Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITION AND METHOD FOR PREVENTING OR REDUCING LOW SPEED
PRE-IGNITION IN DIRECT INJECTED SPARK-IGNITED ENGINES
FIELD OF THE INVENTION
This disclosure relates to a lubricant composition that contains at least
one metal hydride compound. The disclosure also relates to a lubricant
composition
IO that contains at least one metal or metalloid hydrogen atom donor
compound for a
direct injected, boosted, spark ignited internal combustion engine. This
disclosure
also relates to a method for preventing or reducing low speed pre-ignition in
an
engine lubricated with a formulated oil. The formulated oil has a composition
comprising at least one oil soluble or oil dispersible metal or metalloid
hydrogen
IS atom donor compound.
BACKGROUND OF THE INVENTION
In recent years, engine manufacturers have developed smaller
(downsized) engines which provide higher power densities and excellent
performance while reducing frictional and pumping losses. This is accomplished
by
20 increasing boost pressures with the use of turbochargers or mechanical
superchargers, and by down-speeding the engine by using higher transmission
gear
ratios allowed by higher torque generation at lower engine speeds. However,
higher
torque at lower engine speeds has been found to cause random pre-ignition in
engines at low speeds, a phenomenon known as Low Speed Pre-Ignition, or LSPI,
25 resulting in extremely high cylinder peak pressures, which can lead to
catastrophic
engine failure. The possibility of LSPI prevents engine manufacturers from
fully
optimizing engine torque at lower engine speed in such smaller, high-output
engines.
One of the leading theories surrounding the cause of low speed pre-
ignition (LSPI) is at least in part, due to auto-ignition of engine oil
droplets that enter
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the engine combustion chamber from the piston crevice under high pressure,
during
periods in which the engine is operating at low speeds, and compression stroke
time
is longest (Amann et al.. SAE 2012-01-1140).
Although some engine knocking and pre-ignition problems can be and
are being resolved through the use of new engine technology, such as
electronic
controls and knock sensors, and through the optimization of engine operating
conditions, there is a need for lubricating oil compositions which can
decrease or
prevent the LSP1 problem, and also improve or maintain other performance such
as
wear and oxidation protection.
The present inventors have discovered a solution for addressing the
problem of LSPI through the use of a metal hydride compound.
SUMMARY OF THE INVENTION
Disclosed is a lubricating engine oil composition for use in down-sized
boosted engines comprising a lubricating oil base stock as a major component,
one
or more silicon hydrides, germanium hydrides, and tin hydrides as minor
component;
wherein the downsized engine ranges from 0.5 liters to 3.6 liters.
Also disclosed is a method for preventing or reducing low speed pre-ignition
in
a direct injected, boosted, spark ignited internal combustion engine, said
method
comprising the step of lubricating the crankcase of the engine with a
lubricating oil
composition comprising from about 25 to about 3000 ppm of a metal or metalloid
from
the metal or metalloid hydrogen atom donor from one or more silicon hydrides,
germanium hydrides, and tin hydrides, based on the total weight of the
lubricating oil
composition.
Further disclosed is the use of one or more silicon hydrides, germanium
hydrides, and tin hydrides in a lubricating engine oil composition for
preventing or
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reducing low speed pre-ignition in a direct injected, boosted, spark ignited
internal
combustion engine.
DETAILED DESCRIPTION OF THE INVENTION
The term "boosting" is used throughout the specification. Boosting refers
to running an engine at higher intake pressures than in naturally aspirated
engines. A
.. boosted condition can be reached by use of a turbocharger (driven by
exhaust) or a
supercharger (driven by the engine). "Boosting" allow engine manufacturers to
use
smaller engines, which provide higher power densities, to provide excellent
performance while reducing frictional and pumping losses.
Throughout the specification and claims the expression oil soluble or
IS dispersible is used. By oil soluble or dispersible is meant that an
amount needed to
provide the desired level of activity or performance can be incorporated by
being
dissolved, dispersed or suspended in an oil of lubricating viscosity. Usually,
this means
that at least about 0.001% by weight of the material can be incorporated in a
lubricating
oil composition. For a further discussion of the terms oil soluble and
dispersible,
particularly "stably dispersible", see U.S. Pat. No. 4,320,019 which is
expressly
incorporated herein by reference for relevant teachings in this regard.
The term "sulfated ash" as used herein refers to the non-combustible
residue resulting from detergents and metallic additives in lubricating oil.
Sulfated ash
may be determined using ASTM Test D874.
The term "Total Base Number" or "TBN" as used herein refers to the amount of
base
equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN
numbers
reflect more alkaline products, and therefore a greater alkalinity. TBN was
determined
using ASTM D 2896 test.
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Unless otherwise specified; all percentages are in weight percent.
In general, the level of sulfur in the lubricating oil compositions of the
present invention is less than or equal to about 0.7 wt. ,10, based on the
total weight of
the lubricating oil composition, e.g., a level of sulfur of about 0.01 wt. %
to about 0.70
WI. %, 0.01 to 0.6 wt.%, 0.01 to 0.5 wt.%, 0.01 to 0.4 wt.%, 0.01 to 0.3 wt.%,
0.01 to
0.2 wt.%, 0.01 wt. % to 0.10 wt. %. In one embodiment, the level of sulfur in
the
lubricating oil compositions of the present invention is less than or equal to
about 0.60
wt. 9/....); less than or equal to about 0.50 wt. '%, less than or equal to
about 0.40 wt. %,
less than or equal to about 0.30 wt. %, less than or equal to about 0.20 wt.
%, less
than or equal to about 0.10 wt. % based on the total weight of the lubricating
oil
composition.
In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the present invention is less than or equal to about 0.12 wt.
%, based
on the total weight of the lubricating oil composition, e.g., a level of
phosphorus of
about 0.01 wt. % to about 0.12 wt. %. In one embodiment, the levels of
phosphorus in
the lubricating oil compositions of the present invention is less than or
equal to about
0.11 wt. %, based on the total weight of the lubricating oil composition,
e.g., a level of
phosphorus of about 0.01 wt. % to about 0.11 wt. %. In one embodiment, the
levels
of phosphorus in the lubricating oil compositions of the present invention is
less than
or equal to about 0.10 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.10 wt.
9/0. In
one embodiment, the levels of phosphorus in the lubricating oil compositions
of the
present invention is less than or equal to about 0.09 vvt. %, based on the
total weight
of the lubricating oil composition, e.g., a level of phosphorus of about 0.01
wt. % to
about 0.09 wt. '%. In one embodiment, the levels of phosphorus in the
lubricating oil
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compositions of the present invention is less than or equal to about 0.08 wt.
%, based
on the total weight of the lubricating oil composition, e.g., a level of
phosphorus of
about 0.01 wt. % to about 0.08 wt. 9/Ø In one embodiment, the levels of
phosphorus
in the lubricating oil compositions of the present invention is less than or
equal to about
0.07 wt. %, based on the total weight of the lubricating oil composition,
e.g., a level of
phosphorus of about 0.01 wt. % to about 0.07 wt. ,10. In one embodiment, the
levels
of phosphorus in the lubricating oil compositions of the present invention is
less than
or equal to about 0.05 wt. '%, based on the total weight of the lubricating
oil
composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.05 wt.
%.
In one embodiment, the level of sulfated ash produced by the lubricating
oil compositions of the present invention is less than or equal to about 1.60
wt. % as
determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to
about
1.60 wt. % as determined by ASTM D 874. In one embodiment, the level of
sulfated
ash produced by the lubricating oil compositions of the present invention is
less than
or equal to about 1.00 wt. % as determined by ASTM D 874, e.g., a level of
sulfated
ash of from about 0.10 to about 1.00 wt. % as determined by ASTM D 874. In one
embodiment, the level of sulfated ash produced by the lubricating oil
compositions of
the present invention is less than or equal to about 0.80 wt. % as determined
by ASTM
D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.80 wt. % as
determined by ASTM D 874. In one embodiment, the level of sulfated ash
produced
by the lubricating oil compositions of the present invention is less than or
equal to
about 0.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of
from
about 0.10 to about 0.60 wt. % as determined by ASTM D 874.
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Suitably, the present lubricating oil composition may have a total base
number (TBN) of 4 to 15 mg KOH/g (e.g., 5 to 12 mg KOH/g, 6 to 12 mg KOH/g, or
8
to 12 mg KOH/g).
Low Speed Pre-Ignition is most likely to occur in direct-injected, boosted
(turbocharged or supercharged), spark-ignited (gasoline) internal combustion
engines
that, in operation, generate a break mean effective pressure level of greater
than about
bar (peak torque), such as at least about 18 bar, particularly at least about
20 bar
at engine speeds of from about 1500 to about 2500 rotations per minute (rpm),
such
as at engine speeds of from about 1500 to about 2000 rpm. As used herein,
break
mean effective pressure (BMEP) is defined as the work accomplished during one
15 engine
cycle, divided by the engine swept volume; the engine torque normalized by
engine displacement. The word "brake" denotes the actual torque/power
available at
the engine flywheel, as measured on a dynamometer. Thus, BMEP is a measure of
the useful power output of the engine.
In one embodiment of the invention, the engine is operated at speeds
between 500 rpm and 3000 rpm, or 800 rpm to 2800 rpm, or even 1000 rpm to 2600
rpm. Additionally, the engine may be operated with a break mean effective
pressure
of 10 bars to 30 bars, or 12 bars to 24 bars.
LSPI events, while comparatively uncommon, may be catastrophic in
nature. Hence drastic reduction or even elimination of LSPI events during
normal or
sustained operation of a direct fuel injection engine is desirable. In one
embodiment,
the method of the invention is such that there are less than 150 LSPI
events/million
combustion cycles (can also be expressed as 15 LSPI events/100,000 combustion
cycles) or less than 100 LSPI events/million combustion cycles or less than 70
LSPI
events/million combustion cycles or less than 60 LSPI events/million
combustion
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.. cycles or less than 50 LSPI events/million combustion cycles or less than
40 LSPI
events/million combustion cycles, less than 30 LSPI events/million combustion
cycles,
less than 20 LSPI events/million combustion cycles, less than 10 LSPI
events/million
combustion cycles, or there may be 0 LSPI events/million combustion cycles.
Therefore, in an aspect the present disclosure provides a method for
preventing or reducing low speed pre-ignition in a direct injected, boosted,
spark
ignited internal combustion engine, said method comprising the step of
lubricating the
crankcase of the engine with a lubricating oil composition comprising at least
one
metal hydride compound. In one embodiment, the amount of metal from the at
least
one metal hydride is from about 100 to about 3000 ppm, from about 200 to about
3000
ppm, from about 250 to about 2500 ppm; from about 300 to about 2500 ppm, from
about 350 to about 2500 ppm, from about 400 ppm to about 2500 ppm, from about
500 to about 2500 ppm, from about 600 to about 2500 ppm, from about 700 to
about
2500 ppm, from about 700 to about 2000 ppm, from about 700 to about 1500 ppm
in
the lubricating oil composition. In one embodiment, the amount of metal from
the metal
or metalloid hydrogen atom donor compounds is no more than about 2000 ppm or
no
more than 1500 ppm in the lubricating oil composition.
In one embodiment, the method of the invention provides a reduction in
the number of LSPI events of at least 10 percent, or at least 20 percent, or
at least 30
percent, or at least 50 percent, or at least 60 percent, or at least 70
percent, or at least
80 percent, or at least 90 percent, or at least 95 percent, compared to an oil
that does
not contain the at least one metal hydride compound.
In another aspect, the present disclosure provides a method for reducing
the severity of low speed pre-ignition events in a direct injected, boosted,
spark ignited
internal combustion engine, said method comprising the step of lubricating the
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.. crankcase of the engine with a lubricating oil composition comprising at
least one
metal hydride compound. LSPI events are determined by monitoring peak cylinder
pressure (PP) and the crank angle of 2% mass fraction burn (MFB02) of the fuel
charge in the cylinder. When both criteria are met, it can be said that an
LSPI event
has occurred. The threshold for peak cylinder pressure varies by test, but is
typically
4-5 standard deviations above the average cylinder pressure. Likewise, the
MFB02
crank angle threshold is typically 4-5 standard deviations earlier than the
average
MFB02 crank angle. LSPI events can be reported as average events per test,
events
per 100,000 combustion cycles, events per cycle, and/or combustion cycles per
event.
In one embodiment, the number of LSP1 events, where both MFB02 and Peak
.. Pressure (PP) Requirements that were greater than 90 bar of pressure, is
less than
15 events, less than 14 events, less than 13 events, less than 12 events, less
than 11
events, less than 10 events, less than 9 events, less than 8 events, less than
7 events,
less than 6 events, is less than 5 events, less than 4 events, less than 3
events, less
than 2 events, or less than 1 event per 100,000 combustion cycles. In one
embodiment, the number of LSPI events that were greater than 90 bar was zero
events, or in other words completely suppressed LSPI events greater than 90
bar. In
one embodiment, the number of LSPI events where both rv1FB02 and Peak Pressure
(PP) Requirements that were greater than 100 bar of pressure is less than 15
events,
less than 14 events, less than 13 events, less than 12 events, less than 11
events,
less than 10 events, less than 9 events, less than 8 events, less than 7
events, less
than 6 events, is less than 5 events, less than 4 events, less than 3 events,
less than
2 events, or less than 1 event per 100,000 combustion cycles. In one
embodiment, the
number of LSPI events that were greater than 100 bar was zero events, or in
other
words completely suppressed LSPI events greater than 100 bar. In one
embodiment,
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the number of LSPI events where both MFB02 and Peak Pressure (PP) Requirements
that were greater than 110 bar of pressure is less than 15 events, less than
14 events,
less than 13 events, less than 12 events, less than 11 events, less than 10
events,
less than 9 events, less than 8 events, less than 7 events, less than 6
events, is less
than 5 events, less than 4 events, less than 3 events, less than 2 events, or
less than
1 event per 100,000 combustion cycles In one embodiment, the number of LSPI
events that were greater than 110 bar was zero events, or in other words
completely
suppressed LSPI events greater than 110 bar. For example, the number of LSPI
events where both MFB02 and Peak Pressure (PP) Requirements that were greater
than 120 bar of pressure is less than 15 events, less than 14 events, less
than 13
events, less than 12 events, less than 11 events, less than 10 events, less
than 9
events, less than 8 events, less than 7 events, less than 6 events, is less
than 5 events,
less than 4 events, less than 3 events, less than 2 events, or less than 1
event per
100,000 combustion cycles. In one embodiment, the number of LSPI events that
were
greater than 120 bar was zero events, or in other words completely suppressed
very
severe LSPI events (i.e., events greater than 120 bar).
It has now been found that the occurrence of LSPI in engines susceptible to
the
occurrence of LSPI can be reduced by lubricating such engines with lubricating
oil
compositions containing a metal hydride compound.
The disclosure further provides the method described herein in which
the engine is fueled with a liquid hydrocarbon fuel, a liquid nonhydrocarbon
fuel, or
mixtures thereof.
Lubricating oil compositions suitable for use as passenger car motor oils
conventionally comprise a major amount of oil of lubricating viscosity and
minor
amounts of performance enhancing additives, including ash-containing
compounds.
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Conveniently, the metals as described herein are introduced into the
lubricating oil
compositions used in the practice of the present disclosure by one or more
metal or
metalloid hydrogen atom donor compounds.
Oil of Lubricating viscosity/Base Oil Component
The oil of lubricating viscosity for use in the lubricating oil compositions
of this disclosure, also referred to as a base oil, is typically present in a
major amount,
e.g., an amount of greater than 50 wt. To, preferably greater than about 70
wt. %, more
preferably from about 80 to about 99.5 wt. % and most preferably from about 85
to
about 98 wt %, based on the total weight of the composition. The expression
"base
oil" as used herein shall be understood to mean a base stock or blend of base
stocks
which is a lubricant component that is produced by a single manufacturer to
the same
specifications (independent of feed source or manufacturers location); that
meets the
same manufacturers specification; and that is identified by a unique formula,
product
identification number, or both. The base oil for use herein can be any
presently known
or later-discovered oil of lubricating viscosity used in formulating
lubricating oil
compositions for any and all such applications, e.g., engine oils, marine
cylinder oils,
functional fluids such as hydraulic oils, gear oils, transmission fluids, etc.
Additionally,
the base oils for use herein can optionally contain viscosity index improvers,
e.g.,
polymeric alkylmethacrylates; olefinic copolymers, e.g., an ethylene-propylene
copolymer or a styrene-diene copolymer; and the like and mixtures thereof.
)5 As one
skilled in the art would readily appreciate, the viscosity of the
base oil is dependent upon the application. Accordingly, the viscosity of a
base oil for
use herein will ordinarily range from about 2 to about 2000 centistokes (cSt)
at 100''
Centigrade (C.). Generally, individually the base oils used as engine oils
will have a
kinematic viscosity range at 100 C. of about 2 cSt to about 30 cSt,
preferably about
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3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt and
will be
selected or blended depending on the desired end use and the additives in the
finished
oil to give the desired grade of engine oil, e.g., a lubricating oil
composition having an
SAE Viscosity Grade of OW, OW-4, OW-8, OW-12, OW-16, OW-20, OW-26, OW-30, OW-
40, OW-50, OW-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-
30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15\N-40, 30, 40 and the like.
Group I base oils generally refer to a petroleum derived lubricating base
oil having a saturates content of less than 90 wt. % (as determined by ASTM D
2007)
and/or a total sulfur content of greater than 300 ppm (as determined by ASTM D
2622,
ASTM D 4294, ASTM D 4297 or ASTM D 3120) and has a viscosity index (V1) of
greater than or equal to 80 and less than 120 (as determined by ASTM D 2270).
Group II base oils generally refer to a petroleum derived lubricating base
oil having a total sulfur content equal to or less than 300 parts per million
(ppm) (as
determined by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), a
saturates content equal to or greater than 90 weight percent (as determined by
ASTM
D 2007), and a viscosity index (VI) of between 80 and 120 (as determined by
ASTM
D 2270).
Group III base oils generally refer to a petroleum derived lubricating base
oil having less than 300 ppm sulfur, a saturates content greater than 90
weight percent,
and a VI of 120 or greater.
)5 Group IV base oils are polyalphaolefins (PAOs).
Group V base oils include all other base oils not included in Group I, II,
111, or IV.
The lubricating oil composition can contain minor amounts of other base
oil components. For example, the lubricating oil composition can contain a
minor
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amount of a base oil derived from natural lubricating oils, synthetic
lubricating oils or
mixtures thereof. Suitable base oil includes base stocks obtained by
isomerization of
synthetic wax and slack wax, as well as hydrocracked base stocks produced by
hydrocracking (rather than solvent extracting) the aromatic and polar
components of
the crude. Suitable natural oils include mineral lubricating oils such as, for
example,
liquid petroleum oils, solvent-treated or acid-treated mineral lubricating
oils of the
paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from
coal or
shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard
oil), and the
like.
Suitable synthetic lubricating oils include, but are not limited to,
hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and
interpolymerized olefins, e.g., polybutylenes, polypropylenes, propylene-
isobutylene
copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes),
poly(1-
decenes), and the like and mixtures thereof; alkylbenzenes such as
dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)-benzenes, and the like;
polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, and the
like;
alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivative,
analogs
and homologs thereof and the like.
Other synthetic lubricating oils include, but are not limited to, oils made
by polymerizing olefins of less than 5 carbon atoms such as ethylene,
propylene,
butylenes, isobutene, pentene, and mixtures thereof. Methods of preparing such
polymer oils are well known to those skilled in the art.
Additional synthetic hydrocarbon oils include liquid polymers of alpha
olefins having the proper viscosity. Especially useful synthetic hydrocarbon
oils are
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the hydrogenated liquid oligomers of 06 to 012 alpha olefins such as, for
example, 1-
decene trimer.
Another class of synthetic lubricating oils include, but are not limited to,
alkylene oxide polymers, i.e., homopolymers, interpolymers, and derivatives
thereof
where the terminal hydroxyl groups have been modified by, for example,
esterification
or etherification. These
oils are exemplified by the oils prepared through
polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl
ethers of
these polyoxyalkylene polymers (e.g., methyl poly propylene glycol ether
having an
average molecular weight of 1,000, diphenyl ether of polyethylene glycol
having a
molecular weight of 500-1000, diethyl ether of polypropylene glycol having a
molecular
weight of 1,000-1,500, etc.) or mono- and polycarboxylic esters thereof such
as, for
example, the acetic esters, mixed 03-08 fatty acid esters, or the 013 oxo acid
diester
of tetraethylene glycol.
Yet another class of synthetic lubricating oils include, but are not limited
to, the esters of dicarboxylic acids e.g., phthalic acid, SUCCilliC acid,
alkyl succinic
acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid,
sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer, malonic acids, alkyl malonic
acids, alkenyl
malonic acids, etc., with a variety of alcohols, e.g., butyl alcohol, hexyl
alcohol, dodecyl
alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether,
propylene
glycol, etc.
Specific examples of these esters include dibutyl adipate, di(2-
ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl
azelate,
diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate,
the 2-
ethylhexyl diester of linoleic acid dimer, the complex ester formed by
reacting one mole
of sebacic acid with two moles of tetraethylene glycol and two moles of 2-
ethylhexanoic acid and the like.
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Esters useful as synthetic oils also include, but are not limited to, those
made from carboxylic acids having from about 5 to about 12 carbon atoms with
alcohols, e.g., methanol, ethanol, etc., polyols and polyol ethers such as
neopentyl
glycol, trimethylol propane, pentaerythritol, dipentaerythritol,
tripentaerythritol, and the
like.
I 0 Silicon-based oils such as, for example, polyalkyl-, polyaryl-,
polyalkoxy-
or polyaryloxy-siloxane oils and silicate oils, comprise another useful class
of synthetic
lubricating oils. Specific examples of these include, but are not limited to,
tetraethyl
silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-
methyl-
hexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-
pentoxy)disiloxane,
15 poly(methyl)siloxanes, poly(methylphenyl)siloxanes, and the like.
Still yet other useful
synthetic lubricating oils include, but are not limited to, liquid esters of
phosphorous
containing acids, e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester
of decane
phosphionic acid, etc., polymeric tetrahydrofurans and the like.
The lubricating oil may be derived from unrefined, refined and rerefined
20 oils, either natural, synthetic or mixtures of two or more of any of
these of the type
disclosed hereinabove. Unrefined oils are those obtained directly from a
natural or
synthetic source (e.g., coal, shale, or tar sands bitumen) without further
purification or
treatment. Examples of unrefined oils include, but are not limited to, a shale
oil
obtained directly from retorting operations, a petroleum oil obtained directly
from
25 distillation or an ester oil obtained directly from an
esterification process, each of which
is then used without further treatment. Refined oils are similar to the
unrefined oils
except they have been further treated in one or more purification steps to
improve one
or more properties. These purification techniques are known to those of skill
in the art
and include, for example, solvent extractions, secondary distillation, acid or
base
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extraction, filtration, percolation, hydrotreating, dewaxing, etc. Rerefined
oils are
obtained by treating used oils in processes similar to those used to obtain
refined oils.
Such rerefined oils are also known as reclaimed or reprocessed oils and often
are
additionally processed by techniques directed to removal of spent additives
and oil
breakdown products.
Lubricating oil base stocks derived from the hydroisomerization of wax
may also be used, either alone or in combination with the aforesaid natural
and/or
synthetic base stocks. Such wax isomerate oil is produced by the
hydroisomerization
of natural or synthetic waxes or mixtures thereof over a hydroisomerization
catalyst.
Natural waxes are typically the slack waxes recovered by the solvent
dewaxing of mineral oils; synthetic waxes are typically the wax produced by
the
Fischer-Tropsch process.
Other useful fluids of lubricating viscosity include non-conventional or
unconventional
base stocks that have been processed, preferably catalytically, or synthesized
to
provide high performance lubrication characteristics.
Metal or Metalloid Hydrogen Atom Donor CompoundsThe lubrication oil
compositions herein can contain one or more metal or metalloid hydrogen atom
donor compounds selected from the group consisting of silicon hydrides,
germanium
hydrides, and tin hydrides.
In one aspect, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
R2 R1
13 (Formula 1),
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where Ri, R2, and R3 are each independently selected from hydrogen atom, a 06-
014 aryl group, saturated or unsaturated 01-030 alkyl group, a 03-010
cycloalkyl
group, -(0R4), -NR5R6, -0(=0)R7, or chlorine atom, such that not more than one
of
R1, R2, and R3 are a hydrogen atom; R4 is a 06-014 aryl group, saturated or
unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl group, R5 is H, a 06-
014
aryl group, saturated or unsaturated 01-030 alkyl group, or a 03-010
cycloalkyl
group. R6 is H, a 06-014 aryl group, saturated or unsaturated 01-030 alkyl
group, or
a 03-010 cycloalkyl group, R7 is a 06-014 aryl group, saturated or unsaturated
01-
030 alkyl group, or a 03-010 cycloalkyl group; and M is a silicon atom,
germanium
atom, or tin atom.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
R. H
¨1V1-
(Formula 2),
where R2 and R3 are each independently selected from a 06-014 aryl group,
alkyl
group, or a 03-010 cycloalkyl group, -(0R4), -NR5R6, -0(=0)R7, or chlorine
atom, R4
is a 06-014 aryl group, saturated or unsaturated 01-030 alkyl group, or a 03-
010
cycloalkyl group, R5 is H, a 06-014 aryl group, saturated or unsaturated 01-
030
alkyl group, or a 03-010 cycloalkyl group, R6 is hi, a 06-014 aryl group,
saturated or
unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl group, Ri is a 06-014
aryl
group, saturated or unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl
group:
.. and M is a silicon atom, germanium atom, or tin atom.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
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P R
-2.6õ
F3 (Formula 3),
where Ri, R.2, and R3 are each independently selected from hydrogen atom, a 06-
014 aryl group, saturated or unsaturated 01-030 alkyl group, a 03-010
cycloalkyl
group, -(0R4), -NR5R6, -0(=0)R7, or chlorine atom, such that not more than one
of
Ri, R2, and R3 are a hydrogen atom: R4 is a 06-014 aryl group, saturated or
unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl group, R5 is H. a 06-
014
aryl group, saturated or unsaturated C1-030 alkyl group, or a 03-C10
cycloalkyl
group, R6 is H. a 06-014 aryl group, saturated or unsaturated 01-030 alkyl
group, or
a 03-010 cycloalkyl group, and R7 is a C6-C14 aryl group, saturated or
unsaturated
01-030 alkyl group, or a 03-010 cycloalkyl group.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
R2,thi,H
13 (Formula 4),
where R2 and P.3 are each independently selected from hydrogen atom, a 06-014
aryl group, saturated or unsaturated 01-030 alkyl group, a 03-010 cycloalkyl
group,
-(0R4), -NR5R6, -0(=0)R7, or chlorine atom, R4 is a 06-014 aryl group,
saturated or
unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl group, R5 is H, a 06-
014
aryl group, saturated or unsaturated 01-030 alkyl group, or a 03-010
cycloalkyl
group, R6 is H, a 06-014 aryl group, saturated or unsaturated 01-030 alkyl
group, or
a 03-C10 cycloalkyl group, and R7 is a 06-014 aryl group, saturated or
unsaturated
01-030 alkyl group, or a 03-C10 cycloalkyl group.
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In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
R2,G R
1:3 (Formula 5),
where Ri, R2, and R3 are each independently selected from hydrogen atom, a 06-
014 aryl group, saturated or unsaturated 01-030 alkyl group, a 03-010
cycloalkyl
group, -(0R4), -NR5R6, -0(=0)R7, or chlorine atom, such that not more than one
of
Ri, R2, and R3 are a hydrogen atom: R4 is a 06-014 aryl group, saturated or
unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl group, R5 is H. a 06-
014
aryl group, saturated or unsaturated 01-030 alkyl group, or a 03-010
cycloalkyl
group, R6 is H, a 06-014 aryl group, saturated or unsaturated 01-030 alkyl
group, or
a 03-010 cycloalkyl group, and R7 is a 06-014 aryl group, saturated or
unsaturated
01-030 alkyl group, or a 03-010 cycloalkyl group.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
R2,Sin' R1
k, (Formula 6),
.. where Ri, R2, and R3 are each independently selected from hydrogen atom, a
06-
014 aryl group, saturated or unsaturated 01-030 alkyl group, a 03-010
cycloalkyl
group, -(0R4), -NR5R6, -0(=0)R7, or chlorine atom, such that not more than one
of
Ri, R2, and R3 are a hydrogen atom; RA is a 06-014 aryl group, saturated or
unsaturated 01-030 alkyl group, or a 03-010 cycloalkyl group, R5 is H, a 06-
014
aryl group, saturated or unsaturated 01-030 alkyl group, or a 03-010
cycloalkyl
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group, R6 is H, a 06-014 aryl group, saturated or unsaturated 01-030 alkyl
group, or
a 03-C10 cycloalkyl group, and R7 is a 06-014 aryl group, saturated or
unsaturated
01-030 alkyl group, or a 03-010 cycloalkyl group.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
Rs - R8 - R8
(Formula 7),
where is R8 is a 06-014 aryl group; saturated or unsaturated 01-030 alkyl
group; or
a 03-C10 cycloalkyl group; and n is 0 or an integer from 1 to 400.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
Me - Me Me
1/le ktle Me
-n
(Formula 8);
where n is 0 or an integer from 1 to 400.
In one embodiment, the one or more metal or metalloid hydrogen atom donor
compounds have the following formula:
R9 H
0\c'
H
(Formula 9)
wherein R9 is a 06-C14 aryl group, saturated or unsaturated C1-030 alkyl
group;
and m is an integer from 1 to 20.
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In one embodiment, the metal or metalloid hydrogen atom donor compound is
one in which the hydride is directly bonded to the metal atom. In one
embodiment,
the metal hydride is not a silazane.
Generally, the amount of the metal or metalloid hydrogen atom donor
compound can be from about 0.001 wt. % to about 25 wt. %, from about 0.05 wt.
% to
ID about 20 wt. %, or from about 0.1 wt. % to about 15 wt. %, or from about
0.1 wt. % to
about 5 wt. ,4), from about, 0.1 wt. % to about 4.0 wt. %, based on the total
weight of
the lubricating oil composition.
In an aspect, the present disclosure provides a lubricating engine oil
composition for a direct injected, boosted, spark ignited internal combustion
engine
IS comprising at least one metal hydride compound. In one embodiment, the
amount of
metal from the at least one metal or metalloid hydrogen atom donor compound is
from
about 25 to about 3000 ppm, from about 100 to about 3000 ppm, from about 200
to
about 3000 ppm, or from about 250 to about 2500 ppm, from about 300 to about
2500
ppm, from about 350 to about 2500 ppm, from about 400 ppm to about 2500 ppm,
20 from about 500 to about 2500 ppm, from about 600 to about 2500 ppm, from
about
700 to about 2500 ppm, from about 700 to about 2000 ppm, from about 700 to
about
1500 ppm. In one embodiment, the amount of metal from the metal or metalloid
hydrogen atom donor compound is no more than about 2000 ppm or no more than
about 1500 ppm. The metals in each of these embodiments being selected from
25 silicon, germanium, tin or a combination thereof.
In one embodiment, the metal or metalloid hydrogen atom donor
compounds can be combined with conventional lubricating oil detergent
additives
which contain magnesium and/or calcium. In one embodiment the calcium
detergent(s) can be added in an amount sufficient to provide the lubricating
oil
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composition from 0 to about 2400 ppm of calcium metal, from 0 to about 2200
ppm of
calcium metal, from 100 to about 2000 ppm of calcium metal, from 200 to about
1800
ppm of calcium metal, or from about 100 to about 1800 ppm, or from about 200
to
about 1500 ppm, or from about 300 to about 1400 ppm, or from about 400 to
about
1400 ppm, of calcium metal in the lubricating oil composition. In one
embodiment the
.. magnesium detergent(s) can be added in an amount sufficient to provide the
lubricating oil composition from about 100 to about 1000 ppm of magnesium
metal, or
from about 100 to about 600 ppm, or from about 100 to about 500 ppm, or from
about
200 to about 500 ppm of magnesium metal in the lubricating oil composition.
In one embodiment, the metal or metalloid hydrogen atom donor
.. compounds can be combined with conventional lubricating oil detergent
additives
which contain lithium. In one embodiment the lithium detergent(s) can be added
in an
amount sufficient to provide the lubricating oil composition from 0 to about
2400 ppm
of lithium metal, from 0 to about 2200 ppm of lithium metal, from 100 to about
2000
ppm of lithium metal, from 200 to about 1800 ppm of lithium metal, or from
about 100
.. to about 1800 ppm, or from about 200 to about 1500 ppm, or from about 300
to about
1400 ppm, or from about 400 to about 1400 ppm, of lithium metal in the
lubricating oil
composition.
In one embodiment, the metal or metalloid hydrogen atom donor
compounds can be combined with conventional lubricating oil detergent
additives
.. which contain sodium. In one embodiment the sodium detergent(s) can be
added in
an amount sufficient to provide the lubricating oil composition from 0 to
about 2400
ppm of sodium metal, from 0 to about 2200 ppm of sodium metal, from 100 to
about
2000 ppm of sodium metal, from 200 to about 1800 ppm of sodium metal, or from
about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or from
about
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300 to about 1400 ppm, or from about 400 to about 1400 ppm, of sodium metal in
the
lubricating oil composition.
In one embodiment, the metal or metalloid hydrogen atom donor
compound can be combined with conventional lubricating oil detergent additives
which
contain potassium. In one embodiment the potassium detergent(s) can be added
in
an amount sufficient to provide the lubricating oil composition from 0 to
about 2400
ppm of potassium metal, from 0 to about 2200 ppm of potassium metal, from 100
to
about 2000 ppm of potassium metal, from 200 to about 1800 ppm of potassium
metal,
or from about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or
from
about 300 to about 1400 ppm, or from about 400 to about 1400 ppm, of potassium
metal in the lubricating oil composition.
In one embodiment, the disclosure provides a lubricating engine oil
composition comprising a lubricating oil base stock as a major component; and
at least
one metal hydride compound, as a minor component; and wherein the engine
exhibits
greater than 50% reduced low speed pre-ignition, based on normalized low speed
pre-
ignition (LSPI) counts per 100,000 engine cycles, engine operation at between
500
and 3,000 revolutions per minute and brake mean effective pressure (BMEP)
between
10 and 30 bar, as compared to low speed pre-ignition performance achieved in
an
engine using a lubricating oil that does not comprise of at least one metal
hydride
compound.
)5 In one aspect, the disclosure provides a lubricating engine oil
composition for use in a down-sized boosted engine comprising a lubricating
oil base
stock as a major component; and at least one metal hydride compound, as a
minor
component; where the downsized engine ranges from about 0.5 to about 3.6
liters,
from about 0.5 to about 3.0 liters, from about 0.8 to about 3.0 liters, from
about 0.5 to
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about 2.0 liters, or from about 1.0 to about 2.0 liters. The engine can have
two, three,
four, five or six cylinders.
In an aspect, the present disclosure provides the use of a at least one
metal or metalloid hydrogen atom donor compound for preventing or reducing low
speed pre-ignition in a direct injected, boosted, spark ignited internal
combustion
engine.
Lubricating Oil Additives
In addition to the metal or metalloid hydrogen atom donor compounds
described herein, the lubricating oil composition can comprise additional
lubricating
oil additives.
The lubricating oil compositions of the present disclosure may also
contain other conventional additives that can impart or improve any desirable
property of the lubricating oil composition in which these additives are
dispersed or
dissolved. Any additive known to a person of ordinary skill in the art may be
used in
the lubricating oil compositions disclosed herein. Some suitable additives
have been
described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd
Edition,
London, Springer, (1996); and Leslie R. Rudnick, "Lubricant Additives:
Chemistry
and Applications," New York, Marcel Dekker (2003), both of which are
incorporated
herein by reference. For example, the lubricating oil compositions can be
blended
with antioxidants, anti-wear agents, metal detergents, rust inhibitors,
dehazing
agents, demulsifying agents, metal deactivating agents, friction modifiers,
pour point
depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless
dispersants, multifunctional agents, dyes, extreme pressure agents and the
like and
mixtures thereof. A variety of the additives are known and commercially
available.
These additives, or their analogous compounds, can be employed for the
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preparation of the lubricating oil compositions of the disclosure by the usual
blending
procedures.
The lubricating oil composition of the present invention can contain one
or more detergents. Metal-containing or ash-forming detergents function as
both
detergents to reduce or remove deposits and as acid neutralizers or rust
inhibitors,
thereby reducing wear and corrosion and extending engine life. Detergents
generally
comprise a polar head with a long hydrophobic tail. The polar head comprises a
metal salt of an acidic organic compound. The salts may contain a
substantially
stoichiometric amount of the metal in which case they are usually described as
normal or neutral salts. A large amount of a metal base may be incorporated by
reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic
gas
(e.g., carbon dioxide).
Detergents that may be used include oil-soluble neutral and oyerbased
sulfonates, phenates, suifurized phenates, thiophosphonates, salicylates, and
naphthenates and other oil-soluble carboxylates of a metal, particularly the
alkali or
alkaline earth metals, e.g.; barium, sodium, potassium, lithium, calcium, and
magnesium. The most commonly used metals are calcium and magnesium, which
may both be present in detergents used in a lubricant, and mixtures of calcium
and/or
magnesium with sodium.
The lubricating oil composition of the present invention can contain one or
more
anti-wear agents that can reduce friction and excessive wear. Any anti-wear
agent
known by a person of ordinary skill in the art may be used in the lubricating
oil
composition. Non-limiting examples of suitable anti-wear agents include
zinc
dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of
dithiophosphates, metal
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(e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamates, metal (e.g.,
Zn, Pb, Sb
and the like) salts of fatty acids, boron compounds, phosphate esters,
phosphite
esters, amine salts of phosphoric acid esters or thiophosphoric acid esters,
reaction
products of dicyclopentadiene and thiophosphoric acids and combinations
thereof.
The amount of the anti-wear agent may vary from about 0.01 wt. % to about 5
wt. %,
from about 0.05 wt. % to about 3 wt. ,10, or from about 0.1 wt. % to about 1
wt. 9/0,
based on the total weight of the lubricating oil composition.
In certain embodiments, the anti-wear agent is or comprises a
dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate
compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an
alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese,
nickel
or copper. In some embodiments, the metal is zinc. In other embodiments, the
alkyl
group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to
about 22
carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12
carbon
atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the
alkyl
group is linear or branched.
The amount of the dihydrocarbyl dithiophosphate metal salt including the
zinc dialkyl dithiophosphate salts in the lubricating oil composition
disclosed herein is
measured by its phosphorus content. In some embodiments, the phosphorus
content
of the lubricating oil composition disclosed herein is from about 0.01 wt. %
to about
0.14 wt. %, based on the total weight of the lubricating oil composition.
The lubricating oil composition of the present invention can contain one
or more friction modifiers that can lower the friction between moving parts.
Any
friction modifier known by a person of ordinary skill in the art may be used
in the
lubricating oil composition. Non-limiting examples of suitable friction
modifiers
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include fatty carboxylic acids; derivatives (e.g., alcohol, esters, borated
esters,
amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-
alkyl
substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters,
amides,
metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric
acids or
phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-
alkyl
.. substituted amides and combinations thereof. In some embodiments examples
of
friction modifiers include, but are not limited to, alkoxylated fatty amines;
borated
fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated
alkoxylated
fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters,
borated
glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No.
6,372,696, the
contents of which are incorporated by reference herein; friction modifiers
obtained
from a reaction product of a 04 to 075, or a 06 to 024, or a 06 to 020, fatty
acid ester
and a nitrogen-containing compound selected from the group consisting of
ammonia,
and an alkanolamine and the like and mixtures thereof. The amount of the
friction
modifier may vary from about 0.01 wt. % to about 10 wt. %, from about 0.05 wt.
% to
about 5 wt. 910, or from about 0.1 wt. % to about 3 wt. 9/0, based on the
total weight of
the lubricating oil composition.
The lubricating oil composition of the disclosure can contain a
molybdenum-containing friction modifier. The molybdenum-containing friction
modifier
can be any one of the known molybdenum-containing friction modifiers or the
known
molybdenum-containing friction modifier compositions.
Preferred molybdenum-containing friction modifier is, for example, sulfurized
oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate,
amine-molybdenum complex compound, oxymolybdenum diethylate amide, and
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oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate
friction modifier.
The lubricating oil composition of the invention generally contains the
molybdenum-containing friction modifier in an amount of 0.01 to 0.15 wt. % in
terms
of the molybdenum content.
The lubricating oil composition of the invention preferably contains an
organic oxidation inhibitor in an amount of 0.01-5 wt. %, preferably 0.1-3 wt.
%. The
oxidation inhibitor can be a hindered phenol oxidation inhibitor or a
diarylamine
oxidation inhibitor. The diarylamine oxidation inhibitor is advantageous in
giving a base
number originating from the nitrogen atoms. The hindered phenol oxidation
inhibitor is
advantageous in producing no NOx gas.
Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-
butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-
butyl-o-
cresol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-
butylphenol),
2,2'-methylenebis(4-methy1-6-t-butylphenol), 4,4'-
thiobis(2-methyl-6-t-butylphenol),
2,2-thio-diethylenebis[3-(3,5-di-t-buty1-4-hydroxyphenyl)propionate], octyl 3-
(3,5-di-t-
buty1-4-hydroxyphenyl)propionate, octadecyl 3-
(3,5-di-t-buty1-4-
hydroxyphenyl)propionate, and octyl 3-
(3,54-buty1-4-hydroxy-3-
methylphenyl)propionate, and commercial products such as, but not limited to,
lrganox
L1350 (BASF), Naugalube 531 (Chemtura), and Ethanox 3760 (SI Group).
)5 Examples of the diarylamine oxidation inhibitors include
alkyldiphenylamine having a mixture of alkyl groups of 3 to 9 carbon atoms,
p,p-
dioctyldiphenylam ine, phenyl-naphthylamine, phenyl-naphthylamine, alkylated-
naphthylamine, and alkylated phenyl-naphthylamine. The diarylamine oxidation
inhibitors can have from Ito 3 alkyl groups.
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Each of the hindered phenol oxidation inhibitor and diarylamine oxidation
inhibitor can
be employed alone or in combination. If desired, other oil soluble oxidation
inhibitors
can be employed in combination with the above-mentioned oxidation
inhibitor(s).
The lubricating oil composition of the invention may further contain an
oxymolybdenum complex of succinimide, particularly a sulfur-containing
oxymolybdenum complex of succinimide. The sulfur-containing oxymolybdenum
complex of succinimide can provide increased oxidation inhibition when it is
employed
in combination with the above-mentioned phenolic or amine oxidation
inhibitors.
In the preparation of lubricating oil formulations, it is common practice to
introduce the additives in the form of 10 to 80 wt. % active ingredient
concentrates in
hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent.
Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40,
parts by weight of lubricating oil per part by weight of the additive package
in forming
finished lubricants, e.g. crankcase motor oils. The purpose of concentrates,
of
course, is to make the handling of the various materials less difficult and
awkward as
well as to facilitate solution or dispersion in the final blend.
Processes of Preparing Lubricating Oil Compositions
The lubricating oil compositions disclosed herein can be prepared by
any method known to a person of ordinary skill in the art for making
lubricating oils.
In some embodiments, the base oil can be blended or mixed with the metal or
metalloid hydrogen atom donor compounds described herein. Optionally, one or
more other additives in additional to the metal or metalloid hydrogen atom
donor
compounds can be added. The metal or metalloid hydrogen atom donor compounds
and the optional additives may be added to the base oil individually or
simultaneously. In some embodiments, the metal or metalloid hydrogen atom
donor
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.. compounds and the optional additives are added to the base oil individually
in one or
more additions and the additions may be in any order. In other embodiments,
the
metal or metalloid hydrogen atom donor compounds and the additives are added
to
the base oil simultaneously, optionally in the form of an additive
concentrate. In
some embodiments, the solubilizing of the metal or metalloid hydrogen atom
donor
I 0 compounds or any solid additives in the base oil may be assisted by
heating the
mixture to a temperature from about 25 CC to about 200 C, from about 50 CC to
about 150 C or from about 75 C to about 125 C.
Any mixing or dispersing equipment known to a person of ordinary skill
in the art may be used for blending, mixing or solubilizing the ingredients.
The
.. blending, mixing or solubilizing may be carried out with a blender, an
agitator, a
disperser, a mixer (e.g., planetary mixers and double planetary mixers), a
homogenizer (e.g., Gaulin homogenizers and Rannie homogenizers), a mill (e.g.,
colloid mill, ball mill and sand mill) or any other mixing or dispersing
equipment
known in the art.
Application of the Lubricating Oil Compositions
The lubricating oil composition disclosed herein may be suitable for use
as motor oils (that is, engine oils or crankcase oils), in a spark-ignited
internal
combustion engine, particularly a direct injected, boosted, engine that is
susceptible
to low speed pre-ignition.
)5 The following examples are presented to exemplify embodiments of
the
invention but are not intended to limit the invention to the specific
embodiments set
forth. Unless indicated to the contrary, all parts and percentages are by
weight. All
numerical values are approximate. When numerical ranges are given, it should
be
understood that embodiments outside the stated ranges may still fall within
the
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.. scope of the invention. Specific details described in each example should
not be
construed as necessary features of the invention.
EXAMPLES
The following examples are intended for illustrative purposes only and
do not limit in any way the scope of the present invention.
The test compounds were blended in lube oil and their capacity for
reducing LSPI events were determined using the test method described below.
Low Speed Pre-ignition events were measured in a Ford 2.0L
Ecoboost engine. This engine is a turbocharged gasoline direct injection (GD1)
engine. The Ford Ecoboost engine is operated in four-roughly 4 hour
iterations. The
engine is operated at 1750 rpm and 1.7 MPa break mean effective pressure
(BMEP)
with an oil sump temperature of 95 C. The engine is run for 175,000
combustion
cycles in each stage, and LSP1 events are counted.
LSPI events are determined by monitoring peak cylinder pressure (PP)
and the crank angle of 2% mass fraction burn (MFB02) of the fuel charge in the
.. cylinder. 'Mien both criteria are met, it can be said that an LSP1 event
has occurred.
The threshold for peak cylinder pressure varies by test, but is typically 4-5
standard
deviations above the average cylinder pressure. Likewise, the MFB02 threshold
is
typically 4-5 standard deviations earlier than the average MFB02 (represented
in
crank angle degrees). LSPI events can be reported as average events per test,
.. events per 100,000 combustion cycles, events per cycle, and/or combustion
cycles
per event. The results for this test is shown below.
An additive associated with a test lubricant that reduces the LSPI
frequency, when compared to the corresponding baseline lubricant, is
considered an
additive that mitigates LSPI frequency. The test results are set forth in
Table 1.
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PCT/IB2020/050913
Baseline Formulation
The base line formulation contained a Group 2 base oil, a mixture of primary
and secondary dialkyl zinc dithiophosphates in an amount to provide 737-814
ppm
phosphorus to the lubricating oil composition, a mixture of polyisobutenyl
succinimide
dispersants (borated and ethylene carbonate post-treated), a molybdenum
l0 succinimide complex, an alkylated diphenylamine antioxidant, a borated
friction
modifier, a foam inhibitor, a pour point depressant, and an olefin copolymer
viscosity
index improver.
The lubricating oil compositions were blended into a 5W-30 viscosity grade
oil.
Metal or metalloid hydrogen atom donor Compound A
15 (Triphenylsilane)
Triphenylsilane was commercially available from Millipore Sigma or Gelest .
Metal or metalloid hydrogen atom donor Compound B
(Tributylgermane)
Tributylgermane was commercially available from Millipore Sigma .
Example 1
A lubricating oil composition was prepared by adding 458 ppm of
silicon from the triphenylsilane and 2164 ppm of calcium from a combination of
overbased Ca sulfonate and phenate detergents to the baseline formulation.
Comparative Example 1
25 A lubricating oil composition was prepared by adding 2255 ppm of
calcium from a combination of overbased Ca sulfonate and phenate detergents to
the baseline formulation.
Example 2
CA 03128820 2021-08-03
WO 2020/161635
PCT/IB2020/050913
A lubricating oil composition was prepared by adding 1483 ppm of
germanium from the tributylgermane and 2204 ppm of calcium from a combination
of
overbased Ca sulfonate and phenate detergents to the baseline formulation.
Table 1. LSPI Test Results in Ford LSPI Test
E 1 Comp. Reduction Ex. Reduction
x.
Ex. 1 in LSPI 2 in LSPI
activity Ex 1 activity Ex 2
Si (ppm) from compound A 454 0 NA 0 NA
Ca (ppm) 2164 2255 NA 2204 NA
Ge (ppm) from compound B NA 1483 NA
0 0
Average Events 8.5 19.25 56% 10 48%
Average Events > 90 bar 3.25 13.25 75% 5.75 56%
Average Events > 100 bar 1.75 10.75 84% 5 53%
Average Events > 110 bar 1.75 9.0 81% 4.25 52%
Average Events > 120 bar 1.75 8.25 79% 4 51%
*Counts all cycles of LSPI where both MFB02 and Peak Pressure Requirements are
U) met.
The data shows that Applicant's inventive examples comprising a metal
or metalloid hydrogen atom donor compound of the disclosure provided
significantly
better LSPI performance both in terms of number of events and also the number
of
severe LSPI events than the comparative examples which did not contain the
metal
or metalloid hydrogen atom donor in the Ford engines. Severity is reduced by
decreasing the number of high pressure events (i.e. over 120 bar) that can
damage
an engine.
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