Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
LUBRICATING COMPOSITION AND METHOD OF LUBRICATING AN
INTERNAL COMBUSTION ENGINE
FIELD OF INVENTION
[0001] The disclosed technology relates to lubricants, particularly for
internal combustion
engines including diesel engines. In particular, the disclosed technology
relates to lower
viscosity lubricating compositions which provide improved protection against
adhesive wear.
BACKGROUND OF THE INVENTION
[0002] A common wear issue in internal combustion engines is adhesive
wear, also known
as stick-tear wear. Adhesive wear occurs when material from two mated metal
parts is
transferred unevenly from one part to the other due to a lubricant's inability
to maintain
separation of the two parts or inability to maintain a low enough temperature
in the system. In
these cases, the mated parts develp micro-welds which are then torn away as
the two parts
move away from each other. Adhesive wear is often addressed by increasing the
viscosisty of
the lubricant and/or by increasing the amount of anti-wear addtives in the
lubricating
composition.
[0003] Certain lubricating compositions, such as crankcase
lubricants, are being
formulated with lower high temperature high shear (HTHS) viscosities in order
to improve fuel
economy. In addition, some lubricating compositions are being formulated with
lower levels
of anti-wear additives, in particular, phosphorous or sulfur containing anti-
wear additives, for
environmental reasons. However, the reduction in HTHS viscosity and/or anti-
wear additives
generally causes an increase in adhesive wear on the metal to metal surfaces.
[0004] Therefore, there exists a need for a lower HTHS viscosity
lubricant which is still
able to provide protection from adhesive wear. In addition, there exists a
need for lubricating
compositions containing lower levels of phosphorous or sulfur that maintain
adequate adhesive
wear performance.
SUMMARY OF THE INVENTION
[0005] In one embodiment, the present invention is directed to a
lubricating composition
comprising an oil of lubricating viscosity, one or more metal-containing
sulfur-free detergents
derived from an alkylphenol in an amount to deliver at least 0.2 weight
percent alkylphenol-
containing soap to the composition, one or more alkaline earth metal sulfonate
detergents in an
amount to deliver at least 0.8% by weight sulfonate soap to the composition, 1
wt % to 4.5 wt
% of one or more polyisobutenyl succinimide dispersants, and 0.1 wt % to 1.2
wt % of a
dispersant viscosity modifier derived from a polyolefin having a number
average molecular
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weight of at least 20,000, wherein the lubricant composition contains less
than 0.2 wt % of a
sulfur-coupled phenate detergent.
[0006] In another embodiment, the present invention is directed to a
method of lubricating
a compression ignition internal combustion engine comprising supplying to the
engine a low
phosphorus lubricant composition comprising an oil of lubricating viscosity,
one or more
metal-containing sulfur-free detergents derived from an alkylphenol in an
amount to deliver at
least 0.2 weight percent alkylphenol-containing soap to the composition, one
or more alkaline
earth metal sulfonate detergents in an amount to deliver at least 0.8% by
weight sulfonate soap
to the composition, 1 wt % to 4.5 wt % of one or more polyisobutenyl
succinimide dispersants,
and 0.1 wt % to 1.2 wt % of a dispersant viscosity modifier derived from a
polyolefin having
a number average molecular weight of at least 20,000, wherein the lubricant
composition
contains less than 0.2 wt % of a sulfur-coupled phenate detergent.
[0007] In another embodiment, the present invention is directed to a
method of reducing
adhesive wear in a compression engine lubricated with a low phosphorus
lubricant
composition, comprising supplying to the engine a lubricant composition
comprising an oil of
lubricating viscosity, one or more metal-containing sulfur-free detergents
derived from an
alkylphenol in an amount to deliver at least 0.2 weight percent alkylphenol-
containing soap to
the composition, one or more alkaline earth metal sulfonate detergents in an
amount to deliver
at least 0.8% by weight sulfonate soap to the composition, 1 wt % to 4.5 wt %
of one or more
polyisobutenyl succinimide dispersants, and 0.1 wt % to 1.2 wt % of a
dispersant viscosity
modifier derived from a polyolefin having a number average molecular weight of
at least
20,000, wherein the lubricant composition contains less than 0.2 wt % of a
sulfur-coupled
phenate detergent.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The disclosed technology provides a lubricating composition and a
method for
lubricating an internal combustion engine. The lubricating composition of the
present
invention comprises an oil of lubricating viscosity, one or more metal-
containing sulfur-free
detergents derived from an alkylphenol in an amount to deliver at least 0.2
weight percent
alkylphenol-containing soap to the composition, 1 wt % to 4.5 wt % of one or
more
polyisobutenyl succinimide dispersants, one or more alkaline earth metal
sulfonate detergents
in an amount to deliver at least 0.8% by weight sulfonate soap to the
composition, and 0.1 wt
% to 1.2 wt % of a dispersant viscosity modifier derived from a polyolefin
having a number
average molecular weight of at least 20,000, wherein the lubricant composition
contains less
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than 0.2 wt % of a sulfur-coupled phenate detergent. Information about the
components and
other details of the lubricating composition of the invention are described
below.
Oils of Lubricating Viscosity
[0009] The lubricating composition comprises an oil of lubricating
viscosity. Such oils
include natural and synthetic oils, oil derived from hydrocracking,
hydrogenation, and
hydrofinishing, unrefined, refined and re-refined oils and mixtures thereof.
The varoius types
of oils of lubricating viscosity are desribed herein below and may be used in
the lubricating
composition of the present invention.
[0010] Unrefined oils are those obtained directly from a natural or
synthetic source
generally without (or with little) further purification treatment.
[0011] Refined oils are similar to the unrefined oils except they
have been further treated
in one or more purification steps to improve one or more properties.
Purification techniques
are known in the art and include solvent extraction, secondary distillation,
acid or base
extraction, filtration, percolation and the like.
[0012] Re-refined oils are also known as reclaimed or reprocessed oils, and
are obtained
by processes similar to those used to obtain refined oils and often are
additionally processed
by techniques directed to removal of spent additives and oil breakdown
products.
[0013] Natural oils useful in making the inventive lubricants include
animal oils, vegetable
oils (e.g., castor oil,), mineral lubricating oils such as liquid petroleum
oils and solvent-treated
or acid-treated mineral lubricating oils of the paraffinic, naphthenic or
mixed paraffinic-
naphthenic types and oils derived from coal or shale or mixtures thereof
[0014] Synthetic lubricating oils are useful and include hydrocarbon
oils such as
polymerised and interpolymerised olefins (e.g., polybutylenes, polypropylenes,
propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-
decenes), and
mixtures thereof alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes,
di-(2-ethyl hexyl)-b enz en es); polyphenyls (e.g., biphenyl s, terphenyls,
alkylated polyphenyls);
diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and
alkylated diphenyl
sulfides and the derivatives, analogs and homologs thereof or mixtures thereof
[0015] Other synthetic lubricating oils include polyol esters (such
as Priolubeg3970),
diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl
phosphate, trioctyl
phosphate, and the diethyl ester of decane phosphonic acid), or polymeric
tetrahydrofurans.
Synthetic oils may be produced by Fischer-Tropsch reactions and typically may
be
hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils
may be
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prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as
other gas-to-liquid
oils.
[0016] Oils of lubricating viscosity may also be defined as specified
in the American
Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five
base oil groups are
as follows: Group I (sulfur content >0.03 wt %, and/or <90 wt % saturates,
viscosity index
80-120); Group II (sulfur content <0.03 wt %, and >90 wt % saturates,
viscosity index 80-120);
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).
[0017] The oil of lubricating viscosity may also be an API Group II+ base
oil, which term
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.
[0018] The oil of lubricating viscosity may also be an API Group III+ base
oil, which term
refers to a Group III+ base oil having a viscosity index greater than or equal
to 130. Group III+
are known in the art and is described in "Lube Report", dated February 26,
2014 in an article
entitled "SK Sees Group III Shortfall", by Nancy DeMarco. The article may be
obtained from
http ://www. as elub e. com/m edi a/11910/sk sees group iii shortfall .pdf.
[0019] 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.
[0020] The oil of lubricating viscosity may comprise an API Group I,
or Group II, or Group
III, or Group IV, or Group V oil, or mixtures thereof.
[0021] The amount of the oil of lubricating viscosity present may be
typically the balance
remaining after subtracting from 100 wt % the sum of the amount of the
additive as described
herein above, and the other performance additives.
[0022] 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 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 disclosed
technology 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.
[0023] In one embodiment the lubricating composition may be a non-
aqueous composition.
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[0024] The oil of lubricating viscosity may refer to a single base
oil or a mixture of base
oils. The oil of lubricating viscosity used in the lubricating composition of
the present
invention may have a kinematic viscosity of 2 cSt to 20 cSt (or mm2/s) at 100
C, as measured
by ASTM D445-14. The lubricating composition may be liquid, i.e., not a gel or
semi-solid, at
ambient temperatures (5-30 C).
Detergents
[0025] The lubricating composition of the present invention contains
a metal containing
sulfur-free detergent and an alkaline earth metal containing sulfonate
detergent. In addition,
the lubricating composition may contain small amounts of sulfur-coupled
phenate detergents.
[0026] As used herein the term "soap" means the surfactant portion of a
detergent and does
not include a metal base, such as calcium carbonate. The "soap content", metal
ratio and TBN
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. The
term "soap" may also be referred to as a detergent substrate. For example, the
sulfonate
detergents described herein, the soap may be a neutral salt of an
alkylbenzenesulfonic acid.
[0027] In addition, as used herein all total base number values cited
are determined by
ASTM Method D2896-11.
[0028] Metal-containing detergents are often referred to as
"overbased metal detergents."
Overbased metal detergents may be viewed as comprising an oil-soluble neutral
metal salt
component and a metal carbonate component. Overbased materials, otherwise
referred to as
overbased or superbased salts, are generally homogeneous Newtonian systems
characterized
by a metal content in excess of that which would be present for neutralization
according to the
stoichiometry of the metal and the particular acidic organic compound reacted
with the metal.
The overbased materials are prepared by reacting an acidic material (typically
an inorganic
acid or lower carboxylic acid, in one embodiment carbon dioxide) with a
mixture comprising
an acidic organic compound, a reaction medium comprising at least one inert,
organic solvent
(e.g., mineral oil, naphtha, toluene, xylene) for the acidic organic material,
a stoichiometric
excess of a metal base, and a promoter such as a phenol or alcohol and
optionally ammonia.
The acidic organic material will normally have a sufficient number of carbon
atoms, for
instance, as a hydrocarbyl sub stituent, to provide a reasonable degree of
solubility in oil. The
amount of excess metal is commonly expressed in terms of metal ratio. The term
"metal ratio"
is the ratio of the total equivalents of the metal to the equivalents of the
acidic organic
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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.
[0029] Overbased detergents are often characterized by Total Base
Number (TBN ¨ ASTM
D2896-11). TBN is the amount of strong acid needed to neutralize all of the
overbased
material's basicity, expressed as potassium hydroxide equivalents (mg KOH per
gram of
sample). Since overbased detergents are commonly provided in a form which
contains a certain
amount of diluent oil, for example, 40-50% oil, the actual TBN value for such
a detergent will
depend on the amount of such diluent oil present, irrespective of the
"inherent" basicity of the
overbased material. For the purposes of the present invention, the TBN of an
overbased
detergent is to be recalculated to an oil-free basis. Detergents which are
useful in the
lubricating composition of the present invention may have a TBN (oil-free
basis) of 100 to 800,
and in one embodiment 150 to 750, and in another, 400 to 700. If multiple
detergents are
employed, the overall TBN of the detergent component (that is, an average of
all the specific
detergents together) will typically be in the above ranges.
[0030] The metal compounds 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).
The Group 1 metals of the metal compound include Group la alkali metals such
as sodium,
potassium, and lithium, as well as Group lb metals such as copper. The Group 1
metals can
be sodium, potassium, lithium and copper, and in one embodiment sodium or
potassium, and
in another embodiment, sodium. The Group 2 metals of the metal base include
the Group 2a
alkaline earth metals such as magnesium, calcium, and barium, as well as the
Group 2b metals
such as zinc or cadmium. In one embodiment, the Group 2 metals are magnesium,
calcium,
barium, or zinc, and in another embodiments magnesium or calcium. In certain
embodiments,
the metal is calcium or sodium or a mixture of calcium and sodium. Generally
the metal
compounds are delivered as metal salts. The anionic portion of the salt can be
hydroxide,
oxide, carbonate, borate, or nitrate.
[0031] The lubricating composition of the present invention comprises
an overbased
detergent. In particular, the lubricating composition of the present invention
comprises one or
more deterents dervived from an alkylphenol. In one embodiment, the metal
containing
dergent derived from an alkylphenol is sulfur-free.
[0032] In one embodiment, the metal-containing detergent derived from
an alkylphenol
may be an overbased phenate detergent. The phenols useful in making phenate
detergents can
be represented by the formula (R1)a-Ar-(OH)b, wherein le is an aliphatic
hydrocarbyl group of
4 to 400 carbon atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon
atoms; Ar is an aromatic
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group (which can be a benzene group or another aromatic group such as
naphthalene); a and b
are independently numbers of at least one, the sum of a and b being in the
range of two up to
the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar.
In one
embodiment, a and b are independently numbers in the range of 1 to 4, or 1 to
2. Rl and a are
typically such that there are an average of at least 8 aliphatic carbon atoms
provided by the Rl
groups for each phenol compound. Phenate detergents are also sometimes
provided as sulfur-
bridged species. The lubricating composition of the present invention may
comprise at least
one sulfur-free phenate detergent. In another embodiment, the lubricating
composition
contains less than 0.2 wt %, or even less than 0.15 wt %. of a sulfur-coupled
phenate detergent.
In another embodiment, the lubricating composition is substantially free of
sulfur-coupled
phenate detergents. In still another embodiment, the lubricating composition
is free of sulfur-
coupled phenate detergents.
[0033] In one embodiment, the overbased alkyl-phenol based detergent
may be an
overbased saligenin detergent. Overbased saligenin detergents are commonly
overbased
magnesium salts which are based on saligenin derivatives. A general example of
such a
saligenin derivative can be represented by Formula (1):
OM OM
xY
0 0 _____ X
RILp RIL _ m
p
wherein X comprises -CHO or -CH2OH, Y comprises -CH2- or -CH2OCH2-, and
wherein such
-CHO groups typically comprise at least 10 mole percent of the X and Y groups;
M is hydrogen,
ammonium, or a valence of a metal ion (that is to say, in the case of a
multivalent metal ion,
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),
Rl is a hydrocarbyl
group containing 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 Rl
substituent and that the total
number of carbon atoms in all Rl groups is at least 7. When m is 1 or greater,
one of the X
groups can be hydrogen. In one embodiment, M is a valence 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 synthesis (Column 8 and Example 1)
and preferred
amounts of the various species of X and Y (Column 6).
[0034] In another embodiment, the overbased alkyl-phenol based
detergent may also
comprise salixarate detergents. Salixarate detergents are overbased materials
that can be
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represented by a substantially linear compound comprising at least one unit of
formula (2) or
formula (3):
R4
HO R7 R5
(2)
cooR3 (3)
R6
each end of the compound having a terminal group of formula (4) or (5):
R4
(R2)j
HO
R5
COOR3 R6
(4) (5)
such groups being linked by divalent bridging groups A, which may be the same
or different
for each linkage; wherein in formulas (2)-(5) R3 is hydrogen or 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 R4 is
hydroxyl and R5
and R7 are independently either hydrogen, a hydrocarbyl group, or hetero-
substituted
hydrocarbyl group, or else R5 and R7 are both hydroxyl and R4 is hydrogen, a
hydrocarbyl
group, or a hetero-substituted hydrocarbyl group; provided that at least one
of R4, R5, R6 and
R7 is hydrocarbyl containing at least 8 carbon atoms; and wherein the
molecules on average
contain at least one of unit (2) or (4) and at least one of unit (3) or (5)
and the ratio of the total
number of units (2) and (4) to the total number of units of (3) and (5) in the
composition is
about 0.1:1 to about 2:1. The divalent bridging group "A," which may be the
same or different
in each occurrence, includes -CH2- (methylene bridge) and -CH2OCH2- (ether
bridge), either
of which may be derived from formaldehyde or a formaldehyde equivalent (e.g.,
paraform,
formalin).
[0035] 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
macrocyclic, structure,
although both structures are intended to be encompassed by the term
"salixarate."
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[0036] The alkyl-phenol based overbased detergent used in the
lubricating composition of
the invention may also be an overbased salicylate which may be an alkali metal
salt or an
alkaline earth metal salt of a substituted salicylic acid. The salicylic acids
may be hydrocarbyl-
substituted salicylic acids wherein each substituent contains an average of at
least 8 carbon
atoms per substituent and 1 to 3 substituents per molecule. The substituents
can be polyalkene
substituents, where polyalkenes include homopolymers and interpolymers of
polymerizable
olefin monomers of 2 to 16, or 2 to 6, or 2 to 4 carbon atoms. The olefins may
be monoolefins
such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a
polyolefinic monomer,
such as diolefinic monomer, such 1,3-butadiene and isoprene. In one
embodiment, the
hydrocarbyl substituent group or groups on the salicylic acid contains 7 to
300 carbon atoms
and can be an alkyl group having a molecular weight of 150 to 2000. The
polyalkenes and
polyalkyl groups are prepared by conventional procedures, and substitution of
such groups onto
salicylic acid can be effected by known methods. Alkyl salicylates may be
prepared from an
alkylphenol by Kolbe-Schmitt reaction; alternatively, calcium salicylate can
be produced by
direct neutralization of alkylphenol and subsequent carbonation. Overbased
salicylate
detergents and their methods of preparation are disclosed in U.S. Patents
4,719,023 and
3,372,116.
[0037] In addition to a metal-containing sulfur-free detergent
derived from an alkylphenol
as described above, the lubricating composition of the present invention also
comprises an
overbased sulfonate detergent. In one embodiment, the overbased sulfonate
detergent
comprieses an alkaline-earth metal containing sulfonate detergent. The
sulfonate detergents of
the disclosed technology are known to a person skilled in the art.
[0038] Sulfonate detergents are derived from sulfonic acids. Suitable
sulfonic acids
include sulfonic and thiosulfonic acids. Sulfonic acids include the mono- or
polynuclear
aromatic or cycloaliphatic compounds. Oil-soluble sulfonates can be
represented for the most
part by one of the following formulas: R2-T-(503-)a and R3-(503-)b, where T is
a cyclic nucleus
such as typically benzene; 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. Examples of
R3 are alkyl,
alkenyl, alkoxyalkyl, and carboalkoxyalkyl groups. The groups T, R2, and R3
can also contain
other inorganic or organic substituents. In the above formulas, a and b are at
least 1. In one
embodiment the sulfonate detergent may be a predominantly linear
alkylbenzenesulfonate
detergent having a metal ratio of at least 8 as described in paragraphs [0026]
to [0037] of
US Patent Application 2005065045. In some embodiments the linear alkyl group
may be
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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.
[0039] In another embodiment, the lubricating composition comprises a
sulfonate
detergent, such as a magnesium, sodium or zinc overbased sulfonate. Typically
any additional
sulfonate detergent may be a magnesium or sodium sulfonate detergent, with
magnesium
sulfonate the more typical.
[0040] In one embodiment, the lubricating composition comprises a 300
TBN or higher
alkaline earth metal sulfonate detergent having a metal ratio of 10 to 40, and
a 82 to 100 TBN
or lower alkaline earth metal sulfonate detergent having a metal ratio of 3 to
9.
[0041] In one embodiment, the lubricating composition comprises a 300
TBN or higher
alkaline earth metal sulfonate detergent, which comprises a magnesium
sulfonate detergent
having a metal ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal
sulfonate detergent,
which comprises a calcium sulfonate detergent having a metal ratio of 1 to 5.
[0042] In another embodiment, the lubricating composition comprises a 300
TBN or higher
alkaline earth metal sulfonate detergent, which comprises a mixture of a
calcium sulfonate
detergent having a metal ratio of 10 to 40 and a magnesium sulfonate detergent
having a metal
ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal sulfonate
detergent, which
comprises a calcium sulfonate detergent having a metal ratio of 1 to 5.
[0043] The 300 TBN or higher alkaline earth metal sulfonate detergent and
the 80 TBN or
lower alkaline earth metal sulfonate detergent may be prepared from the same
or different
hydrocarbyl-substituted sulfonic acids. Typically the hydrocarbyl-substituted
sulfonic acids are
alkyl-substituted sulfonic acids.
[0044] The sulfonate may be prepared from a mono- or di- hydrocarbyl-
substituted
benzene (or toluene, naphthalene, indenyl, indanyl, or bicyclopentadienyl)
sulfonic acid,
wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35 or 9 to 30
carbon atoms.
[0045] 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.
[0046] In one embodiment the hydrocarbyl-substituted sulfonic acid
may include
polypropene benzenesulfonic acid and C16-C24 alkyl benzenesulfonic acid, or
mixtures thereof.
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[0047] In one embodiment the 300 TBN sulfonate detergent may be a
predominantly linear
alkylbenzene sulfonate detergent having a metal ratio of having a metal ratio
of 10 to 40 as is
described in paragraphs [0026] to [0037] of US Patent Application 2005065045
(and granted
as US 7,407,919). The predominantly linear alkylbenzene sulfonate detergent
may be
particularly useful for assisting in improving fuel economy.
[0048] Typically the 300 TBN or higher alkaline earth metal sulfonate
detergent has a
metal ratio of 12 to 30, or 12 to 22, or 16 to 20, or 10 to 20, or 20 to 30,
or 22 to 25. In one
embodiment the 300 TBN metal ratio may be 16 to 20, and in another embodiment
22 to 25.
[0049] In one embodiment the lubricating composition comprises a
calcium sulfonate
detergent having a metal ratio of 10 to 40, and a calcium sulfonate detergent
having a metal
ratio of 3 to 9.
[0050] In one embodiment the lubricating composition comprises a
calcium sulfonate
detergent having a metal ratio of 10 to 40, a calcium sulfonate detergent
having a metal ratio
of 3 to 9, and a magnesium sulfonate detergent having a metal ratio of 12 to
40.
[0051] The magnesium sulfonate detergent may have a TBN of 300 to 800, or
450 to
700 mg KOH/g; and a metal ratio of 12 to 40, or 14 to 25. The magnesium
sulfonate may have
the same or different hydrocarbyl-substituted sulfonic acids, and are defined
the same as
described above for calcium sulfonate detergents.
[0052] Other overbased detergents can include overbased detergents
having a Mannich
base structure, as disclosed in U.S. Patent 6,569,818.
[0053] Overbased materials are well known to those skilled in the
art. Patents describing
techniques for making basic salts of sulfonic acids, carboxylic acids,
(hydrocarbyl-substituted)
phenols, phosphonic acids, and mixtures of any two or more of these include
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.
[0054] The lubricating composition of the present invention comprsies
one or more metal-
containing sulfur-free detergents derived from alkyl-phenol, as described
above, in an amount
sufficient to deliver at least 0.2 weight percent alkylphenol-containing soap
to the composition.
In some embodiments, the metal-containing sulfur-free detergent may be
selected from phenate
detergents, alkylsalicylate deteregents, Mg saligenin, or Ca salixarate.
[0055] The lubricating composition of the present invention also
comprises one or more
sulfonate detergents in an amount to deliver at least 0.8 weight percent
sulfonate soap to the
composition. In one embodiment, the sulfonate detergent is an alkaline earth
metal sulfuonate
detergent.
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Succinimide Dispersant
[0056] The lubricating composition further comprises a succinimide
dispersant. In one
embodiment, the lubricating composition comprises 1 wt % to 4.5 wt % or 1 wt %
to 4 wt %
polyisobutylene succinimide dispersant.
[0057] Succinimide dispersants may be derived from polyisobutylene
succinimide,
wherein the polyisobutylene from which polyisobutylene succinimide may be
derived has a
number average molecular weight of 350 to 5000, or 750 to 3000 or 1550 to
2500.
[0058] In certain embodiments, the dispersant is prepared by a
process that involves the
presence of small amounts of chlorine or other halogen, as described in U.S.
Patent
7,615,521 (see, e.g., col. 4, lines 18-60 and preparative example A). Such
dispersants
typically have some carbocyclic structures in the attachment of the
hydrocarbyl sub stituent
to the acidic or amidic "head" group. In other embodiments, the dispersant is
prepared by
a thermal process involving an "ene" reaction, without the use of any chlorine
or other
halogen, as described in U.S. Patent 7,615,521; dispersants made in this
manner are often
derived from high vinylidene (i.e. greater than 50% terminal vinylidene)
polyisobutylene(See col. 4, line 61 to col. 5, line 30 and preparative example
B). Such
dispersants typically do not contain the above-described carbocyclic
structures at the point
of attachment. In certain embodiments, the dispersant is prepared by free
radical catalyzed
polymerization of high-vinylidene polyisobutylene with an ethylenically
unsaturated
acylating agent, as described in United States Patent 8,067,347.
[0059] Dispersants may be derived from, as the polyolefin, high
vinylidene
polyisobutylene, that is, having greater than 50, 70, or 75% terminal
vinylidene groups (a
and l isomers). In certain embodiments, the succinimide dispersant may be
prepared by the
direct alkylation route. In other embodiments it may comprise a mixture of
direct alkylation
and chlorine-route dispersants.
[0060] Suitable dispersants for use in the compositions of the
present invention include
succinimide dispersants. 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 succinimide dispersant.
[0061] The dispersant may also be post-treated by conventional methods by a
reaction with
any of a variety of agents. Among these are boron compounds, urea, thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic
acids, hydrocarbon-
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substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and
phosphorus
compounds.
[0062] The dispersant of polyisobutylene succinimide may be derived
from an aliphatic
polyamine, or mixtures thereof In one embodiment, the lubricating composition
comprises a
non-borated succinimide dispersant.
[0063] 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, diethylenetriamine, triethylenetetramine,
tetraethylene-
pentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof
[0064] Polyisobutylene succinimide dispersants and their preparation
are disclosed, 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.
[0065] The polyisobutylene succinimide may have a carbonyl to nitrogen
ratio of 1:1 to
1:5, or 1:1 to 1:4, or 1:1.3 to 3: or 1:1.5 to 1:2, or 1:1.4 to 1:0.6.
[0066] In one embodiment the polyisobutylene succinimide dispersant
may include an
amine-functionalized additive may be derived from an amine having at least 3
or 4 aromatic
groups.
[0067] As used herein the term "an aromatic group" is used in the ordinary
sense of the
term and is known to be defined by Hiickel theory of 4n+2 It electrons per
ring system.
Accordingly, one aromatic group may have 6, or 10, or 14 it electrons. Hence a
benzene ring
has 6 it electrons, a naphthylene ring has 10 it electrons and an acridine
group has
14 it electrons.An example of the amine having at least 3 or 4 aromatic groups
may be
represented by Formula (6):
N
H2N."/ INH2 ___________
R2
(6)
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wherein independently each variable,
Rl may be hydrogen or a C1-5 alkyl group (typically hydrogen);
R2 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
U may be an aliphatic, alicyclic or aromatic group, with the proviso that when
U may be
aliphatic, the aliphatic group may be linear or branched alkylene group
containing 1 to 5, or 1
to 2 carbon atoms; and
w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).
[0068] An example of the amine having at least 3 or 4 aromatic groups
may be represented
by Formula (6a):
N
H2N NH2
R1
R2
Formula (6a)
wherein independently each variable,
Rl may be hydrogen or a C1-5 alkyl group (typically hydrogen);
R2 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
U may be an aliphatic, alicyclic or aromatic group, with the proviso that when
U may be
aliphatic, the aliphatic group may be linear or branched alkylene group
containing 1 to 5, or 1
to 2 carbon atoms; and
w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).
[0069] Alternatively, the compound of Formula (6a) may also be
represented by:
NHU NH2
100
I
H2NRi NH2
R2
wherein each variable U, Rl, and R2 are the same as described above and w may
be 0 to 9 or 0
to 3 or 0 to 1 (typically 0).
[0070] Examples of an amine having at least 3 or 4 aromatic groups
may be represented by
any of the following Formulae (7) and/or (8):
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H2N NH2
H2
(7)
or
NH2
HN
H2N 1401 14.1 C 1 I NH2
H2
(8)
[0071] In one
embodiment the amine having at least 3 or 4 aromatic groups may include
mixtures of compounds represented by the formulae disclosed above. A person
skilled in the
art will appreciate that compounds of Formulae (7) and (8) may also react with
the aldehyde
described below to form acridine derivatives. Acridine derivatives that may be
formed include
compounds illustrated represented by Formula (7a) or (8a) to (8c) below. In
addition to these
compounds represented these formulae, a person skilled in the art will also
appreciate that other
acridine structures may be possible where the aldehyde reacts with other with
benzyl groups
bridged with the >NH group. Examples of acridine structures include those
represented by
Formulae (7a), (8a) or (8b) or (8c):
H2N NH2
H2
(7a)
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NH2
N
H2N NH2
H2
(8a)
Any or all of the N-bridged aromatic rings are capable of such further
condensation and perhaps
aromaticisation. One other of many possible structures include Formula (8b):
NH2
N
H2N C 11.1 NH2
(8b)
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NH2
HN
101
CH2
H2Nc NH2
H2
(8c)
[0072]
Any of the formulae above (7), (7a) (8), or (8a) to (8c) could also have
further
condensation reactions occurring resulting in one or more acridine moieties
forming per
molecule.
[0073]
Examples of the amine having at least 3 or 4 aromatic groups may be bis[p-
(p-
aminoanilino)pheny1]-methane,
2-(7-amino-acridin-2-ylmethyl)-N-4-1444-(4-amino-
phenylamino)-benzy1]-pheny1}-benzene-1,4-diamine,
N-4- 4-4-(4-amino-phenylamino)-
benzy1]-pheny1}-244-(4-amino-phenylamino)-cyclohexa-1,5-dienylmethylFbenzene-
1,4-
diamine, N44-(7-amino-acridin-2-ylmethyl)-phenylFbenzene-1,4-diamine, or
mixtures
thereof
[0074]
In one embodiment the amine having at least 3 or 4 aromatic groups may be
bis[p-
(p-aminoanilino)pheny1]-methane,
2-(7-amino-acridin-2-ylmethyl)-N-4-1444-(4-amino-
phenyl amino)-b enzyl] -phenylI-b enzene-1,4-di amine or mixtures thereof
[0075] The
amine having at least 3 or 4 aromatic groups may be prepared by a process
comprising reacting an aldehyde with an amine (typically 4
aminodiphenylamine). The
resultant amine may be described as an alkylene coupled amine having at least
3 or 4 aromatic
groups, at least one -NH2 functional group, and at least 2 secondary or
tertiary amino groups.
[0076]
The aldehyde may be aliphatic, alicyclic or aromatic. The aliphatic
aldehyde may
be linear or branched. Examples of a suitable aromatic aldehyde include
benzaldehyde or
o-vanillin. Examples of an aliphatic aldehyde include formaldehyde (or a
reactive equivalent
thereof such as formalin or paraformaldehyde), ethanal or propanal. Typically
the aldehyde
may be formaldehyde or benzaldehyde.
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[0077] Alternatively, the amine having at least 3 or 4 aromatic
groups may also be prepared
by the methodology described in Berichte der Deutschen Chemischen Gesellschaft
(1910), 43,
728-39.
[0078] In one embodiment the amine having at least 3 or 4 aromatic
groups may be
obtained/obtainable by a process comprising reacting isatoic anhydride or
alkyl substituted
isatoic anhydride, with an aromatic amine with at least two aromatic groups
and a reactive
primary or secondary amino group. The resultant material may be described as
an anthranilic
derivative.
[0079] In one embodiment the anthranilic derivative may be prepared
in a reaction
containing isatoic anhydride or alkyl substituted isatoic anhydride and an
aromatic amine
selected from the group consisting of xylylenediamine, 4-aminodiphenylamine,
1,4-
dimethylphenylenediamine, and mixtures thereof In one embodiment the aromatic
amine may
be 4-aminodiphenylamine.
[0080] The process described above to prepare the anthranilic
derivative may be carried
out at a reaction temperature in the range of 20 C to 180 C, or 40 C to 110 C.
The process may
or may not be carried out in the presence of a solvent. Examples of a suitable
solvent include
water, diluent oil, benzene, t-butyl benzene, toluene, xylene, chlorobenzene,
hexane,
tetrahydrofuran, or mixtures thereof. The reactions may be performed in either
air or an inert
atmosphere. Examples of suitable inert atmosphere include nitrogen or argon,
typically
nitrogen.
Dispersant Viscosity Modifier
[0081] The lubricating composition of the present invention also
comprises a dispersant
viscosity modifier. The lubricating composition comprises 0.1 to 1.2 wt %
dispersant viscosity
modifier. In one embodiment, the lubricating composition comprises 0.1 to 1.2
wt % of a
dispersant viscosity modifier as described herein that has a number average
molecular weight
of at least 20,000.
[0082] The dispersant viscosity modifier may include functionalized
polyolefins, for
example, ethylene-propylene copolymers that have been functionalized with an
acylating agent
such as maleic anhydride and an amine; polymethacrylates functionalized with
an amine, or
styrene-maleic anhydride copolymers reacted with an amine. More detailed
description of
dispersant viscosity modifiers are disclosed in International Publication
W02006/015130 or
U.S. Patents 4,863,623; 6,107,257; 6,107,258; 6,117,825; and US 7,790,661. In
one
embodiment the dispersant viscosity modifier may include those described in
U.S. Patent
4,863,623 (see column 2, line 15 to column 3, line 52) or in International
Publication
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W02006/015130 (see page 2, paragraph [0008] and preparative examples are
described
paragraphs [0065] to [0073]).
[0083] In one particular embodiment the dispersant viscosity modifier
comprises an olefin
copolymer further functionalized with a dispersant amine group. Typically, the
olefin
copolymer may be an ethylene-propylene copolymer.
[0084] The dispersant amine group may be prepared/derived from
reacting the olefin
copolymer (typically, an ethylene-propylene copolymer) with an acylating agent
(typically
maleic anhydride) and an aromatic amine having a primary or secondary amino
group.
Typically, the dispersant viscosity modifier may be an ethylene-propylene
copolymer acylated
with maleic anhydride and reacted with an aromatic amine.
[0085] The formation of a dispersant viscosity modifier is well known
in the art. The
dispersant viscosity modifier may include for instance those described in U.S.
Patent
US 7,790,661 column 2, line 48 to column 10, line 38.
[0086] In one embodiment the dispersant viscosity modifier may be
prepared by grafting
of an olefinic carboxylic acid acylating agent onto a polymer of 15 to 80 mole
percent of
ethylene, from 20 to 85 mole percent of C3-10 a-monoolefin, and from 0 to 15
mole percent of
non-conjugated diene or triene, said polymer having an average molecular
weight ranging from
5000 to 500,000, and further reacting said grafted polymer with an amine
(typically an aromatic
amine).
[0087] In another embodiment the dispersant viscosity modifier may be a
reaction product
of: (a) a polymer comprising carboxylic acid functionality or a reactive
equivalent thereof, said
polymer having a number average molecular weight of greater than 5,000; and
(b) an amine
component comprising at least one aromatic amine containing at least one amino
group capable
of condensing with said carboxylic acid functionality to provide a pendant
group and at least
one additional group comprising at least one nitrogen, oxygen, or sulfur atom,
wherein said
aromatic amine may be chosen from (i) a nitro-substituted aniline, (ii) an
amine comprising
two aromatic moieties linked by a -C(0)NR- group, a -C(0)0- group, an -0-
group, an -N=N-
group, or an -SO2- group where R may be hydrogen or hydrocarbyl, one of said
aromatic
moieties bearing said condensable amino group, (iii) an aminoquinoline, (iv)
an
aminobenzimidazole, (v) an N,N- dialkylphenylenediamine, (vi), an
aminodiphenylamine (also
N,N-phenyldiamine), and (vii) a ring-substituted benzylamine.
[0088] The aromatic amine of the dispersant viscosity modifier may
also include those
which can be represented by the general structure NH2-Ar or T-NH-Ar, where T
may be alkyl
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or aromatic, Ar may be an aromatic group, including nitrogen-containing or
amino-substituted
aromatic groups and Ar groups including any of the following structures
Rvi
- Rv
Rv
K Rv
-
as well as multiple non-condensed or linked aromatic rings. In these and
related structures, It',
R", and R"' can be independently, among other groups disclosed herein, -H, -C1-
18 alkyl groups,
nitro groups, -NH-Ar, -N=N-Ar, -NH-CO-Ar, -00C-Ar, -00C-C1-18 alkyl, -COO-C1-
18 alkyl,
-OH, -0-(CH2CH2-0)nC1-18 alkyl groups, and -0-(CH2CH20)nAr (where n may be 0
to 10).
[0089]
Aromatic amines include those amines wherein a carbon atom of the aromatic
ring
structure is attached directly to the amino nitrogen. The amines may be
monoamines or
polyamines. The aromatic ring will typically be a mononuclear aromatic ring
(i.e., one derived
from benzene) but can include fused aromatic rings, especially those derived
from naphthalene.
Examples of aromatic amines include aniline, N-alkylanilines such as N-
methylaniline and N-
butylaniline, di-(para-methylphenyl)amine, 4-aminodiphenylamine,
N,N-
dimethylphenylenediamine, naphthylamine, 4-(4-nitrophenylazo)aniline (disperse
orange 3),
sulphamethazine, 4-phenoxyaniline, 3 -
nitroaniline, 4-aminoacetanilide (N-(4-
aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl
amino
salicylate), N-(4-amino-phenyl)-benzamide, various benzyl amines such as 2,5-
dimethoxybenzylamine, 4-phenylazoaniline, and substituted versions of these.
Other examples
include para-ethoxyaniline, para-dodecylaniline, cyclohexyl -substituted
naphthylamine, and
thienyl-substituted aniline. Examples of other suitable aromatic amines
include amino-
substituted aromatic compounds and amines in which the amine nitrogen is a
part of an
aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-
aminoquinoline. Also
included are aromatic amines such as 2-aminobenzimidazole, which contains one
secondary
amino group attached directly to the aromatic ring and a primary amino group
attached to the
imidazole ring. Other amines include N-(4-anilinopheny1)-3-aminobutanamide or
3-amino
propyl imidazole. Yet other amines include 2,5-dimethoxybenzylamine.
[0090]
Additional aromatic amines and related compounds are disclosed in U.S.
Patent
6,107,257 and 6,107,258; some of these include aminocarbazoles,
benzoimidazoles,
aminoindoles, aminopyrroles, amino-indazolinones, aminoperimidines,
mercaptotriazoles,
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aminophenothiazines, aminopyridines, aminopyrazines, aminopyrimidines,
pyridines,
pyrazines, pyrimidines, aminothiadiazoles, aminothiothiadiazoles, and
aminobenzotriaozles.
Other suitable amines include 3-amino-N-(4-anilinopheny1)-N-isopropyl
butanamide, and
N-(4-anilinopheny1)-3-{(3-aminopropy1)-(cocoalkyl)amino} butanamide. Other
aromatic
amines which can be used include various aromatic amine dye intermediates
containing
multiple aromatic rings linked by, for example, amide structures. Examples
include materials
of the general structure:
Rix
41 ?¨ill = NH2
Rviii
and isomeric variations thereof, where Wu' and Rix are independently alkyl or
alkoxy groups
such as methyl, methoxy, or ethoxy. In one instance, Will and Rix are both
¨OCH3 and the
material is known as Fast Blue RR [CAS# 6268-05-9].
[0091] In another instance, Rix may be ¨OCH3 and Will may be ¨CH3,
and the material is
known as Fast Violet B [99-21-8]. When both Rviii and Rix are ethoxy, the
material is Fast Blue
BB [120-00-3]. U.S. Patent 5,744,429 discloses other aromatic amine compounds,
particularly
aminoalkylphenothiazines. N-aromatic substituted acid amide compounds, such as
those
disclosed in U.S. Patent Application 2003/0030033 Al, may also be used for the
purposes of
the disclosed technology. Suitable aromatic amines include those in which the
amine nitrogen
is a substituent on an aromatic carboxyclic compound, that is, the nitrogen is
not sp2 hybridized
within an aromatic ring.
[0092] The aromatic amine may also comprise an amine formed by
reacting an aldehyde
with 4-aminodiphenylamine. The resultant amine may be described as an alkylene
coupled
amine having at least 4 aromatic groups, at least one -NH2 functional group,
and at least 2
secondary or tertiary amino groups. The aldehyde may be aliphatic, alicyclic
or aromatic. The
aliphatic aldehyde may be linear or branched. Examples of a suitable aromatic
aldehyde include
benzaldehyde or o-vanillin. Examples of an aliphatic aldehyde include
formaldehyde (or a
reactive equivalent thereof such as formalin or paraformaldehyde), ethanal or
propanal.
Typically the aldehyde may be formaldehyde or benzaldehyde. Alternatively,
this aromatic
amine may also be prepared by the methodology described in Berichte der
Deutschen
Chemischen Gesellschaft (1910), 43, 728-39.
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[0093] The aromatic amine formed by coupling an aldehyde and 4-
aminodiphenylamine is
described European Patent application EP 2 401 348 A in and may also be
represented by the
formula:
N
N NH H2
I 01
H2Ni NH2
R2
wherein each variable
R' may be hydrogen or a C1-5 alkyl group (typically hydrogen);
R2 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
U may be an aliphatic, alicyclic or aromatic group, with the proviso that when
U may be
aliphatic, the aliphatic group may be linear or branched alkylene group
containing 1 to 5, or 1
to 2 carbon atoms; and
w may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).
[0094] In one embodiment the aromatic amine includes 4-
aminodiphenylamine, aldehyde
(typically formaldehyde) coupled 4-aminodiphenylamine, nitro-aniline (3- nitro-
aniline),
disperse orange-3 (D03), or mixtures thereof.
[0095] The lubricating composition of the present invention comprises a
dispersant
viscosity modifier derived from a polyolefin having a number average molecular
weight of at
least 20,000. In one embodiment, the lubricating composition may contain a
mixture of low
molecular weight and high molecular weight dispersant viscosity modifiers,
provided that the
overall number average molecular weight of the dispersant viscosity modifier
is at least 20,000.
As used herein, low molecular weight dispersant viscosity modifiers are
derived from
polyolefin copolymers having a number average molecular weight below 20,000,
or even
10,000 or lower. High molecular weight dispersant viscosity modifiers are
derived from
polyolefin copolymers having a number average molecular weight of greater than
20,000, or
even 40,000 or greater, or even 45,000 or greater, such as 40,000 to
1,000,000. For instance, in
one embodiment, the lubricating composition of the present invention may
comprise a
dispersant visocisty modifier wherein the dispersant viscosisty modifier
comprises a mixture
of at least one low molecular weight dispersant viscosity modifier derived
from a polyolefin
having a number average molecular weight of less than 20,000, and at least one
high molecular
weight dispersant viscosity modifier derived from a polyolefin having a number
average
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molecular weight of at least 40,000. For example, in the aforementioned
embodiment, the low
molecular weight dispersant vicosity modifier may be derived from a polyolefin
having a
number average molecular weight of 10,000. Further for example, in the
aforementioned
embodiment, the high molecular weight dispersant viscosity modifier may be
derived from a
polyolefin having a number average molecular weight of 45,000 or greater.
Other Performance Additives
[0096] The lubricating composition of the disclosed technology
optionally comprises other
performance additives. The other performance additives include at least one of
antioxidants,
metal deactivators, viscosity modifiers, friction modifiers, antiwear agents,
corrosion
inhibitors, extreme pressure agents, 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.
[0097] The lubricating composition optionally further includes at
least one antiwear agent.
[0098] Examples of suitable antiwear agents include titanium
compounds, esters, amides,
and/or imides of alpha-hydroxycarboxylic acids (such as tartaric acid, malic
acid, citric acid,
glycolic acid), oil soluble amine salts of phosphorus compounds, sulfurized
olefins, metal
dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates),
phosphites (such as
dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as
thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-
coupled thio-
carbamates, and bis(S-alkyldithiocarbamyl) disulfides. The antiwear agent may
in one
embodiment include a tartrate, or tartrimide as disclosed in International
Publication
WO 2006/044411 or Canadian Patent CA 1 183 125. The tartrate or tartrimide may
contain
alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be
at least 8. The
antiwear agent may in one embodiment include a citrate as is disclosed in US
Patent
Application 20050198894.
[0099] Another class of additives includes oil-soluble titanium
compounds as disclosed in
US 7,727,943 and US2006/0014651. The oil-soluble titanium compounds may
function as
antiwear agents, friction modifiers, antioxidants, deposit control additives,
or more than one of
these functions. In one embodiment the oil soluble titanium compound may be a
titanium (IV)
alkoxide. The titanium alkoxide may be 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 may be titanium (IV) isopropoxide. In one
embodiment,
the titanium alkoxide may be titanium (IV) 2-ethylhexoxide. In one embodiment,
the titanium
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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 may be oleic
acid.
[0100] In one embodiment, the oil soluble titanium compound may be a
titanium
carboxylate. In a further embodiment the titanium (IV) carboxylate may be
titanium
neodecanoate.
[0101] The lubricating composition may in one embodiment further
include a phosphorus-
containing antiwear agent. Typically the phosphorus-containing antiwear agent
may be a zinc
dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium
phosphate salts,
or mixtures thereof. Zinc dialkyldithiophosphates are known in the art.
[0102] In one embodiment the lubricating composition may further
include a phosphorus-
containing antiwear agent based upon zinc dialkyldithiophosphate, or mixtures
thereof.
[0103] The zinc dialkyldithiophosphate may be derived from aliphatic
or aromatic
hydrocarbyl alcohols; the hydrocarbyl; alcohols may be primary or secondary
alcohols. A zinc
dialkyldithiophosphate (or ZDDP) derived from secondary alcohols is said to be
a secondary
ZDDP. A ZDDP derived from primary alcohols is said to be a primary ZDDP. ZDDP
prepared
from a mixture of primary and secondary alcohols is said to be a mixed
primary/secondary
ZDDP. In one embodiment the ZDDP may be represented by the following
structure:
Zn
RO I N OR
OR
OR
wherein each R may be independently a primary or secondary hydrocarbyl group
containing
from 1 to 24, for example from 2 to 12 carbon atoms and including groups such
as alkyl,
alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic hydrocarbyl groups. In an
embodiment, R
may be alkyl groups of 2 to 8 carbon atoms. In another embodiment, R may be an
alkyl group
having 5 or more carbon atoms. R may be, for example, ethyl, n-propyl, i-
propyl, n-butyl,
butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl,
2-ethylehexyl,
phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, and butenyl.
[0104] The R group of the zinc dithiophosphate may be derived, for
example, from a
primary alcohol such as methanol, ethanol, propanol, butanol, pentanol,
hexanol, heptanol,
octanol, nonanol, decanol, dodecanol, octadecanol, propenol, butenol, 2-
ethylhexanol: a
secondary alcohol such as isopropyl alcohol, secondary butyl alcohol,
isobutanol,
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3-methylbutan-2-ol, 2-pentanol, 4-methyl-2-pentanol, 2-hexanol, 3-hexanol,
amyl alcohol, an
aryl alcohol such as phenol, substituted phenol (particularly alkylphenol such
as butylphenol,
octylphenol, nonylphenol, dodecylphenol), disubstituted phenol. Certain
primary diols may
also be used to prepare ZDDP; suitable primary diols include ethylene glycol,
propylene gycol,
and esters of polyhydric alcohol such as glycerol monooleate and combinations
thereof ZDDP
may be prepared from a combination of primary alcohols and primary diols.
[0105] In one embodiment the R group of the ZDDP may be independently
a primary alkyl,
a secondary alkyl, an aryl group, or mixtures thereof
[0106] In one embodiment the R group of the ZDDP may be a secondary
alkyl group.
[0107] When present, the amount of metal dialkyldithiophosphate, such as
zinc
dialkyldithiophosphate, is present in amounts sufficient to deliver 0.1 wt %
or less phosphorous
to the lubrcating composition. In one embodiment, the lubricating composition
comprises less
than 0.1 wt % phosphorous. In another embodiment, the lubricating composition
comprises
0.08 wt % or less phosphorous, for example 0.01 wt %, to 0.08 wt %. In another
embodiment,
the lubricating composition of the present invention comprises a metal
dialkyldithiophosphate
such as ZDDP, wherein the alkyl groups in the metal dalkyldithiophosphate have
5 or more
carbon atoms. In another embodiment, the lubricating composition of the
present invention
comprises a metal dialkyldithiophosphate wherein at least about 65 mol % or
even 75 mol %
of the alkyl groups have 5 or more carbon atoms.
[0108] In one embodiment, the lubricating composition of the invention
comprises a metal
dialkyldithiophosphate wherein at least about 65 mol % or even 75 mol % of the
alkyl groups
have 5 or more carbon atoms, such as 5 to 24 carbon atoms, or even 5 to 12
carbon atoms, or
even 6 to 12 carbon atoms, and wherein the lubricating composition comprieses
1 wt % to 4
wt % of a polyisobutenyl succinimide dispersant.
[0109] 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.
[0110] 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.
[0111] Examples of suitable friction modifiers include long chain
fatty acid derivatives of
amines, fatty esters, or fatty epoxides; fatty imidazolines such as
condensation products of
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carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric
acids; fatty
alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; 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 thiourea
and salts thereof.
[0112] Friction modifiers may also encompass materials such as
sulfurized fatty
compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates,
sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic
acid.
[0113] 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.
[0114] Extreme Pressure (EP) agents include compounds that are soluble in
the oil include
sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2
derivatives of
dispersants (typically succinimide dispersants), derivative of chlorinated
hydrocarbon EP
agents and phosphorus EP agents. Examples of such EP agents include
chlorinated wax;
sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-substituted
2,5-dimercapto-
1,3,4-thiadiazole, or oligomers thereof, organic sulfides and polysulfides
such as dibenzyl-
disulfide, bis¨(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized
methyl ester of oleic
acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and
sulfurized Diels-
Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of
phosphorus
sulfide with turpentine or methyl oleate; phosphorus esters such as the
dihydrocarbon and
trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite,
dicyclohexyl phosphite,
pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite,
distearyl phosphite and
polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc
dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl
and
dialkylphosphoric acids or derivatives including, for example, the amine salt
of a reaction
product of a dialkyldithiophosphoric acid with propylene oxide and
subsequently followed by
a further reaction with P205; and mixtures thereof (as described in US
3,197,405).
[0115] Foam inhibitors that may be useful in the compositions of the
disclosed technology
include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate
and optionally
vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl
phosphates,
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polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene
oxide-
propylene oxide) polymers.
[0116] Pour point depressants that may be useful in the compositions
of the disclosed
technology include polyalphaolefins, esters of maleic anhydride-styrene
copolymers,
poly(meth)acrylates, polyacrylates or polyacryl amides.
[0117] Demulsifiers include trialkyl phosphates, and various polymers
and copolymers of
ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.
[0118] Metal deactivators include derivatives of benzotriazoles
(typically tolyltriazole),
1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-
alkyldithiobenzothiazoles.
The metal deactivators may also be described as corrosion inhibitors.
[0119] Seal swell agents include sulpholene derivatives Exxon Necton-
37TM (FN 1380)
and Exxon Mineral Seal OilTM (FN 3200).
Industrial Application
[0120] The lubricating composition of the present invention may be
used for the lubrication
of any of a variety of mechanical equipment types, including, but not limited
to, an internal
combusion engine, by supplying thereto the lubricating composition as
described herein. In
certain embodiments, the engine may be a diesel (compression ignited) engine,
such as a heavy
duty diesel engine. Other possible engines include gasoline (spark-ignited)
engines, and
engines consuming alcohols, gasoline-alcohol mixtures, biodiesel fuels,
various mixed fuels,
synthetic fuels, or gaseous fuels such as natural gas or hydrogen, two-stroke
cycle engines, and
marine diesel engines.
[0121] The internal combustion engine disclosed herein may have a
steel surface on a
cylinder bore, cylinder block, or piston ring.
[0122] The internal combustion engine may have a surface of steel, or
an aluminium alloy,
or an aluminium composite.
[0123] Typically the compression-ignition internal combustion engine
has a maximum
laden mass over 3,500 kg.
[0124] The compression-ignition internal combustion engine may be
referred to as a heavy
duty diesel engine. The laden mass (sometimes referred to as gross vehicle
weight rating
(GVWR)) may be over 2,700 kg (or 6,000 USA pounds) 2,900 kg, or over 3,00 kg,
or over
3,300 kg, or over 3,500 kg, or over 3,700 kg, or over 3,900 kg (or 8,500 USA
pounds).
Typically the upper limit on the laden mass or GVWR may be set by national
government and
may be 10,000 kg, or 9,000 kg, or 8,000 kg, or 7,500 kg. The upper ranges of
laden mass may
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be up to 400,000 kg, or up to 200,000 kg, or up to 60,000 kg, or up to 44,000
kg, or up to
40,000 kg. Typically a laden mass above 120,000 may be for an off-highway
vehicle.
[0125] Heavy duty diesel engines are noted to be limited to all motor
vehicles with a
"technically permissible maximum laden mass" over 3,500 kg, equipped with
compression
ignition engines or positive ignition natural gas (NG) or LPG engines. In
contrast, the European
Union indicates that for new light duty vehicles (passenger cars and light
commercial vehicles)
included within the scope of ACEA testing section "C" have a "technically
permissible
maximum laden mass" not exceeding 2610 kg.
[0126] There is a distinct difference between passenger car, and
heavy duty diesel engines.
The difference in size from over 3,500 kg to not more than 2610 kg means that
engines of both
types will experience significantly different operating conditions such as
load, oil temperatures,
duty cycle and engine speeds. Heavy duty diesel engines are designed to
maximize torque for
hauling payloads at maximum fuel economy while passenger car diesels are
designed for
commuting people and acceleration at maximum fuel economy. The designed
purpose of the
engine hauling versus communing results in different hardware designs and
resulting stresses
imparted to lubricant designed to protect and lubricate the engine. Another
distinct design
difference is the operating revolution per minute (RPM) that each engine
operates at to haul
versus commute. A heavy duty diesel engine such as a typical 12-13 litre truck
engine would
typically not exceed 2200 rpm while a passenger car engine can go up to 4500
rpm.
[0127] In one embodiment the internal combustion engine may be a heavy duty
diesel
compression ignited (or spark assisted compression ignited) internal
combustion engine.
[0128] The lubricating composition of the present invention is
formulated containing the
components and combinations of components as described herein. The lubricating
composition is formulated as a high-temperature high shear fluid having a
dynamic visocisty
of less than 3.5 cP, or even less than 3.1 cP, or even less than 3.05 cP as
meaured according to
ASTM D4683 at 150 C. In addition, the lubricating composition is formulated
to have a
kinematic viscosity at 100 C of 10 cSt or lower as measured according to ASTM
D445-17.
[0129] The following examples provide illustrations of the invention.
These examples are
non-exhaustive and are not intended to limit the scope of the invention.
EXAMPLES
[0130] A series of 10W-30 engine lubricants were prepared containing
the additives
described above as well as other conventional additives known to those of
ordinary skill in the
art. The amounts (wt %) of each additive are shown on table 1 below with the
balance of the
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lubricating composition being the base oil. The lubricating compositions were
evaluated for
their ability to protect against adhesive wear using ASTM WK53775. The
lubricating
compositions and test results are summarized in Table 1.
[0131] TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5
10W-30 10W-30 10W-30 10W-30
10W-30
Group II Base Oil x x x x
x
Group III Base Oil x
GTL Base Oil x x
HV-dispersant 0.7
Other succinimide
3.6 4.4 3.7 3.7
3.4
dispersant
ZDDP 1 (C3/C6) 0.68 1.0 1.0 1.0
0.18
ZDDP 2 (C6 2 )
0.6
High TBN Ca Sulfonate 0.12 0.54 0.52 0.64
0.22
Low TBN Ca Sulfonate 0.67 0.36 0.50 0.58
0.87
High TBN Mg Sulfonate 0.38
0.38
S-coupled Phenate 0.5 0.84 0.29
Methylene coupled phenate 0.37
0.25 0.37
1 (Mg saligenin)
Methylene coupled phenate
0.45
2 (Ca salixarate)
Ashless Antioxidant
(combo of aminic and 2.5 1.37 2.7 2.3
2.75
phenolic)
Low Mn DVM 0.33 0.67 0.33 0.26
0.33
High Mn DVM-VI
0.26 0.20 0.11
0.26
Improver
OCP VI Improver 0.05 0.5 0.46
0.04
Phosphorus (ppm) 759 1119 1100 1099
761
%Calcium 1520 2390 2295 1870
1290
%Magnesium 720 0 3 75
720
KV100 (cSt)
10.0 11.9 11.6 9.5
9.9
ASTM D445-17
HTHS (cP)
(150 C) ASTM D4683 3.08 3.63 3.46 3.03
3.03
Total Dispersant 3.6 4.4 3.7 4.4
3.4
Sulfonate Soap 0.8 0.6 0.7 0.8
1.0
S-coupled Phenol Soap 0.3 0.6 0.16 0
0
5-free Phenol Soap 0.35 0.00 0.41 0.24
0.35
Total Soap 1.42 1.20 1.26 1.04
1.35
Hours to Iron Spike
104 156 160 200
200
ASTM WK53775
[0132] A series of 5W-30 engine lubricants were prepared containing the
additives
described above as well as other conventional additives known to those of
ordinary skill in the
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art. The amounts (wt %) of each additive are shown on table 1 below with the
balance of the
lubricating composition being the base oil. The lubricating compositions were
evaluated for
their ability to protect against adhesive wear using ASTM WK53775. The
lubricating
compositions and test results are summarized in Table 2.
[0133] TABLE 2
Example Example Example Example Example Example
6 7 8 9 10
11
5W-30 5W-30 5W-30 5W-30 5W-30 5W-30
Group III Base Oil x
x
GTL Base Oil x x x x
PAO x
HV-dispersant 1.4 1.4 1.4 1.4 1.4
Other succinimide dispersant 3.7 3.7 3.7 3.7 3.7
3.4
ZDDP 1 (C3/C6) 0.68 0.18 0.68 0.68 0.18
0.18
ZDDP 2 (C6) 0.6 0.6
0.6
High TBN Ca Sulfonate 0.52 0.52 0.52 0.52 0.20
0.22
Low TBN Ca Sulfonate 0.50 0.55 0.50 0.50 0.55
0.87
High TBN Mg Sulfonate 0.42
0.38
S-coupled Phenate 0.29 0.29 0.29 0.29
Methylene coupled phenate 1
0.25 0.37
(Mg saligenin)
Methylene coupled phenate 2
0.45 0.45 0.45 0.45
(Ca salixarate)
Ashless Antioxidant (combo of
2.6 2.6 2.6 2.6 2.8 2.85
aminic and phenolic)
Low Mn DVM 0.33 0.33 0.33 0.33 0.26
0.33
High Mn DVM-VI Improver 0.26 0.26 0.26 0.26 0.24
0.26
Styrene-diene VM 0.3
0.4
Phosphorus (ppm) 770 763 770 770 761
761
%Calcium 2295 2295 2295 2295 950
1290
%Magnesium 3 3 3 3 750
720
KV100 9.7 9.7 9.7 10.5 9.9
10.0
HTHS (150 C)
3.04 3.09 3.04 3.17 3.02 3.00
ASTM D4683
Total Dispersant 5.1 5.1 5.1 5.1 5.1
3.4
Sulfonate Soap 0.7 0.7 0.7 0.7 0.7
1.0
S-coupled Phenol Soap 0.16 0.16 0.16 0.16 0
0
S-free Phenol Soap 0.41 0.41 0.41 0.41 0.24
0.35
Total Soap 1.26 1.26 1.26 1.26 0.98
1.35
Hours to Iron Spike
34 60 64 99.5 140
200
ASTM WK53775
[0134] The formulations of Examples 4, 5, and 11 in particular show
surprisingly improved
performance in protecting against adhesive wear.
[0135] 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
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are initially added. The products formed thereby, including the products
formed upon
employing lubricant composition of the disclosed technology 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 disclosed technology; the disclosed
technology encompasses
lubricant composition prepared by admixing the components described above.
[0136] As used herein reference to the amounts of additives present
in the lubricating
composition disclosed herein are quoted on an oil free basis, i.e., amount of
actives, unless
otherwise indicated.
[0137] As used herein, the transitional term "comprising", which is
synonymous with
"including", "containing", or "characterized by", is inclusive or open-ended
and does not
exclude additional, un-recited elements or method steps. However, in each
recitation of
"comprising" herein, it is intended that the term also encompass, as
alternative embodiments,
the phrases "consisting essentially of' and "consisting of', where "consisting
of' excludes any
element or step not specified and "consisting essentially of' permits the
inclusion of additional
un-recited elements or steps that do not materially affect the basic,
essential and novel charac-
teristics of the composition or method under consideration. In addition, as
used herein, the
phrase "substantially free of' means that the compposition or component may
include trace or
contaminant amounts of a material, but that such materials are not added in
functional amounts.
[0138] As used herein the expression "compression ignited internal
combustion engine" is
intended to encompass internal combustion engines that has at least in part
compression
ignition. As a result the disclosed technology is intended to encompass a
method of lubricating
a compression ignited internal combustion engine, as well as spark assisted
compression
ignited internal combustion engines.
[0139] Each of the documents referred to above is incorporated herein
by reference. Except
in the Examples, or where otherwise explicitly indicated, all numerical
quantities in this
description specifying amounts of materials, reaction conditions, molecular
weights, number
of carbon atoms, and the like, are to be understood as modified by the word
"about". Unless
otherwise indicated, each chemical or composition referred to herein should be
interpreted as
being a commercial grade material which may contain the isomers, by-products,
derivatives,
and other such materials which are normally understood to be present in the
commercial grade.
However, the amount of each chemical component is presented exclusive of any
solvent or
diluent oil, which may be customarily present in the commercial material,
unless otherwise
indicated. It is to be understood that the upper and lower amount, range, and
ratio limits set
forth herein may be independently combined. Similarly, the ranges and amounts
for each
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element of the invention may be used together with ranges or amounts for any
of the other
elements.
[0140] As used herein, the term "hydrocarbyl sub stituent" or
"hydrocarbyl group" is used
in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it refers to a
group having a carbon atom directly attached to the remainder of the molecule
and having
predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
hydrocarbon
substituents, including aliphatic, alicyclic, and aromatic substituents;
substituted hydrocarbon
substituents, that is, substituents containing non-hydrocarbon groups which,
in the context of
this invention, do not alter the predominantly hydrocarbon nature of the sub
stituent; and hetero
substituents, that is, substituents which similarly have a predominantly
hydrocarbon character
but contain other than carbon in a ring or chain. A more detailed definition
of the term
"hydrocarbyl substituent" or "hydrocarbyl group" is described in paragraphs
[0118] to [0119]
of International Publication W02008147704, or a similar definition in
paragraphs [0137] to
[0141] of published application US 2010-0197536.
[0141] As described hereinafter the number average molecular weight of the
dispersant
viscosity modifier and viscosity modifier has been determined using known
methods, such as
GPC analysis using polystyrene standards. Methods for determining molecular
weights of
polymers are well known. The methods are described for instance: (i) P.J.
Flory, "Principles of
Polymer Chemistry", Cornell University Press 91953), Chapter VII, pp 266-315;
or
(ii) "Macromolecules, an Introduction to Polymer Science", F. A. Bovey and F.
H. Winslow,
Editors, Academic Press (1979), pp 296-312.
[0142] While the invention has been explained in relation to its
preferred embodiments, it
is to be understood that various modifications thereof will become apparent to
those skilled in
the art upon reading the specification. Therefore, it is to be understood that
the invention
disclosed herein is intended to cover such modifications as fall within the
scope of the appended
claims.
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