U.S. patent application number 16/782211 was filed with the patent office on 2020-08-13 for composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines.
The applicant listed for this patent is Chevron Oronite Company LLC, Chevron U.S.A. Inc.. Invention is credited to Richard Eugene Cherpeck, Ian G. Elliott, Theresa Liang Gunawan, Amir Gamal Maria, John Robert Miller.
Application Number | 20200255762 16/782211 |
Document ID | / |
Family ID | 69630561 |
Filed Date | 2020-08-13 |
![](/patent/app/20200255762/US20200255762A1-20200813-C00001.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00002.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00003.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00004.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00005.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00006.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00007.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00008.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00009.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00010.png)
![](/patent/app/20200255762/US20200255762A1-20200813-C00011.png)
View All Diagrams
United States Patent
Application |
20200255762 |
Kind Code |
A1 |
Elliott; Ian G. ; et
al. |
August 13, 2020 |
COMPOSITION AND METHOD FOR PREVENTING OR REDUCING LOW SPEED
PRE-IGNITION IN DIRECT INJECTED SPARK-IGNITED ENGINES
Abstract
Disclosed is a lubricating engine oil composition comprising a
lubricating oil base stock as a major component, and at least one
metal or metalloid hydrogen atom donor compound. Also disclosed is
a method for preventing or reducing low speed pre-ignition in a
direct injected, boosted, spark ignited internal combustion engine,
and the use of at least one metal or metalloid hydrogen atom donor
compound in a lubricating engine oil composition for preventing or
reducing low speed pre-ignition in a direct injected, boosted,
spark ignited internal combustion engine.
Inventors: |
Elliott; Ian G.; (Vacaville,
CA) ; Miller; John Robert; (San Rafael, CA) ;
Gunawan; Theresa Liang; (Emeryville, CA) ; Cherpeck;
Richard Eugene; (Cotati, CA) ; Maria; Amir Gamal;
(Fremont, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chevron Oronite Company LLC
Chevron U.S.A. Inc. |
San Ramon
San Ramon |
CA
CA |
US
US |
|
|
Family ID: |
69630561 |
Appl. No.: |
16/782211 |
Filed: |
February 5, 2020 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62802745 |
Feb 8, 2019 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2030/04 20130101;
C10N 2010/02 20130101; C10M 2229/044 20130101; C10M 2215/28
20130101; C10M 125/22 20130101; C10M 2227/09 20130101; C10M
2215/064 20130101; C10N 2010/04 20130101; C10M 139/06 20130101;
C10M 125/04 20130101; C10M 2207/028 20130101; C10M 2207/26
20130101; C10N 2040/255 20200501; C10M 2227/04 20130101; C10M
139/04 20130101; C10M 125/08 20130101; C10M 2223/045 20130101; C10M
2207/262 20130101; C10N 2010/12 20130101; C10M 2201/061 20130101;
C10M 2219/046 20130101; C10N 2040/25 20130101; C10N 2030/42
20200501; C10M 2227/08 20130101; C10M 2227/083 20130101; C10M
2201/05 20130101; C10M 155/02 20130101; C10M 2203/1025 20130101;
C10M 2201/061 20130101; C10N 2010/08 20130101; C10M 2223/045
20130101; C10N 2010/12 20130101; C10M 2215/28 20130101; C10N
2060/06 20130101; C10N 2060/14 20130101 |
International
Class: |
C10M 139/04 20060101
C10M139/04; C10M 139/06 20060101 C10M139/06; C10M 125/22 20060101
C10M125/22; C10M 125/04 20060101 C10M125/04 |
Claims
1. A lubricating oil composition comprising a metal or metalloid
hydrogen atom donor compound selected from the group consisting of
silicon hydrides, germanium hydrides, and tin hydrides.
2. The lubricating oil of claim 1, wherein the metal or metalloid
hydrogen atom donor compound has the following formula:
##STR00010## wherein R.sub.1, R.sub.2, and R.sub.3 are each
independently selected from hydrogen atom, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, a C3-C10 cycloalkyl
group, --(OR.sub.4), --NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or
chlorine atom, such that not more than one of R,.sub.1, R.sub.2,
and R.sub.3 are a hydrogen atom; R.sub.4 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, R.sub.5 is H, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, R.sub.6 is H, a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group, R.sub.7 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group; and M is a silicon atom, germanium atom, or tin atom.
3. The lubricating oil of claim 2, wherein the metal or metalloid
hydrogen atom donor compound has the following formula:
##STR00011## wherein R.sub.2 and R.sub.3 are each independently
selected from a C6-C14 aryl group, alkyl group, or a C3-C10
cycloalkyl group, --(OR.sub.4), --NR.sub.5R.sub.6,
--O(.dbd.O)R.sub.7, or chlorine atom, R.sub.4 is a C6-C14 aryl
group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10
cycloalkyl group, R.sub.5 is H, a C6-C14 aryl group, saturated or
unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl group,
R.sub.6 is H, a C6-C14 aryl group, saturated or unsaturated C1-C30
alkyl group, or a C3-C10 cycloalkyl group, R.sub.7 is a C6-C14 aryl
group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10
cycloalkyl group; and M is a silicon atom, germanium atom, or tin
atom.
4. The lubricating oil of claim 2, wherein the metal or metalloid
hydrogen atom donor compound has the following formula:
##STR00012## wherein R.sub.1, R.sub.2, and R.sub.3 are each
independently selected from hydrogen atom, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, a C3-C10 cycloalkyl
group, --(OR.sub.4), --NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or
chlorine atom, such that not more than one of R.sub.1, R.sub.2, and
R.sub.3 are a hydrogen atom; R.sub.4 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, R.sub.5 is H, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, R.sub.6 is H, a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group, and R.sub.7 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group.
5. The lubricating oil of claim 4, wherein the metal or metalloid
hydrogen atom donor compound has the following formula:
##STR00013## wherein where R.sub.2 and R.sub.3 are each
independently selected from hydrogen atom, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, a C3-C10 cycloalkyl
group, --(OR.sub.4), --NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or
chlorine atom, R.sub.4 is a C6-C14 aryl group, saturated or
unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl group,
R.sub.5 is H, a C6-C14 aryl group, saturated or unsaturated C1-C30
alkyl group, or a C3-C10 cycloalkyl group, R.sub.6 is H, a C6-C14
aryl group, saturated or unsaturated C1-C30 alkyl group, or a
C3-C10 cycloalkyl group, and R.sub.7 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group.
6. The lubricating oil composition of claim 2, wherein the metal or
metalloid hydrogen atom donor compound has the following formula:
##STR00014## wherein R.sub.1, R.sub.2, and R.sub.3 are each
independently selected from hydrogen atom, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, a C3-C10 cycloalkyl
group, --(OR.sub.4), --NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or
chlorine atom, such that not more than one of R.sub.1, R.sub.2, and
R.sub.3 are a hydrogen atom; R.sub.4 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, R.sub.5 is H, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, R.sub.6 is H, a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group, and R.sub.7 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group.
7. The lubricating oil composition of claim 2, wherein the metal or
metalloid hydrogen atom donor compound has the following formula:
##STR00015## wherein R.sub.1, R.sub.2, and R.sub.3 are each
independently selected from hydrogen atom, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, a C3-C10 cycloalkyl
group, --(OR.sub.4), --NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or
chlorine atom, such that not more than one of R.sub.1, R.sub.2, and
R.sub.3 are a hydrogen atom; R.sub.4 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, R.sub.5 is H, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, R.sub.6 is H, a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group, and R.sub.7 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group.
8. The lubricating oil composition of claim 1, wherein the metal or
metalloid hydrogen atom donor compound has the following formula:
##STR00016## wherein is R.sub.8 is a C6-C14 aryl group, saturated
or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl group;
and n is 0 or an integer from 1 to 400.
9. The lubricating oil composition of claim 1, wherein the metal or
metalloid hydrogen atom donor compound has the following formula:
##STR00017## wherein n is 0 or an integer from 1 to 400.
10. The lubricating oil composition of claim 1, wherein the metal
or metalloid hydrogen atom donor compound has the following
formula: ##STR00018## wherein R.sub.9 is a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group; and m is an integer
from 1 to 20.
11. The lubricating oil composition of claim 1, wherein the
composition further comprises a detergent selected from calcium
detergents, magnesium detergents, sodium detergents, lithium
detergents, and potassium detergents.
12. The lubricating oil composition of claim 11, wherein the
detergent is a carboxylate, salicylate, phenate, or sulfonate
detergent.
13. The lubricating oil composition of claim 1, wherein the
composition further comprises a molybdenum containing compound.
14. The lubricating oil composition of claim 1, wherein the
composition further comprises at least one other additive selected
from an ashless dispersant, an ashless antioxidant, a phosphorus-
containing anti-wear additive, a friction modifier, and a polymeric
viscosity modifier.
15. 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 metal from at least one metal or metalloid
hydrogen atom donor compound selected from the group consisting of
silicon hydrides, germanium hydrides, and tin hydrides, based on
the total weight of the lubricating oil composition.
16. Use of at least one metal or metalloid hydrogen atom donor
compound selected from the group consisting of silicon hydrides,
germanium hydrides, and tin hydrides in a lubricating engine oil
composition for preventing or reducing low speed pre-ignition in a
direct injected, boosted, spark ignited internal combustion
engine.
17. The use according to claim 16, wherein the at least one metal
or metalloid hydrogen atom donor compound is present at from about
25 to about 3000 ppm of metal from the metal hydride, based on the
total weight of the lubricating oil composition.
18. The use according to claim 16 wherein the engine is a
down-sized boosted engine ranging from 0.5 liters to 3.6 liters.
Description
FIELD OF THE INVENTION
[0001] This disclosure relates to a lubricant composition that
contains at least one metal hydride compound. The disclosure also
relates to a lubricant composition 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 atom donor
compound.
BACKGROUND OF THE INVENTION
[0002] 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 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, 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.
[0003] 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 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).
[0004] 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 LSPI
problem, and also improve or maintain other performance such as
wear and oxidation protection.
[0005] 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
[0006] 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.
[0007] 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.
[0008] 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 reducing low speed
pre-ignition in a direct injected, boosted, spark ignited internal
combustion engine.
DETAILED DESCRIPTION OF THE INVENTION
[0009] 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.
[0010] Throughout the specification and claims the expression oil
soluble or 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.
[0011] 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.
[0012] 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.
[0013] Unless otherwise specified, all percentages are in weight
percent.
[0014] 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. %, 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 wt. %, 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. %, 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.
[0015] 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. %. 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 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.09 wt. %. In one embodiment, the levels of
phosphorus in the lubricating oil compositions of the present
invention is less than or equal to about 0.08 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. %. 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. %. 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. %.
[0016] 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.
[0017] 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).
[0018] 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 15 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 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.
[0019] 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.
[0020] 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 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.
[0021] 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.
[0022] 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.
[0023] 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 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 LSPI 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 MFB02 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, 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).
[0024] 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.
[0025] 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.
[0026] 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. 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
[0027] 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. %, 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
manufacturer's location); that meets the same manufacturer's
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.
[0028] 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.degree. Centigrade (C.). Generally, individually the base oils
used as engine oils will have a kinematic viscosity range at
100.degree. C. of about 2 cSt to about 30 cSt, preferably about 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 0W, 0W-4, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26,
0W-30, 0W-40, 0W-50, 0W-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, 15W-40,
30, 40 and the like.
[0029] 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 (VI) of
greater than or equal to 80 and less than 120 (as determined by
ASTM D 2270).
[0030] 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).
[0031] 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.
[0032] Group IV base oils are polyalphaolefins (PAOs).
[0033] Group V base oils include all other base oils not included
in Group I, II, III, or IV.
[0034] The lubricating oil composition can contain minor amounts of
other base oil components. For example, the lubricating oil
composition can contain a minor 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.
[0035] 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.
[0036] 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.
[0037] Additional synthetic hydrocarbon oils include liquid
polymers of alpha olefins having the proper viscosity. Especially
useful synthetic hydrocarbon oils are the hydrogenated liquid
oligomers of C.sub.6 to C.sub.12 alpha olefins such as, for
example, 1-decene trimer.
[0038] 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 C.sub.3-C.sub.8 fatty acid esters, or the C.sub.13
oxo acid diester of tetraethylene glycol.
[0039] Yet another class of synthetic lubricating oils include, but
are not limited to, the esters of dicarboxylic acids e.g., phthalic
acid, succinic 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.
[0040] 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.
[0041] 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, 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.
[0042] The lubricating oil may be derived from unrefined, refined
and rerefined 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 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 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.
[0043] 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.
[0044] 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.
[0045] Metal or Metalloid Hydrogen Atom Donor Compounds The
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.
[0046] In one aspect, the one or more metal or metalloid hydrogen
atom donor compounds have the following formula:
##STR00001##
where R.sub.1, R.sub.2, and R.sub.3 are each independently selected
from hydrogen atom, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, a C3-C10 cycloalkyl group, --(OR.sub.4),
--NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or chlorine atom, such that
not more than one of R.sub.1, R.sub.2, and R.sub.3 are a hydrogen
atom; R.sub.4 is a C.sub.6-C.sub.14 aryl group, saturated or
unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl group,
R.sub.5 is H, a C6-C14 aryl group, saturated or unsaturated C1-C30
alkyl group, or a C3-C10 cycloalkyl group, R.sub.6 is H, a C6-C14
aryl group, saturated or unsaturated C1-C30 alkyl group, or a
C3-C10 cycloalkyl group, R7 is a C6-C14 aryl group, saturated or
unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl group; and M
is a silicon atom, germanium atom, or tin atom.
[0047] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00002##
where R.sub.2 and R.sub.3 are each independently selected from a
C6-C14 aryl group, alkyl group, or a C3-C10 cycloalkyl group,
--(OR.sub.4), --NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or chlorine
atom, R.sub.4 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, R.sub.5 is H, a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group, R.sub.6 is H, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, R.sub.7 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group; and M is a
silicon atom, germanium atom, or tin atom.
[0048] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00003##
where R.sub.1, R.sub.2, and R.sub.3 are each independently selected
from hydrogen atom, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, a C3-C10 cycloalkyl group, --(OR.sub.4),
--NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or chlorine atom, such that
not more than one of R.sub.1, R.sub.2, and R.sub.3 are a hydrogen
atom; R.sub.4 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, R.sub.5 is H, a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group, R.sub.6 is H, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, and R.sub.7 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group.
[0049] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00004##
where R.sub.2 and R.sub.3 are each independently selected from
hydrogen atom, a C6-C14 aryl group, saturated or unsaturated C1-C30
alkyl group, a C3-C10 cycloalkyl group, --(OR.sub.4),
--NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or chlorine atom, R.sub.4 is
a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group,
or a C3-C10 cycloalkyl group, R.sub.5 is H, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, R.sub.6 is H, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group, and R.sub.7 is a
C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
a C3-C10 cycloalkyl group.
[0050] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00005##
where R.sub.1, R.sub.2, and R.sub.3 are each independently selected
from hydrogen atom, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, a C3-C10 cycloalkyl group, --(OR.sub.4),
--NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or chlorine atom, such that
not more than one of R.sub.2, and R.sub.3 are a hydrogen atom;
R.sub.4 is a C6-C14 aryl group, saturated or unsaturated C1-C30
alkyl group, or a C3-C10 cycloalkyl group, R.sub.5 is H, a C6-C14
aryl group, saturated or unsaturated C1-C30 alkyl group, or a
C3-C10 cycloalkyl group, R.sub.6 is H, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, and R.sub.7 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group.
[0051] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00006##
where R.sub.1, R.sub.2, and R.sub.3 are each independently selected
from hydrogen atom, a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, a C3-C10 cycloalkyl group, --(OR.sub.4),
--NR.sub.5R.sub.6, --O(.dbd.O)R.sub.7, or chlorine atom, such that
not more than one of R.sub.2, and R.sub.3 are a hydrogen atom;
R.sub.4 is a C6-C14 aryl group, saturated or unsaturated C1-C30
alkyl group, or a C3-C10 cycloalkyl group, R.sub.5 is H, a C6-C14
aryl group, saturated or unsaturated C1-C30 alkyl group, or a
C3-C10 cycloalkyl group, R.sub.6 is H, a C6-C14 aryl group,
saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl
group, and R.sub.7 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group.
[0052] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00007##
where is R.sub.86 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group, or a C3-C10 cycloalkyl group; and n is 0 or an
integer from 1 to 400.
[0053] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00008##
where n is 0 or an integer from 1 to 400.
[0054] In one embodiment, the one or more metal or metalloid
hydrogen atom donor compounds have the following formula:
##STR00009##
wherein R.sub.9 is a C6-C14 aryl group, saturated or unsaturated
C1-C30 alkyl group; and m is an integer from 1 to 20.
[0055] 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.
[0056] 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 about 20 wt. %, or from about 0.1 wt. %
to about 15 wt. %, or from about 0.1 wt. % to about 5 wt. %, from
about, 0.1 wt. % to about 4.0 wt. %, based on the total weight of
the lubricating oil composition.
[0057] In an aspect, the present disclosure provides a lubricating
engine oil composition for a direct injected, boosted, spark
ignited internal combustion engine 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, 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 silicon, germanium, tin or a
combination thereof.
[0058] 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 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.
[0059] 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.
[0060] 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 300 to about 1400 ppm, or from about
400 to about 1400 ppm, of sodium metal in the lubricating oil
composition.
[0061] 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.
[0062] 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.
[0063] 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 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.
[0064] 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
[0065] In addition to the metal or metalloid hydrogen atom donor
compounds described herein, the lubricating oil composition can
comprise additional lubricating oil additives.
[0066] 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 preparation of
the lubricating oil compositions of the disclosure by the usual
blending procedures.
[0067] 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).
[0068] Detergents that may be used include oil-soluble neutral and
overbased sulfonates, phenates, sulfurized 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.
[0069] 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 (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. %, or from about 0.1 wt. % to about 1 wt. %,
based on the total weight of the lubricating oil composition.
[0070] 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.
[0071] 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.
[0072] 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
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. Pat. No.
6,372,696, the contents of which are incorporated by reference
herein; friction modifiers obtained from a reaction product of a
C.sub.4 to C.sub.76, or a C.sub.6 to C.sub.24, or a C.sub.6 to
C.sub.20, 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. %, or from about 0.1 wt. % to about
3 wt. %, based on the total weight of the lubricating oil
composition.
[0073] 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.
[0074] Preferred molybdenum-containing friction modifier is, for
example, sulfurized oxymolybdenum dithiocarbamate, sulfurized
oxymolybdenum dithiophosphate, amine-molybdenum complex compound,
oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride.
Most preferred is a molybdenum dithiocarbamate friction
modifier.
[0075] 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.
[0076] 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.
[0077] 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-methyl-6-t-butylphenol),
4,4'-thiobis(2-methyl-6-t-butylphenol),
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl
3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and octyl
3-(3,54-butyl-4-hydroxy-3-methylphenyl)propionate, and commercial
products such as, but not limited to, Irganox L135.RTM. (BASF),
Naugalube 531.RTM. (Chemtura), and Ethanox 376.RTM. (SI Group).
[0078] Examples of the diarylamine oxidation inhibitors include
alkyldiphenylamine having a mixture of alkyl groups of 3 to 9
carbon atoms, p,p-dioctyldiphenylamine, phenyl-naphthylamine,
phenyl-naphthylamine, alkylated-naphthylamine, and alkylated
phenyl-naphthylamine. The diarylamine oxidation inhibitors can have
from 1 to 3 alkyl groups.
[0079] 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).
[0080] 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.
[0081] 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.
[0082] 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
[0083] 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 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 compounds or any solid additives in the base oil may be
assisted by heating the mixture to a temperature from about
25.degree. C. to about 200.degree. C., from about 50.degree. C. to
about 150.degree. C. or from about 75.degree. C. to about
125.degree. C.
[0084] 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
[0085] 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.
[0086] 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 scope of the invention. Specific details
described in each example should not be construed as necessary
features of the invention.
EXAMPLES
[0087] The following examples are intended for illustrative
purposes only and do not limit in any way the scope of the present
invention.
[0088] The test compounds were blended in lube oil and their
capacity for reducing LSPI events were determined using the test
method described below.
[0089] Low Speed Pre-ignition events were measured in a Ford 2.0 L
Ecoboost engine. This engine is a turbocharged gasoline direct
injection (GDI) 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.degree. C. The engine is run for 175,000
combustion cycles in each stage, and LSPI events are counted.
[0090] 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
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.
[0091] 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.
Baseline Formulation
[0092] 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
succinimide complex, an alkylated diphenylamine antioxidant, a
borated friction modifier, a foam inhibitor, a pour point
depressant, and an olefin copolymer viscosity index improver.
[0093] The lubricating oil compositions were blended into a 5W-30
viscosity grade oil.
Metal or metalloid hydrogen atom donor Compound A
(Triphenylsilane)
[0094] Triphenylsilane was commercially available from Millipore
Sigma.RTM. or Gelest.RTM..
Metal or metalloid hydrogen atom donor Compound B
(Tributylgermane)
[0095] Tributylgermane was commercially available from Millipore
Sigma.RTM..
Example 1
[0096] 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
[0097] 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
[0098] 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-US-00001 TABLE 1 LSPI Test Results in Ford LSPI Test % %
Reduc- Reduc- tion tion in LSPI in LSPI Comp. activity Ex. activity
Ex. 1 Ex. 1 Ex 1 2 Ex 2 Si (ppm) from 454 0 NA 0 NA compound A Ca
(ppm) 2164 2255 NA 2204 NA Ge (ppm) from 0 0 NA 1483 NA compound B
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 met.
[0099] 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.
* * * * *