igo(isoprene)phenol may be represented by the structure
OH OH OH
=Sy Sy
where n = 0 to 4, and m = 1 to 4 and each y can be 1 to 4.
[0049] In certain embodiments, the alkylene-bridged phenate
detergent may
be a saligenin detergent. A saligenin detergent contains a bridged-alkyl
phenol com-
.. pound that may be an alkylene coupled alkylphenol represented by the
structure
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OH OH
X
II
where each R represents the hydrocarbyl group described above having 15 to 60,
or
in some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups containing
30 to
200 or 35 to 80 carbon atoms; methyl groups; and mixtures thereof; where the
each
bridging group (X) may be independently a carbon-containing bridge, or a hydro-
carbylether 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.
[0050] 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
X
OH OH
(V)
where R represents the hydrocarbyl group described above having substantially
or
completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon
atoms;
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl
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groups; and mixtures thereof; where the each bridging group (X) may be inde-
pendently a carbon-containing bridge, or an alkylene group, or a methylene
group;
and n may be an integer from 1 to 10.
[0051] The bridged alkylphenol detergents may be neutral or
overbased or su-
perbased. Such overbased detergents are generally single phase, homogeneous
New-
tonian 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.
[0052] 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,
salixarate or saligenin. In one embodiment, the overbased detergent comprises
a salt
of an alkylamine or quaternary ammonium compound. Overbased salixarates, phen-
ates and saligenins typically have a total base number (TBN) (by ASTM D3896)
of
120 to 600 mg KOH/g.
[0053] In certain embodiments, the alkylphenol detergent composition
may be
an alkylsalicylate or salicylate detergent. A salicylate detergent may be a
neutral or
overbased metal salt of alkylsalicylic acid. Alkylsalicylic acid may be
represented by
the formula (VI)
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OH 0
1401 OH
(VI)
where R represents the hydrocarbyl group described above having substantially
or
completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon
atoms;
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl
groups; and mixtures thereof.
[0054] The alkylsalicylate may be a neutral or nearly neutral salt
of alkylsali-
cylic 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
ammonium salt, a metal salt, or mixtures thereof.
[0055] Amines suitable for use in the preparation of the neutral
amine salted
alkylsalicylate are not overly limited and may include any alkyl amine, di- or
tri-alkyl
amine, though generally are fatty acid amines derived from fatty carboxylic
acids.
The alkyl group present in the amine may contain from 10 to 30 carbon atoms,
or
from 12 to 18 carbon atoms, and may be linear or branched. In some
embodiments,
the alkyl group may be linear and unsaturated. Typical amines include 2-
ethylexhyl-
amine, pentadecylamine, octadecylamine, cetyl amine, oleylamine, decylamine,
do-
decylamine, dimethyldodecylamine, tridecyl amine, heptadecylamine, octadecyla-
mine, stearylamine, and any combination thereof. In some embodiments, the
fatty
acid derived amine salt of an alkylsalicylic acid may be a salt of oleylamine.
In certain
embodiments, the amine may be a gamma-aminoester compound; aminoesters of this
type may be derived from Michael addition of a primary amine to an alkyl
diester of
itaconic acid represented by the formula
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0
Rio
NHR12
where Rio and Rii are hydrocarbyl groups containing 2 to 30 carbon atoms, and
Ri2
is a hydrocarbyl group containing 4 to 50 carbon atoms. In some embodiments,
R12
of the aminoester compound is an alkyl group that has at least one hydrocarbyl
group
5 substituted at the 1-, or 2-position of the alkyl group. In one
embodiment, the ami-
noester is dibutyl 2-(((2-ethylhexyl)-amino)methyl)succinate.
[0056] 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-
10 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.
15 [0057] The alkylphenol-containing detergents, be they
phenates, saligenins,
salixrates, or salicylates, may be metal-containing detergents. Metal-
containing de-
tergents 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-
20 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
"metal ratio is also explained in standard textbook entitled "Chemistry and
Technol-
ogy of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik,
Cop-
yright 2010, page 219, sub-heading 7.25.
[0058] In one embodiment the overbased metal-containing alkylphenol
deter-
gent may be calcium or magnesium overbased detergent. In one embodiment, the
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overbased detergent may comprise a calcium alkylphenol detergent with a metal
ratio
of at least 1.5, at least 3, at least 5, or at least 7. In certain
embodiments, the overbased
calcium alkylphenol detergent may have a metal ratio of 1.5 to 25, 2.5 to 20
or 5 to
16.
[0059] 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
defined as the amount necessary to deliver an amount, or range of amounts, of
TBN
to the lubricant composition. In certain embodiments, the alkylphenol-
containing de-
tergent 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.
[0060] Overbased detergents may also be defined as the ratio of the
neutral
detergent salt, also referred to as detergent soap, and the detergent ash. The
overbased
detergent may have a weight ratio of ash to soap of 3:1 to 1:8, or 1.5:1 to 1
to 4.1, or
1.3:1 to 1:3.4.
[0061] The product of the disclosed technology may beneficially be
used as an
additive in a lubricant. The amount of the alkylphenol detergent in a
lubricant may be
0.1 to 8 percent by weight, on an oil-free basis, but including the calcium
carbonate
and other salts present in an overbased composition. When present as an
overbased
detergent, the amount may typically be in the range of 0.1 to 25 weight
percent, or 0.2
to 28, or 0.3 to 20, or 0.5 to 15 percent. The higher amounts are typical of
marine
diesel cylinder lubricants, e.g., 1 or 3 or 5 percent up to 25, 20, or 15
percent. Amounts
used in gasoline or heavy-duty diesel engines (not marine) will typically be
in lower
ranges, such as 0.1 to 10 percent or 0.5 to 5 or 1 to 3 percent by weight.
When used as
a substantially neutral or non-overbased salt, its amount may typically be
correspond-
ingly less for each of the engine types, e.g., 0.1 to 10 percent or 0.2 to 8
or 0.3 to 6
percent.
[0062] In certain embodiments, the amount of the alkylphenol
detergent in a
lubricant may be measured as the amount of alkylphenol-containing soap that is
pro-
vided to the lubricant composition, irrespective of any overbasing. In one
embodi-
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ment, the lubricant composition may contain 0.05 weight percent to 1.5 weight
per-
cent alkylphenol-containing soap, or 0.1 weight percent to 0.9 weight percent
al-
kylphenol-containing soap. In one embodiment, the alkylphenol-containing soap
pro-
vides 20 percent by weight to 100 percent by weight of the total detergent
soap in the
lubricating composition. In one embodiment the alkylphenol-containing soap pro-
vides 30 percent by weight to 80 percent by weight of the total detergent
soap, or 40
percent by weight to 75 percent by weight of the total detergent soap of the
lubricat-
ing composition.
[0063] A lubricant composition may contain alkylphenol-containing
deter-
gents different from that of the disclosed technology. In one embodiment, the
lubri-
cant composition of the disclosed technology comprises the alkylphenol
detergent of
the disclosed technology in an amount 0.1 to 25 weight percent, or 0.2 to 23,
or 0.3 to
20, or 0.5 to 15 weight percent, and is free of or substantially free of an
alkylphenol-
containing detergent derived from alkylphenol which is derived from oligomers
of pro-
pylene, especially tetrapropenyl. "Substantially free of' in this case means
no more
than 0.01 weight percent or an amount considered to arise through
contamination or
other unintentional means. In some embodiments, the lubricant composition can
in-
clude the alkylphenol detergent at 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 lubricating
composition.
Oil of Lubricating Viscosity
[0064] Another aspect of the technology is a lubricant containing
the alkylphe-
nol detergent composition. The lubricating composition includes an oil of
lubricating
viscosity. Such oils include natural and synthetic oils, oil derived from
hydrocrack-
ing, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or
mix-
tures 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 hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment
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oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as
well
as other gas-to-liquid oils.
[0065] Oils of lubricating viscosity may also be defined as
specified in the
American Petroleum Institute (API) Base Oil Interchangeability Guidelines
(2011).
The five base oil groups are as follows: Group I (sulfur content >0.03 wt %,
and/or <90
wt % saturates, viscosity index 80 to less than 120); Group II (sulfur content
<0.03 wt
%, and >90 wt % saturates, viscosity index 80 to less than 120); Group III
(sulfur
content <0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV
(all
polyalphaolefins (PA0s)); and Group V (all others not included in Groups I,
II, III, or
IV). The oil of lubricating viscosity may also be a Group II+ base oil, which
is an
unofficial API category that refers to a Group II base oil having a viscosity
index
greater than or equal to 110 and less than 120, as described in SAE
publication "Design
Practice: Passenger Car Automatic Transmissions," fourth Edition, AE-29, 2012,
page
12-9, as well as in US 8,216,448, column 1 line 57. The oil of lubricating
viscosity
may also be a Group III+ base oil, which, again, is an unofficial API category
that
refers to a Group III base oil having a viscosity index of greater than 130,
for example
130 to 133 or even greater than 135, such as 135-145. Gas to liquid ("GTL")
oils are
sometimes considered Group III+ base oils.
[0066] The oil of lubricating viscosity may be an API Group IV oil,
or mixtures
thereof, i.e., a polyalphaolefin. The polyalphaolefin may be prepared by
metallocene
catalyzed processes or from a non-metallocene process. The oil of lubricating
viscosity
may also comprise an API Group I, Group II, Group III, Group IV, Group V oil
or
mixtures thereof. Often the oil of lubricating viscosity is an API Group I,
Group II,
Group II+, Group III, Group IV oil or mixtures thereof. Alternatively the oil
of lubri-
cating viscosity is often an API Group II, Group II+, Group III or Group IV
oil or
mixtures thereof. Alternatively the oil of lubricating viscosity is often an
API Group
II, Group II+, Group III oil or mixtures thereof.
[0067] The oil of lubricating viscosity, or base oil, will overall
have a kinematic
viscosity at 100 C of 2 to 10 cSt or, in some embodiments 2.25 to 9 or 2.5 to
6 or 7 or
8 cSt, as measured by ASTM D445. Kinematic viscosities for the base oil at 100
C
of from about 3.5 to 6 or from 6 to 8 cSt are also suitable.
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[0068] The amount of the oil of lubricating viscosity present is
typically the
balance remaining after subtracting from 100 wt % the sum of the amount of the
per-
formance additives in the composition. Illustrative amounts may include 50 to
99 per-
cent by weight, or 60 to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent.
[0069] The lubricating composition may be in the form of a concentrate
and/or
a fully formulated lubricant. If the lubricating composition of the invention
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 components of the
invention 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.
[0070] A lubricating composition may be prepared by adding the
product of
the process described herein to an oil of lubricating viscosity, optionally in
the pres-
ence of other performance additives (as described herein below).
[0071] The other performance additives can include at least one of
metal de-
activators, viscosity modifiers (other than the soot dispersing additive of
the present
invention), detergents, friction modifiers, antiwear agents, corrosion
inhibitors, dis-
persants (other than those of the present invention), extreme pressure agents,
antiox-
idants, foam inhibitors, demulsifiers, pour point depressants, seal swelling
agents and
mixtures thereof. Typically, fully-formulated lubricating oil will contain one
or more
of these performance additives.
[0072] In one embodiment the invention provides a lubricating
composition
further comprising an overbased metal-containing detergent in addition to the
al-
kylphenol-containing detergent of the present invention. The metal of the
metal-con-
taining detergent may be zinc, sodium, calcium, barium, or magnesium.
Typically the
metal of the metal-containing detergent may be sodium, calcium, or magnesium.
[0073] The overbased metal-containing detergent may be chosen from
sul-
fonates, non-sulfur containing phenates, sulfur containing phenates,
salixarates, sa-
licylates, and mixtures thereof, or borated equivalents thereof. The overbased
deter-
gent may be borated with a borating agent such as boric acid.
[0074] The overbased metal-containing detergent may also include "hybrid"
detergents formed with mixed surfactant systems including phenate and/or
sulfonate
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components, e.g. phenate/salicylates, sulfonate/phenates,
sulfonate/salicylates, sul-
fonates/phenates/salicylates, as described; for example, in US Patents
6,429,178;
6,429,179; 6,153,565; and 6,281,179. Where, for example, a "hybrid" sul-
fonate/phenate detergent is employed, the "hybrid" detergent would be
considered
5 equivalent to amounts of distinct phenate and sulfonate detergents
introducing like
amounts of phenate and sulfonate soaps, respectively.
[0075] Typically, an overbased metal-containing detergent may be a
zinc, so-
dium, calcium or magnesium salt of a sulfonate, a phenate, sulfur containing
phenate,
salixarate or salicylate. Overbased sulfonates, salixarates, phenates and
salicylates
10 typically have a total base number of 120 to 700 TBN.
[0076] Typically, the overbased metal-containing detergent may be a
calcium
or magnesium overbased detergent.
[0077] In another embodiment the lubricating composition further
comprises
a calcium sulfonate overbased detergent having a TBN of 120 to 700. The
overbased
15 sulfonate detergent may have a metal ratio of 12 to less than 20, or 12
to 18, or 20 to
30, or 22 to 25.
[0078] Overbased sulfonates typically have a total base number of
120 to 700,
or 250 to 600, or 300 to 500 (on an oil free basis). Overbased detergents are
known
in the art. In one embodiment the sulfonate detergent may be a predominantly
linear
20 alkylbenzene sulfonate 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). Linear alkyl benzenes may have the benzene ring attached
anywhere
on the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof.
The pre-
dominantly linear alkylbenzene sulfonate detergent may be particularly useful
for
25 assisting in improving fuel economy. In one embodiment the sulfonate
detergent may
be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds
as dis-
closed in paragraphs [0046] to [0053] of US Patent Application 2008/0119378.
[0079] In one embodiment the lubricating composition further
comprises
0.01 wt % to 2 wt %, or 0.1 to 1 wt % of a detergent different from the
alkylphenol
detergent of the disclosed technology, wherein the further detergent is chosen
from
sulfonates, non-sulfur containing phenates, sulfur containing phenates,
sulfonates,
salixarates, salicylates, and mixtures thereof, or borated equivalents
thereof.
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[0080] In one embodiment the lubricating composition further
comprises a
"hybrid"detergent formed with mixed surfactant systems including phenate
and/or
sulfonate components, e.g. phenate/salicylates, sulfonate/phenates,
sulfonate/salicy-
lates, or sulfonates/phenates/salicylates.
[0081] The lubricating composition in a further embodiment comprises an an-
tioxidant, wherein the antioxidant comprises a phenolic or an aminic
antioxidant or
mixtures thereof. The antioxidants include diarylamines, alkylated
diarylamines, hin-
dered phenols, or mixtures thereof. When present the antioxidant is present at
0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt % of the
lubricating
composition.
[0082] The diarylamine or alkylated diarylamine may be a phenyl-a-
naphthyl-
amine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine,
or
mixtures thereof. The alkylated diphenylamine may include di-nonylated
diphenyla-
mine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine,
di-decylated diphenylamine, decyl diphenylamine and mixtures thereof. In one
em-
bodiment the diphenylamine may include nonyl diphenylamine, dinonyl diphenyla-
mine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In
another
embodiment the alkylated diphenylamine may include nonyl diphenylamine, or di-
nonyl diphenylamine. The alkylated diarylamine may include octyl, di-octyl,
nonyl,
di-nonyl, decyl or di-decyl phenylnapthylamines.
[0083] The hindered phenol antioxidant often contains a secondary
butyl
and/or a tertiary butyl group as a sterically hindering group. The phenol
group may
be further substituted with a hydrocarbyl group (typically linear or branched
alkyl)
and/or a bridging group linking to a second aromatic group. Examples of
suitable
hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methy1-2,6-di-
tert-
butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-
butyl¨phenol or
4-butyl-2,6-di-tert-butylphenol, or 4-dodecy1-2,6-di-tert-butyl¨phenol. In one
em-
bodiment the hindered phenol antioxidant may be an ester and may include,
e.g.,
IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-
containing
hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
[0084] The lubricating composition may in a further embodiment
include a
dispersant, or mixtures thereof. The dispersant may be a succinimide
dispersant, a
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Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid
ester, am-
ide, or ester-amide, or mixtures thereof. In one embodiment the dispersant may
be
present as a single dispersant. In one embodiment the dispersant may be
present as a
mixture of two or three different dispersants, wherein at least one may be a
succin-
imide dispersant.
[0085] The succinimide dispersant may be derived from an aliphatic
polyam-
ine, or mixtures thereof. The aliphatic polyamine may be aliphatic polyamine
such as
an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures
thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine.
In
one embodiment the aliphatic polyamine may be chosen from ethylenediamine, di-
ethyl enetri amine, triethylenetetramine, tetra¨ethylene¨pentamine, pentaethyl
ene-
hexamine, polyamine still bottoms, and mixtures thereof.
[0086] In one embodiment the dispersant may be a polyolefin succinic
acid
ester, amide, or ester-amide. For instance, a polyolefin succinic acid ester
may be a
polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A
poly-
olefin succinic acid ester-amide may be a polyisobutylene succinic acid
reacted with
an alcohol (such as pentaerythritol) and a polyamine as described above.
[0087] The dispersant may be an N-substituted long chain alkenyl
succin-
imide. An example of an N substituted long chain alkenyl succinimide is
polyisobu-
tylene succinimide. Typically the polyisobutylene from which polyisobutylene
suc-
cinic anhydride is derived has a number average molecular weight of 350 to
5000, or
550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are
dis-
closed, for instance in US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281,
3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680,
3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP
Patent
Application 0 355 895 A.
[0088] The dispersants may also be post-treated by conventional
methods by
a reaction with any of a variety of agents. Among these are boron compounds
(such
as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulfide,
aldehydes,
ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted
succinic
anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In
one
embodiment the post-treated dispersant is borated. In one embodiment the post-
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28
treated dispersant is reacted with dimercaptothiadiazoles. In one embodiment
the
post-treated dispersant is reacted with phosphoric or phosphorous acid. In one
em-
bodiment the post-treated dispersant is reacted with terephthalic acid and
boric acid
(as described in US Patent Application US2009/0054278.
[0089] When present, the dispersant may be present at 0.01 wt % to 20 wt %,
or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1 to 3
wt %
of the lubricating composition.
[0090] The succinimide dispersant may comprise a polyisobutylene
succin-
imide, wherein the polyisobutylene from which polyisobutylene succinimide is
de-
rived has a number average molecular weight of 350 to 5000, or 750 to 2500.
[0091] In one embodiment the friction modifier may be chosen from
long
chain fatty acid derivatives of amines, long chain fatty esters, or
derivatives of long
chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric
acids; fatty
alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty
glycolates; and
fatty glycolamides. The friction modifier may be present at 0 wt % to 6 wt %,
or 0.01
wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the
lubricating
composition.
[0092] As used herein the term "fatty alkyl" or "fatty" in relation
to friction
modifiers means a carbon chain having 10 to 22 carbon atoms, typically a
straight
carbon chain.
[0093] Examples of suitable friction modifiers include long chain
fatty acid
derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines
such as con-
densation products of carboxylic acids and polyalkylene-polyamines; amine
salts of
alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty
alkyl tar-
tramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated
fatty
epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated
fatty
amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty
amines
including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of
fatty
acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated
alcohols;
condensation products of carboxylic acids and polyalkylene polyamines; or
reaction
products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or
thiou-
rea and salts thereof.
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[0094] Friction modifiers may also encompass materials such as
sulfurised
fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum di-
thiocarbamates, sunflower oil or soybean oil monoester of a polyol and an
aliphatic
carboxylic acid.
[0095] In another embodiment the friction modifier may be a long chain
fatty
acid ester. In another embodiment the long chain fatty acid ester may be a
mono-ester
and in another embodiment the long chain fatty acid ester may be a
triglyceride.
[0096] The lubricating composition optionally further includes at
least one an-
tiwear agent. Examples of suitable antiwear agents include titanium compounds,
tar-
trates, tartrimides, oil soluble amine salts of phosphorus compounds,
sulfurized ole-
fins, metal dihydrocarbyldithiophosphates (such as zinc
dialkyldithiophosphates),
phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing
compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic
ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)
disulfides.
[0097] The antiwear agent may in one embodiment include a tartrate, or tar-
trimide as disclosed in International Publication W02006/044411 or Canadian
Patent
CA 1183125. The tartrate or tartrimide may contain alkyl-ester groups, where
the
sum of carbon atoms on the alkyl groups is at least 8. The antiwear agent may
in one
embodiment include a citrate as is disclosed in US Patent Application
2005/0198894.
[0098] Another class of additives includes oil-soluble titanium compounds
as
disclosed in US 7,727,943 and US2006/0014651. The oil-soluble titanium com-
pounds may function as antiwear agents, friction modifiers, antioxidants,
deposit con-
trol additives, or more than one of these functions. In one embodiment the oil
soluble
titanium compound is a titanium (IV) alkoxide. The titanium alkoxide is formed
from
a monohydric alcohol, a polyol or mixtures thereof. The monohydric alkoxides
may
have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium
alkoxide is
titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide is tita-
nium (IV) 2 ethylhexoxide. In one embodiment, the titanium compound comprises
the alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the 1,2-
vicinal diol
comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic
acid.
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[0099] In one embodiment, the oil soluble titanium compound is a
titanium
carboxylate. In a further embodiment the titanium (IV) carboxylate is titanium
ne-
odecanoate.
[0100] The lubricating composition may in one embodiment further
include a
5 phosphorus-containing antiwear agent. Typically the phosphorus-containing
anti-
wear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate,
phosphonate,
and ammonium phosphate salts, or mixtures thereof. Zinc
dialkyldithiophosphates
are known in the art. The antiwear agent may be present at 0 wt % to 3 wt %,
or 0.1
wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricating composition. In
some
10 .. embodiments, the antiwear agent may be present in an amount sufficient
to provide
from 0 to 0.12 wt% phosphorus to the lubricating composition, or from 0.01 to
0.08
wt%, or 0.03 to 0.08 wt%, or even 0.025 to 0.06 wt% phosphorus.
[0101] Extreme Pressure (EP) agents that are soluble in the oil
include sulfur-
and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2
derivatives of
15 dispersants (typically succinimide dispersants), derivative of
chlorinated hydrocar-
bon EP agents and phosphorus EP agents. Examples of such EP agents include
chlo-
rinated wax; sulfurized olefins (such as sulfurized isobutylene), a
hydrocarbyl-sub-
stituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, organic
sulfides and
polysulfides such as dibenzyldisulfide, bis¨(chlorobenzyl) disulfide, dibutyl
tetrasul-
20 .. fide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol,
sulfurized dipen-
tene, sulfurized terpene, and sulfurized Diels-Alder adducts;
phosphosulfurized hy-
drocarbons such as the reaction product of phosphorus sulfide with turpentine
or me-
thyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon
phos-
phites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite,
pen-
25 tylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite,
distearyl phos-
phite and polypropylene substituted phenol phosphite; metal thiocarbamates
such as
zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of
alkyl and
dialkylphosphoric acids or derivatives including, for example, the amine salt
of a
reaction product of a dialkyldithiophosphoric acid with propylene oxide and
subse-
30 quently followed by a further reaction with P205; and mixtures thereof
(as described
in US 3,197,405).
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[0102] Foam inhibitors that may be useful in the lubricant
compositions of the
disclosed technology include polysiloxanes, copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including
fluorinated
polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides,
poly-
propylene oxides and (ethylene oxide-propylene oxide) polymers.
[0103] Other viscosity modifiers may include a block copolymer
comprising
(i) a vinyl aromatic monomer block and (ii) a conjugated diene olefin monomer
block
(such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styrene-
iso-
prene copolymer), a polymethacrylate, or mixtures thereof.
[0104] Pour point depressants that may be useful in the lubricant
compositions
of the disclosed technology include polyalphaolefins, esters of maleic
anhydride-sty-
rene copolymers, poly(meth)acrylates, polyacrylates or polyacrylami des.
[0105] Demulsifiers include trialkyl phosphates, and various
polymers and co-
polymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof.
[0106] Metal deactivators include derivatives of benzotriazoles (typically
tol-
yltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-
alkyl-
dithiobenzothiazoles. The metal deactivators may also be described as
corrosion in-
hibitors.
[0107] Seal swell agents include sulfolene derivatives Exxon
Necton37TM
(FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
[0108] In an embodiment, the lubricating composition can be employed
to lu-
bricate a mechanical device. The mechanical device can be associated with an
auto-
motive vehicle. For example, the mechanical device may be a driveline device.
[0109] Driveline devices include automatic transmissions, manual
transmis-
sion, dual clutch transmissions, or an axle or differential. A driveline
device lubricating
composition in different embodiments may have a composition as disclosed in
the follow-
ing table:
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Additive Embodiments (wt %)
A
Alkylphenol Detergent 0.01 to 2 0.01 to 2 0.01 to 2 0.01
to 2
Dispersant 1 to 4 0.1 to 10, 2 to 0 to 5 1 to 6
7
Extreme Pressure Agent 3 to 6 0 to 6 0 to 3 0 to 6
Overbased Detergent 0 to 1 0.01 to 3, 0.5 to 6 0.01 to
2
0.025 to 2
Antioxidant 0 to 5 0.01 to 10 or 0 to 3 0 to 2
2
Friction Modifier 0 to 5 0.01 to 5 0.1 to 1.5 0 to 5
Viscosity Modifier 0.1 to 70 0.1 to 15 1 to 60 0.1 to
70
Any Other Performance Additive 0 to 10 0 to 8 or 10 0 to 6 0 to 10
Oil of Lubricating Viscosity Balance to 100 %
Footnote:
The viscosity modifier in the table above may also be considered as an
alternative to an
oil of lubricating viscosity.
Column A may be representative of an automotive or axle gear lubricant.
Column B may be representative of an automatic transmission lubricant.
Column C may be representative of an off-highway lubricant.
Column D may be representative of a manual transmission lubricant.
[0110] The mechanical device can be an internal combustion engine, such as,
for example, a spark ignited internal combustion engine or a compression
ignition
internal combustion engine. An engine lubricant composition in different
embodi-
ments may have a composition as disclosed in the following table:
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Additive Embodiments (wt %)
A
Alkylphenol Detergent 0.05 to 10 0.2 to 5 0.5 to 2
Corrosion Inhibitor 0.05 to 2 0.1 to 1 0.2 to 0.5
Other Overbased Detergent 0 to 9 0.5 to 8 1 to 5
Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2
Dispersant 0 to 12 0 to 8 0.5 to 6
Antioxidant 0.1 to 13 0.1 to 10 0.5 to 5
Antiwear Agent 0.1 to 15 0.1 to 10 0.3 to 5
Friction Modifier 0.01 to 6 0.05 to 4 0.1 to 2
Viscosity Modifier 0 to 10 0.5 to 8 1 to 6
Any Other Performance Additive 0 to 10 0 to 8 0 to 6
Oil of Lubricating Viscosity Balance to 100 %
[0111] The mechanical device may also be in a hydraulic system. A
hydraulic
lubricant may also comprise a formulation defined in the following table:
Hydraulic Lubricant compositions
Additive Embodiments (wt %)
A
Alkylphenol detergent as de- 0.01 to 2.0 0.01 to 1.5 0.01 to 1.0
scribed herein
Antioxidant 0 to 4.0 0.02 to 3.0 0.03 to 1.5
Dispersant 0 to 2.0 0.005 to 1.5 0.01 to 1.0
Other Detergent - beside al- 0 to 5.0 0.001 to 1.5 0.005 to 1.0
kylphenol detergent as de-
scribed herein
Anti-wear Agent 0 to 5.0 0.001 to 2 0.1 to 1.0
Friction Modifier 0 to 3.0 0.02 to 2 0.05 to 1.0
Viscosity Modifier 0 to 10.0 0.5 to 8.0 1.0 to 6.0
Any Other Performance Addi- 0 to 1.3 0.00075 to 0.5 0.001 to 0.4
tive (antifoam / demulsi-
fier/pour point depressant)
Metal Deactivator 0 to 0.1 0.01 to 0.04 0.015 to 0.03
Rust Inhibitor 0 to 0.2 0.03 to 0.15 0.04 to 0.12
Extreme Pressure Agent 0 to 3.0 0.005 to 2 0.01 to 1.0
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Oil of Lubricating Viscosity Balance to Balance to 100 Balance to
100% 100%
[0112] The disclosed technology further provides a method of
lubricating a
circulating oil system.
[0113] The disclosed technology further provides a method of
lubricating a
turbine system.
[0114] The alkylphenol can be employed to lubricate any of the
foregoing me-
chanical devices by supplying to the mechanical device the aforementioned
lubricat-
ing compositions.
[0115] The amount of each chemical component described is presented
exclu-
sive of any solvent or diluent oil, which may be customarily present in the
commercial
material, that is, on an active chemical basis, unless otherwise indicated.
However,
unless otherwise indicated, each chemical or composition referred to herein
should be
interpreted as being a commercial grade material which may contain the
isomers, by-
products, derivatives, and other such materials which are normally understood
to be
present in the commercial grade.
[0116] 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.
[0117] 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.
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[0118] 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
5 stated value.
[0119] Each of the documents referred to above is incorporated
herein by ref-
erence, 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
document qualifies as prior art or constitutes the general knowledge of the
skilled per-
10 .. son in any jurisdiction. Except in the Examples, or where otherwise
explicitly indi-
cated, all numerical quantities in this description specifying amounts of
materials, re-
action conditions, 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 amount, range, and ratio limits set forth herein may be independently
combined.
15 Similarly, the ranges and amounts for each element of the invention can
be used to-
gether with ranges or amounts for any of the other elements.
[0120] As used herein, the transitional term "comprising," which is
synony-
mous with "including," "containing," or "characterized by," is inclusive or
open-
ended and does not exclude additional, un-recited elements or method steps.
How-
20 ever, in each recitation of "comprising" herein, it is intended that the
term also encom-
pass, as alternative embodiments, the phrases "consisting essentially of" and
"consist-
ing of," where "consisting of' excludes any element or step not specified and
"con-
sisting essentially of' permits the inclusion of additional un-recited
elements or steps
that do not materially affect the essential or basic and novel characteristics
of the com-
25 .. position or method under consideration.
[0121] 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-
30 vention is to be limited only by the following claims.
