Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICATING COMPOSITIONS FOR DIESEL PARTICULATE FILTER
PERFORMANCE
TECHNICAL FIELD
[0001] The disclosure relates to lubricant compositions exhibiting reduced
clogging
in diesel engine particulate filters.
BACKGROUND
[0002] Passenger and light-duty vehicles may be equipped with either a
compression
(diesel) or spark-ignition (gasoline) internal combustion engine. Generally
engine oils are
specially formulated for use in one or the other. However, it can be
beneficial to lubricate a
spark-ignition engine with an engine oil formulated for a compression engine.
Further, some
diesel engine oils are tested to meet both diesel and gasoline engine oil
specifications (i.e.,
mixed specifications), and, thus are recommend for use with either engine-
type. Therefore,
an oil that meets both diesel engine and gasoline engine specifications and
that can handle
each of these diverse engine conditions is desirable.
[0003] Vehicles having a compression ignition engine are often equipped
with diesel
particulate filters. Such filters can become clogged with particulate matter.
This particulate
matter is caused by the adverse effects of ash, sulphur, and phosphorus.
Reducing levels of
phosphorus and sulphur can be accomplished by reducing the amount of zinc
dithiophosphate
and employing low sulphur base oils, for example.
[0004] The major sources of ash in lubricating oil compositions are
generally the
metal detergents and zinc dithiophosphate anti-wear additives employed
therein. To mitigate
clogging in the diesel particulate filters, current methods involve reducing
the presence of
detergents. However, reducing the amount of detergents has an adverse effect
on the basicity
of the lubricating oil composition which is essential for neutralizing acidic
by-products of
combustion/oxidation. Therefore, it is desirable to reduce the adverse effects
of ash on diesel
particulate filters without compromising the basicity of the lubricating oil
composition by
reducing the amount of detergents.
[0005] Boosted spark-ignited internal combustions engines such as
turbocharged or
supercharged internal combustion engines may exhibit an abnormal combustion
phenomenon
known as stochastic pre-ignition or low-speed pre-ignition (or "LSPI"). LSPI
is a pre-ignition
event that may include very high pressure spikes, early combustion during an
inappropriate
crank angle, and knock. All of these, individually and in combination, have
the potential to
cause degradation and/or severe damage to the engine.
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[0006] Pre-ignition is a form of combustion that results of ignition of the
air-fuel
mixture in the combustion chamber prior to the desired ignition of the air-
fuel mixture by the
igniter. Pre-ignition has typically been a problem during high speed engine
operation since
heat from operation of the engine may heat a part of the combustion chamber to
a sufficient
temperature to ignite the air-fuel mixture upon contact. This type of pre-
ignition is sometimes
referred to as hot-spot pre-ignition.
[0007] More recently, intermittent abnormal combustion has been observed in
boosted
internal combustion engines at low speeds and medium-to-high loads. For
example, during
operation of the engine at 3,000 rpm or less, under load, with a brake mean
effective pressure
(BMEP) of at least 1,000 kPa, low-speed pre-ignition (LSP1) may occur in a
random and
stochastic fashion. During low speed engine operation, the compression stroke
time is longest.
[0008] U.S. Application Publication no. 2007/0129266 Al relates to a
lubricating oil
composition comprising a base oil and one or more magnesium detergents for the
reduction of
clogging in a diesel particulate filter.
[0009] U.S. Application Publication no. 2003/182847 Al relates to fuel
additives,
lubricating oil additives for diesel engines having diesel particulate
filters, comprising
molybdenum compounds with a measured sulfated ash content of 1.0 wt% or less,
a sulfur
content of 0.3 wt% or less, and a molybdenum content of 100 ppm or more.
SUMMARY AND TERMS
[0010] The present disclosure relates to a lubricating oil composition
including a
calcium-containing detergent and a magnesium-containing detergent, and methods
for
reducing clogging in a diesel particulate filter including a step of operating
an engine
equipped with a diesel particulate filter and lubricated with the lubricating
oil composition
including a calcium-containing detergent and a magnesium-containing detergent.
[0011] In a first aspect, the disclosure relates to a lubricating oil
composition
including one or more calcium-containing detergents and one or more magnesium-
containing
detergents. The lubricating oil composition of the present disclosure includes
greater than 50
wt.% of a base oil of lubricating viscosity, an amount of one or more calcium-
containing
detergents to provide less than 1700 ppm calcium, an amount of one or more
magnesium-
containing detergents to provide less than 450 ppm magnesium, an amount of one
or more
molybdenum-containing compounds to provide less than 450 ppm of molybdenum,
from
about 700 ppm to about 900 ppm of phosphorus, and a total measured sulfated
ash content of
no greater than 1.0 wt.%, as measured by ASTM D874, all based on the total
weight of the
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lubricating oil composition, and a ratio, in ppm, of calcium from the one or
more calcium-
containing detergents to magnesium from the one or more magnesium-containing
detergents
of 1:1 or more.
[0012] In the foregoing embodiment, the lubricating oil composition may
provide a
diesel particulate filter delta pressure (AP) vs. oil consumption result of
0.6 kPa/kg or less,
0.5 kPa/kg or less or 0.45 kPa/kg or less, as measured in a VW PV 1485 test
after 144 hours.
[0013] In each of the foregoing embodiments, the lubricating oil
composition may be
effective to reduce low speed pre-ignition events in a boosted internal
combustion engine
lubricated with the lubricating oil composition relative to a number of low
speed pre-ignition
events in the same engine lubricated with reference lubricating oil R-1; or
the reduction of
LSPI events may be 50% or greater reduction and the LSPI events are LSPI
counts during
25,000 engine cycles, wherein the engine is operated at 2000 revolutions per
minute with
brake mean effective pressure of 1,800 kPa.
[0014] In each of the foregoing embodiments, the one or more magnesium-
containing
detergents may provide 440 ppm or less of magnesium, or 430 ppm or less of
magnesium, or
420 ppm or less of magnesium, or 410 ppm or less of magnesium, based on a
total weight of
the lubricating oil composition.
[0015] In each of the foregoing embodiments, the ratio of total calcium
from the one
or more calcium-containing detergents in ppm to total magnesium from the one
or more
magnesium-containing detergents may be more than 2.0, or more than 2.5, or
more than 3.0,
or more than 3.5, or less than 10.0, or less than 9.0, or less than 8.5, or
more than 1.0 to less
than 10Ø
[0016] In each of the foregoing embodiments, the one or more calcium-
containing
detergents may be overbased, having a total base number of greater than 200 mg
KOH/g, or
greater than 225 mg KOH/g, or greater than 250 mg KOH/g, as measured by the
method of
ASTM D-2896.
[0017] In each of the foregoing embodiments, the one or more calcium-
containing
detergents may be present in an amount sufficient to provide less than 1670
ppm calcium, or
less than 1500 ppm calcium, or less than 1400 ppm calcium, or more than 1350
ppm to less
than 1700 ppm calcium to the total weight of the lubricating oil composition.
[0018] In each of the foregoing embodiments, the total measured sulfated
ash content
may be less than 0.8 wt.%, or more than 0.6 wt.% to less than 1.0 wt.%, or
more than 0.6
wt.% to less than 0.8 wt.%, each as measured by ASTM D874.
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[0019] In each of the foregoing embodiments, the lubricating oil
composition may
provide an amount of one or more calcium-containing detergents having a total
base number
of up to 175 mg KOH/g as measured by the method of ASTM D-2896, if present,
provides
less than 50 ppm of calcium, or less than 20 ppm of calcium, or less than 5
ppm of calcium,
or about 0 ppm of calcium, to the total weight of the lubricating oil
composition.
[0020] In each of the foregoing embodiments, the lubricating oil
composition may
contain less than 100 ppm of boron, or less than 75 ppm of boron, or less than
50 ppm of
boron, or less than 10 ppm of boron, or about 0 ppm of boron, based on a total
weight of the
lubricating oil composition.
[0021] In each of the foregoing embodiments, the lubricating oil
composition may
have more than 0 ppm of boron and a ratio of total metal in ppm to total boron
in ppm of
more than 7.5, or more than 50, or more than 75.
[0022] In each of the foregoing embodiments, the lubricating oil
composition may
contain 0 ppm to less than 100 ppm of boron, or 0 ppm to less than 75 ppm of
boron, or 0
ppm to less than 50 ppm of boron, or 0 ppm to less than 10 ppm of boron.
[0023] In each of the foregoing embodiments, the one or more magnesium-
containing
detergents may be overbased having a total base number of greater than 225 mg
KOH/g, or
greater than 250 mg KOH/g, or greater than 300 mg KOH/g, or greater than 350
mg KOH/g,
or greater than 400 mg KOH/g, as measured by the method of ASTM D-2896.
[0024] In each of the foregoing embodiments, the one or more calcium-
containing
detergents may optionally exclude a calcium salicylate detergent.
[0025] In each of the foregoing embodiments, the one or more magnesium-
containing
detergents may be an ovcrbased magnesium sultimate detergent having a total
base number
of greater than 225 mg KOH/g, or greater than 250 mg KOH/g, or greater than
300 mg
KOH/g, or greater than 350 mg KOH/g, or greater than 400 mg KOH/g, as measured
by the
method of ASTM D-2896.
[0026] In each of the foregoing embodiments, the lubricating oil
composition may be
an engine oil composition.
[0027] In a second aspect, the present disclosure relates to a method for
reducing
clogging in a diesel particulate filter, including a step of operating an
engine equipped with a
diesel particulate filter and lubricated with a lubricating oil composition
comprising greater
than 50 wt.% of a base oil of lubricating viscosity, an amount of one or more
calcium-
containing detergents to provide less than 1700 ppm calcium, an amount of one
or more
magnesium-containing detergents to provide less than 450 ppm magnesium, an
amount of
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one or more molybdenum-containing compounds to provide less than 450 ppm of
molybdenum, from about 700 ppm to about 900 ppm of phosphorus, and a total
measured
sulfated ash content of no greater than 1.0 wt.%, as measured by ASTM D874,
all based on
the total weight of the lubricating oil composition, and a ratio, in ppm, of
calcium from the
one or more calcium-containing detergents to magnesium from the one or more
magnesium-
containing detergents of 1:1 or more.
[0028] In this second embodiment, the lubricating oil composition may
provide a
diesel particulate filter delta pressure (AP) vs. oil consumption result of
0.6 kPa/kg or less,
0.5 kPa/kg or less or 0.45 kPa/kg or less, as measured in a VW PV 1485 test
after 144 hours.
[0029] In each of the foregoing second embodiments, the lubricating oil
composition
may be effective to reduce low speed pre-ignition events in a boosted internal
combustion
engine lubricated with the lubricating oil composition relative to a number of
low speed pre-
ignition events in the same engine lubricated with reference lubricating oil R-
1; or the
reduction of LSPI events may be 50% or greater reduction and the LSPI events
are LSPI
counts during 25,000 engine cycles, wherein the engine is operated at 2000
revolutions per
minute with brake mean effective pressure of 1,800 kPa.
[0030] In each of the foregoing second emhodiments, the one or more
magnesium-
containing detergents may provide 440 ppm or less of magnesium, or 430 ppm or
less of
magnesium, or 420 ppm or less of magnesium, or 410 ppm or less of magnesium,
based on a
total weight of the lubricating oil composition.
[0031] In each of the foregoing second embodiments, the ratio of total
calcium from
the one or more calcium-containing detergents in ppm to total magnesium from
the one or
more magnesium-containing detergents may be more than 2.0, or more than 2.5,
or more than
3.0, or more than 3.5, or less than 10.0, or less than 9.0, or less than 8.5,
or more than 1.0 to
less than 10Ø
[0032] In each of the foregoing second embodiments, the one or more calcium-
containing detergents may be overbased, having a total base number of greater
than 200 mg
KOH/g, or greater than 225 mg KOH/g, or greater than 250 mg KOH/g, as measured
by the
method of ASTM D-2896.
[0033] In each of the foregoing second embodiments, the one or more calcium-
containing detergents may be present in an amount sufficient to provide less
than 1670 ppm
calcium, or less than 1500 ppm calcium, or less than 1400 ppm calcium, or more
than 1350
ppm to less than 1700 ppm calcium to the total weight of the lubricating oil
composition.
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[0034] In each of the foregoing second embodiments, the total measured
sulfated ash
content may be less than 0.8 wt.%, or more than 0.6 wt.% to less than 1.0
wt.%, each as
measured by ASTM D874.
[0035] In each of the foregoing second embodiments, the lubricating oil
composition
may provide an amount of one or more calcium-containing detergents having a
total base
number of up to 175 mg KOH/g as measured by the method of ASTM D-2896, if
present,
provides less than 50 ppm of calcium, or less than 20 ppm of calcium, or less
than 5 ppm of
calcium, or about 0 ppm of calcium, to the total weight of the lubricating oil
composition.
[0036] In each of the foregoing second embodiments, the lubricating oil
composition
may contain less than 100 ppm of boron, or less than 75 ppm of boron, or less
than 50 ppm of
boron, or less than 10 ppm of boron, or about 0 ppm of boron, based on a total
weight of the
lubricating oil composition.
[0037] In each of the foregoing second embodiments, the lubricating oil
composition
may have more than 0 ppm of boron and a ratio of total metal in ppm to total
boron in ppm of
more than 7.5, or more than 50, or more than 500.
[0038] In each of the foregoing embodiments, the lubricating oil
composition may
contain 0 ppm to less than 100 ppm of boron, or 0 ppm to less than 75 ppm of
boron, or 0
ppm to less than 50 ppm of boron, or 0 ppm to less than 10 ppm of boron.
[0039] In each of the foregoing second embodiments, the one or more
magnesium-
containing detergents may be overbased having a total base number of greater
than 225 mg
KOH/g, or greater than 250 mg KOH/g, or greater than 300 mg KOH/g, or greater
than 350
mg KOH/g, or greater than 400 mg KOH/g, as measured by the method of ASTM D-
2896.
[0040] In each of the foregoing second embodiments, the one or more calcium-
containing detergents may optionally exclude a calcium salicylate detergent.
[0041] In each of the foregoing second embodiments, the one or more
magnesium-
containing detergents may be an overbased magnesium sulfonate detergent having
a total
base number of greater than 225 mg KOH/g, or greater than 250 mg KOH/g, or
greater than
300 mg KOH/g, or greater than 350 mg KOH/g, or greater than 400 mg KOH/g, as
measured
by the method of ASTM D-2896.
[0042] In each of the foregoing second embodiments, the lubricating oil
composition
may be an engine oil composition.
[0043] The following definitions of terms are provided in order to clarify
the
meanings of certain terms as used herein.
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[0044] The terms "oil composition," "lubrication composition," "lubricating
oil
composition," "lubricating oil," "lubricant composition," "lubricating
composition," "fully
formulated lubricant composition," "lubricant," "crankcase oil," "crankcase
lubricant,"
"engine oil," "engine lubricant," "motor oil," and "motor lubricant" are
considered
synonymous, fully interchangeable terminology referring to the finished
lubrication product
comprising a major amount of a base oil plus a minor amount of an additive
composition.
[0045] As used herein, the terms "additive package," "additive
concentrate,"
"additive composition," "engine oil additive package," "engine oil additive
concentrate,"
"crankcase additive package," "crankcase additive concentrate," "motor oil
additive
package," "motor oil concentrate," are considered synonymous, fully
interchangeable
terminology referring the portion of the lubricating oil composition excluding
the major
amount of base oil stock mixture. The additive package may or may not include
the viscosity
index improver or pour point depressant.
[0046] The term "overbased" relates to metal salts, such as metal salts of
sulfonates,
carboxylates, salicylates, and/or phenates, wherein the amount of metal
present exceeds the
stoichiometric amount. Such salts may have a conversion level in excess of
100% (i.e., they
may comprise more than 100% of the theoretical amount of metal needed to
convert the acid
to its "normal," "neutral" salt). The expression "metal ratio," often
abbreviated as MR, is used
to designate the ratio of total chemical equivalents of metal in the overbased
salt to chemical
equivalents of the metal in a neutral salt according to known chemical
reactivity and
stoichiometry. In a normal or neutral salt, the metal ratio is one and in an
overbased salt, MR,
is greater than one. They are commonly referred to as overbased, hyperbased,
or superbased
salts and may be salts of organic sulfur acids, carboxylic acids, salicylates,
and/or phenols.
[0047] As used herein, the term "hydrocarbyl substituent" or ''hydrocarbyl
group" is
used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it refers
to a group having a carbon atom directly attached to the remainder of the
molecule and having
a predominantly hydrocarbon character. Each hydrocarbyl group is independently
selected
from hydrocarbon substituents, and substituted hydrocarbon suhstituents
containing one or
more of halo groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro
groups, nitroso
groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen
and nitrogen,
and wherein no more than two non-hydrocarbon substituents are present for
every ten carbon
atoms in the hydrocarbyl group.
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[0048] As used herein, the term "hydrocarbylene substituent" or
"hydrocarbylene
group" is used in its ordinary sense, which is well-known to those skilled in
the art.
Specifically, it refers to a group that is directly attached at two locations
of the molecule to the
remainder of the molecule by a carbon atom and having predominantly
hydrocarbon character.
Each hydrocarbylene group is independently selected from divalent hydrocarbon
substituents,
and substituted divalent hydrocarbon substituents containing halo groups,
alkyl groups, aryl
groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups,
mercapto groups,
nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups,
imidazolyl groups,
oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents
is present
for every ten carbon atoms in the hydrocarbylene group.
[0049] As used herein, the term "percent by weight", unless expressly
stated otherwise,
means the percentage the recited component represents to the weight of the
entire composition.
[0050] The terms "soluble," "oil-soluble," or "dispersible" used herein
may, but does
not necessarily, indicate that the compounds or additives are soluble,
dissolvable, miscible, or
capable of being suspended in the oil in all proportions. The foregoing terms
do mean,
however, that they are, for instance, soluble, suspendable, dissolvable, or
stably dispersible in
oil to an extent sufficient to exert their intended effect in the environment
in which the oil is
employed. Moreover, the additional incorporation of other additives may also
permit
incorporation of higher levels of a particular additive, if desired.
[0051] The term "TBN" as employed herein is used to denote the Total Base
Number
in mg KOH/g as measured by the method of ASTM D2896 or ASTM D4739 or DIN 51639-
[0052] The term "alkyl" as employed herein refers to straight, branched,
cyclic,
and/or substituted saturated chain moieties of from about 1 to about 100
carbon atoms.
[0053] The term "alkenyl" as employed herein refers to straight, branched,
cyclic,
and/or substituted unsaturated chain moieties of from about 3 to about 10
carbon atoms.
[0054] The term "aryl" as employed herein refers to single and multi-ring
aromatic
compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy,
halo
substituents, and/or heteroatoms including, but not limited to, nitrogen,
oxygen, and sulfur.
[0055] The clogging of diesel particulate filters can be measured by the
Volkswagen
(VW) diesel particulate filter test (DFT), VW PV 1485. The VW PV 1485 test
measures the
amount of sulfated ash deposits clogged into the diesel particulate filter of
vehicles, thereby
reducing filter life, raising back pressure in the vehicle engine and causing
increased fuel
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consumption. The diesel particulate filter test measures the increase in
backpressure versus
oil consumption, after 144 hours of an ash loading phase.
[0056] A reduction in low speed pre-ignition events may be expressed as an
"LSPI
Ratio." The term, "LSPI Ratio" refers to a ratio of the number of low speed
pre-ignition
events in a boosted internal combustion engine lubricated with the lubricating
oil composition
of the disclosure to a number of low speed pre-ignition events in the same
boosted internal
combustion engine lubricated with reference lubricating oil R-1 described
herein. A
lubricating oil composition that reduces the LSPI ratio is effective to reduce
low speed pre-
ignition events in a boosted internal combustion engine lubricated with the
lubricating oil
composition relative to a number of low speed pre-ignition events in the same
engine
lubricated with reference lubricating oil R-1.
[0057] Lubricants, combinations of components, or individual components of
the
present description may be suitable for use in various types of internal
combustion engines.
Suitable engine types may include, but are not limited to heavy duty diesel,
passenger car,
light duty diesel, medium speed diesel, or marine engines. An internal
combustion engine
may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled
engine, a bio-
fueled engine, a mixed diesel/biofuel fueled engine, a mixed gasoline/biofuel
fueled engine,
an alcohol fueled engine, a mixed gasoline/alcohol fueled engine, a compressed
natural gas
(CNG) fueled engine, or mixtures thereof. A diesel engine may be a compression
ignited
engine. A gasoline engine may be a spark-ignited engine such as a boosted
spark-ignited
engine. An internal combustion engine may also be used in combination with an
electrical or
battery source of power. An engine so configured is commonly known as a hybrid
engine.
The internal combustion engine may be a 2-stroke, 4-stroke, or rotary engine.
Suitable
internal combustion engines include marine diesel engines (such as inland
marine), aviation
piston engines, low-load diesel engines, and motorcycle, automobile,
locomotive, and truck
engines.
[0058] Passenger and light-duty vehicles may be equipped with either a
compression
(diesel) or spark-ignition (gasoline) internal combustion engine. Generally
engine oils are
specially formulated for use in one or the other. However, it can be
beneficial to lubricate a
spark-ignition engine with an engine oil formulated for a diesel engine.
Further, some diesel
engine oils are tested to meet both diesel and gasoline engine oil
specifications (i.e., mixed
specifications), and, thus are recommend for use with either engine-type.
Therefore, an oil
that meets both diesel engine and gasoline engine specifications and that can
handle each of
these diverse engine conditions is desirable.
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[0059] The internal combustion engine may contain components of one or more
of an
aluminum-alloy, lead, tin, copper, cast iron, magnesium, ceramics, stainless
steel,
composites, and/or mixtures thereof. The components may be coated, for
example, with a
diamond-like carbon coating, a lubrited coating, a phosphorus-containing
coating,
molybdenum-containing coating, a graphite coating, a nano-particle-containing
coating,
and/or mixtures thereof. The aluminum-alloy may include aluminum silicates,
aluminum
oxides, or other ceramic materials. In one embodiment the aluminum-alloy is an
aluminum-
silicate surface. As used herein, the term "aluminum alloy" is intended to be
synonymous
with "aluminum composite" and to describe a component or surface comprising
aluminum
and another component intermixed or reacted on a microscopic or nearly
microscopic level,
regardless of the detailed structure thereof. This would include any
conventional alloys with
metals other than aluminum as well as composite or alloy-like structures with
non-metallic
elements or compounds such with ceramic-like materials.
[0060] The lubricating oil composition for an internal combustion engine
may be
suitable for any engine lubricant irrespective of the sulfur, phosphorus, or
ash (ASTM D-874)
content. The sulfur content of the engine oil lubricant may be about 1 wt% or
less, or about
0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about
0.2 wt% or less.
In one embodiment the sulfur content may be in the range of about 0.001 wt% to
about 0.5
wt%, or about 0.01 wt% to about 0.3 wt%. The phosphorus content may be from
about 700
ppm to about 900 ppm, or from no more than 850 ppm. The total measured
sulfated ash
content may be no less than 0.5 wt% to no greater than 1.0 wt%õ or less than
0.8 wt%, or
more than 0.5 wt% to less than 1.0 wt%, or more than 0.6 wt% to less than 1.0
wt%, as
measured by ASTM D874. In another embodiment, the sulfur content may be about
0.4 wt%
or less, the phosphorus content may be about 0.08 wt% or less, and the
measured sulfated ash
is no less than 0.5 wt% to 1 wt% or less. In yet another embodiment the sulfur
content may
be about 0.3 wt% or less, the phosphorus content is about 0.05 wt% or less,
and the measured
sulfated ash may be about 0.8 wt% or less.
[0061] In one embodiment the lubricating oil composition is an engine oil,
wherein
the lubricating oil composition may have (i) a sulfur content of about 0.5 wt%
or less, (ii) a
phosphorus content of about 0.1 wt% or less. and (iii) a measured sulfated ash
content of no
less than 0.5 wt% to no greater than 1.0 wt%.
[0062] In one embodiment, the lubricating oil composition contains less
than 10 ppm
of boron, or less than 50 ppm or boron, or less than 10 ppm or boron, or 0 ppm
of boron,
based on a total weight of the lubricating oil composition. In another
embodiment, the
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lubricating oil composition has more than 0 ppm of boron and the ratio of
total metal in ppm
to total boron in ppm is more than 7.5, or more than 50, or more than 500.
[0063] In one embodiment the lubricating oil composition is suitable for a
2-stroke or
a 4-stroke marine diesel internal combustion engine. In one embodiment the
marine diesel
combustion engine is a 2-stroke engine. In some embodiments, the lubricating
oil
composition is not suitable for a 2-stroke or a 4-stroke marine diesel
internal combustion
engine for one or more reasons, including but not limited to, the high sulfur
content of fuel
used in powering a marine engine and the high TBN required for a marine-
suitable engine oil
(e.g., above about 40 TBN in a marine-suitable engine oil).
[0064] In some embodiments, the lubricating oil composition is suitable for
use with
engines powered by low sulfur fuels, such as fuels containing about 1 to about
5% sulfur.
Highway vehicle fuels contain about 15 ppm sulfur (or about 0.0015% sulfur).
[0065] Low speed diesel typically refers to marine engines, medium speed
diesel
typically refers to locomotives, and high speed diesel typically refers to
highway vehicles.
The lubricating oil composition may be suitable for only one of these types or
all.
[0066] Further, lubricants of the present description may be suitable to
meet one or
more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-
5+, GF-6,
PC-11, CF, CK-4, FA-4, CF-4, CH-4, CI-4, CJ-4, API SG, SJ, SL, SM, SN, SN+,
ACEA
Al/B1, A2/B2, A3/B3, A3/B4, A5/B5, Cl. C2, C3, C4, C5, E4/E6/E7/E9, Euro
5/6,Jaso DL-
1, Low SAPS, Mid SAPS, or original equipment manufacturer specifications such
as
Dexosil" 1, Dexos TM 2, MB-Approval 229.1, 229.3, 229.5, 229.31, 229.51,
229.52, 229.6,
229.71, 226.5, 226.51, 228.0/.1, 228.2/.3, 228.31, 228.5, 228.51, 228.61, VW
501.01, 502.00,
503.00/503.01, 504.00, 505.00, 505.01, 506.00/506.01, 507.00, 508.00, 509.00,
508.88,
509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-
14 FE+,
Longlife-17 PE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71
2294,
B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71
2008,
Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-
M2C945-A, WSS-M2C913A, WSS-M2C913-13, WSS-M2C913-C, WSS-M2C913-D, WSS-
M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 Gl, G2, M2,
Ni, N2, Z2, Si, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land
Rover
STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007,
STJLR.51.5122, or any past or future PCMO or HDD specifications not mentioned
herein.
In some embodiments for passenger car motor oil (PCMO) applications, the
amount of
phosphorus in the finished fluid is 1000 ppm or less or 900 ppm or less or 800
ppm or less.
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[0067] Other hardware may not be suitable for use with the disclosed
lubricant. A
"functional fluid" is a term which encompasses a variety of fluids including
but not limited to
tractor hydraulic fluids, power transmission fluids including automatic
transmission fluids,
continuously variable transmission fluids and manual transmission fluids,
hydraulic fluids,
including tractor hydraulic fluids, some gear oils, power steering fluids,
fluids used in wind
turbines, compressors, some industrial fluids, and fluids related to power
train components. It
should be noted that within each of these fluids such as, for example,
automatic transmission
fluids, there are a variety of different types of fluids due to the various
transmissions having
different designs which have led to the need for fluids of markedly different
functional
characteristics. This is contrasted by the term "lubricating fluid" which is
not used to
generate or transfer power.
[0068] With respect to tractor hydraulic fluids, for example, these fluids
are all-
purpose products used for all lubricant applications in a tractor except for
lubricating the
engine. These lubricating applications may include lubrication of gearboxes,
power take-off
and clutch(cs), rear axles, reduction gears, wet brakes, and hydraulic
accessories.
[0069] When the functional fluid is an automatic transmission fluid, the
automatic
transmission fluids must have enough friction for the clutch plates to
transfer power.
However, the friction coefficient of fluids has a tendency to decline due to
the temperature
effects as the fluid heats up during operation. It is important that the
tractor hydraulic fluid or
automatic transmission fluid maintain its high friction coefficient at
elevated temperatures,
otherwise brake systems or automatic transmissions may fail. This is not a
function of an
engine oil.
[0070] Tractor fluids, and for example Super Tractor Universal Oils (STU0s)
or
Universal Tractor Transmission Oils (UTT0s), may combine the performance of
engine oils
with transmissions, differentials, final-drive planetary gears, wet-brakes,
and hydraulic
performance. While many of the additives used to formulate a UTTO or a STUO
fluid are
similar in functionality, they may have deleterious effect if not incorporated
properly. For
example, some anti-wear and extreme pressure additives used in engine oils can
be extremely
corrosive to the copper components in hydraulic pumps. Detergents and
dispersants used for
gasoline or diesel engine performance may be detrimental to wet brake
performance. Friction
modifiers specific to quiet wet brake noise, may lack the thermal stability
required for engine
oil performance. Each of these fluids, whether functional, tractor, or
lubricating, are designed
to meet specific and stringent manufacturer requirements.
12
[0071] The present disclosure provides novel lubricating oil blends
formulated for use
as automotive crankcase lubricants. The present disclosure provides novel
lubricating oil
blends formulated for use as 2T and/or 4T motorcycle crankcase lubricants.
Embodiments of
the present disclosure may provide lubricating oils suitable for crankcase
applications and
having improvements in the following characteristics: air entrainment, alcohol
fuel
compatibility, antioxidancy, antiwear performance, biofuel compatibility, foam
reducing
properties, friction reduction, fuel economy, preignition prevention, rust
inhibition, sludge
and/or soot dispersability, piston cleanliness, deposit formation, and water
tolerance.
[0072] Engine oils of the present disclosure may be formulated by the
addition of one
or more additives, as described in detail below, to an appropriate base oil
formulation. The
additives may be combined with a base oil in the form of an additive package
(or concentrate)
or; alternatively, may be combined individually with a base oil (or a mixture
of both). The
fully formulated engine oil may exhibit improved performance properties, based
on the
additives added and their respective proportions.
[0073] Additional details and advantages of the disclosure will be set
forth in part in
the description which follows, and/or may be learned by practice of the
disclosure. It is to be
understood that both the foregoing general description and the following
detailed description
are exemplary and explanatory only and are not restrictive of the disclosure,
as claimed.
DETAILED DESCRIPTION
[0074] Various embodiments of the disclosure provide a lubricating oil
composition
and methods for reducing clogging in a diesel particulate filter. The
lubricating oil composition
may be useful in compression (diesel) engines and/or spark-ignited (gasoline)
engines. In
particular, engines in which the lubricating oil composition may be employed
may include
boosted internal combustion engines such as turbocharged and supercharged
internal
combustion engines. The boosted internal combustion engines include spark-
ignited, direct
injection and/or port-fuel injection engines. Preferably, the boosted internal
combustion engine
is a spark-ignited internal combustion engine or a direct injection engine.
[0075] In a first aspect, the present disclosure provides a lubricating
oil composition
that includes greater than 50 wt.% of a base oil of lubricating viscosity, an
amount of one or
more calcium-containing detergents to provide less than 1700 ppm calcium, an
amount of one
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or more magnesium-containing detergents to provide less than 450 ppm
magnesium, an amount
of one or more molybdenum-containing compounds to provide less than 450 ppm
molybdenum, from about 700 ppm to about 900 ppm of phosphorus, based on the
total weight
of the lubricating oil composition, and a total measured sulfated ash content
of no greater than
1.0 wt.%, as measured by ASTM D874, all based on the total weight of the
lubricating oil
composition, and a ratio, in ppm, of calcium from the one or more calcium-
containing
detergents to magnesium from the one or more magnesium-containing detergents
of 1:1 or
more.
[0076] In a second aspect, the present invention relates to a method of
reducing
clogging in a diesel particulate filter, including a step of operating an
engine equipped with a
diesel particulate filter and lubricated with the lubricating oil composition
herein.
[0077] The foregoing lubricating oil compositions and methods may provide a
diesel
particulate filter delta pressure (AP) vs. oil consumption result of 0.6
kPa/kg or less, 0,5 kPa/kg
or less, or 0.45 kPa/kg or less, as measured in a VW PV 1485 test after 144
hours.
[0078] Preferably, the lubricating oil compositions and methods arc also
effective to
reduce low speed pre-ignition events in a boosted internal combustion engine
lubricated with
the lubricating oil composition relative to a number of low speed pre-ignition
events in the
same engine lubricated with reference lubricating oil R-1: or to provide a
reduction of LSPI
events is 50% or greater reduction and the LSPI events are LSPI counts during
25,000 engine
cycles, wherein the engine is operated at 2000 revolutions per minute with
brake mean effective
pressure of 1,800 kPa.
[0079] As described in more detail below, the embodiments of the disclosure
may
provide a significant and unexpected improvement in reducing clogging in a
diesel particulate
filter and optionally, a significant reduction low speed pre-ignition events
while maintaining a
relatively high calcium detergent concentration in the lubricating oil
composition.
Base Oil
[0080] The base oil used in the lubricating oil compositions may be
selected from any
of the base oils in Groups I-V as specified in the American Petroleum
Institute (API) Base
Oil Interchangeability Guidelines. The five base oil groups are as follows:
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Base oil Saturates Viscosity
Sulfur (%)
Category (%) Index
Group I > 0.03 and/or <90 80 to 120
Group 11 <0.03 and >90 80 to 120
Group III <0.03 and >90 >120
All
Group IV polyalphaolefins
(PA0s)
All others not
included in
Group V
Groups I, II, III, or
IV
[0081] Groups I, II, and III are mineral oil process stocks. Group IV base
oils contain
true synthetic molecular species, which are produced by polymerization of
olefinically
unsaturated hydrocarbons. Many Group V base oils arc also true synthetic
products and may
include diesters, polyol esters, polyalkylene glycols, alkylated aromatics,
polyphosphate
esters, polyvinyl ethers, and/or polyphenyl ethers, and the like, but may also
be naturally
occurring oils, such as vegetable oils. It should be noted that although Group
III base oils are
derived from mineral oil, the rigorous processing that these fluids undergo
causes their
physical properties to be very similar to some true synthetics, such as PAOs.
Therefore, oils
derived from Group III base oils may be referred to as synthetic fluids in the
industry. Group
II+ may comprise high viscosity index Group II.
[0082] The base oil used in the disclosed lubricating oil composition may
be a
mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blends,
or mixtures thereof.
Suitable oils may be derived from hydrocracking, hydrogenation,
hydrofinishing, unrefined,
refined, and re-refined oils, and mixtures thereof.
[0083] Unrefined oils are those derived from a natural, mineral, or
synthetic source
without or with little further purification treatment. Refined oils are
similar to the unrefined
oils except that they have been treated in one or more purification steps,
which may result in
the improvement of one or more properties. Examples of suitable purification
techniques are
solvent extraction, secondary distillation, acid or base extraction,
filtration, percolation, and
the like. Oils refined to the quality of an edible may or may not be useful.
Edible oils may
also be called white oils. In some embodiments, lubricating oil compositions
are free of
edible or white oils.
[0084] Re-refined oils are also known as reclaimed or reprocessed oils.
These oils are
obtained similarly to refined oils using the same or similar processes. Often
these oils are
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additionally processed by techniques directed to removal of spent additives
and oil
breakdown products.
[0085] Mineral oils may include oils obtained by drilling or from plants
and animals
or any mixtures thereof. For example such oils may include, hut are not
limited to, castor oil,
lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as
well as mineral
lubricating oils, such as liquid petroleum oils and solvent-treated or acid-
treated mineral
lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic
types. Such oils
may be partially or fully hydrogenated, if desired. Oils derived from coal or
shale may also
be useful.
[0086] Useful synthetic lubricating oils may include hydrocarbon oils such
as
polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes,
polypropylenes,
propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or
oligomers of
1-decene, e.g., poly(1-decenes), such materials being often referred to as a-
olefins, and
mixtures thereof; alkyl-benzenes (e.g. doclecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls,
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. Polyalphaolefins are typically hydrogenated materials.
[0087] Other synthetic lubricating oils include polyol esters, 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 hydroisomerized Fi
scher-
Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a
Fischer-
Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
[0088] The major amount of base oil included in a lubricating composition
may be
selected from the group consisting of Group I, Group II, a Group III, a Group
IV, a Group V,
and a combination of two or more of the foregoing, and wherein the major
amount of base oil
is other than base oils that arise from provision of additive components or
viscosity index
improvers in the composition. In another embodiment, the major amount of base
oil included
in a lubricating composition may be selected from the group consisting of
Group II, a Group
III, a Group IV, a Group V, and a combination of two or more of the foregoing,
and wherein
the major amount of base oil is other than base oils that arise from provision
of additive
components or viscosity index improvers in the composition.
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[0089] The amount of the oil of lubricating viscosity present may be the
balance
remaining after subtracting from 100 wt% the sum of the amount of the
performance
additives inclusive of viscosity index improver(s) and/or pour point
depressant(s) and/or
other top treat additives. For example, the oil of lubricating viscosity that
may he present in a
finished fluid may be a major amount, such as greater than about 50 wt%,
greater than about
60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than
about 85 wt%, or
greater than about 90 wt%.
Detergents
[0090] The lubricating oil composition comprises one or more calcium-
containing
detergents and optionally one or more magnesium-containing detergents. The one
or more
calcium-containing detergents and the one or more magnesium-containing
detergents may be
independently selected from neutral, low based, or overbased detergents, and
mixtures
thereof. Suitable detergent substrates include phenates, sulfur containing
phenates, sulfonates,
calixarates, salixaratcs, salicylates, carboxylic acids, phosphorus acids,
mono- and/or di-
thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or
methylene
bridged phenols. Suitable detergents and their methods of preparation are
described in
greater detail in numerous patent publications, including US 7,732,390 and
references cited
therein.
[0091] The detergent substrate may be salted with an alkali or alkaline
earth metal
such as, but not limited to, calcium, magnesium, potassium, sodium, lithium,
barium, or
mixtures thereof. In some embodiments, the detergent is free of barium. A
suitable detergent
may include alkali or alkaline earth metal salts of petroleum sultimic acids
and long chain
mono- or di-alkylarylsulfonic acids with the aryl group being benzyl, tolyl,
and xylyl.
Examples of suitable additional detergents include, but are not limited to,
calcium phenates,
calcium sulfur containing phenates, calcium sulfonates, calcium calixarates,
calcium
salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus
acids, calcium
mono- and/or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur
coupled alkyl
phenol compounds, calcium methylene bridged phenols, magnesium phenates,
magnesium
sulfur containing phenates, magnesium sulfonates, magnesium calixarates,
magnesium
salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium
phosphorus
acids, magnesium mono- and/or di-thiophosphoric acids, magnesium alkyl
phenols,
magnesium sulfur coupled alkyl phenol compounds, magnesium methylene bridged
phenols,
sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium
calixarates,
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sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium
phosphorus acids,
sodium mono- and/or di-thiophosphoric acids, sodium alkyl phenols, sodium
sulfur coupled
alkyl phenol compounds, or sodium methylene bridged phenols.
[0092] Overbased detergents are well known in the art and may be alkali or
alkaline
earth metal overbased detergent additives. Such detergent additives may be
prepared by
reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide
gas. The
substrate is typically an acid, for example, an acid such as an aliphatic
substituted sulfonic
acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted
phenol.
[0093] The terminology "overbased" relates to metal salts, such as metal
salts of
sulfonates, carboxylates, and phenates, wherein the amount of metal present
exceeds the
stoichiometric amount. Such salts may have a conversion level in excess of
100% (i.e., they
may comprise more than 100% of the theoretical amount of metal needed to
convert the acid
to its "normal," "neutral" salt). The expression "metal ratio," often
abbreviated as MR, is
used to designate the ratio of total chemical equivalents of metal in the
overbased salt to
chemical equivalents of the metal in a neutral salt according to known
chemical reactivity and
stoichiometry. In a normal or neutral salt, the metal ratio is one and in an
overbased salt,
MR, is greater than one. They are commonly referred to as overbased,
hyperbased, or
superbased salts and may be salts of organic sulfur acids, carboxylic acids,
or phenols.
[0094] An overbased detergent of the lubricating oil composition may have a
total
base number (TBN) of about 200 mg KOH/gram or greater, or as further examples,
about 250
mg KOH/gram or greater, or about 350 mg KOH/gram or greater, or about 375 mg
KOH/gram or greater, or about 400 mg KOH/gram or greater.
[0095] Examples of suitable ova-based detergents include, but are not
limited to,
overbased calcium phenates, overbased calcium sulfur containing phenates,
overbased
calcium sulfonates, overbased calcium calixarates, overbased calcium
salixarates, overbased
calcium salicylates, overbased calcium carboxylic acids, overbased calcium
phosphorus
acids, overbased calcium mono- and/or di-thiophosphoric acids, overbased
calcium alkyl
phenols, overbased calcium sulfur coupled alkyl phenol compounds, overbased
calcium
methylene bridged phenols, overbased magnesium phenates, overbased magnesium
sulfur
containing phenates, overbased magnesium sulfonates, overbased magnesium
calixarates,
overbased magnesium salixarates, overbased magnesium salicylates, overbased
magnesium
carboxylic acids, overbased magnesium phosphorus acids, overbased magnesium
mono-
and/or di-thiophosphoric acids, overbascd magnesium alkyl phenols, ovcrbased
magnesium
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sulfur coupled alkyl phenol compounds, or overbased magnesium methylene
bridged
phenols.
[0096] An overbased calcium detergent may have a total base number of at
least 150
mg KOH/g, at least ahout 225 mg KOH/g, at least 225 mg KOH/g to about 400 mg
KOH/g,
at least about 225 mg KOH/g to about 350 mg KOH/g or about 230 to about 350 mg
KOH/g,
all as measured by the method of ASTM D-2896. When such detergent compositions
are
formed in an inert diluent, e.g. a process oil, usually a mineral oil, the
total base number
reflects the basicity of the overall composition including diluent, and any
other materials
(e.g., promoter, etc.) that may be contained in the detergent composition.
[0097] The overbased detergent may have a metal to substrate ratio of from
1.1:1, or
from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.
[0098] In some embodiments, a detergent is effective at reducing or
preventing rust in
an engine.
[0099] The total detergent may be present up to 10 wt%, or about up to 8
wt%, or
about up to 4 wt%, or greater than about 4 wt% to about 8 wt%, based on a
total weight of the
lubricating oil composition.
[00100] The one or more calcium-containing detergents may he present in an
amount
to provide less than 1700 ppm calcium, or less than 1670 ppm calcium, or less
than 1500 ppm
calcium, or less than 1400 ppm calcium; or more than 1350 ppm to less than
1700 ppm
calcium, or more than 1350 ppm to less than 1670 ppm calcium, or more than
1350 ppm to
less than 1500 ppm calcium, or more than 1350 ppm to less than 1400 ppm
calcium based on
the total weight of the lubricating oil composition.
[00101] In some embodiments, the one or more calcium-containing detergents
is
overbased having a total base number of greater than 200 mg KOH/g, greater
than 225 mg
KOH/g, or greater than 250 mg KOH/g or more, as measured by the method of ASTM
D-
2896.
[00102] In some embodiments, the one or more calcium-containing detergents
excludes calcium salicylate.
[00103] In another embodiment, the lubricating oil composition may include
one or
more calcium-containing detergents having a total base number of up to 175 mg
KOH/g as
measured by the method of ASTM D-2896, and provides less than 50 ppm of
calcium, or less
than 20 ppm of calcium; or less than 5 ppm of calcium, or about 0 ppm of
calcium to the total
weight of the lubricating oil composition.
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[00104] The one or more magnesium-containing detergents may be present in
an
amount to provide less than 450 ppm magnesium, or 450 ppm or less of
magnesium, or 440
ppm or less of magnesium, or 430 ppm or less of magnesium, or 420 ppm or less
of
magnesium, or 410 ppm or less of magnesium, or less than 400 ppm of magnesium,
or less
than 350 ppm of magnesium, or less than 300 ppm of magnesium.
[00105] In some embodiments, the one or more magnesium-containing
detergents is
overbased having a total base number of greater than 225 mg KOH/g, or greater
than 250 mg
KOH/g, or greater than 300 mg KOH/g, or greater than 350 mg KOH/g, or greater
than 400
mg KOH/g, as measured by the method of ASTM D-2896.
[00106] In other embodiments, the one or more magnesium-containing
detergents is
an overbased magnesium sulfonate detergent having a total base number of
greater than 225
mg KOH/g, or greater than 250 mg KOH/g, or greater than 300 mg KOH/g, or
greater than
350 mg KOH/g, or greater 400 mg KOH/g, as measured by the method of ASTM D-
2896.
[00107] In some embodiments, the ratio, in ppm, of calcium from the one or
more
calcium-containing detergents to magnesium from the one or more magnesium-
containing
detergents is 1 or more, or more than 2.0, or more than 2.5, or more than 3.0,
or more than
3.5, or less than 10.0, or less than 9.0, or less than 8.5, or more than 1.0
to less than 10Ø
[00108] In an alternative embodiment, the lubricating oil composition
optionally
contains not more than 15 ppm of magnesium or not more than 10 ppm of
magnesium from
detergents.
Molybdenum-containing component
[00109] The lubricating oil compositions herein comprises one or more
molybdenum-
containing compounds. An oil-soluble molybdenum compound may have the
functional
performance of an antiwear agent, an antioxidant, a friction modifier, or
mixtures thereof. An
oil-soluble molybdenum compound may include molybdenum dithiocarbamates,
molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts
of
molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates,
molybdenum
sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-
molybdenum compound, and/or mixtures thereof. The molybdenum sulfides include
molybdenum disulfide. The molybdenum disulfide may be in the form of a stable
dispersion.
In one embodiment the oil-soluble molybdenum compound may be selected from the
group
consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphatcs,
amine
.=
salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil-
soluble
molybdenum compound may be a molybdenum dithiocarbamate.
[00110] Suitable examples of molybdenum compounds which may
be used include
commercial materials sold under the trade names such as Molyvan 822TM,
MolyvanTM A,
Molyvan 2000Tm and Molyvan 855TM from R. T. Vanderbilt Co., Ltd., and
SakuraLubeTM S-
165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka
Corporation, and mixtures thereof. Suitable molybdenum components are
described in US
5,650,381; US RE 37,363 El; US RE 38,929 El; and US RE 40,595 El. Preferably,
the one
or more molybdenum-containing compounds may be the reaction product of a fatty
acid ester
and molybdenum oxide. Preferably, the fatty acid ester has from 4 to 30 carbon
atoms, or
from 6 to 20 carbon atoms.
[00111] Additionally, the molybdenum compound may be an
acidic molybdenum
compound. Included are molybdic acid, ammonium molybdate, sodium molybdate,
potassium molybdate, and other alkaline metal molybdates and other molybdenum
salts, e.g.,
hydrogen sodium molybdate, Mo0C14, MoO2Br2, Mo203C16, molybdenum trioxide or
similar acidic molybdenum compounds. Alternatively, the compositions can be
provided with
molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as
described,
for example, in U.S. Pat. Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387;
4,265,773;
4,261,843; 4,259,195 and 4,259,194; and WO 94/06897.
[00112] Another class of suitable organo-molybdenum compounds
are trinucl ear
molybdenum compounds, such as those of the formula Mo3SkLnQz and mixtures
thereof,
wherein S represents sulfur, L represents independently selected ligands
having organo
groups with a sufficient number of carbon atoms to render the compound soluble
or
dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is
selected from the group
of neutral electron donating compounds such as water, amines, alcohols,
phosphines, and
ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At
least 21 total
carbon atoms may be present among all the ligands' organo groups, such as at
least 25, at
least 30, or at least 35 carbon atoms. Additional suitable molybdenum
compounds are
described in U.S. Pat. No. 6,723,685.
[00113] The oil-soluble molybdenum compound may be present in
an amount
sufficient to provide less than about 450 ppm, or less than about 420 ppm, or
less than about
400 ppm, or less than about 390 ppm of molybdenum, or more than 5 ppm of
molybdenum,
or more than 50 ppm of molybdenum, or more than 80 ppm of molybdenum, or more
than
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100 ppm of molybdenum, or more than 5 ppm to less than 450 ppm of molybdenum,
or more
than 50 ppm to less than 420 ppm of molybdenum, or more than 80 ppm to less
than 400 ppm
of molybdenum, or more than 100 ppm to less than 390 ppm of molybdenum, based
on the
total weight of the lubricating oil composition.
[00114] The lubricating oil composition may also include one or more
optional
components selected from the various additives set forth below.
Boron-Containing Compounds
[00115] The lubricating oil compositions herein may optionally contain one
or more
boron-containing compounds.
[00116] Examples of boron-containing compounds include borate esters,
borated fatty
amines, borated epcoddes, borated detergents, and borated dispersants, such as
borated
succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057.
[00117] The boron-containing compound, if present, can be used in an amount
sufficient to provide up to about 8 wt%, about 0.01 wt% to about 7 wt%, about
0.05 wt% to
about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil
composition.
[00118] In some embodiments of the invention, the lubricating oil
composition may
contain less than 100 ppm of boron, or less than 75 ppm of boron, or less than
50 ppm of
boron, or less than 10 ppm of boron, or about 0 ppm of boron, based on a total
weight of the
lubricating oil composition.
[00119] In some embodiments, the lubricating oil composition may have more
than 0
ppm of boron and a ratio of total metal in ppm to total boron in ppm of more
than 7.5, or
more than 50, or more than 500.
Antioxidants
[00120] The lubricating oil compositions herein also may optionally contain
one or
more antioxidants. Antioxidant compounds are known and include for example,
phenates,
phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized
esters, aromatic
amines, alkylated diphenylamines (e.g., nonyl diphenylamine, di-nonyl
diphenylamine, octyl
diphenylamine, di-octyl diphenylamine), phenyl-alpha-naphthylamines, alkylated
phenyl-
alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols,
oil-soluble
molybdenum compounds, macromolecular antioxidants, or mixtures thereof.
Antioxidant
compounds may be used alone or in combination.
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[00121] The hindered phenol antioxidant may contain 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 and/or a bridging group linking to a
second aromatic
group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-
butylphenol, 4-
methy1-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-
di-tert-
butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecy1-2,6-di-tert-
butylphenol. In one
embodiment the hindered phenol antioxidant may be an ester and may include,
e.g.,
IrganoxTM L-135 available from BASF or an addition product derived from 2,6-di-
tert-
butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1
to about 18,
or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about
4 carbon atoms.
Another commercially available hindered phenol antioxidant may be an ester and
may
include EthanoxTM 4716 available from Albemarle Corporation.
[00122] Useful antioxidants may include diarylamines and high molecular
weight
phenols. In an embodiment, the lubricating oil composition may contain a
mixture of a
diarylamine and a high molecular weight phenol, such that each antioxidant may
be present
in an amount sufficient to provide up to about 5%, by weight, based upon the
final weight of
the lubricating oil composition. In an embodiment, the antioxidant may be a
mixture of about
0.3 to about 1.5% diarylamine and about 0.4 to about 2.5% high molecular
weight phenol, by
weight, based upon the final weight of the lubricating oil composition.
[00123] Examples of suitable olefins that may be sulfurized to form a
sulfurized olefin
include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene,
heptene, octene,
nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hex
adecene,
heptadeccne, octadecene, nonadecene, eicoscne or mixtures thereof. In one
embodiment,
hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof
and their
dimers, trimers and tetramers are especially useful olefins. Alternatively,
the olefin may be a
Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester,
such as,
butylacrylate.
[00124] Another class of sulfurized olefin includes sulfurized fatty acids
and their
esters. The fatty acids are often obtained from vegetable oil or animal oil
and typically
contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and
their esters
include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures
thereof. Often, the
fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil,
cottonseed oil,
sunflower seed oil or mixtures thereof. Fatty acids and/or ester may be mixed
with olefins,
such as a-olefins.
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[00125] In another alternative embodiment the antioxidant composition also
contains a
molybdenum-containing antioxidant in addition to the phenolic and/or aminic
antioxidants
discussed above. When a combination of these three antioxidants is used,
preferably the ratio
of phenolic to aminic to molybdenum-containing is (0 to 2) : (0 to 2) : (0 to
1).
[00126] The one or more antioxidant(s) may be present in ranges about 0 wt%
to about
20 wt%, or about 0.1 wt% to about 10 wt%, or about 0.6 wt% to about 5 wt%, or
about 1.0 to
about 3 wt% of the lubricating oil composition.
Antiwear Agents
[00127] The lubricating oil compositions herein also may optionally contain
one or
more antiwear agents. Examples of suitable antiwear agents include, but are
not limited to, a
metal thiophosphate; a metal dialkyldithiophosphate; a phosphoric acid ester
or salt thereof; a
phosphate ester(s); a phosphite; a phosphorus-containing carboxylic ester,
ether, or amide; a
sulfurized olefin; thiocarbamate-containing compounds including, thiocarbamate
esters,
alkylene-coupled thiocarbamatcs, and bis(S-alkyldithiocarbamyl)disulfides; and
mixtures
thereof. A suitable antiwear agent may be a molybdenum dithiocarbamate. The
phosphorus
containing antiwear agents are more fully described in European Patent 612
839. The metal
in the dialkyl dithio phosphate salts may be an alkali metal, alkaline earth
metal, aluminum,
lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful
antiwear agent
may be zinc dialkyldithiophosphate.
[00128] Further examples of suitable antiwear agents include titanium
compounds,
tartrates, tartrimides, oil soluble amine salts of phosphorus compounds,
sulfurized olefins,
phosphitcs (such as dibutyl phosphite), phosphonates, thiocarbamatc-containing
compounds,
such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers,
alkylene-coupled
thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. 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.
[00129] The antiwear agent may be present in ranges including about 0 wt%
to about
15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%,
or about 0.1
wt% to about 3 wt% of the lubricating oil composition.
Additional Optional Detergents
[00130] The lubricating oil composition may comprise one or more neutral
and/or low
based detergents, as well as overbased detergents that do not contain calcium
and mixtures
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thereof. Suitable detergent substrates include phenates, sulfur containing
phenates, sulfonates,
calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids,
mono- and/or di-
thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or
methylene
bridged phenols. Suitable detergents and their methods of preparation are
described in greater
detail in numerous patent publications, including US 7,732,390 and references
cited therein.
The detergent substrate may be salted with an alkali or alkaline earth metal
such as, but not
limited to, calcium, magnesium, potassium, sodium, lithium, barium, or
mixtures thereof. In
some embodiments, the detergent is free of barium. A suitable detergent may
include alkali or
alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or
di-
alkylarylsulfonic acids with the aryl group being benzyl, tolyl, and xylyl.
Examples of suitable
detergents include, but are not limited to, calcium phenates, calcium sulfur
containing phenates,
calcium sulfonates, calcium calixarates, calcium salixarates, calcium
salicylates, calcium
carboxylic acids, calcium phosphorus acids, calcium mono- and/or di-
thiophosphoric acids,
calcium alkyl phenols, calcium sulfur coupled alkyl phenol compounds, calcium
methylene
bridged phenols, magnesium phenates, magnesium sulfur containing phenates,
magnesium
sulfonates, magnesium calixarates, magnesium salixarates, magnesium
salicylates, magnesium
carboxylic acids, magnesium phosphorus acids, magnesium mono- and/or di-
thiophosphoric
acids, magnesium alkyl phenols, magnesium sulfur coupled alkyl phenol
compounds,
magnesium methylene bridged phenols, sodium phenates, sodium sulfur containing
phenates,
sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates,
sodium
carboxylic acids, sodium phosphorus acids, sodium mono- and/or di-
thiophosphoric acids,
sodium alkyl phenols, sodium sulfur coupled alkyl phenol compounds, or sodium
methylene
bridged phenols.
[00131] Overbased detergent additives are well known in the art and may be
alkali or
alkaline earth metal overbased detergent additives. Such detergent additives
may be prepared
by reacting a metal oxide or metal hydroxide with a substrate and carbon
dioxide gas. The
substrate is typically an acid, for example, an acid such as an aliphatic
substituted sulfonic acid,
an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.
[00132] The terminology "overbased" relates to metal salts, such as metal
salts of
sulfonates, carboxylates, and phenates, wherein the amount of metal present
exceeds the
stoichiometric amount. Such salts may have a conversion level in excess of
100% (i.e., they
may comprise more than 100% of the theoretical amount of metal needed to
convert the acid
to its "normal," "neutral" salt). The expression "metal ratio," often
abbreviated as MR, is used
to designate the ratio of total chemical equivalents of metal in the overbased
salt to chemical
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equivalents of the metal in a neutral salt according to known chemical
reactivity and
stoichiometry. In a normal or neutral salt, the metal ratio is one and in an
overbased salt, MR,
is greater than one. They are commonly referred to as overbased, hyperbased,
or superbased
salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.
[00133] An overbased detergent of the lubricating oil composition may have
a total base
number (TBN) of greater than 225 mg KOH/gram, or as further examples, about
250 mg
KOH/gram or greater, or about 350 mg KOH/gram or greater, or about 375 mg
KOH/gram or
greater, or about 400 mg KOH/gram or greater.
[00134] Examples of suitable overbased detergents include, but are not
limited to,
overbased magnesium phenates, overbased magnesium sulfur containing phenates,
overbased
magnesium sulfonates, overbased magnesium calixarates, overbased magnesium
salixarates,
overbased magnesium salicylates, overbased magnesium carboxylic acids,
overbased
magnesium phosphorus acids, overbased magnesium mono- and/or di-thiophosphoric
acids,
overbased magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl
phenol
compounds, or overbased magnesium methylene bridged phenols.
[00135] The overbased detergent may have a metal to substrate ratio of from
1.1:1, or
from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.
[00136] The low-based/neutral detergent has a TBN of up to 175 mg KOH/g, or
up to
150 mg KOH/g. The low-based/neutral detergent may include a calcium-containing
detergent.
The low-based neutral calcium-containing detergent may be selected from a
calcium sulfonate
detergent, a calcium phenate detergent and a calcium salicylate detergent. In
some
embodiments, the low-based/neutral detergent is a calcium-containing detergent
or a mixture
of calcium-containing detergents. In some embodiments, the low-based/neutral
detergent is a
calcium sulfonate detergent or a calcium phenate detergent.
[00137] The low-based/neutral detergent may comprise at least 2.5 wt.% of
the total
detergent in the lubricating oil composition. In some embodiments, at least 4
wt. %, or at least
6 wt.%, or at least 8 wt.%, or at least 10 wt.% or at least 12 wt.% or at
least 20 wt.% of the total
detergent in the lubricating oil composition is a low-based/neutral detergent
which may
optionally be a low-based/neutral calcium-containing detergent.
[00138] In certain embodiments, the one or more low-based/neutral
detergents provide
from about 50 to about 1000 ppm calcium by weight to the lubricating oil
composition based
on a total weight of the lubricating oil composition. In some embodiments, the
one or more
low-based/neutral calcium-containing detergents provide from 75 to less than
800 ppm, or from
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100 to 600 ppm, or from 125 to 500 ppm by weight calcium to the lubricating
oil composition
based on a total weight of the lubricating oil composition.
[00139] In some embodiments, a detergent is effective at reducing or
preventing rust in
an engine.
Dispersants
[00140] The lubricating oil composition may optionally further comprise one
or more
dispersants or mixtures thereof. Dispersants are often known as ashless-type
dispersants
because, prior to mixing in a lubricating oil composition, they do not contain
ash-forming
metals and they do not normally contribute any ash when added to a lubricant.
Ashless type
dispersants are characterized by a polar group attached to a relatively high
molecular weight
hydrocarbon chain, polymer, or copolymer. Typical ashless dispersants include
N-substituted
long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl
succinimides
include polyisobutylene succinimides with a number average molecular weight of
the
polyisobutylene substituent in the range about 350 to about 50,000, or 350 to
about 5,000, or
350 to about 3,000 and polyalphaolefin succinimides with a number average
molecular
weight of the polyalphaolefin substituent in the range of about 350 to about
10,000, or 350 to
about 5,000 or 350 to about 3,000, as measured by gel permeation
chromatography (GPC),
using polystyrene as a calibration reference. Suitable polyalphaolefins
include ethylene-
alpha olefin copolymers such as ethylene-propylene copolymers.
[00141] Succinimide dispersants and their preparation are disclosed, for
instance in
U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The polyolefin may be
prepared from
polymerizable monomers containing about 2 to about 16, or about 2 to about 8,
or about 2 to
about 6 carbon atoms. Succinimide dispersants are typically the imide formed
from a
polyamine, typically a poly(ethyleneamine).
[00142] Preferred amines are selected from polyamines and hydroxyamines.
Examples
of polyamines that may be used include, but are not limited to, diethylene
triamine (DETA),
triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and higher
homologues such
as pentaethylamine hexamine (PEHA), and the like.
[00143] A suitable heavy polyamine is a mixture of polyalkylene-polyamines
comprising small amounts of lower polyamine oligomers such as TEPA and PEHA
(pentaethylene hexamine) but primarily oligomers with 6 or more nitrogen
atoms, 2 or more
primary amines per molecule, and more extensive branching than conventional
polyamine
mixtures. A heavy polyamine preferably includes polyamine oligomers containing
7 or more
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nitrogens per molecule and with 2 or more primary amines per molecule. The
heavy
polyamine comprises more than 28 wt. % (e.g. >32 wt. %) total nitrogen and an
equivalent
weight of primary amine groups of 120-160 grams per equivalent.
[00144] Suitable polyamines are commonly known as PAM, and contain a
mixture of
ethylene amines where TEPA and pentaethylene hexamine (PEHA) are the major
part of the
polyamine, usually less than about 80%.
[00145] Typically PAM has 8.7-8.9 milliequivalents of primary amine per
gram (an
equivalent weight of 115 to 112 grams per equivalent of primary amine) and a
total nitrogen
content of about 33-34 wt. %. Heavier cuts of PAM oligomers with practically
no TEPA and
only very small amounts of PEHA but containing primarily oligomers with more
than 6
nitrogens and more extensive branching, may produce dispersants with improved
dispersancy.
[00146] In an embodiment the present disclosure further comprises at least
one
polyisobutylene succinimide dispersant derived from polyisobutylene with
number average
molecular weight in the range about 350 to about 50,000, or to about 5000, or
to about 3000,
as measured by gel permeation chromatography (GPC), using polystyrene as a
calibration
reference. The polyisobutylene succinimide may be used alone or in combination
with other
dispersants.
[00147] In some embodiments, polyisobutylene, when included, may have
greater than
50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or
greater than
90 mol% content of terminal double bonds. Such PIB is also referred to as
highly reactive
PIB ("HR-PIB"). HR-PIB having a number average molecular weight ranging from
about
800 to about 5000 is suitable for use in embodiments of the present
disclosure. Conventional
PIB typically has less than 50 mol%, less than 40 mol%, less than 30 mol%,
less than 20
mol%, or less than 10 mol% content of terminal double bonds.
[00148] An HR-PIB having a number average molecular weight ranging from
about
900 to about 3000 may be suitable. Such HR-PIB is commercially available, or
can be
synthesized by the polymerization of isobutene in the presence of a non-
chlorinated catalyst
such as boron trifluoride, as described in US Patent No. 4,152,499 to Boerzel,
et al. and U.S.
Patent No. 5,739,355 to Gateau, et al. When used in the aforementioned thermal
ene
reaction, HR-PIB may lead to higher conversion rates in the reaction, as well
as lower
amounts of sediment formation, due to increased reactivity. A suitable method
is described in
U.S. Patent No. 7,897,696.
28
[00149] In one embodiment the present disclosure further comprises at least
one
dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The
PIBSA may
have an average of between about 1.0 and about 2.0 succinic acid moieties per
polymer.
" [00150] .. The % actives of the alkenyl or alkyl succinic anhydride can be
determined
using a chromatographic technique. This method is described in column 5 and 6
in U.S. Pat.
No. 5,334,321.
[00151] The percent conversion of the polyolefin is calculated from the %
actives
using the equation in column 5 and 6 in U.S. Pat. No. 5,334,321.
[00162] Unless stated otherwise, all percentages are in weight percent and
all
molecular weights are number average molecular weights.
[00153] In one embodiment, the dispersant may be derived from a
polyalphaolefin
(PAO) succinic anhydride.
[00154] In one embodiment, the dispersant may be derived from olefin maleic
anhydride
copolymer. As an example, the dispersant may be described as a poly-PIBSA.
[00165] In an embodiment, the dispersant may be derived from an anhydride
which is
grafted to an ethylene-propylene copolymer.
[00156] One class of suitable dispersants may be Mannich bases. Mannich
bases are
materials that are formed by the condensation of a higher molecular weight,
alkyl substituted
phenol, a polyalkylene polyamine, and an aldehyde such as formaldehyde.
Mannich bases
are described in more detail in U.S. Patent No. 3,634,515.
[00167] .. A suitable class of dispersants may be high molecular weight esters
or half
ester amides.
[00158] A suitable dispersant may also be post-treated by conventional
methods by a
reaction with any of a variety of agents. Among these are boron, urea,
thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic
acids, hydrocarbon-
substituted succinic anhydrides, maleic anhydride, nitriles, epoxides,
carbonates, cyclic
carbonates, hindered phenolic esters, and phosphorus compounds. See US
7,645,726; US
7,214,649; and US 8,048,831.
[00159] In addition to the carbonate and boric acids post-treatments both
the
compounds may be post-treated, or further post-treatment, with a variety of
post-treatments
designed to improve or impart different properties. Such post-treatments
include those
summarized in columns 27-29 of U.S. Pat. No. 5,241,003. Such treatments
include,
treatment with:
Inorganic phosphorous acids or anhydrates (e.g., U.S. Pat. Nos. 3,403,102 and
4,648,980);
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Organic phosphorous compounds (e.g., U.S. Pat. No. 3,502,677);
Phosphorous pentasulfides;
Boron compounds as already noted above (e.g., U.S. Pat. Nos. 3,178,663 and
4,652,387);
Carboxylic acid, polycarboxylic acids, anhydrides and/or acid halides (e.g.,
U.S. Pat. Nos.
3,708,522 and 4,948,386);
Epoxides polyepoxiates or thioexpoxides (e.g., U.S. Pat. Nos. 3,859,318 and
5,026,495);
Aldehyde or ketone (e.g., U.S. Pat. No. 3,458,530);
Carbon disulfide (e.g., U.S. Pat. No. 3,256,185);
Glycirlol (e.g., U.S. Pat. No. 4,617,137);
Urea, thourea or guanidine (e.g., U.S. Pat. Nos. 3,312,619; 3,865,813; and
British Patent GB
1,065,595);
Organic sulfonic acid (e.g.. U.S. Pat. No. 3,189,544 and British Patent GB
2.140,811);
Alkenyl cyanide (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569);
Diketene (e.g., U.S. Pat. No. 3,546,243);
A diisocyanatc (e.g.. U.S. Pat. No. 3,573,205);
Alkane sultone (e.g., U.S. Pat. No. 3,749,695);
1,3-Dicarbonyl Compound (e.g., U.S. Pat. No. 4,579,675);
Sulfate of alkoxylated alcohol or phenol (e.g., U.S. Pat. No. 3,954,639);
Cyclic lactone (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246;
4,963,275; and
4,971,711);
Cyclic carbonate or thiocarbonate linear monocarbonate or polycarbonate, or
chloroformate
(e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170);
Nitrogen-containing carboxylic acid (e.g., U.S. Pat. 4,971,598 and British
Patent GB
2,140,811);
Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. No.
4,614,522);
Lactam, thiolactam, thiolactone or ditholactone (e.g., U.S. Pat. Nos.
4,614,603 and
4,666,460);
Cyclic carbonate or thiocarbonate, linear monocarbonate or plycarbonate, or
chloroformate
(e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,646,860; and 4,670,170);
Nitrogen-containing carboxylic acid (e.g., U.S. Pat. No. 4,971,598 and British
Patent GB
2,440,811);
Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. No.
4,614,522);
Lactam, thiolactam, thiolactone or dithiolactonc (e.g., U.S. Pat. Nos.
4,614,603, and
4,666,460);
Cyclic carbamate, cyclic thiocarbamate or cyclic dithiocarbamate (e.g., U.S.
Pat. Nos.
4,663,062 and 4,666,459);
Hydroxyaliphatic carboxylic acid (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318;
4,713,189);
Oxidizing agent (e.g., U.S. Pat. No. 4,379,064);
Combination of phosphorus pentasulfide and a polyalkylene polyamine (e.g.,
U.S. Pat. No.
3,185,647);
Combination of carboxylic acid or an aldehyde or ketone and sulfur or sulfur
chloride (e.g.,
U.S. Pat. Nos. 3,390,086; 3,470,098);
Combination of a hydrazine and carbon disulfide (e.g. U.S. Pat. No.
3,519,564);
Combination of an aldehyde and a phenol (e.g., U.S. Pat. Nos. 3,649,229;
5,030,249;
5,039,307);
Combination of an aldehyde and an 0-diester of dithiophosphoric acid (e.g.,
U.S. Pat. No.
3,865,740);
Combination of a hydroxyaliphatic carboxylic acid and a boric acid (e.g., U.S.
Pat. No.
4,554,086);
Combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and a
phenol (e.g.,
U.S. Pat. No. 4,636,322);
Combination of a hydroxyaliphatic carboxylic acid and then an aliphatic
dicarboxylic acid
(e.g., U.S. Pat. No. 4,663,064);
Combination of formaldehyde and a phenol and then glycolic acid (e.g., U.S.
Pat. No.
4,699,724);
Combination of a hydroxyaliphatic carboxylic acid or oxalic acid and then a
diisocyanate
(e.g. U.S. Pat. No.4,713,191);
Combination of inorganic acid or anhydride of phosphorus or a partial or total
sulfur analog
thereof and a boron compound (e.g., U.S. Pat. No. 4,857,214);
Combination of an organic diacid then an unsaturated fatty acid and then a
nitrosoaromatic
amine optionally followed by a boron compound and then a glycolating agent
(e.g., U.S. Pat.
No. 4,973,412);
Combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278);
Combination of an aldehyde and a triazole then a boron compound (e.g., U.S.
Pat. No.
4,981,492);
Combination of cyclic lactone and a boron compound (e.g., U.S. Pat. No.
4,963,275 and
4,971,711).
31
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[00160] The TBN of a suitable dispersant may be from about 10 to about 65
on an oil-
free basis, which is comparable to about 5 to about 30 TBN if measured on a
dispersant
sample containing about 50% diluent oil.
The dispersant, if present, can he used in an amount sufficient to provide up
to about 20 wt%,
based upon the final weight of the lubricating oil composition. Another amount
of the
dispersant that can be used may be about 0.1 wt% to about 15 wt%, or about 0.1
wt% to
about 10 wt%, or about 3 wt% to about 10 wt%, or about 1 wt% to about 6 wt%,
or about 7
wt% to about 12 wt%, based upon the final weight of the lubricating oil
composition. In
some embodiments, the lubricating oil composition utilizes a mixed dispersant
system. A
single type or a mixture of two or more types of dispersants in any desired
ratio may be used.
Friction Modifiers
[00161] The lubricating oil compositions herein also may optionally contain
one or
more friction modifiers. Suitable friction modifiers may comprise metal
containing and
metal-free friction modifiers and may include, but arc not limited to,
imidazolincs, amides,
amines, succinimides, allwxylated amines, alkoxylated ether amines, amine
oxides,
amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, amino
guanadine,
alkanolamides, phosphonates, metal-containing compounds, glycerol esters,
sulfurized fatty
compounds and olefins, sunflower oil other naturally occurring plant or animal
oils,
dicarboxylic acid esters, esters or partial esters of a polyol and one or more
aliphatic or
aromatic carboxylic acids, and the like.
[00162] Suitable friction modifiers may contain hydrocarbyl groups that are
selected
from straight chain, branched chain, or aromatic hydrocarbyl groups or
mixtures thereof, and
may be saturated or unsaturated. The hydrocarbyl groups may be composed of
carbon and
hydrogen or hetero atoms such as sulfur or oxygen. The hydrocarbyl groups may
range from
about 12 to about 25 carbon atoms. In some embodiments 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, or a di-ester, or a (tri)glyceride. The friction modifier may be a
long chain fatty
amide, a long chain fatty ester, a long chain fatty epoxide derivatives, or a
long chain
imidazoline.
[00163] Other suitable friction modifiers may include organic, ashless
(metal-free),
nitrogen-free organic friction modifiers. Such friction modifiers may include
esters formed
by reacting carboxylic acids and anhydrides with alkanols and generally
include a polar
terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic
hydrocarbon
32
chain. An example of an organic ashless nitrogen-free friction modifier is
known generally as
glycerol monooleate (GMO) which may contain mono-, di-, and tri-esters of
oleic acid. Other
suitable friction modifiers are described in U.S. Pat. No. 6,723,685.
[00164] Aminic friction modifiers may include amines or polyamines. Such
compounds can have hydrocarbyl groups that are linear, either saturated or
unsaturated, or a
mixture thereof and may contain from about 12 to about 25 carbon atoms.
Further examples
of suitable friction modifiers include alkoxylated amines and alkoxylated
ether amines. Such
compounds may have hydrocarbyl groups that are linear, either saturated,
unsaturated, or a
mixture thereof. They may contain from about 12 to about 25 carbon atoms.
Examples
include ethoxylated amines and ethoxylated ether amines.
[00166] The amines and amides may be used as such or in the form of an
adduct or
reaction product with a boron compound such as a boric oxide, boron halide,
metaborate,
boric acid or a mono-, di- or tri-alkyl borate. Other suitable friction
modifiers are described in
U.S. Pat. No. 6,300,291.
[00166] A friction modifier may optionally be present in ranges such as
about 0 wt% to
about 10 wt%, or about 0.01 wt% to about 8 wt%, or about 0.1 wt% to about 4
wt%.
Additional Molybdenum-containing component
[00167] The lubricating oil compositions herein also may optionally
contain additional
molybdenum-containing compounds. An oil-soluble molybdenum compound may have
the
functional performance of an antiwear agent, an antioxidant, a friction
modifier, or mixtures
thereof. An oil-soluble molybdenum compound may include molybdenum
dithiocarbamates,
molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts
of
molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates,
molybdenum
sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-
molybdenum compound, and/or mixtures thereof. The molybdenum sulfides include
molybdenum disulfide. The molybdenum disulfide may be in the form of a stable
dispersion.
In one embodiment the oil-soluble molybdenum compound may be selected from the
group
consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates,
amine
salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil-
soluble
molybdenum compound may be a molybdenum dithiocarbamate.
[00168] Suitable examples of molybdenum compounds which may be used
include
commercial materials sold under the trade names such as Molyvan 822TM,
MolyvanTM A,
33
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Molyvan 2000' and Molyvan 855 from R. T. Vanderbilt Co., Ltd., and
SakuraLubeTM S-
165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka
Corporation, and mixtures thereof. Suitable molybdenum components are
described in US
5,650,381; US RE 37,363 El; US RE 38,929 El; and US RE 40,595 El.
[00169] Additionally, the molybdenum compound may be an acidic molybdenum
compound. Included are molybdic acid, ammonium molybdate, sodium molybdate,
potassium molybdate, and other alkaline metal molybdates and other molybdenum
salts, e.g.,
hydrogen sodium molybdate, Mo0C14, MoO2Br2, Mo203C16, molybdenum trioxide or
similar acidic molybdenum compounds. Alternatively, the compositions can be
provided with
molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as
described,
for example, in U.S. Pat. Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387;
4,265,773;
4,261,843; 4,259,195 and 4,259,194; and WO 94/06897.
[00170] Another class of suitable organo-molybdenum compounds are
trinuclear
molybdenum compounds, such as those of the formula Mo3SkLnQz and mixtures
thereof,
wherein S represents sulfur, L represents independently selected ligands
having organo
groups with a sufficient number of carbon atoms to render the compound soluble
or
dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is
selected from the group
of neutral electron donating compounds such as water, amines, alcohols,
phosphines, and
ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At
least 21 total
carbon atoms may be present among all the ligands' organo groups, such as at
least 25, at
least 30, or at least 35 carbon atoms. Additional suitable molybdenum
compounds are
described in U.S. Pat. No. 6,723,685.
[00171] The oil-soluble molybdenum compound may be present in an amount
sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about
700 ppm, about
1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about
250 ppm
of molybdenum.
Transition Metal-containing compounds
[00172] In another embodiment, the oil-soluble compound may be a
transition metal
containing compound or a metalloid. The transition metals may include, but are
not limited
to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum,
tungsten, and the
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like. Suitable metalloids include, but are not limited to, boron, silicon,
antimony, tellurium,
and the like.
[00173] In an embodiment, an oil-soluble transition metal-containing
compound may
function as antiwear agents, friction modifiers, antioxidants, deposit control
additives, or more
than one of these functions. In an embodiment the oil-soluble transition metal-
containing
compound may be an oil-soluble titanium compound, such as a titanium (IV)
alkoxide. Among
the titanium containing compounds that may be used in, or which may be used
for preparation
of the oils-soluble materials of, the disclosed technology are various Ti (IV)
compounds such
as titanium (IV) oxide; titanium (IV) sulfide: titanium (IV) nitrate; titanium
(IV) alkoxides such
as titanium methoxide, titanium ethoxide, titanium propoxide, titanium
isopropoxide, titanium
butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes
including but
not limited to titanium phenates; titanium carboxylates such as titanium (IV)
2-ethy1-1-3-
hexanedioate or titanium citrate or titanium oleate; and titanium (IV)
(triethanolaminato)isopropoxide. Other forms of titanium encompassed within
the disclosed
technology include titanium phosphates such as titanium dithiophosphatcs
(e.g.,
dialkyldithiophosphates) and titanium sulfonates (e.g.,
alkylbenzenesulfonates), or, generally,
the reaction product of titanium compounds with various acid materials to form
salts, such as
oil-soluble salts. Titanium compounds can thus be derived from, among others,
organic acids,
alcohols, and glycols. Ti compounds may also exist in dimeric or oligomeric
form, containing
Ti¨O¨Ti structures. Such titanium materials are commercially available or can
be readily
prepared by appropriate synthesis techniques which will be apparent to the
person skilled in
the art. They may exist at room temperature as a solid or a liquid, depending
on the particular
compound. They may also be provided in a solution form in an appropriate inert
solvent.
[00174] In one embodiment, the titanium can be supplied as a Ti-modified
dispersant,
such as a succinimide dispersant. Such materials may be prepared by forming a
titanium mixed
anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic
anhydride, such
as an alkenyl- (or alkyl) succinic anhydride. The resulting titanate-succinate
intermediate may
be used directly or it may be reacted with any of a number of materials, such
as (a) a polyamine-
based succinimide/amide dispersant having free, condensable ¨NH functionality;
(b) the
components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyl-
(or alkyl-)
succinic anhydride and a polyamine, (c) a hydroxy-containing polyester
dispersant prepared by
the reaction of a substituted succinic anhydride with a polyol, aminoalcohol,
polyamine, or
mixtures thereof. Alternatively, the titanate-succinate intermediate may be
reacted with other
agents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or
polyols, or fatty
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acids, and the product thereof either used directly to impart Ti to a
lubricant, or else further
reacted with the succinic dispersants as described above. As an example, 1
part (by mole) of
tetraisopropyl titanate may be reacted with about 2 parts (by mole) of a
polyisobutene-
substituted succinic anhydride at 140-150 C for 5 to 6 hours to provide a
titanium modified
dispersant or intermediate. The resulting material (30 g) may be further
reacted with a
succinimide dispersant from polyisobutene-substituted succinic anhydride and a
polyethylenepolyamine mixture (127 grams + diluent oil) at 150 C for 1.5
hours, to produce
a titanium-modified succinimide dispersant.
[00175] Another titanium containing compound may be a reaction product of
titanium
alkoxide and C6 to C25 carboxylic acid. The reaction product may be
represented by the
following formula:
0
-0 -O-R)
wherein n is an integer selected from 2, 3 and 4, and R is a hydrocarbyl group
containing
from about 5 to about 24 carbon atoms, or by the formula:
0 R3 Ti
./.
)
R2 ____________________________ 0 R4/
/n
wherein m + n = 4 and n ranges from 1 to 3. R4 is an alkyl moiety with carbon
atoms ranging
from 1-8, Ri is selected from a hydrocarbyl group containing from about 6 to
25 carbon
atoms, and R/ and R3 are the same or different and are selected from a
hydrocarbyl group
containing from about 1 to 6 carbon atoms, or by the formula:
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R3
R2
R4 R4 (R2
\
0 0 0 O
0 0 R3
R3
C) Ri
0
R2 0
0
R1
R4
R4 X R2
R3
Ri
wherein x ranges from 0 to 3, Ri is selected from a hydrocarbyl group
containing from about
6 to 25 carbon atoms, R2. and R3 are the same or different and are selected
from a
hydrocarbyl group containing from about 1 to 6 carbon atoms, and R4 is
selected from a
group consisting of either H, or C6 to C25 carboxylic acid moiety.
[00176] Suitable carboxylic acids may include, but are not limited to
caproic acid,
caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
arachidic acid, oleic acid,
erticic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid,
phenylacetic acid,
benzoic acid, neodecanoic acid, and the like.
[00177] In an embodiment the oil soluble titanium compound may be present
in the
lubricating oil composition in an amount to provide from 0 to 3000 ppm
titanium by weight
or 25 to about 1500 ppm titanium by weight or about 35 ppm to 500 ppm titanium
by weight
or about 50 ppm to about 300 ppm.
Viscosity Index Improvers
[00178] The lubricating oil compositions herein also may optionally contain
one or
more viscosity index improvers. Suitable viscosity index improvers may include
polyolefins,
olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated
styrene-
isoprene polymers, styrene/maleic ester copolymers, hydrogenated
styrenc/butadiene
copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride
copolymers,
polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl
aryl conjugated
diene copolymers, or mixtures thereof. Viscosity index improvers may include
star polymers
and suitable examples are described in US Publication No. 20120101017A1.
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[00179] The lubricating oil compositions herein also may optionally contain
one or
more dispersant viscosity index improvers in addition to a viscosity index
improver or in lieu
of a viscosity index improver. Suitable dispersant viscosity index improvers
may include
functionalized polyolefins, for example, ethylene-propylene copolymers that
have been
functionalized with the reaction product of an acylating agent (such as maleic
anhydride) and
an amine; polymethacrylates functionalized with an amine, or esterified maleic
anhydride-
styrene copolymers reacted with an amine.
[00180] The total amount of viscosity index improver and/or dispersant
viscosity index
improver may be about 0 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%,
about 0.1
wt% to about 12 wt%, or about 0.5 wt% to about 10 wt%, of the lubricating oil
composition.
Other Optional Additives
[00181] Other additives may be selected to perform one or more functions
required of
a lubricating fluid. Further, one or more of the mentioned additives may be
multi-functional
and provide functions in addition to or other than the function prescribed
herein.
[00182] A lubricating oil composition according to the present disclosure
may
optionally comprise other performance additives. The other performance
additives may be in
addition to specified additives of the present disclosure and/or may comprise
one or more of
metal deactivators, viscosity index improvers, detergents, ashless TBN
boosters, friction
modifiers, antiwear agents, corrosion inhibitors, rust inhibitors,
dispersants, dispersant
viscosity index improvers, extreme pressure agents, antioxidants, foam
inhibitors,
demulsifiers, emulsifiers, pour point depressants, seal swelling agents and
mixtures thereof.
Typically, fully-formulated lubricating oil will contain one or more of these
performance
additives.
[00183] Suitable metal deactivators may include derivatives of
benzotriazoles
(typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles,
benzimidazoles, 2-
alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors
including
copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl
acetate;
demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene
oxides,
polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point
depressants
including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates
or
polyacrylamides.
[00184] Suitable foam inhibitors include silicon-based compounds, such as
siloxane.
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[00185] Suitable pour point depressants may include a
polymethylmethaerylates or
mixtures thereof. Pour point depressants may be present in an amount
sufficient to provide
from about 0 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, or about
0.02 wt% to
about 0.04 wt% based upon the final weight of the lubricating oil composition.
[00186] Suitable rust inhibitors may be a single compound or a mixture of
compounds
having the property of inhibiting corrosion of ferrous metal surfaces. Non-
limiting examples
of rust inhibitors useful herein include oil-soluble high molecular weight
organic acids, such
as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic
acid, linoleic acid,
linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble
polycarboxylic acids
including dimer and trimer acids, such as those produced from tall oil fatty
acids, oleic acid,
and linoleic acid. Other suitable corrosion inhibitors include long-chain
alpha, omega-
dicarboxylic acids in the molecular weight range of about 600 to about 3000
and
alkenylsuccinic acids in which the alkenyl group contains about 10 or more
carbon atoms
such as, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and
hexadecenylsuccinic acid.
Another useful type of acidic corrosion inhibitors are the half esters of
alkenyl succinic acids
having about 8 to about 24 carbon atoms in the alkenyl group with alcohols
such as the
polyglycols. The corresponding half amides of such alkenyl succinic acids are
also useful. A
useful rust inhibitor is a high molecular weight organic acid. In some
embodiments, an
engine oil is devoid of a rust inhibitor.
[00187] The rust inhibitor, if present, can be used in an amount sufficient
to provide
about 0 wt% to about 5 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to
about 2 wt%,
based upon the final weight of the lubricating oil composition.
[00188] In general terms, a suitable lubricant may include additive
components in the
ranges listed in the following table.
39
Table 2
Wt. % Wt. %
Component (Suitable (Suitable
Embodiments) Embodiments)
Dispersant(s) 0.1 - 20.0 1.0 - 10.0
Antioxidant(s) 0.1 - 5.0 0.01 - 3.0
Detergent(s) 0.1 - 15.0 0.2 - 8.0
Ashless TBN booster(s) 0.0- 1.0 0.01 -0.5
Corrosion inhibitor(s) 0.0 - 5.0 0.0 -2.0
Molybdenum containing compound 0.1 - 1.0 0.20 - 0.55
Metal dihydrocarbyldithiophosphate(s) 0.1 - 6.0 0.1 -4.0
Ash-free phosphorus compound(s) 0.0 - 6.0 0.0 -4.0
Antifoaming agent(s) 0.0 -5.0 0.001 -0.15
Antiwear agent(s) 0.0 - 1.0 0.0 - 0.8
Pour point depressant(s) 0.0 - 5.0 0.01 - 1.5
Viscosity index improver(s) (on a
0.0 - 25.0 0.1 - 15.0
liquid/dilute basis)
Dispersant viscosity index improver(s) 0.0- 10.0 0.0 - 5.0
Friction modifier(s) 0.01 -5.0 0.05,- 2.0
= Base oil(s) Balance Balance
Total 100 100
[00189] The percentages of each component above represent the weight
percent of
each component, based upon the weight of the final lubricating oil
composition. The
remainder of the lubricating oil composition consists of one or more base
oils.
[00190] Additives used in formulating the compositions described herein
may be
blended into the base oil individually or in various sub-combinations.
However, it may be
suitable to blend all of the components concurrently using an additive
concentrate (i.e.,
additives plus a diluent, such as a hydrocarbon solvent).
EXAMPLES
[00191] Continue to [00192].
[00192] A series of tests were carried out to determine the impact of
calcium and
magnesium detergents and their contributions of ash content on the clogging of
diesel
particulate filters and to low speed pre-ignition events. =
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[00193] Each of the
lubricating oil compositions contained a major amount of a base
oil and a base conventional dispersant inhibitor (DI) package. The DI package
contained
conventional amounts of dispersant(s), antiwear additive(s), antioxidant(s),
friction
modifier(s), antifoam agent(s), process oil(s), viscosity index improver(s),
and pour point
depressant(s), as set forth in Table 3. Specifically, the DI package contained
a succinimide
dispersant, a molybdenum-containing compound, an antioxidant, and an antifoam
agent. The
major amount of base oil was a mixture of Group III and Group IV base oils.
The
components that were varied are specified in the Tables and discussion of the
Examples
below. All the values listed are states as weight percent of the component in
the lubricating
oil compositions (i.e., active ingredient plus diluent oil, if any) unless
specified otherwise.
Table 3 ¨ DI Package Composition Ranges
Component Wt. %
Antioxidant(s) 0.5 to 2.5
Antiwear agent(s), including any metal dihydrocarbyl dithiophosphate 0.5 to
1.5
Antifoaming agent(s) 0.001 to
0.05
Detergent(s) 1.0-2.0
Dispersant (s) 5.0-9.0
Metal-containing friction modifier(s) 0.03 ¨ 1.5
Metal free friction modifier(s) 0 to 0.5
Pour point depressant(s) 0.05 to 0.5
Process oil 0.25 to 1.0
[00194] Sulfated ash (SASH) was calculated for total of metallic elements
that
contribute to SASH in the lubricant composition according to the following
factors that were
multiplied by the amount of each metallic element in the lubricant composition
according to:
http://konnaris.com/portals/0/search/calculations.htm.
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Element Factor I Element Factor
Barium 1.70 Magnesium 4.95
Boron 3.22 Manganese 1.291
Calcium 3.40 Molybdenum , 1.50
Copper 1.252 Potassium = 2.33
Lead 1.464 Sodium 3.09
Lithium 7.92 Zinc 1.50
[00195] The VW PV 1485 test is a diesel particulate filter test used to
measure the
clogging tendency of diesel particulate filters. The diesel particulate filter
test is carried out in
a VW 1.9 Liter, 4 cylinder turbocharged direct injection diesel engine. One
complete test
includes 6 test cycles. The first five stages are run to condition the engine,
and the last stage
implements the ash loading for 144 hours.
[00196] Improvement in reducing clogging in a diesel particulate filter is
recognized
when the delta pressure (AP) versus oil consumption (OC) is 0.6 kPa/kg or
less. A further
improvement in clogging is recognized when the AP versus OC is 0.5 kPa/kg or
less, an even
further improvement in clogging is recognized when the AP versus OC is 0.45
kPa/kg or less.
[00197] Reference oil R-1 was formulated from about 80.7 wt.% of a Group
111 base oil,
12.1 wt.% of HiTECO 11150 PCMO Additive Package available from Afton Chemical
Corporation and 7.2 wt.% of a 35 SSI ethylene/propylene copolymer viscosity
index improver.
HiTECO 11150 passenger car motor oil additive package is an API SN, ILSAC-GF-
5, and
ACEA A5/B5 qualified DI package. R-1 also showed the following and properties
and partial
elemental analysis:
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Reference Oil R-1
10.9 Kinematic Viscosity at 100 C. (inni2/sec)
3.3 TBS, APPARENT_VISCOSITY, cPa
2438 calcium (ppmw)
< 10 magnesium (ppmw)
80 molybdenum (ppmw)
772 phosphorus (ppmw)
855 zinc (ppmw)
9.0 Total Base Number ASTM D-2896 (mg KOH/g)
165 Viscosity Index
[00198] The following examples were evaluated for VW DPF performance.
Table 4
Description Example 1 Example 2 Example 3 Example 4
Overbased
Ca
1365 1378 1638 1638
Detergent(s)
(ppm Ca)
Overbased
Mg
6 367 232 402
Detergent(s)
(ppm Mg)
Molybdenum
containing
335 319 335 381
compound(s)
(ppm Mo)
Phosphorus
content 728 741 759 781
(ppm
S/ASH
content 0.6 0.8 0.8 0.8
(wt.%)
Ca/Mg ratio
(ppm 227.5 3.8 7.1 4.1
Ca/ppm Mg)
VW PV 1485
0.32 0.43 0.6 0.43
test
(kPa/kg) a (pass) (pass) (pass) (pass)
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[00199] The results shown in inventive examples 2 and 3 indicate that a
lower ratio of
total Ca ppm from the detergents to the total Mg ppm from the detergents
provides a
reduction in clogging, when the level of sulfated ash content is held
constant.
[00200] Further, the results shown in Table 4 indicate that the VW PV 1485
test does
not restrict the formulation to 0.6 % sulfated ash, since inventive examples 2
and 3 pass the
VW PV 1485 test with a sulfated ash content of 0.8 %.
[00201] Low Speed Pre-Ignition (LSPI) events were measured in a GM 2.0
Liter, 4
cylinder Ecotec turbocharged gasoline direct injection (TGDi) engine. One
complete LSPI
fired engine test consisted of 4 test cycles. Within a single test cycle, two
operational stages
or segments are repeated in order to generate LSPI events. In stage A, when
LSPI is most
likely to occur, the engine is operated at about 2000 rpm and about 1,800 kPa
brake mean
effective pressure (BMEP). In stage B, when LSPI is not likely to occur, the
engine is
operated at about 1500 rpm and about 1,700 kPa BMEP. For each stage, data is
collected
over 25,000 engine cycles. The structure of a test cycle is as follows: stage
A ¨ stage A ¨
stage B ¨ stage B ¨ stage A ¨ stage A. Each stage is separated by an idle
period. Because
LSPI is statistically significant during stage A, the LSPI event data that was
considered in the
present examples only included LSPI events generated during stage A operation.
Thus, for
one complete LSPI fired engine test, data was typically generated over a total
of 16 stages
and was used to evaluate performance of comparative and inventive oils.
[00202] LSPI events were determined by monitoring peak cylinder pressure
(PP) and
when 2% of the combustible material in the combustion chamber burns (MFB02).
The
threshold for peak cylinder pressure is calculated for each cylinder and for
each stage and is
typically 65,000 to 85,000 kPa. The threshold for MFB02 is calculated for each
cylinder and
for each stage and typically ranges from about 3.0 to about 7.5 Crank Angle
Degree (CAD)
After Top Dead Center (ATDC). An LSPI was recorded when both the PP and MFB02
thresholds were exceeded in a single engine cycle. LSPI events can be reported
in many
ways. In order to remove ambiguity involved with reporting counts per engine
cycle, where
different fired engine tests can be conducted with a different number of
engine cycles, the
relative number of LSPI events of comparative and inventive oils were reported
as an "LSPI
Ratio". In this way improvement relative to some standard response is clearly
demonstrated.
[00203] In the following examples, the LSPI Ratio was reported as a ratio
of the LSPI
events of a test oil relative to the LSPI events of Reference Oil "R-1".
[00204] Considerable improvement in LSPI is recognized when there is
greater than
50% reduction in LSPI events relative to R-1 (an LSPI Ratio of less than 0.5).
A further
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improvement in LSPI is recognized when there is greater than 70% reduction in
LSPI events
(an LSPI Ratio of less than 0.3), an even further improvement in LSPI is
recognized when
there is greater than 75% reduction in LSPI events (an LSPI Ratio of less than
0.25), and an
even further improvement in LSPI is recognized when there is greater than 80%
reduction in
LSPI events relative to R-1 (an LSPI Ratio of less than 0.20), and an even
further
improvement in LSPI is recognized when there is greater than 90% reduction in
LSPI events
relative to R-1 (an LSPI Ratio of less than 0.1). The LSPI Ratio for R-1
reference oil is thus
deemed to be 1.00.
[00205] In the following examples, the LSPI Ratio was reported as a ratio
of the LSPI
events of a test oil relative to the LSPI events of Reference Oil "R-1".
Table 5
Description R-1 Example 1 Example 5 Example 6
Overbased Ca
Detergent 1365 1385 1605
(ppm Ca)
Overbased Mg
Detergent 6 381 6
(ppm Mg)
Molybdenum containing
compound 335 334 318
(ppm Mo)
Phosphorus content
728 732 739
(ppm
S/ASH content
0.62 0.7
(wt.%)
Ca/Mg ratio
227.5 '?
(ppm Ca/ppm Mg)
VW PV 1485 test 0.32
Not measured Not measured
(kPa/kg) a (pass)
LSPI Ratio 1 0.05 0.15 0.19
[00206] The foregoing examples show that various lubricating oil
formulations of the
present invention may provide significant reductions in LSPI events. In
addition, Example 1
demonstrates that a lubricating oil of the present invention can pass the
diesel particulate
clogging test and significantly reduce LSPI events. This may be particularly
useful in
boosted spark-ignited combustion engines equipped with a diesel particulate
filter.
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[00207] Other embodiments of the present disclosure will be apparent to
those skilled
in the art from consideration of the specification and practice of the
embodiments disclosed
herein. As used throughout the specification and claims, "a" and/or "an" may
refer to one or
more than one. Unless otherwise indicated, all numbers expressing quantities
of ingredients,
properties such as molecular weight, percent, ratio, reaction conditions, and
so forth used in
the specification and claims are to be understood as being modified in all
instances by the
term "about," whether or not the term "about" is present. Accordingly, unless
indicated to
the contrary, the numerical parameters set forth in the specification and
claims are
approximations that may vary depending upon the desired properties sought to
be obtained by
the present disclosure. At the very least, and not as an attempt to limit the
application of the
doctrine of equivalents to the scope of the claims, each numerical parameter
should at least be
construed in light of the number of reported significant digits and by
applying ordinary
rounding techniques. Notwithstanding that the numerical ranges and parameters
setting forth
the broad scope of the disclosure are approximations, the numerical values set
forth in the
specific examples are reported as precisely as possible. Any numerical value,
however,
inherently contains certain errors necessarily resulting from the standard
deviation found in
their respective testing measurements. It is intended that the specification
and examples be
considered as exemplary only, with a true scope and spirit of the disclosure
being indicated
by the following claims.
[00208] The foregoing embodiments are susceptible to considerable variation
in
practice. Accordingly, the embodiments are not intended to be limited to the
specific
exemplifications set forth hereinabove. Rather, the foregoing embodiments are
within the
spirit and scope of the appended claims, including the equivalents thereof
available as a
matter of law.
[00209] The patentees do not intend to dedicate any disclosed embodiments
to the
public, and to the extent any disclosed modifications or alterations may not
literally fall
within the scope of the claims, they are considered to be part hereof under
the doctrine of
equivalents.
[00210] It is to be understood that each component, compound, substituent
or parameter
disclosed herein is to be interpreted as being disclosed for use alone or in
combination with
one or more of each and every other component, compound, substituent or
parameter disclosed
herein.
[00211] It is also to be understood that each amount/value or range of
amounts/values
for each component, compound, substituent or parameter disclosed herein is to
be interpreted
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as also being disclosed in combination with each amount/value or range of
amounts/values
disclosed for any other component(s), compounds(s), substituent(s) or
parameter(s) disclosed
herein and that any combination of amounts/values or ranges of amounts/values
for two or
more component(s), compounds(s), substituent(s) or parameters disclosed herein
are thus also
disclosed in combination with each other for the purposes of this description.
[00212] It is further understood that each range disclosed herein is to be
interpreted as a
disclosure of each specific value within the disclosed range that has the same
number of
significant digits. Thus, a range of from 1-4 is to be interpreted as an
express disclosure of the
values 1, 2, 3 and 4.
[00213] It is further understood that each lower limit of each range
disclosed herein is
to be interpreted as disclosed in combination with each upper limit of each
range and each
specific value within each range disclosed herein for the same component,
compounds,
substituent or parameter. Thus, this disclosure to be interpreted as a
disclosure of all ranges
derived by combining each lower limit of each range with each upper limit of
each range or
with each specific value within each range, or by combining each upper limit
of each range
with each specific value within each range.
[00214] Furthermore, specific amounts/values of a component, compound,
substituent
or parameter disclosed in the description or an example is to be interpreted
as a disclosure of
either a lower or an upper limit of a range and thus can be combined with any
other lower or
upper limit of a range or specific amount/value for the same component,
compound, substituent
or parameter disclosed elsewhere in the application to form a range for that
component,
compound, substituent or parameter.
47
