U.S. patent application number 17/185614 was filed with the patent office on 2021-12-02 for use of zirconium compound to improve low speed pre-ignition performance.
This patent application is currently assigned to Afton Chemical Corporation. The applicant listed for this patent is Afton Chemical Corporation. Invention is credited to Ashutosh Gupta, Joseph Remias, Joseph W. Roos.
Application Number | 20210371765 17/185614 |
Document ID | / |
Family ID | 1000005463021 |
Filed Date | 2021-12-02 |
United States Patent
Application |
20210371765 |
Kind Code |
A1 |
Remias; Joseph ; et
al. |
December 2, 2021 |
USE OF ZIRCONIUM COMPOUND TO IMPROVE LOW SPEED PRE-IGNITION
PERFORMANCE
Abstract
A lubricating oil composition, and a method of reducing LSPI
events employing the lubricating oil composition, including a base
oil of lubricating viscosity, and an additive composition
including: one or more overbased calcium-containing detergent(s)
sufficient to provide at least 500 ppmw of calcium, and a
zirconium-containing nanoparticle(s) and/or one or more
zirconium-containing compound(s) sufficient to provide greater than
0 ppmw to 6000 ppmw of zirconium, wherein the nanoparticles have a
size of from 1 to 500 nm, as measured by Dynamic Light Scattering,
an amount of one or more molybdenum-containing compound present in
an amount sufficient to provide no greater than 100 ppmw of
molybdenum, and wherein the additive composition has a weight ratio
of ppmw of zirconium provided by the zirconium-containing
nanoparticle(s) and/or the one or more zirconium-containing
compound(s) to the ppmw of calcium provided by the one or more
overbased-calcium-containing detergent(s) of greater than about
0.01 to less than 5.
Inventors: |
Remias; Joseph; (Glen Allen,
VA) ; Gupta; Ashutosh; (Richmond, VA) ; Roos;
Joseph W.; (Mechanicsville, VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Afton Chemical Corporation |
Richmond |
VA |
US |
|
|
Assignee: |
Afton Chemical Corporation
Richmond
VA
|
Family ID: |
1000005463021 |
Appl. No.: |
17/185614 |
Filed: |
February 25, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2010/04 20130101;
C10M 141/10 20130101; C10N 2030/04 20130101; C10N 2030/45 20200501;
C10N 2010/08 20130101; C10N 2030/52 20200501; C10N 2040/25
20130101; C10M 125/10 20130101; C10N 2030/02 20130101; C10M 137/06
20130101; C10M 159/24 20130101; C10N 2010/12 20130101; C10N 2020/06
20130101 |
International
Class: |
C10M 141/10 20060101
C10M141/10; C10M 137/06 20060101 C10M137/06; C10M 159/24 20060101
C10M159/24; C10M 125/10 20060101 C10M125/10 |
Claims
1. A lubricating oil composition comprising: greater than 50 wt. %
of a base oil of lubricating viscosity, and an additive composition
comprising: an amount of one or more overbased calcium-containing
detergent(s) having a total base number of greater than 225 mg
KOH/g, measured by the method of ASTM D-2896 sufficient to provide
at least 500 ppmw of calcium to the lubricating oil composition,
based on a total weight of the lubricating oil composition, and an
amount of zirconium-containing nanoparticle(s) and/or one or more
zirconium-containing compound(s) sufficient to provide greater than
0 ppmw to 6000 ppmw of zirconium to the lubricating oil
composition, based on the total weight of the lubricating oil
composition, wherein the nanoparticles have a size of from 1 to 500
nm, as measured by Dynamic Light Scattering, an amount of one or
more molybdenum-containing compound present in an amount sufficient
to provide no greater than 100 ppmw of molybdenum, based on a total
weight of the lubricating oil composition, and wherein the additive
composition has a weight ratio of ppmw of zirconium provided by the
zirconium-containing nanoparticle(s) and/or the one or more
zirconium-containing compound(s) to the ppmw of calcium provided by
the one or more overbased-calcium-containing detergent(s) of
greater than about 0.01 to less than 5; from about 600 ppmw to
about1000 ppmw of phosphorus, based on the total weight of the
lubricating oil composition; and a total sulfated ash content of no
greater than 1.5 wt. %, as measured by ASTM D874, based on the
total weight of the lubricating oil composition.
2. The lubricating oil composition of claim 1, wherein the
lubricating oil composition is effective to reduce low speed
pre-ignition events in a boosted internal combustion engine
lubricated with the lubricating oil composition relative to a
number of low speed pre-ignition events in the same engine
lubricated with reference lubricating oil R-1; or the reduction of
LSPI events is 50% or greater reduction and the LSPI events are
LSPI counts during 25,000 engine cycles, wherein the engine is
operated at 2000 revolutions per minute with brake mean effective
pressure of 1,800 kPa, wherein R-1 is formulated from about 80.7
wt. % of a Group III base oil, 12.1 wt. % of passenger car motor
oil additive package and 7.2 wt. % of a 35 SSI ethylene/propylene
copolymer viscosity index improver, wherein the passenger car motor
oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5
qualified DI package and R-1 also showed the following properties
and partial elemental analysis: TABLE-US-00011 10.9 Kinematic
Viscosity at 100.degree. C., (mm.sup.2/sec) 3.3 HTHS at 150.degree.
C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum
(ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number
ASTM D-2896 (mg KOH/g) 165 Viscosity Index
3. The lubricating oil composition of claim 1, wherein the one or
more overbased calcium-containing detergent(s) has a total base
number of greater than 250 mg KOH/g or more as measured by the
method of ASTM D-2896.
4. The lubricating oil composition of claim 1, wherein the weight
ratio of the ppmw of zirconium provided by the zirconium-containing
nanoparticles and/or one or more zirconium-containing compound(s)
to the ppmw of calcium provided by the one or more overbased
calcium-containing detergent(s) is from 0.02 to 4.
5. The lubricating oil composition of claim 1, wherein the
lubricating oil composition contains greater than 1 ppmw of boron
based on the total weight of the lubricating oil composition; or
wherein the one or more overbased calcium-containing detergent(s)
is present in an amount to provide at least 600 ppmw of calcium to
less than 3000 ppmw calcium to the lubricating oil composition,
based on the total weight of the lubricating oil composition.
6. The lubricating oil composition of claim 1, wherein the
zirconium-containing nanoparticle(s) and/or one or more
zirconium-containing compound(s) is present in an amount to provide
at least 5 ppmw zirconium to the lubricating oil composition, based
on the total weight of the lubricating oil composition.
7. The lubricating oil composition of claim 1, further comprising
one or more magnesium-containing detergents present in an amount
sufficient to provide greater than 500 ppmw to less 1000 ppmw of
magnesium to the lubricating oil composition, based on the total
weight of the lubricating oil composition; or wherein the one or
more magnesium-containing detergents comprises an overbased
magnesium sulfonate detergent having a total base number of greater
than 225 mg KOH/g, as measured by the method of ASTM D-2896.
8. The lubricating oil composition of claim 1, wherein the one or
more zirconium-containing compound(s) is selected from zirconium
(IV) oxides, zirconium (IV) sulfides, zirconium (IV) nitrates,
zirconium (IV) alkoxides, zirconium phenates, zirconium
carboxylates, zirconium salicylates, zirconium sulfonates,
zirconium halides, and mixtures thereof.
9. The lubricating oil composition of claim 8, wherein the one or
more zirconium-containing compound(s) is a zirconium carboxylate,
wherein the carboxylate group comprising from 3 to 20 carbon
atoms.
10. The lubricating oil composition of claim 9, wherein the
zirconium carboxylate is selected from the group consisting of
zirconium 2-ethylhexanoate, zirconium isooctanoate, zirconium
isononanoate, zirconium isobutyrate, zirconium neopentanoate,
zirconium neooctanoate, zirconium neononanoate, zirconium
neodecanoate, and zirconium naphthenate; or wherein the one or more
zirconium-containing compound(s) comprises an organometallic
zirconium compound; or wherein the lubricating oil composition
comprising an amount of zirconium-containing nanoparticles.
11. The lubricating oil composition of claim 1, wherein the
lubricating oil composition is an engine oil composition.
12. A method for reducing low-speed pre-ignition events in a
boosted internal combustion engine comprising: lubricating a
boosted internal combustion engine with a lubricating oil
composition comprising greater than 50 wt. % of a base oil of
lubricating viscosity and an additive composition comprising an
amount of one or more overbased calcium-containing detergent(s)
having a total base number of greater than 225 mg KOH/g, measured
by the method of ASTM D-2896 sufficient to provide at least 500
ppmw calcium to the lubricating oil composition, based on a total
weight of the lubricating oil composition, and an amount of one or
more zirconium-containing nanoparticles(s) and/or
zirconium-containing compounds sufficient to provide greater than 0
ppmw to 6000 ppmw of zirconium to the lubricating oil composition,
based on the total weight of the lubricating oil composition,
wherein the nanoparticles have a size of from 1 to 500 nm, as
measured by Dynamic Light Scattering, at least one
molybdenum-containing compound present in an amount sufficient to
provide no greater than 100 ppmw of molybdenum, based on a total
weight of the lubricating oil composition, and wherein the additive
composition has a weight ratio of the ppmw of zirconium provided by
the zirconium-containing nanoparticles and/or one or more
zirconium-containing compound(s) to the ppmw of calcium provided by
the one or more overbased calcium-containing detergent(s) of
greater than about 0.01 to less than 5, and the lubricating oil
composition contains from about 600 ppmw to about 1000 ppmw of
phosphorus, based on the total weight of the lubricating oil
composition; and a total sulfated ash content of no greater than
1.5 wt. %, as measured by ASTM D874, based on the total weight of
the lubricating oil composition; and operating the engine
lubricated with the lubricating oil composition.
13. The method of claim 12, wherein the method is effective to
reduce low speed pre-ignition events in a boosted internal
combustion engine lubricated with the lubricating oil composition
relative to a number of low speed pre-ignition events in the same
engine lubricated with reference lubricating oil R-1; or the
reduction of LSPI events is 50% or greater reduction and the LSPI
events are LSPI counts during 25,000 engine cycles, wherein the
engine is operated at 2,000 revolutions per minute with brake mean
effective pressure of 1,800 kPa, wherein R-1 is formulated from
about 80.7 wt. % of a Group III base oil, 12.1 wt. % of passenger
car motor oil additive package and 7.2 wt. % of a 35 SSI
ethylene/propylene copolymer viscosity index improver, wherein the
passenger car motor oil additive package is an API SN, ILSAC-GF-5,
and ACEA A5/B5 qualified DI package and R-1 also showed the
following properties and partial elemental analysis: TABLE-US-00012
10.9 Kinematic Viscosity at 100.degree. C., (mm.sup.2/sec) 3.3 HTHS
at 150.degree. C., (cP) 2438 calcium (ppmw) <10 magnesium (ppmw)
80 molybdenum (ppmw) 772 phosphorus (ppmw) 855 zinc (ppmw) 9.0
Total Base Number ASTM D-2896 (mg KOH/g) 165 Viscosity Index
14. The method of claim 12, wherein the one or more overbased
calcium-containing detergent(s) has a total base number of greater
than 250 mg KOH/g or more as measured by the method of ASTM
D-2896.
15. The method of claim 12, wherein the weight ratio of the ppmw of
zirconium provided by the zirconium-containing nanoparticles and/or
one or more zirconium-containing compound(s) to the ppmw of calcium
provided by the one or more overbased calcium-containing
detergent(s) is from 0.02 to 4.
16. The method of claim 12, wherein the lubricating oil composition
contains greater than 1 ppmw of boron based on the total weight of
the lubricating oil composition; or wherein the one or more
overbased calcium-containing detergent(s) is present in an amount
to provide at least 600 ppmw of calcium to less than 3000 ppmw
calcium to the lubricating oil composition, based on the total
weight of the lubricating oil composition.
17. The method of claim 12, wherein the zirconium-containing
nanoparticles and/or the one or more zirconium-containing
compound(s) is present in an amount to provide at least 5 ppmw
zirconium to the lubricating oil composition, based on the total
weight of the lubricating oil composition.
18. The method of claim 12, further comprising one or more
magnesium-containing detergents present in an amount sufficient to
provide greater than 500 ppmw to less 1000 ppmw magnesium to the
lubricating oil composition, based on the total weight of the
lubricating oil composition; or wherein the one or more
magnesium-containing detergents comprises an overbased magnesium
sulfonate detergent having a total base number of greater than 225
mg KOH/g, as measured by the method of ASTM D-2896.
19. The method of claim 12, wherein the one or more
zirconium-containing compound(s) is selected from zirconium (IV)
oxides, zirconium (IV) sulfides, zirconium (IV) nitrates, zirconium
(IV) alkoxides, zirconium phenates, zirconium carboxylates,
zirconium salicylates, zirconium sulfonates, zirconium halides, and
mixtures thereof; or wherein the one or more zirconium-containing
compound(s) comprises an organometallic zirconium compound or
zirconium nanoparticles.
20. The method of claim 12, wherein the lubricating oil composition
is an engine oil composition.
Description
TECHNICAL FIELD
[0001] The disclosure relates to lubricating oil compositions for
reducing low-speed pre-ignition (LSPI) events in a boosted internal
combustion engine. More specifically, the disclosure relates to a
lubricating oil composition comprising an additive composition
including an amount of one or more overbased calcium-containing
detergent(s), and an amount of zirconium-containing nanoparticles
and/or one or more zirconium-containing compound(s).
BACKGROUND
[0002] Boosted spark-ignited internal combustions engines such as
turbocharged or supercharged internal combustion engines may
exhibit an abnormal combustion phenomenon known as stochastic
pre-ignition or low-speed pre-ignition (or "LSPI"). LSPI is a
pre-ignition event that may include very high pressure spikes,
early combustion during an inappropriate crank angle, and knock.
All of these, individually and in combination, have the potential
to cause degradation and/or severe damage to the engine.
[0003] Pre-ignition is a form of combustion that results in
ignition in the combustion chamber prior to the desired ignition of
the air-fuel mixture by the igniter. Pre-ignition has typically
been a problem during high speed engine operation since heat from
operation of the engine may heat a part of the combustion chamber
to a sufficient temperature to ignite the air-fuel mixture upon
contact. This type of pre-ignition is sometimes referred to as
hot-spot pre-ignition.
[0004] More recently, intermittent abnormal combustion has been
observed in boosted internal combustion engines at low speeds and
medium-to-high loads. For example, during operation of the engine
at 3,000 rpm or less, under load, with a brake mean effective
pressure (BMEP) of at least 1,000 kPa, low-speed pre-ignition
(LSPI) may occur in a random and stochastic fashion. During low
speed engine operation, the compression stroke time is longest.
[0005] International Publication no. WO 2017/147380 A1 relates to
lubricating oil compositions comprising an oil soluble metal
compound, wherein the metal of the oil soluble metal compound may
be a group (IV) metal for reducing low speed pre-ignition events in
a spark-ignited direct injection internal combustion engine. WO
2017/147380 A1 exemplifies lubricating oil compositions containing
titanium.
SUMMARY AND TERMS
[0006] The disclosure relates to a lubricating oil composition
including greater than 50 wt. % of a base oil of lubricating
viscosity, and an additive composition including one or more
overbased calcium-containing detergent(s) and zirconium-containing
nanoparticles and/or one or more zirconium-containing
compound(s).
[0007] The following sentences describe some embodiments of the
invention.
[0008] 1. In a first aspect, the present invention relates to a
lubricating oil composition comprising: [0009] greater than 50 wt.
% of a base oil of lubricating viscosity, and
[0010] an additive composition comprising: [0011] an amount of one
or more overbased calcium-containing detergent(s) having a total
base number of greater than 225 mg KOH/g, measured by the method of
ASTM D-2896 sufficient to provide at least 500 ppmw of calcium to
the lubricating oil composition, based on a total weight of the
lubricating oil composition, and [0012] an amount of
zirconium-containing nanoparticle(s) and/or one or more
zirconium-containing compound(s) sufficient to provide greater than
0 ppmw to 6000 ppmw of zirconium to the lubricating oil
composition, based on the total weight of the lubricating oil
composition, wherein the nanoparticles have a size of from 1 to 500
nm, as measured by Dynamic Light Scattering, [0013] an amount of
one or more molybdenum-containing compound present in an amount
sufficient to provide no greater than 100 ppmw of molybdenum, based
on a total weight of the lubricating oil composition, and [0014]
wherein the additive composition has a weight ratio of ppmw of
zirconium provided by the zirconium-containing nanoparticle(s)
and/or the one or more zirconium-containing compound(s) to the ppmw
of calcium provided by the one or more overbased-calcium-containing
detergent(s) of greater than about 0.01 to less than 5; from about
600 ppmw to about 1000 ppmw of phosphorus, based on the total
weight of the lubricating oil composition; and a total sulfated ash
content of no greater than 1.5 wt. %, as measured by ASTM D874,
based on the total weight of the lubricating oil composition.
[0015] 2. The lubricating oil composition of sentence 1, wherein
the lubricating oil composition may be effective to reduce low
speed pre-ignition events in a boosted internal combustion engine
lubricated with the lubricating oil composition relative to a
number of low speed pre-ignition events in the same engine
lubricated with reference lubricating oil R-1; or the reduction of
LSPI events is 50% or greater reduction and the LSPI events are
LSPI counts during 25,000 engine cycles, wherein the engine is
operated at 2000 revolutions per minute with brake mean effective
pressure of 1,800 kPa, [0016] wherein R-1 is formulated from about
80.7 wt. % of a Group III base oil, 12.1 wt. % of passenger car
motor oil additive package and 7.2 wt. % of a 35 SSI
ethylene/propylene copolymer viscosity index improver, wherein the
passenger car motor oil additive package is an API SN, ILSAC-GF-5,
and ACEA A5/B5 qualified DI package and R-1 also showed the
following properties and partial elemental analysis:
TABLE-US-00001 [0016] 10.9 Kinematic Viscosity at 100.degree. C.,
(mm.sup.2/sec) 3.3 HTHS at 150.degree. C., (cP) 2438 calcium (ppmw)
<10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw)
855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165
Viscosity Index
[0017] 3. The lubricating oil composition of any one of sentences
1-2, wherein the one or more overbased calcium-containing
detergent(s) may have a total base number of greater than 250 mg
KOH/g or more as measured by the method of ASTM D-2896. [0018] 4.
The lubricating oil composition of any one of sentences 1-3,
wherein the weight ratio of the ppmw of zirconium provided by the
zirconium-containing nanoparticles and/or one or more
zirconium-containing compound(s) to the ppmw of calcium provided by
the one or more overbased calcium-containing detergent(s) may be
from 0.02 to 4, or from 0.03 to 3, or from 0.04 to 2.75. [0019] 5.
The lubricating oil composition of any one of sentences 1-4,
wherein the lubricating oil composition may contain greater than 1
ppmw of boron, or greater than 5 ppmw of boron, or greater than 10
ppmw of boron, or greater than 30 ppmw of boron to the lubricating
oil composition, based on the total weight of the lubricating oil
composition. [0020] 6. The lubricating oil composition of any one
of sentences 1-5, wherein the one or more overbased
calcium-containing detergent(s) may be present in an amount to
provide at least 600 ppmw of calcium to less than 3000 ppmw
calcium, or from 700 ppmw of calcium to less than 2800 ppmw of
calcium, or from 800 ppmw of calcium to less than 2500 ppmw of
calcium, or from 2000 ppmw of calcium to 3500 ppmw of calcium, or
from 2100 ppmw of calcium to 3500 ppmw of calcium, or from 2100
ppmw of calcium to 3100 ppmw of calcium to the lubricating oil
composition, based on the total weight of the lubricating oil
composition. [0021] 7. The lubricating oil composition of any one
of sentences 1-6, wherein the zirconium-containing nanoparticle(s)
and/or one or more zirconium-containing compound(s) may be present
in an amount to provide at least 5 ppmw zirconium, or at least 50
ppmw zirconium, or at least 75 ppmw zirconium, or from 75 ppmw
zirconium to less than 2400 ppmw zirconium, or from 200 ppmw
zirconium to less than 2400 ppmw zirconium, or from 400 ppmw
zirconium to less than 2000 ppmw zirconium to the lubricating oil
composition, based on the total weight of the lubricating oil
composition. [0022] 8. The lubricating oil composition of any one
of sentences 1-7, may further comprise one or more
magnesium-containing detergents present in an amount sufficient to
provide greater than 500 ppmw to less 1000 ppmw of magnesium to the
lubricating oil composition, based on the total weight of the
lubricating oil composition. [0023] 9. The lubricating oil
composition of sentence 8, wherein the one or more
magnesium-containing detergents may comprise an overbased magnesium
sulfonate detergent having a total base number of greater than 225
mg KOH/g, as measured by the method of ASTM D-2896. [0024] 10. The
lubricating oil composition of any one of sentences 1-9, wherein
the one or more zirconium-containing compound(s) may be selected
from zirconium (IV) oxides, zirconium (IV) sulfides, zirconium (IV)
nitrates, zirconium (IV) alkoxides, zirconium phenates, zirconium
carboxylates, zirconium salicylates, zirconium sulfonates,
zirconium halides, and mixtures thereof. [0025] 11. The lubricating
oil composition of sentence 10, wherein the one or more
zirconium-containing compound(s) may be a zirconium carboxylate,
wherein the carboxylate group comprising from 3 to 20 carbon atoms,
or from 4 to 15 carbon atoms, or from 6 to 10 carbon atoms. [0026]
12. The lubricating oil composition of sentence 11, wherein the
zirconium carboxylate may be selected from the group consisting of
zirconium 2-ethylhexanoate, zirconium isooctanoate, zirconium
isononanoate, zirconium isobutyrate, zirconium neopentanoate,
zirconium neooctanoate, zirconium neononanoate, zirconium
neodecanoate, and zirconium naphthenate. [0027] 13. The lubricating
oil composition of any one of sentences 1-9, wherein the one or
more zirconium-containing compound(s) may comprise an
organometallic zirconium compound. [0028] 14. The lubricating oil
composition of any one of sentences 1-9, wherein the lubricating
oil composition may comprise an amount of zirconium-containing
nanoparticles. [0029] 15. The lubricating oil compositions of
sentence 14, wherein the zirconium-containing nanoparticles may be
zirconium dioxide. [0030] 16. The lubricating oil composition of
any one of sentences 1-15, wherein the total sulfated ash content
is less than 1.2 wt. %, or less than 1.0 wt. %, or less than 0.8
wt. %, or more than 0.5 wt. % to less than 0.8 wt. % or more than
0.6 wt. % to less than 0.8 wt. %, each as measured by ASTM D874.
[0031] 17. The lubricating oil composition of any one of sentences
1-16, wherein the additive composition may provide from about less
than 900 ppmw of phosphorus, or less than 800 ppmw of phosphorus,
based on the total weight of the lubricating oil composition.
[0032] 18. The lubricating oil composition of any one of sentences
1-17, wherein the lubricating oil composition may be an engine oil
composition. [0033] 19. In a second aspect, the present invention
relates to methods for reducing low-speed pre-ignition events in a
boosted internal combustion engine comprising:
[0034] lubricating a boosted internal combustion engine with a
lubricating oil composition comprising greater than 50 wt. % of a
base oil of lubricating viscosity and an additive composition
comprising
[0035] an amount of one or more overbased calcium-containing
detergent(s) having a total base number of greater than 225 mg
KOH/g, measured by the method of ASTM D-2896 sufficient to provide
at least 500 ppmw of calcium to the lubricating oil composition,
based on a total weight of the lubricating oil composition, and
[0036] an amount of one or more zirconium-containing
nanoparticles(s) and/or zirconium-containing compounds sufficient
to provide greater than 0 ppmw to 6000 ppmw of zirconium to the
lubricating oil composition, based on the total weight of the
lubricating oil composition, wherein the nanoparticles have a size
of from 1 to 500 nm, as measured by Dynamic Light Scattering,
[0037] at least one molybdenum-containing compound present in an
amount sufficient to provide no greater than 100 ppmw of
molybdenum, based on a total weight of the lubricating oil
composition, and
[0038] wherein the additive composition has a weight ratio of the
ppmw of zirconium provided by the zirconium-containing
nanoparticles and/or one or more zirconium-containing compound(s)
to the ppmw of calcium provided by the one or more overbased
calcium-containing detergent(s) of greater than about 0.01 to less
than 5, and
[0039] the lubricating oil composition contains from about 600 ppmw
to about 1000 ppmw of phosphorus, based on the total weight of the
lubricating oil composition; and a total sulfated ash content of no
greater than 1.5 wt. %, as measured by ASTM D874, based on the
total weight of the lubricating oil composition; and
[0040] operating the engine lubricated with the lubricating oil
composition. [0041] 20. The method of sentence 19, wherein the
method may be effective to reduce low speed pre-ignition events in
a boosted internal combustion engine lubricated with the
lubricating oil composition relative to a number of low speed
pre-ignition events in the same engine lubricated with reference
lubricating oil R-1; or the reduction of LSPI events is 50% or
greater reduction and the LSPI events are LSPI counts during 25,000
engine cycles, wherein the engine is operated at 2,000 revolutions
per minute with brake mean effective pressure of 1,800 kPa,
[0042] wherein R-1 is formulated from about 80.7 wt. % of a Group
III base oil, 12.1 wt. % of passenger car motor oil additive
package and 7.2 wt. % of a 35 SSI ethylene/propylene copolymer
viscosity index improver, wherein the passenger car motor oil
additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified
DI package and R-1 also showed the following properties and partial
elemental analysis:
TABLE-US-00002 10.9 Kinematic Viscosity at 100.degree. C.,
(mm.sup.2/sec) 3.3 HTHS at 150.degree. C., (cP) 2438 calcium (ppmw)
<10 magnesium (ppmw) 80 molybdenum (ppmw) 772 phosphorus (ppmw)
855 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g) 165
Viscosity Index
[0043] 21. The method of any one of sentences 19-20, wherein the
one or more overbased calcium-containing detergent(s) may have a
total base number of greater than 250 mg KOH/g or more as measured
by the method of ASTM D-2896. [0044] 22. The method of any one of
sentences 19-21, wherein the weight ratio of the ppmw of zirconium
provided by the zirconium-containing nanoparticles and/or one or
more zirconium-containing compound(s) to the ppmw of calcium
provided by the one or more overbased calcium-containing
detergent(s) may be from 0.02 to 4, or from 0.03 to 3, or from 0.04
to 2.75. [0045] 23. The method of any one of sentences 19-22,
wherein the lubricating oil composition contains greater than 1
ppmw of boron, or greater than 5 ppmw of boron, or greater than 10
ppmw of boron, or greater than 30 ppmw of boron to the lubricating
oil composition, based on the total weight of the lubricating oil
composition. [0046] 24. The method of any one of sentences 19-23,
wherein the one or more overbased calcium-containing detergent(s)
may be present in an amount to provide at least 600 ppmw of calcium
to less than 3000 ppmw calcium, or from 700 ppmw of calcium to less
than 2800 ppmw of calcium, or from 800 ppmw of calcium to less than
2500 ppmw of calcium, or from 2000 ppmw of calcium to 3500 ppmw of
calcium, or from 2100 ppmw of calcium to 3500 ppmw of calcium, or
from 2100 ppmw of calcium to 3100 ppmw of calcium to the
lubricating oil composition, based on the total weight of the
lubricating oil composition. [0047] 25. The method of any one of
sentences 19-24, wherein the one or more zirconium-containing
nanoparticle(s) and/or the one or more zirconium-containing
compound(s) may be present in an amount to provide at least 5 ppmw
zirconium or at least 50 ppmw zirconium or at least 75 ppmw
zirconium, or from 75 ppmw zirconium to less than 2400 ppmw
zirconium, or from 200 ppmw zirconium to less than 2400 ppmw
zirconium, or from 400 ppmw zirconium to less than 2000 ppmw
zirconium to the lubricating oil composition, based on the total
weight of the lubricating oil composition. [0048] 26. The method of
any one of sentences 19-25, may further comprise one or more
magnesium-containing detergents present in an amount sufficient to
provide greater than 500 ppmw to less 1000 ppmw of magnesium to the
lubricating oil composition, based on the total weight of the
lubricating oil composition. [0049] 27. The method of sentence 26,
wherein the one or more magnesium-containing detergents may include
an overbased magnesium sulfonate detergent having a total base
number of greater than 225 mg KOH/g, as measured by the method of
ASTM D-2896. [0050] 28. The method of any one of sentences 19-27,
wherein the one or more zirconium-containing compound(s) may be
selected from zirconium (IV) oxides, zirconium (IV) sulfides,
zirconium (IV) nitrates, zirconium (IV) alkoxides, zirconium
phenates, zirconium carboxylates, zirconium salicylates, zirconium
sulfonates, zirconium halides, and mixtures thereof. [0051] 29. The
method of sentence 28, wherein the one or more zirconium-containing
compound(s) may be a zirconium carboxylate, wherein the carboxylate
group comprising from 3 to 20 carbon atoms, or from 4 to 15 carbon
atoms, or from 6 to 10 carbon atoms. [0052] 30. The method of
sentence 29, wherein the zirconium carboxylate may be selected from
the group consisting of zirconium 2-ethylhexanoate, zirconium
isooctanoate, zirconium isononanoate, zirconium isobutyrate,
zirconium neopentanoate, zirconium neooctanoate, zirconium
neononanoate, zirconium neodecanoate, and zirconium naphthenate.
[0053] 31. The method of any one of sentences 19-27, wherein the
one or more zirconium-containing compound(s) may include an
organometallic zirconium compound or zirconium nanoparticles.
[0054] 32. The method of any one of sentences 19-31, wherein the
total sulfated ash content may be less than 1.2 wt. %, or less than
1.0 wt. %, or less than 0.8 wt. %, or more than 0.5 wt. % to less
than 0.8 wt. % or more than 0.6 wt. % to less than 0.8 wt. %, each
as measured by ASTM D874. [0055] 33. The method of any one of
sentences 19-32, wherein the lubricating oil composition may be an
engine oil composition. [0056] 34. The method of any one of
sentences 19-33, wherein the additive composition may provide from
about less than 900 ppmw of phosphorus, or less than 800 ppmw of
phosphorus, based on the total weight of the lubricating oil
composition. [0057] 35. The lubricating oil of any one of sentences
1-18, wherein the maximum total metal from the zirconium provided
by the zirconium-containing nanoparticles and/or one or more
zirconium-containing compound(s) and calcium provided by the one or
more overbased calcium-containing detergent is less than 7545 ppmw;
or is up to 7510 ppmw; or is at least 950 ppmw to less than 7545
ppmw; or is at least 2350 ppmw to less than 7545 ppmw. [0058] 36.
The method of any one of sentences 19-34, wherein the maximum total
metal from the zirconium provided by the zirconium-containing
nanoparticles and/or one or more zirconium-containing compound(s)
and calcium provided by the one or more overbased
calcium-containing detergent is less than 7545 ppmw; or is up to
7510 ppmw; or is at least 950 ppmw to less than 7545 ppmw; or is at
least 2350 ppmw to less than 7545 ppmw. [0059] 37. The lubricating
oil of any one of sentences 1 18 and 35, wherein the one or more
molybdenum-containing compounds is present in an amount sufficient
to contribute no greater than 80 ppmw molybdenum, or no greater
than 50 ppmw molybdenum, or no greater than 20 ppmw molybdenum, or
no greater than 15 ppmw, or greater than 0 ppmw molybdenum, or
greater than 5 ppmw molybdenum, or combinations thereof, based on
the total weight of the lubricating oil composition. [0060] 38. The
method of any one of sentences 19 34 and 36, wherein the at least
one molybdenum-containing compounds is present in an amount
sufficient to contribute no greater than 80 ppmw molybdenum, or no
greater than 50 ppmw molybdenum, or no greater than 20 ppmw
molybdenum, or no greater than 15 ppmw, or greater than 0 ppmw
molybdenum, or greater than 5 ppmw molybdenum, or combinations
thereof, based on the total weight of the lubricating oil
composition.
[0061] The following definitions of terms are provided in order to
clarify the meanings of certain terms as used herein.
[0062] The terms "oil composition," "lubrication composition,"
"lubricating oil composition," "lubricating oil," "lubricant
composition," "lubricating composition," "fully formulated
lubricant composition," "lubricant," "crankcase oil," "crankcase
lubricant," "engine oil," "engine lubricant," "motor oil," and
"motor lubricant" are considered synonymous, fully interchangeable
terminology referring to the finished lubrication product
comprising a major amount of a base oil plus a minor amount of an
additive composition.
[0063] As used herein, the terms "additive package," "additive
concentrate," "additive composition," "engine oil additive
package," "engine oil additive concentrate," "crankcase additive
package," "crankcase additive concentrate," "motor oil additive
package," "motor oil concentrate," are considered synonymous, fully
interchangeable terminology referring the portion of the
lubricating oil composition excluding the major amount of base oil
stock mixture. The additive package may or may not include the
viscosity index improver or pour point depressant.
[0064] The term "overbased" relates to metal salts, such as metal
salts of sulfonates, carboxylates, salicylates, and/or phenates,
wherein the amount of metal present exceeds the stoichiometric
amount. Such salts may have a conversion level in excess of 100%
(i.e., they may comprise more than 100% of the theoretical amount
of metal needed to convert the acid to its "normal," "neutral"
salt). The expression "metal ratio," often abbreviated as MR, is
used to designate the ratio of total chemical equivalents of metal
in the overbased salt to chemical equivalents of the metal in a
neutral salt according to known chemical reactivity and
stoichiometry. In a normal or neutral salt, the metal ratio is one
and in an overbased salt, MR, is greater than one. They are
commonly referred to as overbased, hyperbased, or superbased salts
and may be salts of organic sulfur acids, carboxylic acids,
salicylates, and/or phenols.
[0065] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having a predominantly hydrocarbon character. Each
hydrocarbyl group is independently selected from hydrocarbon
substituents, and substituted hydrocarbon substituents containing
one or more of halo groups, hydroxyl groups, alkoxy groups,
mercapto groups, nitro groups, nitroso groups, amino groups,
pyridyl groups, furyl groups, imidazolyl groups, oxygen and
nitrogen, and wherein no more than two non-hydrocarbon substituents
are present for every ten carbon atoms in the hydrocarbyl
group.
[0066] As used herein, the term "hydrocarbylene substituent" or
"hydrocarbylene group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group that is directly attached at two locations of the molecule
to the remainder of the molecule by a carbon atom and having
predominantly hydrocarbon character. Each hydrocarbylene group is
independently selected from divalent hydrocarbon substituents, and
substituted divalent hydrocarbon substituents containing halo
groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl
groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro
groups, nitroso groups, amino groups, pyridyl groups, furyl groups,
imidazolyl groups, oxygen and nitrogen, and wherein no more than
two non-hydrocarbon substituents is present for every ten carbon
atoms in the hydrocarbylene group.
[0067] As used herein, the term "percent by weight", unless
expressly stated otherwise, means the percentage the recited
component represents to the weight of the entire composition.
[0068] The terms "soluble," "oil-soluble," or "dispersible" used
herein may, but does not necessarily, indicate that the compounds
or additives are soluble, dissolvable, miscible, or capable of
being suspended in the oil in all proportions. The foregoing terms
do mean, however, that they are, for instance, soluble,
suspendable, dissolvable, or stably dispersible in oil to an extent
sufficient to exert their intended effect in the environment in
which the oil is employed. Moreover, the additional incorporation
of other additives may also permit incorporation of higher levels
of a particular additive, if desired.
[0069] The term "TBN" as employed herein is used to denote the
Total Base Number in mg KOH/g as measured by the method of ASTM
D2896 or ASTM D4739 or DIN 51639-1.
[0070] The term "alkyl" as employed herein refers to straight,
branched, cyclic, and/or substituted saturated chain moieties of
from about 1 to about 100 carbon atoms.
[0071] The term "alkenyl" as employed herein refers to straight,
branched, cyclic, and/or substituted unsaturated chain moieties of
from about 3 to about 10 carbon atoms.
[0072] The term "aryl" as employed herein refers to single and
multi-ring aromatic compounds that may include alkyl, alkenyl,
alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or
heteroatoms including, but not limited to, nitrogen, oxygen, and
sulfur.
[0073] Lubricants, combinations of components, or individual
components of the present description may be suitable for use in
various types of internal combustion engines. Suitable engine types
may include, but are not limited to heavy duty diesel, passenger
car, light duty diesel, medium speed diesel, or marine engines. An
internal combustion engine may be a diesel fueled engine, a
gasoline fueled engine, a natural gas fueled engine, a bio-fueled
engine, a mixed diesel/biofuel fueled engine, a mixed
gasoline/biofuel fueled engine, an alcohol fueled engine, a mixed
gasoline/alcohol fueled engine, a compressed natural gas (CNG)
fueled engine, or mixtures thereof. A diesel engine may be a
compression ignited engine. A gasoline engine may be a
spark-ignited engine. An internal combustion engine may also be
used in combination with an electrical or battery source of power.
An engine so configured is commonly known as a hybrid engine. The
internal combustion engine may be a 2-stroke, 4-stroke, or rotary
engine. Suitable internal combustion engines include marine diesel
engines (such as inland marine), aviation piston engines, low-load
diesel engines, and motorcycle, automobile, locomotive, and truck
engines.
[0074] The internal combustion engine may contain components of one
or more of an aluminum-alloy, lead, tin, copper, cast iron,
magnesium, ceramics, stainless steel, composites, and/or mixtures
thereof. The components may be coated, for example, with a
diamond-like carbon coating, a lubrited coating, a
phosphorus-containing coating, molybdenum-containing coating, a
graphite coating, a nano-particle-containing coating, and/or
mixtures thereof. The aluminum-alloy may include aluminum
silicates, aluminum oxides, or other ceramic materials. In one
embodiment the aluminum-alloy is an aluminum-silicate surface. As
used herein, the term "aluminum alloy" is intended to be synonymous
with "aluminum composite" and to describe a component or surface
comprising aluminum and another component intermixed or reacted on
a microscopic or nearly microscopic level, regardless of the
detailed structure thereof. This would include any conventional
alloys with metals other than aluminum as well as composite or
alloy-like structures with non-metallic elements or compounds such
with ceramic-like materials.
[0075] The lubricating oil composition for an internal combustion
engine may be suitable for any engine lubricant irrespective of the
sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The
sulfur content of the engine oil lubricant may be about 1 wt % or
less, or about 0.8 wt % or less, or about 0.5 wt % or less, or
about 0.3 wt % or less, or about 0.2 wt % or less. In one
embodiment the sulfur content may be in the range of about 0.001 wt
% to about 0.5 wt %, or about 0.01 wt % to about 0.3 wt %. The
phosphorus content may be about 0.2 wt % or less, or about 0.1 wt %
or less, or about 0.085 wt % or less, or about 0.08 wt % or less,
or even about 0.06 wt % or less, about 0.055 wt % or less, or about
0.05 wt % or less. In one embodiment the phosphorus content may be
about 50 ppmw to about 1000 ppmw, or about 325 ppmw to about 850
ppmw. The total sulfated ash content may be about 1.5 wt % or less,
or about 1.2 wt % or less, or about 1.0 wt % or less, or about 0.8
wt % or less. In one embodiment the sulfated ash content may be
about 0.5 wt % to about 0.8 wt %, or more than 0.6 wt % to less
than 0.8 wt. %. In another embodiment, the sulfur content may be
about 0.4 wt % or less, the phosphorus content may be about 0.08 wt
% or less, and the sulfated ash is about 1 wt % or less. In yet
another embodiment the sulfur content may be about 0.3 wt % or
less, the phosphorus content is about 0.05 wt % or less, and the
sulfated ash may be about 0.8 wt % or less.
[0076] In one embodiment the lubricating oil composition is an
engine oil, wherein the lubricating oil composition may have (i) a
sulfur content of about 0.5 wt % or less, (ii) a phosphorus content
of about 0.1 wt % or less, and (iii) a sulfated ash content of
about 1.5 wt % or less.
[0077] In one embodiment the lubricating oil composition is
suitable for a 2-stroke or a 4-stroke marine diesel internal
combustion engine. In one embodiment the marine diesel combustion
engine is a 2-stroke engine. In some embodiments, the lubricating
oil composition is not suitable for a 2-stroke or a 4-stroke marine
diesel internal combustion engine for one or more reasons,
including but not limited to, the high sulfur content of fuel used
in powering a marine engine and the high TBN required for a
marine-suitable engine oil (e.g., above about 40 TBN in a
marine-suitable engine oil).
[0078] In some embodiments, the lubricating oil composition is
suitable for use with engines powered by low sulfur fuels, such as
fuels containing about 1 to about 5% sulfur. Highway vehicle fuels
contain about 15 ppmw sulfur (or about 0.0015% sulfur).
[0079] Low speed diesel typically refers to marine engines, medium
speed diesel typically refers to locomotives, and high speed diesel
typically refers to highway vehicles. The lubricating oil
composition may be suitable for only one of these types or all.
[0080] Further, lubricants of the present description may be
suitable to meet one or more industry specification requirements
such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4,
FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, ACEA A1/B1,
A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro
5/6,JASO DL-1, Low SAPS, Mid SAPS, or original equipment
manufacturer specifications such as DexosTM 1, DexosTM 2,
MB-Approval 229.1, 229.3, 229.5, 229.51/229.31, 229.52, 229.6,
229.71, 226.5, 226.51, 228.0/.1, 228.2/.3, 228.31, 228.5, 228.51,
228.61, VW 501.01, 502.00, 503.00/503.01, 504.00, 505.00, 505.01,
506.00/506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW
Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE,
Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen
Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71
2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700,
RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A,
WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D,
WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat
9.55535 G1, G2, M2, N1, N2, Z2, 51, S2, S3, S4, T2, DS1, DSX, GH2,
GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004,
STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122 or any
past or future PCMO or HDD specifications not mentioned herein. In
some embodiments for passenger car motor oil (PCMO) applications,
the amount of phosphorus in the finished fluid is 1000 ppmw or less
or 900 ppmw or less or 800 ppmw or less.
[0081] Other hardware may not be suitable for use with the
disclosed lubricant. A "functional fluid" is a term which
encompasses a variety of fluids including but not limited to
tractor hydraulic fluids, power transmission fluids including
automatic transmission fluids, continuously variable transmission
fluids and manual transmission fluids, hydraulic fluids, including
tractor hydraulic fluids, some gear oils, power steering fluids,
fluids used in wind turbines, compressors, some industrial fluids,
and fluids related to power train components. It should be noted
that within each of these fluids such as, for example, automatic
transmission fluids, there are a variety of different types of
fluids due to the various transmissions having different designs
which have led to the need for fluids of markedly different
functional characteristics. This is contrasted by the term
"lubricating fluid" which is not used to generate or transfer
power.
[0082] With respect to tractor hydraulic fluids, for example, these
fluids are all-purpose products used for all lubricant applications
in a tractor except for lubricating the engine. These lubricating
applications may include lubrication of gearboxes, power take-off
and clutch(es), rear axles, reduction gears, wet brakes, and
hydraulic accessories.
[0083] When the functional fluid is an automatic transmission
fluid, the automatic transmission fluids must have enough friction
for the clutch plates to transfer power. However, the friction
coefficient of fluids has a tendency to decline due to the
temperature effects as the fluid heats up during operation. It is
important that the tractor hydraulic fluid or automatic
transmission fluid maintain its high friction coefficient at
elevated temperatures, otherwise brake systems or automatic
transmissions may fail. This is not a function of an engine
oil.
[0084] Tractor fluids, and for example Super Tractor Universal Oils
(STUOs) or Universal Tractor Transmission Oils (UTTOs), may combine
the performance of engine oils with transmissions, differentials,
final-drive planetary gears, wet-brakes, and hydraulic performance
While many of the additives used to formulate a UTTO or a STUO
fluid are similar in functionality, they may have deleterious
effect if not incorporated properly. For example, some anti-wear
and extreme pressure additives used in engine oils can be extremely
corrosive to the copper components in hydraulic pumps. Detergents
and dispersants used for gasoline or diesel engine performance may
be detrimental to wet brake performance Friction modifiers specific
to quiet wet brake noise, may lack the thermal stability required
for engine oil performance Each of these fluids, whether
functional, tractor, or lubricating, are designed to meet specific
and stringent manufacturer requirements.
[0085] The present disclosure provides novel lubricating oil blends
formulated for use as automotive crankcase lubricants. The present
disclosure provides novel lubricating oil blends formulated for use
as 2T and/or 4T motorcycle crankcase lubricants. Embodiments of the
present disclosure may provide lubricating oils suitable for
crankcase applications and having improvements in the following
characteristics: air entrainment, alcohol fuel compatibility,
antioxidancy, antiwear performance, biofuel compatibility, foam
reducing properties, friction reduction, fuel economy, preignition
prevention, rust inhibition, sludge and/or soot dispersability,
piston cleanliness, deposit formation, and water tolerance.
[0086] Engine oils of the present disclosure may be formulated by
the addition of one or more additives, as described in detail
below, to an appropriate base oil formulation. The additives may be
combined with a base oil in the form of an additive package (or
concentrate) or, alternatively, may be combined individually with a
base oil (or a mixture of both). The fully formulated engine oil
may exhibit improved performance properties, based on the additives
added and their respective proportions.
[0087] Additional details and advantages of the disclosure will be
set forth in part in the description which follows, and/or may be
learned by practice of the disclosure. The details and advantages
of the disclosure may be realized and attained by means of the
elements and combinations particularly pointed out in the appended
claims. It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory only and are not restrictive of the disclosure, as
claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0088] FIG. 1 shows the LSPI test results for a lubricating oil
composition with varying zirconium to calcium weight ratios.
[0089] FIG. 2 shows the average LSPI frequency for a high-calcium
baseline engine oil formulation and another engine oil formulation
demonstrating that the addition of zirconia nanoparticles to a
high-calcium baseline engine oil formulation reduced the average
number of LSPI events.
DETAILED DESCRIPTION
[0090] Various embodiments of the disclosure provide a lubricating
oil composition and methods for reducing low speed pre-ignition.
The lubricating oil composition may be useful in compression
(diesel) engines and/or spark-ignited (gasoline) engines. In
particular, engines in which the lubricating oil composition may be
employed may include boosted internal combustion engines such as
turbocharged and supercharged internal combustion engines. The
boosted internal combustion engines include spark-ignited, direct
injection and/or port-fuel injection engines. Preferably, the
boosted internal combustion engine is a spark-ignited internal
combustion engine or a direct injection engine.
[0091] In one aspect, the disclosure relates to lubricating oil
compositions formulated for reducing the number of low speed
pre-ignition events in a boosted internal combustion engine
lubricated with the lubricating oil composition. The lubricating
oil composition includes:
[0092] greater than 50 wt. % of a base oil of lubricating
viscosity, and
[0093] an additive composition including:
[0094] an amount of one or more overbased calcium-containing
detergent(s) having a total base number of greater than 225 mg
KOH/g, measured by the method of ASTM D-2896 sufficient to provide
at least 500 ppmw calcium to the lubricating oil composition, based
on a total weight of the lubricating oil composition, and
[0095] an amount of zirconium nanoparticles and/or one or more
zirconium-containing compound(s) sufficient to provide greater than
0 ppmw to 6000 ppmw of zirconium to the lubricating oil
composition, based on the total weight of the lubricating oil
composition,
[0096] at least one of a molybdenum-containing compound present in
an amount sufficient to provide no greater than 100 ppmw of
molybdenum, based on a total weight of the lubricating oil
composition, and
[0097] wherein the additive composition has a weight ratio of ppmw
of zirconium provided by the one or more zirconium-containing
compound(s) to the ppmw of calcium provided by the one or more
overbased-calcium-containing detergent(s) of greater than about
0.01 to less than 5; from about 600 ppmw to about 1000 ppmw of
phosphorus, based on the total weight of the lubricating oil
composition; and a total sulfated ash content of no greater than
1.5 wt. %, as measured by ASTM D874, based on the total weight of
the lubricating oil composition.
[0098] The lubricating oil composition of the disclosure, including
the additive composition, can reduce the number of low speed
pre-ignition events in a boosted internal combustion engine
lubricated with the lubricating oil composition relative to a
number of low speed pre-ignition events in the same engine
lubricated with a same lubricating oil composition with reference
lubricating oil R-1, which the features of R-1 are discussed
below.
Base Oil
[0099] The base oil used in the lubricating oil compositions may be
selected from any of the base oils in Groups I-V as specified in
the American Petroleum Institute (API) Base Oil Interchangeability
Guidelines. The five base oil groups are as follows:
TABLE-US-00003 Base oil Saturates Viscosity Category Sulfur (%) (%)
Index Group I >0.03 and/or <90 80 to 120 Group II
.ltoreq.0.03 and .gtoreq.90 80 to 120 Group III .ltoreq.0.03 and
.gtoreq.90 .gtoreq.120 Group IV All polyalphaolefins (PAOs) Group V
All others not included in Groups I, II, III, or IV
[0100] Groups I, II, and III are mineral oil process stocks. Group
IV base oils contain true synthetic molecular species, which are
produced by polymerization of olefinically unsaturated
hydrocarbons. Many Group V base oils are also true synthetic
products and may include diesters, polyol esters, polyalkylene
glycols, alkylated aromatics, polyphosphate esters, polyvinyl
ethers, and/or polyphenyl ethers, and the like, but may also be
naturally occurring oils, such as vegetable oils. It should be
noted that although Group III base oils are derived from mineral
oil, the rigorous processing that these fluids undergo causes their
physical properties to be very similar to some true synthetics,
such as PAOs. Therefore, oils derived from Group III base oils may
be referred to as synthetic fluids in the industry. Group II+may
comprise high viscosity index Group II.
[0101] The base oil used in the disclosed lubricating oil
composition may be a mineral oil, animal oil, vegetable oil,
synthetic oil, synthetic oil blends, or mixtures thereof. Suitable
oils may be derived from hydrocracking, hydrogenation,
hydrofinishing, unrefined, refined, and re-refined oils, and
mixtures thereof.
[0102] Unrefined oils are those derived from a natural, mineral, or
synthetic source without or with little further purification
treatment. Refined oils are similar to the unrefined oils except
that they have been treated in one or more purification steps,
which may result in the improvement of one or more properties.
Examples of suitable purification techniques are solvent
extraction, secondary distillation, acid or base extraction,
filtration, percolation, and the like. Oils refined to the quality
of an edible may or may not be useful. Edible oils may also be
called white oils. In some embodiments, lubricating oil
compositions are free of edible or white oils.
[0103] Re-refined oils are also known as reclaimed or reprocessed
oils. These oils are obtained similarly to refined oils using the
same or similar processes. Often these oils are additionally
processed by techniques directed to removal of spent additives and
oil breakdown products.
[0104] Mineral oils may include oils obtained by drilling or from
plants and animals or any mixtures thereof. For example, such oils
may include, but are not limited to, castor oil, lard oil, olive
oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as
mineral lubricating oils, such as liquid petroleum oils and
solvent-treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic or mixed paraffinic-naphthenic types. Such
oils may be partially or fully hydrogenated, if desired. Oils
derived from coal or shale may also be useful.
[0105] Useful synthetic lubricating oils may include hydrocarbon
oils such as polymerized, oligomerized, or interpolymerized olefins
(e.g., polybutylenes, polypropylenes, propyleneisobutylene
copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers
of 1-decene, e.g., poly(1-decenes), such materials being often
referred to as a-olefins, and mixtures thereof; alkyl-benzenes
(e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,
di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls,
terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated
diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl
sulfides and the derivatives, analogs and homologs thereof or
mixtures thereof. Polyalphaolefins are typically hydrogenated
materials.
[0106] Other synthetic lubricating oils include polyol esters,
diesters, liquid esters of phosphorus-containing acids (e.g.,
tricresyl phosphate, trioctyl phosphate, and the diethyl ester of
decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic
oils may be produced by Fischer-Tropsch reactions and typically may
be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one
embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid
synthetic procedure as well as other gas-to-liquid oils.
[0107] The major amount of base oil included in a lubricating
composition may be selected from the group consisting of Group I,
Group II, a Group III, a Group IV, a Group V, and a combination of
two or more of the foregoing, and wherein the major amount of base
oil is other than base oils that arise from provision of additive
components or viscosity index improvers in the composition. In
another embodiment, the major amount of base oil included in a
lubricating composition may be selected from the group consisting
of Group II, a Group III, a Group IV, a Group V, and a combination
of two or more of the foregoing, and wherein the major amount of
base oil is other than base oils that arise from provision of
additive components or viscosity index improvers in the
composition.
[0108] The amount of the oil of lubricating viscosity present may
be the balance remaining after subtracting from 100 wt. % the sum
of the amount of the performance additives inclusive of viscosity
index improver(s) and/or pour point depressant(s) and/or other top
treat additives. For example, the oil of lubricating viscosity that
may be present in a finished fluid may be a major amount, such as
greater than about 50 wt. %, greater than about 60 wt. %, greater
than about 70 wt. %, greater than about 80 wt. %, greater than
about 85 wt. %, or greater than about 90 wt. %.
The Overbased Calcium-Containing Detergent
[0109] The additive composition may include an amount of one or
more overbased calcium-containing detergent(s) having a total base
number of greater than 225 mg KOH/g, measured by the method of ASTM
D-2896 sufficient to provide at least 500 ppmw calcium to the
lubricating oil composition, based on a total weight of the
lubricating oil composition.
[0110] Suitable detergent substrates include phenates, sulfur
containing phenates, sulfonates, calixarates, salixarates,
salicylates, carboxylic acids, phosphorus acids, mono- and/or
di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol
compounds, or methylene bridged phenols. Suitable detergents and
their methods of preparation are described in greater detail in
numerous patent publications, including U.S. Pat. No. 7,732,390 and
references cited therein. A suitable detergent may include alkali
or alkaline earth metal salts of petroleum sulfonic acids and long
chain mono- or di-alkylarylsulfonic acids with the aryl group being
benzyl, tolyl, and xylyl.
[0111] Overbased detergents are well known in the art and may be
alkali or alkaline earth metal overbased detergents. Such
detergents may be prepared by reacting a metal oxide or metal
hydroxide with a substrate and carbon dioxide gas. The substrate is
typically an acid, for example, an acid such as an aliphatic
substituted sulfonic acid, an aliphatic substituted carboxylic
acid, or an aliphatic substituted phenol.
[0112] The terminology "overbased" relates to metal salts, such as
metal salts of sulfonates, carboxylates, and phenates, wherein the
amount of metal present exceeds the stoichiometric amount. Such
salts may have a conversion level in excess of 100% (i.e., they may
comprise more than 100% of the theoretical amount of metal needed
to convert the acid to its "normal," "neutral" salt). The
expression "metal ratio", often abbreviated as MR, is used to
designate the ratio of total chemical equivalents of metal in the
overbased salt to chemical equivalents of the metal in a neutrals
salt according to known chemical reactivity and stoichiometry. In a
normal or neutral salt, the metal ratio is 1 and in an overbased
salt or low based salt, MR, is greater than 1. They are commonly
referred to as overbased, hyberbased, or superbased salts and may
be salts of organic sulfur acids, carboxylic acids, or phenols.
[0113] The overbased calcium-containing detergent may have a TBN of
greater than about 225 mg KOH/gram or greater, or a TBN of about
250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or
greater, of a TBN of about 350 mg KOH/gram or greater, or a TBN of
about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram
or greater, as measured by the method of ASTM D-2896.
[0114] Examples of suitable overbased calcium-containing detergents
include, but are not limited to, overbased calcium phenates,
overbased calcium sulfur-containing phenates, overbased calcium
sulfonates, overbased calcium calixarates, overbased calcium
salixarates, overbased calcium salicylates, overbased calcium
carboxylic acids, overbased calcium phosphorus acids, overbased
calcium mono- and/or di-thiophosphoric acids, overbased calcium
alkyl phenols, overbased calcium sulfur coupled alkyl phenol
compounds, or overbased calcium methylene bridged phenols.
Preferably, the one or more overbased calcium-containing
detergent(s) is selected from an overbased calcium sulfonate
detergent, an overbased calcium phenate detergent, and an overbased
calcium salicylate detergent. Even more preferably, the overbased
calcium-containing detergent is an overbased calcium sulfonate
detergent.
[0115] The overbased calcium-containing detergent may have a metal
to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from
5:1, or from 7:1, or from 10:1 or from 12:1.
[0116] In some embodiments, the one or more overbased
calcium-containing detergent is present in an amount sufficient to
provide at least 500 ppmw calcium, or at least 600 ppmw of calcium
to less than 3000 ppmw calcium, or from about 700 ppmw of calcium
to less than 2800 ppmw of calcium, or from about 800 ppmw of
calcium to less than about 2500 ppmw of calcium to the lubricating
oil composition, or from 2000 ppmw of calcium to 3500 ppmw of
calcium, or from 2100 ppmw of calcium to 3500 ppmw of calcium, or
from 2100 ppmw of calcium to 3100 ppmw of calcium, based on the
total weight of the lubricating oil composition.
[0117] In some embodiments, the additive composition has a weight
ratio of ppmw of zirconium provided by the zirconium-containing
nanoparticles and/or the one or more zirconium-containing
compound(s) to the ppmw of calcium provided by the one or more
overbased calcium-containing detergent(s) of greater than about
0.01 to less than 5, or from about 0.02 to about 4, or from about
0.03 to about 3, or from about 0.04 to 2.75.
[0118] In some embodiments, the additive composition has a weight
ratio of the ppmw of calcium provided by the one or more overbased
calcium-containing detergent(s) to the ppmw of zirconium provided
by the zirconium-containing nanoparticles and/or the one or more
zirconium-containing compound(s) of greater than about 0.1 to less
than 500, or from about 0.2 to about 480.
Zirconium-Containing Nanoparticles/Zirconium-Containing
Compound
[0119] The additive composition may include an amount of
zirconium-containing nanoparticles and/or one or more
zirconium-containing compound(s) sufficient to provide greater than
0 ppmw to 6000 ppmw of zirconium to the lubricating oil
composition, based on the total weight of the lubricating oil
composition. In other words, the lubricating oil composition may
have greater than 0 ppmw to 6000 ppmw of zirconium provided by an
amount of: a) zirconium-containing nanoparticles; b) one or more
zirconium-containing compound(s); or c) an amount of
zirconium-containing nanoparticles and one or more
zirconium-containing compound(s).
[0120] The zirconium-containing compounds are preferably oil
soluble or dispersible in the oil (e.g. nanoparticles) and may
function as antiwear agents, friction modifiers, antioxidants,
deposit control additives, or have more than one of these
functions. In certain embodiments the inclusion of zirconium in the
lubricating oil composition by use of one or more
zirconium-containing compounds unexpectedly reduces the number of
LSPI events and hence the LSPI Ratio.
[0121] The zirconium-containing compound may be in the form of
elemental zirconium, organozirconium, zirconium oxide,
sulphur-containing organozirconium, sulphur- and phosphorus-free
zirconium sources, and the like. Other examples of suitable
zirconium-containing compounds may include zirconium carboxylates,
zirconium phenates, zirconium alkoxides, zirconium aminic
compounds, zirconium sulfonates, zirconium salicylates, zirconium
di-ketones, zirconium crown ethers, and the like. Other than the
sulfonates, the zirconium-containing compound may contain
phosphorus and sulfur or may be substantially devoid of
phosphorous, or substantially devoid of sulfur, or substantially
devoid of phosphorus and sulfur. By "substantially devoid of
phosphorous" is meant that the nanoparticles/compounds, when
formulated into lubricant formulations, deliver less than 0.12
weight percent of phosphorous to the finished lubricant
formulation, and, more preferably, deliver less than 0.08 weight
percent of phosphorous to the finished lubricant formulation. This
applies at least to the antioxidant and the friction modifier. By
"substantially devoid of sulfur" is meant that the
nanoparticles/compounds, when formulated into lubricant
formulations, deliver less than 0.7 weight percent of sulfur to the
finished lubricant formulation, and, more preferably, deliver less
than 0.4 weight percent of sulfur to the finished lubricant
formulation. This applies at least to the antioxidant and the
friction modifier. The compounds may contain from about 3 to about
200 or more carbon atoms in a hydrocarbyl component of the
compound.
[0122] In some embodiments, the zirconium-containing compound may
be selected from zirconium 2-ethylhexanoate, zirconium octoate,
zirconium acetylacetonate, zirconium butoxide, zirconium
dibutoxide, zirconium tert-butoxide, bis(cyclopentadienyl)zirconium
dihydride, zirconium propoxide, zirconium ethoxide, alkylated
zirconium salicylate, alkylated zirconium phenate, alkylated
zirconium sulfonate, zirconium salts, and the like. Illustrative
zirconium salts include, for example, zirconium oleate, zirconium
stearate, zirconium palmitate, zirconium laurate, and the like
[0123] Examples of metal oxygenates include, but are not limited
to, C.sub.1-C.sub.20 alkyl zirconates, such as the metal complexes,
esters or reaction products of ethylene glycol, propylene glycol,
octylene glycol, butanol, polybutanol, isopropanol, nonyl alcohol,
2-ethylhexanol, and iso-octyl alcohol. Aryl and aralkyl esters of
zirconium may also be used such as tetraphenyl esters, tetrabenzyl
esters, diethyl diphenyl esters, and the like of zirconium.
[0124] Zirconium complex or reaction products of carboxylic acids
may also be used. Such compounds may be made by reacting an alkali
metal salt hydrate or aqueous solution of an organic acid, the
amine salt hydrate or aqueous solution of the organic acid, and/or
the ammonium salt hydrate or aqueous solution of the organic acid
with the aqueous solution of metal halide and subsequently
oxidizing the reaction product.
[0125] Other zirconium organic compounds that may be used include,
but are not limited to metal phenates, metal salicylates, metal
phosphates, metal sulfonates, and sulphurized metal phenates,
wherein each aromatic group has one or more aliphatic groups to
impart hydrocarbon solubility. For example, in the metal
sulfonates, each sulphonic acid moiety is attached to an aromatic
nucleus which in turn usually contains one or more aliphatic
substituents.
[0126] The metal salt of an alkylphenol or sulfurized alkylphenol
is referred to as a neutral salt or soap. The metal used to
neutralize the alkylphenol or sulfurized alkylphenol can be
titanium, manganese, zirconium or any of the other commonly used
metals such as calcium, sodium, magnesium and barium oxides and
hydroxides etc. Accordingly, the sulfonates, salicylates,
phosphates, and phenates described above may include sodium,
potassium, calcium, and/or magnesium sulfonates, salicylates,
phosphates, and phenates in combination with the zirconium
sulfonates, salicylates, phosphates, and phenates. The highly basic
salts of phenols or sulphurized phenols are often referred to as
"overbased" phenates or "overbased sulphurized" phenates. For
example, zirconium may be incorporated in a detergent additive as a
carbonate salt arising from overbasing the detergent.
[0127] Other hydrocarbon soluble metal compounds may include
dispersants, detergents, viscosity index improvers, antiwear
additives, and other antioxidant compounds that are reacted to
contain zirconium. For example, an ethylene copolymer or
polyisobutylene based succinimide, Mannich or oil soluble
dispersant additive, as described below, may be reacted with a
metal alkoxide or any other suitable metal containing reagent to
provide a metal containing dispersant.
[0128] Preferably, the one or more zirconium containing compounds
is selected from zirconium (IV) oxides, zirconium (IV) sulfides,
zirconium (IV) nitrates, zirconium (IV) alkoxides, zirconium
phenates, zirconium carboxylates, zirconium salicylates, zirconium
sulfonates, zirconium halides, and mixtures thereof. Preferably,
the one or more zirconium containing compounds is a zirconium
carboxylate. The carboxylate group can comprise from 3 to 20 carbon
atoms, or from 4 to 15 carbon atoms, or from 6 to 10 carbon atoms.
The zirconium carboxylate can be synthesized using a metal alkoxide
such zirconium propoxide which is reacted with a carboxylic acid.
Examples of metal carboxylates include, but are not limited to,
zirconium products of the following carboxylic acids: formic,
acetic, proprionic, butyric, pentanoic, hexanoic, heptanoic,
octanoic, nonanoic, decanoic, dodecanoic, valeric, caproic,
caprylic, lauric, myristic, palmitic, stearic, oleic, linoleic,
linolenic, cyclohexanecarboxylic, phenylacetic, benzoic, and
neodecanoic acids. The carboxylic acid can be substituted with one
to three C.sub.1-C.sub.5 alkyl groups. Preferably, the zirconium
carboxylate contains one to three tertiary carbons in each
carboxylate moiety, or one to two tertiary carbons in each
carboxylate moiety, or one tertiary carbon in each carboxylate
moiety such as in zirconium 2-ethylhexanoate.
[0129] In some embodiments, the one or more zirconium containing
compound(s) comprise of an organometallic zirconium compound or
zirconium nanoparticles.
[0130] In some embodiments, the present invention may include
zirconium-containing nanoparticles, for example, various forms of
zirconia (zirconium dioxide) or other particulate
zirconium-containing compounds. Nanoparticles are defined as
compounds having three external dimensions in the range of from 1
to 500 nm, or from 1 to 400 nm, or from 1 to 300 nm, or from 1 to
250 nm, as measured by Dynamic Light Scattering in accordance with
ASTM E2490-09 (2015).
[0131] In some embodiments, the zirconium dioxide nanoparticles may
be treated with surface treatment agents to form oil-soluble
zirconium dioxide particles. Suitable surface treatment agents
include those that are reactive with the hydroxyl groups along the
surface of the surface of the particles. In some embodiments,
suitable surface treatment agents include organosilanes. In some
embodiments, suitable organosilanes include one organic substituent
and three hydrolysable substitutents. Exemplary organosilanes
include: [2-(3-cyclohexenyl) ethyl] trimethoxysilane,
trimethoxy(7-octen-1-yl) silane, isooctyl trimethoxy-silane,
N-(3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate,
N-(3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate,
3-(methacryloyloxy)propyltrimethoxysilane, allyl trimethoxysilane,
3-acryloxypropyltrimethoxysilane, 3-(methacryloyloxy)
propyltriethoxysilane, 3-(methacryloyloxy)
propylmethyldimethoxysilane,
3-acryloyloxypropyl)methyldimethoxysilane, -9
-3-(methacryloyloxy)propyldimethylethoxysilane, 3-(methacryloyloxy)
propyldimethylethoxysilane, vinyldimethylethoxysilane,
phenyltrimethoxysilane, n-octyltrimethoxysilane,
dodecyltrimethoxysilane, isooctyltrimethoxysilane
octadecyltrimethoxysilane, propyltrimethoxysilane,
hexyltrimethoxysilane, vinylmethyldiacetoxysilane,
vinylmethyldiethoxysilane, vinyltriacetoxysilane,
vinyltriethoxysilane, vinyltriisopropoxysilane,
vinyltrimethoxysilane, vinyltriphenoxysilane,
vinyltri-tbutoxysilane, vinyltris-isobutoxysilane,
vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy) silane,
styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane,
Heptamethyl(2-ltris(2-methoxyethoxy)silyllethylltrisiloxane (as
described in US 20030220204) polydimethylsiloxane, arylsilanes,
including, e.g., substituted and unsubstituted arylsilanes,
alkylsilanes, including, e.g., substituted and unsubstituted alkyl
silanes, including, e.g., methoxy and hydroxy substituted alkyl
silanes, and combinations of two or more of the foregoing.
[0132] Other suitable surface treatments for use with the zirconia
dioxide particles include acrylic acid, methacrylic acid, oleic
acid, stearic acid, dodecanoic acid,
2.upsilon.-(2-methoxyethoxylethoxyl acetic acid (MEEAA),
betacarboxyethylacrylate, 2-(2-methoxyethosy)acetic acid,
methoxyphenyl acetic acid, and combinations of two or more of the
foregoing. In some embodiments, a silane surface modifier
comprising a polyether chain may be used, such as Silquest
A-1230.
[0133] In some embodiments, the zirconium-containing nanoparticles
and/or one or more zirconium containing compound(s) is present in
an amount to provide greater than 0 ppmw zirconium, or at least 5
ppmw zirconium, or at least 50 ppmw zirconium or at least 75 ppmw
zirconium, or from 75 ppmw zirconium to less than 2400 ppmw
zirconium, or from 200 ppmw zirconium to less than 2400 ppmw
zirconium, or from 400 ppmw zirconium to less than 2000 ppmw
zirconium to the lubricating oil composition, based on the total
weight of the lubricating oil composition.
Molybdenum-Containing Component
[0134] The additive composition may include an amount of one or
more molybdenum-containing compound(s) sufficient to provide no
greater than 100 ppmw of molybdenum, based on a total weight of the
lubricating oil composition.
[0135] The one or more molybdenum-containing compound(s) of the
present invention are preferably oil-soluble. The one or more
molybdenum-containing compound(s) may have the functional
performance of an antiwear agent, an antioxidant, a friction
modifier, or mixtures thereof. The one or more oil-soluble
molybdenum-containing compound(s) may be selected from molybdenum
dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum
dithiophosphinates, amine salts of molybdenum compounds, molybdenum
xanthates, molybdenum thioxanthates, molybdenum sulfides,
molybdenum carboxylates, molybdenum alkoxides, a trinuclear
organo-molybdenum compound, and/or mixtures thereof. The molybdenum
sulfides include molybdenum disulfide. The molybdenum disulfide may
be in the form of a stable dispersion. In one embodiment the one or
more oil-soluble molybdenum-containing compound(s) may be selected
from the group consisting of molybdenum dithiocarbamates,
molybdenum dialkyldithiophosphates, amine salts of molybdenum
compounds, and mixtures thereof. In one embodiment the one or more
oil-soluble molybdenum-containing compound(s) may be a molybdenum
dithiocarbamate.
[0136] Suitable examples of molybdenum compounds which may be used
include commercial materials sold under the trade names such as
Molyvan 822.TM., Molyvan.TM. A, Molyvan 2000.TM. and Molyvan
855.TM. from R. T. Vanderbilt Co., Ltd., and Sakura-Lube.TM. S-165,
S-200, S-300, 5-310G, S-525, S-600, S-700, and S-710 available from
Adeka Corporation, and mixtures thereof. Suitable molybdenum
components are described in U.S. Pat. No. 5,650,381; US RE 37,363
E1; US RE 38,929 E1; and US RE 40,595 E1, incorporated herein by
reference in their entireties. Preferably, the one or more
molybdenum-containing compounds may be the reaction product of a
fatty acid ester and molybdenum oxide. Preferably, the fatty acid
ester has from 4 to 30 carbon atoms, or from 6 to 20 carbon
atoms.
[0137] Additionally, the molybdenum compound may be an acidic
molybdenum compound. Included are molybdic acid, ammonium
molybdate, sodium molybdate, potassium molybdate, and other
alkaline metal molybdates and other molybdenum salts, e.g.,
hydrogen sodium molybdate, MoOCl.sub.4, MoO.sub.2Br.sub.2,
Mo.sub.2O.sub.3Cl.sub.6, molybdenum trioxide or similar acidic
molybdenum compounds. Alternatively, the compositions can be
provided with molybdenum by molybdenum/sulfur complexes of basic
nitrogen compounds as described, for example, in U.S. Pat. Nos.
4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843;
4,259,195 and 4,259,194; and WO 94/06897, incorporated herein by
reference in their entireties.
[0138] Another class of suitable organo-molybdenum compounds are
trinuclear molybdenum compounds, such as those of the formula
Mo.sub.3S.sub.kL.sub.nQ.sub.z and mixtures thereof, wherein S
represents sulfur, L represents independently selected ligands
having organo groups with a sufficient number of carbon atoms to
render the compound soluble or dispersible in the oil, n is from 1
to 4, k varies from 4 through 7, Q is selected from the group of
neutral electron donating compounds such as water, amines,
alcohols, phosphines, and ethers, and z ranges from 0 to 5 and
includes non-stoichiometric values. At least 21 total carbon atoms
may be present among all the ligands' organo groups, such as at
least 25, at least 30, or at least 35 carbon atoms. Additional
suitable molybdenum compounds are described in U.S. Pat. No.
6,723,685, herein incorporated by reference in its entirety. The
one or more oil-soluble molybdenum-containing compound(s) may be
present in an amount sufficient to provide no greater than 100 ppmw
molybdenum, or no greater than 80 ppmw molybdenum, or no greater
than 50 ppmw molybdenum, or no greater than 20 ppmw molybdenum, or
no greater than 15 ppmw, or greater than 0 ppmw molybdenum, or
greater than 5 ppmw molybdenum, or combinations thereof, based on
the total weight of the lubricating oil composition.
[0139] In another embodiments, the invention may provide a
lubricating composition that is free of or substantially free of
molybdenum-containing compounds. For purpose herein, the term "free
of or substantially free of" means no intentionally added amount of
material is present in the compositions but does allow for minute
(less than 10 ppm) amounts of molybdenum, which may be regarded as
a contaminant.
The Magnesium-Containing Detergent
[0140] The additive composition may include an amount of one or
more magnesium-containing detergent(s) present in an amount
sufficient to provide greater than 500 ppmw to less than 1500 ppmw
of magnesium to the lubricating oil composition, based on the total
weight of the lubricating oil composition.
[0141] Suitable detergent substrates include phenates, sulfur
containing phenates, sulfonates, calixarates, salixarates,
salicylates, carboxylic acids, phosphorus acids, mono- and/or
di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol
compounds, or methylene bridged phenols. Suitable detergents and
their methods of preparation are described in greater detail in
numerous patent publications, including U.S. Pat. No. 7,732,390 and
references cited therein. A suitable detergent may include alkali
or alkaline earth metal salts of petroleum sulfonic acids and long
chain mono- or di-alkylarylsulfonic acids with the aryl group being
benzyl, tolyl, and xylyl. Examples of suitable additional
detergents include, but are not limited to, magnesium phenates,
magnesium sulfur containing phenates, magnesium sulfonates,
magnesium calixarates, magnesium salixarates, magnesium
salicylates, magnesium carboxylic acids, magnesium phosphorus
acids, magnesium mono- and/or di-thiophosphoric acids, magnesium
alkyl phenols, magnesium sulfur coupled alkyl phenol compounds,
magnesium methylene bridged phenols, sodium phenates, sodium sulfur
containing phenates, sodium sulfonates, sodium calixarates, sodium
salixarates, sodium salicylates, sodium carboxylic acids, sodium
phosphorus acids, sodium mono- and/or di-thiophosphoric acids,
sodium alkyl phenols, sodium sulfur coupled alkyl phenol compounds,
or sodium methylene bridged phenols.
[0142] Overbased and low-based detergents are well known in the art
and may be alkali or alkaline earth metal overbased detergents.
Such detergents may be prepared by reacting a metal oxide or metal
hydroxide with a substrate and carbon dioxide gas. The substrate is
typically an acid, for example, an acid such as an aliphatic
substituted sulfonic acid, an aliphatic substituted carboxylic
acid, or an aliphatic substituted phenol.
[0143] The terminology "overbased" or "low-based" relates to metal
salts, such as metal salts of sulfonates, carboxylates, and
phenates, wherein the amount of metal present exceeds the
stoichiometric amount. Such salts may have a conversion level in
excess of 100% (i.e., they may comprise more than 100% of the
theoretical amount of metal needed to convert the acid to its
"normal," "neutral" salt). The expression "metal ratio", often
abbreviated as MR, is used to designate the ratio of total chemical
equivalents of metal in the overbased salt to chemical equivalents
of the metal in a neutrals salt according to known chemical
reactivity and stoichiometry. In a normal or neutral salt, the
metal ratio is 1 and in an overbased salt or low based salt, MR, is
greater than 1. They are commonly referred to as overbased,
hyberbased, or superbased salts and may be salts of organic sulfur
acids, carboxylic acids, or phenols.
[0144] The overbased magnesium-containing detergent can have a TBN
of greater 225 mg KOH/gram, or as further examples, a TBN of about
250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or
greater, or a TBN of about 350 mg KOH/gram or greater, or a TBN of
about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram
or greater.
[0145] Examples of suitable overbased magnesium-containing
detergents include, but are not limited to, overbased magnesium
phenates, overbased magnesium sulfur containing phenates, overbased
magnesium sulfonates, overbased magnesium calixarates, overbased
magnesium salixarates, overbased magnesium salicylates, overbased
magnesium carboxylic acids, overbased magnesium phosphorus acids,
overbased magnesium mono- and/or di-thiophosphoric acids, overbased
magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl
phenol compounds, or overbased magnesium methylene bridged
phenols.
[0146] The overbased detergent may have a metal to substrate ratio
of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1,
or from 10:1.
[0147] In some embodiments, a detergent is effective at reducing or
preventing rust in an engine.
[0148] In some embodiments, the one or more magnesium-containing
detergents includes a low-based/neutral magnesium-containing
detergent having a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g
or at least 5 mg KOH/g, or at least 25 mg KOH/g, or at least 50
KOH/g. In some embodiments, the low-based/neutral
magnesium-containing detergent is selected from low-based/neutral
magnesium phenate detergents, low-based/neutral magnesium sulfur
containing phenate detergents, and low-based/neutral magnesium
sulfonates. Preferably, the low-based/neutral magnesium-containing
detergent is a low-based/neutral magnesium phenate detergent or a
low-based/neutral magnesium sulfonate detergent.
[0149] The low-based/neutral magnesium detergent comprises at least
2.5 wt. % of the total detergent in the lubricating oil
composition. In some embodiments, at least 4 wt. %, or at least 6
wt. %, or at least 8 wt. %, or at least 10 wt. % or at least 12 wt.
% or at least 20 wt. % of the total detergent in the lubricating
oil composition is a low-based/neutral detergent which may
optionally be a low-based/neutral calcium-containing detergent.
[0150] In some embodiments, the one or more magnesium-containing
detergents is present in an amount to provide greater than 500 ppmw
of magnesium, or from 500 ppmw of magnesium to 1500 ppmw of
magnesium, or from about 600 ppmw of magnesium to 1300 ppmw of
magnesium, or from about 700 ppmw of magnesium to 1200 ppmw of
magnesium, or from about 800 ppmw of magnesium to 1000 ppmw of
magnesium to the lubricating oil composition, based on the total
weight of the lubricating oil composition.
Boron-Containing Compounds
[0151] The additive composition may include an amount of one or
more boron-containing compound(s).
[0152] Examples of boron-containing compounds include borate
esters, borated fatty amines, borated epoxides, borated detergents,
and borated dispersants, such as borated succinimide dispersants,
as disclosed in U.S. Pat. No. 5,883,057.
[0153] The boron-containing compound, if present, can be present in
the lubricating oil composition in an amount of about 8 wt %, about
0.01 wt % to about 7 wt %, about 0.05 wt % to about 5 wt %, or
about 0.1 wt % to about 3 wt % based on the total weight of the
lubricating oil composition.
[0154] In some embodiments of the invention, the one or more
boron-containing compound(s) is present in an amount to provide
greater than 1 ppmw of boron, or greater than 5 ppmw of boron, or
greater than 10 ppmw of boron, or greater than 30 ppmw of boron to
the lubricating oil composition, based on the total weight of the
lubricating oil composition.
[0155] In some embodiments, the lubricating oil composition may
have more than 0 ppmw of boron and a ratio of total metal from the
detergent in ppmw to total boron in ppmw of more than 7.5, or more
than 50, or more than 500.
[0156] The lubricating oil composition may also include one or more
optional components selected from the various additives set forth
below.
[0157] Antioxidants
[0158] The lubricating oil compositions herein also may optionally
contain one or more antioxidants. Antioxidant compounds are known
and include for example, phenates, phenate sulfides, sulfurized
olefins, phosphosulfurized terpenes, sulfurized esters, aromatic
amines, alkylated diphenylamines (e.g., nonyl diphenylamine,
di-nonyl diphenylamine, octyl diphenylamine, di-octyl
diphenylamine), phenyl-alpha-naphthylamines, alkylated
phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols,
hindered phenols, oil-soluble molybdenum compounds, macromolecular
antioxidants, or mixtures thereof. Antioxidant compounds may be
used alone or in combination.
[0159] The hindered phenol antioxidant may contain a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group may be further substituted with a
hydrocarbyl group and/or a bridging group linking to a second
aromatic group. Examples of suitable hindered phenol antioxidants
include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,
4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol
or 4-butyl-2,6-di-tert-butylphenol, or
4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered
phenol antioxidant may be an ester and may include, e.g.,
Irganox.TM. L-135 available from BASF or an addition product
derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein
the alkyl group may contain about 1 to about 18, or about 2 to
about 12, or about 2 to about 8, or about 2 to about 6, or about 4
carbon atoms. Another commercially available hindered phenol
antioxidant may be an ester and may include Ethanox.TM. 4716
available from Albemarle Corporation.
[0160] Useful antioxidants may include diarylamines and high
molecular weight phenols. In an embodiment, the lubricating oil
composition may contain a mixture of a diarylamine and a high
molecular weight phenol, such that each antioxidant may be present
in an amount sufficient to provide up to about 5%, by weight, based
upon the final weight of the lubricating oil composition. In an
embodiment, the antioxidant may be a mixture of about 0.3 to about
1.5% diarylamine and about 0.4 to about 2.5% high molecular weight
phenol, by weight, based upon the final weight of the lubricating
oil composition.
[0161] Examples of suitable olefins that may be sulfurized to form
a sulfurized olefin include propylene, butylene, isobutylene,
polyisobutylene, pentene, hexene, heptene, octene, nonene, decene,
undecene, dodecene, tridecene, tetradecene, pentadecene,
hexadecene, heptadecene, octadecene, nonadecene, eicosene or
mixtures thereof. In one embodiment, hexadecene, heptadecene,
octadecene, nonadecene, eicosene or mixtures thereof and their
dimers, trimers and tetramers are especially useful olefins.
Alternatively, the olefin may be a Diels-Alder adduct of a diene
such as 1,3-butadiene and an unsaturated ester, such as, butyl
acrylate.
[0162] Another class of sulfurized olefin includes sulfurized fatty
acids and their esters. The fatty acids are often obtained from
vegetable oil or animal oil and typically contain about 4 to about
22 carbon atoms. Examples of suitable fatty acids and their esters
include triglycerides, oleic acid, linoleic acid, palmitoleic acid
or mixtures thereof. Often, the fatty acids are obtained from lard
oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower
seed oil or mixtures thereof. Fatty acids and/or ester may be mixed
with olefins, such as .alpha.-olefins.
[0163] In another alternative embodiment the antioxidant
composition also contains a molybdenum-containing antioxidant in
addition to the phenolic and/or aminic antioxidants discussed
above. When a combination of these three antioxidants is used,
preferably the ratio of phenolic to aminic to molybdenum-containing
is (0 to 2):(0 to 2):(0 to 1).
[0164] The one or more antioxidant(s) may be present in ranges
about 0 wt % to about 20 wt %, or about 0.1 wt % to about 10 wt %,
or about 1 wt % to about 5 wt %, of the lubricating oil
composition.
[0165] Antiwear Agents
[0166] The lubricating oil compositions herein also may optionally
contain one or more antiwear agents. Examples of suitable antiwear
agents include, but are not limited to, a metal thiophosphate; a
metal dialkyldithiophosphate; a phosphoric acid ester or salt
thereof; a phosphate ester(s); a phosphite; a phosphorus-containing
carboxylic ester, ether, or amide; a sulfurized olefin;
thiocarbamate-containing compounds including, thiocarbamate esters,
alkylene-coupled thiocarbamates, and
bis(S-alkyldithiocarbamyl)disulfides; and mixtures thereof. A
suitable antiwear agent may be a molybdenum dithiocarbamate. The
phosphorus containing antiwear agents are more fully described in
European Patent 612 839. The metal in the dialkyl dithio phosphate
salts may be an alkali metal, alkaline earth metal, aluminum, lead,
tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A
useful antiwear agent may be zinc dialkyldithiophosphate.
[0167] Further examples of suitable antiwear agents include
titanium compounds, tartrates, tartrimides, oil soluble amine salts
of phosphorus compounds, sulfurized olefins, phosphites (such as
dibutyl phosphite), phosphonates, thiocarbamate-containing
compounds, such as thiocarbamate esters, thiocarbamate amides,
thiocarbamic ethers, alkylene-coupled thiocarbamates, and
bis(S-alkyldithiocarbamyl) disulfides. The tartrate or tartrimide
may contain alkyl-ester groups, where the sum of carbon atoms on
the alkyl groups may be at least 8. The antiwear agent may in one
embodiment include a citrate.
[0168] The antiwear agent may be present in ranges including about
0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or
about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt %
of the lubricating oil composition.
Additional Optional Detergents
[0169] The lubricating oil composition may further comprise one or
more neutral and/or low based detergents, as well as overbased
detergents other than the detergents discussed above. Suitable
detergent substrates include phenates, sulfur containing phenates,
sulfonates, calixarates, salixarates, salicylates, carboxylic
acids, phosphorus acids, mono- and/or di-thiophosphoric acids,
alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene
bridged phenols. Suitable detergents and their methods of
preparation are described in greater detail in numerous patent
publications, including U.S. Pat. No. 7,732,390 and references
cited therein. The detergent substrate may be salted with an alkali
or alkaline earth metal such as, but not limited to, calcium,
potassium, sodium, lithium, barium, or mixtures thereof. In some
embodiments, the detergent is free of barium. A suitable detergent
may include alkali or alkaline earth metal salts of petroleum
sulfonic acids and long chain mono- or di-alkylarylsulfonic acids
with the aryl group being benzyl, tolyl, and xylyl. Examples of
suitable detergents include, but are not limited to, calcium
phenates, calcium sulfur containing phenates, calcium sulfonates,
calcium calixarates, calcium salixarates, calcium salicylates,
calcium carboxylic acids, calcium phosphorus acids, calcium mono-
and/or di-thiophosphoric acids, calcium alkyl phenols, calcium
sulfur coupled alkyl phenol compounds, calcium methylene bridged
phenols, sodium phenates, sodium sulfur containing phenates, sodium
sulfonates, sodium calixarates, sodium salixarates, sodium
salicylates, sodium carboxylic acids, sodium phosphorus acids,
sodium mono- and/or di-thiophosphoric acids, sodium alkyl phenols,
sodium sulfur coupled alkyl phenol compounds, or sodium methylene
bridged phenols.
[0170] Overbased detergent additives are well known in the art and
may be alkali or alkaline earth metal overbased detergent
additives. Such detergent additives may be prepared by reacting a
metal oxide or metal hydroxide with a substrate and carbon dioxide
gas. The substrate is typically an acid, for example, an acid such
as an aliphatic substituted sulfonic acid, an aliphatic substituted
carboxylic acid, or an aliphatic substituted phenol.
[0171] The terminology "overbased" relates to metal salts, such as
metal salts of sulfonates, carboxylates, and phenates, wherein the
amount of metal present exceeds the stoichiometric amount. Such
salts may have a conversion level in excess of 100% (i.e., they may
comprise more than 100% of the theoretical amount of metal needed
to convert the acid to its "normal," "neutral" salt). The
expression "metal ratio," often abbreviated as MR, is used to
designate the ratio of total chemical equivalents of metal in the
overbased salt to chemical equivalents of the metal in a neutral
salt according to known chemical reactivity and stoichiometry. In a
normal or neutral salt, the metal ratio is one and in an overbased
salt, MR, is greater than one. They are commonly referred to as
overbased, hyperbased, or superbased salts and may be salts of
organic sulfur acids, carboxylic acids, or phenols.
[0172] An overbased detergent of the lubricating oil composition
may have a total base number (TBN) of greater than 225 mg KOH/gram,
or as further examples, about 250 mg KOH/gram or greater, or about
350 mg KOH/gram or greater, or about 375 mg KOH/gram or greater, or
about 400 mg KOH/gram or greater.
[0173] The overbased detergent may have a metal to substrate ratio
of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1,
or from 10:1.
[0174] The low-based/neutral detergent has a TBN of up to 175 mg
KOH/g, or up to 150 mg KOH/g. The low-based/neutral detergent may
include a calcium-containing detergent. The low-based neutral
calcium-containing detergent may be selected from a calcium
sulfonate detergent, a calcium phenate detergent and a calcium
salicylate detergent. In some embodiments, the low-based/neutral
detergent is a calcium-containing detergent or a mixture of
calcium-containing detergents. In some embodiments, the
low-based/neutral detergent is a calcium sulfonate detergent or a
calcium phenate detergent.
[0175] The low-based/neutral detergent may comprise at least 2.5
wt. % of the total detergent of the lubricating oil composition. In
some embodiments, at least 4 wt. %, or at least 6 wt. %, or at
least 8 wt. %, or at least 10 wt. % or at least 12 wt. % or at
least 20 wt. % of the total detergent in the lubricating oil
composition is a low-based/neutral detergent which may optionally
be a low-based/neutral calcium-containing detergent.
[0176] In certain embodiments, the one or more low-based/neutral
detergents provide from about 50 to about 1000 ppmw calcium to the
lubricating oil composition based on a total weight of the
lubricating oil composition. In some embodiments, the one or more
low-based/neutral calcium-containing detergents provide from 75 to
less than 800 ppmw, or from 100 to 600 ppmw, or from 125 to 500
ppmw calcium to the lubricating oil composition based on a total
weight of the lubricating oil composition.
[0177] In some embodiments, a detergent is effective at reducing or
preventing rust in an engine.
Dispersant
[0178] The lubricating oil composition may optionally further
comprise one or more dispersants or mixtures thereof. Dispersants
are often known as ashless-type dispersants because, prior to
mixing in a lubricating oil composition, they do not contain
ash-forming metals and they do not normally contribute any ash when
added to a lubricant. Ashless type dispersants are characterized by
a polar group attached to a relatively high molecular weight
hydrocarbon chain. Typical ashless dispersants include
N-substituted long chain alkenyl succinimides. Examples of
N-substituted long chain alkenyl succinimides include
polyisobutylene succinimide with the number average molecular
weight of the polyisobutylene substituent being in the range about
350 to about 50,000, or to about 5,000, or to about 3,000, as
measured by GPC. Succinimide dispersants and their preparation are
disclosed, for instance in U.S. Pat. No. 7,897,696 or U.S. Pat. No.
4,234,435. The polyolefin may be prepared from polymerizable
monomers containing about 2 to about 16, or about 2 to about 8, or
about 2 to about 6 carbon atoms. Succinimide dispersants are
typically the imide formed from a polyamine, typically a
poly(ethyleneamine)
[0179] Preferred amines are selected from polyamines and
hydroxyamines Examples of polyamines that may be used include, but
are not limited to, diethylene triamine (DETA), triethylene
tetramine (TETA), tetraethylene pentamine (TEPA), and higher
homologues such as pentaethylamine hexamine (PEHA), and the
like.
[0180] A suitable heavy polyamine is a mixture of
polyalkylene-polyamines comprising small amounts of lower polyamine
oligomers such as TEPA and PEHA (pentaethylene hexamine) but
primarily oligomers with 6 or more nitrogen atoms, 2 or more
primary amines per molecule, and more extensive branching than
conventional polyamine mixtures. A heavy polyamine preferably
includes polyamine oligomers containing 7 or more nitrogens per
molecule and with 2 or more primary amines per molecule. The heavy
polyamine comprises more than 28 wt. % (e.g. >32 wt. %) total
nitrogen and an equivalent weight of primary amine groups of
120-160 grams per equivalent.
[0181] Suitable polyamines are commonly known as PAM and contain a
mixture of ethylene amines where TEPA and pentaethylene hexamine
(PEHA) are the major part of the polyamine, usually less than about
80%.
[0182] Typically, PAM has 8.7-8.9 milliequivalents of primary amine
per gram (an equivalent weight of 115 to 112 grams per equivalent
of primary amine) and a total nitrogen content of about 33-34 wt.
%. Heavier cuts of PAM oligomers with practically no TEPA and only
very small amounts of PEHA but containing primarily oligomers with
more than 6 nitrogens and more extensive branching, may produce
dispersants with improved dispersancy.
[0183] In an embodiment the present disclosure further comprises at
least one polyisobutylene succinimide dispersant derived from
polyisobutylene with a number average molecular weight in the range
about 350 to about 50,000, or to about 5000, or to about 3000, as
determined by GPC. The polyisobutylene succinimide may be used
alone or in combination with other dispersants.
[0184] In some embodiments, polyisobutylene, when included, may
have greater than 50 mol %, greater than 60 mol %, greater than 70
mol %, greater than 80 mol %, or greater than 90 mol % content of
terminal double bonds. Such PIB is also referred to as highly
reactive PIB ("HR-PIB"). HR-PIB having a number average molecular
weight ranging from about 800 to about 5000, as determined by GPC,
is suitable for use in embodiments of the present disclosure.
Conventional PIB typically has less than 50 mol %, less than 40 mol
%, less than 30 mol %, less than 20 mol %, or less than 10 mol %
content of terminal double bonds.
[0185] An HR-PIB having a number average molecular weight ranging
from about 900 to about 3000 may be suitable, as determined by GPC.
Such HR-PIB is commercially available, or can be synthesized by the
polymerization of isobutene in the presence of a non-chlorinated
catalyst such as boron trifluoride, as described in U.S. Pat. No.
4,152,499 to Boerzel, et al. and U.S. Pat. No. 5,739,355 to Gateau,
et al. When used in the aforementioned thermal ene reaction, HR-PIB
may lead to higher conversion rates in the reaction, as well as
lower amounts of sediment formation, due to increased reactivity. A
suitable method is described in U.S. Pat. No. 7,897,696.
[0186] In one embodiment the present disclosure further comprises
at least one dispersant derived from polyisobutylene succinic
anhydride ("PIB SA"). The PIB SA may have an average of between
about 1.0 and about 2.0 succinic acid moieties per polymer.
[0187] The % actives of the alkenyl or alkyl succinic anhydride can
be determined using a chromatographic technique. This method is
described in column 5 and 6 in U.S. Pat. No. 5,334,321.
[0188] The percent conversion of the polyolefin is calculated from
the % actives using the equation in column 5 and 6 in U.S. Pat. No.
5,334,321.
[0189] Unless stated otherwise, all percentages are in weight
percent and all molecular weights are number average molecular
weights determined by gel permeation chromatography (GPC) using
commercially available polystyrene standards (with a number average
molecular weight of 180 to about 18,000 as the calibration
reference).
[0190] In one embodiment, the dispersant may be derived from a
polyalphaolefin (PAO) succinic anhydride.
[0191] In one embodiment, the dispersant may be derived from olefin
maleic anhydride copolymer. As an example, the dispersant may be
described as a poly-PIBSA.
[0192] In an embodiment, the dispersant may be derived from an
anhydride which is grafted to an ethylene-propylene copolymer.
[0193] A suitable class of nitrogen-containing dispersants may be
derived from olefin copolymers (OCP), more specifically,
ethylene-propylene dispersants which may be grafted with maleic
anhydride. A more complete list of nitrogen-containing compounds
that can be reacted with the functionalized OCP are described in
U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and
5,075,383; and/or are commercially available. Further details of
the ethylene-alpha olefin copolymers and dispersants made therefrom
may be found in PCT/US18/37116 filed at the U.S. Receiving Office,
the disclosure of which is hereby incorporated by reference in its
entirety.
[0194] One class of suitable dispersants may be Mannich bases.
Mannich bases are materials that are formed by the condensation of
a higher molecular weight, alkyl substituted phenol, a polyalkylene
polyamine, and an aldehyde such as formaldehyde. Mannich bases are
described in more detail in U.S. Pat. No. 3,634,515.
[0195] A suitable class of dispersants may be high molecular weight
esters or half ester amides.
[0196] A suitable dispersant may also be post-treated by
conventional methods by a reaction with any of a variety of agents.
Among these are boron, urea, thiourea, dimercaptothiadiazoles,
carbon disulfide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, maleic anhydride,
nitriles, epoxides, carbonates, cyclic carbonates, hindered
phenolic esters, and phosphorus compounds. U.S. Pat. Nos.
7,645,726; 7,214,649; and 8,048,831 are incorporated herein by
reference in their entireties.
[0197] In addition to the carbonate and boric acids post-treatments
both the compounds may be post-treated, or further post-treatment,
with a variety of post-treatments designed to improve or impart
different properties. Such post-treatments include those summarized
in columns 27-29 of U.S. Pat. No. 5,241,003, hereby incorporated by
reference. Such treatments include, treatment with:
[0198] Inorganic phosphorous acids or anhydrates (e.g., U.S. Pat.
Nos. 3,403,102 and 4,648,980);
[0199] Organic phosphorous compounds (e.g., U.S. Pat. No.
3,502,677);
[0200] Phosphorous pentasulfides;
[0201] Boron compounds as already noted above (e.g., U.S. Pat. Nos.
3,178,663 and 4,652,387);
[0202] Carboxylic acid, polycarboxylic acids, anhydrides and/or
acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386);
[0203] Epoxides polyepoxiates or thioexpoxides (e.g., U.S. Pat.
Nos. 3,859,318 and 5,026,495);
[0204] Aldehyde or ketone (e.g., U.S. Pat. No. 3,458,530);
[0205] Carbon disulfide (e.g., U.S. Pat. No. 3,256,185);
[0206] Glycidol (e.g., U.S. Pat. No. 4,617,137);
[0207] Urea, thourea or guanidine (e.g., U.S. Pat. Nos. 3,312,619;
3,865,813; and British Patent GB 1,065,595);
[0208] Organic sulfonic acid (e.g., U.S. Pat. No. 3,189,544 and
British Patent GB 2,140,811);
[0209] Alkenyl cyanide (e.g., U.S. Pat. Nos. 3,278,550 and
3,366,569);
[0210] Diketene (e.g., U.S. Pat. No. 3,546,243);
[0211] A diisocyanate (e.g., U.S. Pat. No. 3,573,205);
[0212] Alkane sultone (e.g., U.S. Pat. No. 3,749,695);
[0213] 1,3-Dicarbonyl Compound (e.g., U.S. Pat. No. 4,579,675);
[0214] Sulfate of alkoxylated alcohol or phenol (e.g., U.S. Pat.
No. 3,954,639);
[0215] Cyclic lactone (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515;
4,668,246; 4,963,275; and 4,971,711);
[0216] Cyclic carbonate or thiocarbonate linear monocarbonate or
polycarbonate, or chloroformate (e.g., U.S. Pat. Nos. 4,612,132;
4,647,390; 4,648,886; 4,670,170);
[0217] Nitrogen-containing carboxylic acid (e.g., U.S. Pat.
4,971,598 and British Patent GB 2,140,811);
[0218] Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S.
Pat. No. 4,614,522);
[0219] Lactam, thiolactam, thiolactone or ditholactone (e.g., U.S.
Pat. Nos. 4,614,603 and 4,666,460);
[0220] Cyclic carbonate or thiocarbonate, linear monocarbonate or
plycarbonate, or chloroformate (e.g., U.S. Pat. Nos. 4,612,132;
4,647,390; 4,646,860; and 4,670,170);
[0221] Nitrogen-containing carboxylic acid (e.g., U.S. Pat. No.
4,971,598 and British Patent GB 2,440,811);
[0222] Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S.
Pat. No. 4,614,522);
[0223] Lactam, thiolactam, thiolactone or dithiolactone (e.g., U.S.
Pat. Nos. 4,614,603, and 4,666,460);
[0224] Cyclic carbamate, cyclic thiocarbamate or cyclic
dithiocarbamate (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459);
[0225] Hydroxyaliphatic carboxylic acid (e.g., U.S. Pat. Nos.
4,482,464; 4,521,318; 4,713,189);
[0226] Oxidizing agent (e.g., U.S. Pat. No. 4,379,064);
[0227] Combination of phosphorus pentasulfide and a polyalkylene
polyamine (e.g., U.S. Pat. No. 3,185,647);
[0228] Combination of carboxylic acid or an aldehyde or ketone and
sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086;
3,470,098);
[0229] Combination of a hydrazine and carbon disulfide (e.g. U.S.
Pat. No. 3,519,564);
[0230] Combination of an aldehyde and a phenol (e.g., U.S. Pat.
Nos. 3,649,229; 5,030,249; 5,039,307);
[0231] Combination of an aldehyde and an O-diester of
dithiophosphoric acid (e.g., U.S. Pat. No. 3,865,740);
[0232] Combination of a hydroxyaliphatic carboxylic acid and a
boric acid (e.g., U.S. Pat. No. 4,554,086);
[0233] Combination of a hydroxyaliphatic carboxylic acid, then
formaldehyde and a phenol (e.g., U.S. Pat. No. 4,636,322);
[0234] Combination of a hydroxyaliphatic carboxylic acid and then
an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064);
[0235] Combination of formaldehyde and a phenol and then glycolic
acid (e.g., U.S. Pat. No. 4,699,724);
[0236] Combination of a hydroxyaliphatic carboxylic acid or oxalic
acid and then a diisocyanate (e.g. U.S. Pat. No.4,713,191);
[0237] Combination of inorganic acid or anhydride of phosphorus or
a partial or total sulfur analog thereof and a boron compound
(e.g., U.S. Pat. No. 4,857,214);
[0238] Combination of an organic diacid then an unsaturated fatty
acid and then a nitrosoaromatic amine optionally followed by a
boron compound and then a glycolating agent (e.g., U.S. Pat. No.
4,973,412);
[0239] Combination of an aldehyde and a triazole (e.g., U.S. Pat.
No. 4,963,278);
[0240] Combination of an aldehyde and a triazole then a boron
compound (e.g., U.S. Pat. No. 4,981,492);
[0241] Combination of cyclic lactone and a boron compound (e.g.,
U.S. Pat. No. 4,963,275 and 4,971,711). The above-mentioned patents
are herein incorporated in their entireties.
[0242] The TBN of a suitable dispersant may be from about 10 to
about 65 mg KOH/g dispersant, on an oil-free basis, which is
comparable to about 5 to about 30 TBN if measured on a dispersant
sample containing about 50% diluent oil. TBN is measured by the
method of ASTM D2896.
[0243] The dispersant, if present, can be used in an amount
sufficient to provide up to about 20 wt %, based upon the final
weight of the lubricating oil composition. Another amount of the
dispersant that can be used may be about 0.1 wt % to about 15 wt %,
or about 0.1 wt % to about 10 wt %, or about 3 wt % to about 10 wt
%, or about 1 wt % to about 6 wt %, or about 7 wt % to about 12 wt
%, based upon the final weight of the lubricating oil composition.
In some embodiments, the lubricating oil composition utilizes a
mixed dispersant system. A single type or a mixture of two or more
types of dispersants in any desired ratio may be used.
Friction Modifiers
[0244] The lubricating oil compositions herein also may optionally
contain one or more friction modifiers. Suitable friction modifiers
may comprise metal containing and metal-free friction modifiers and
may include, but are not limited to, imidazolines, amides, amines,
succinimides, alkoxylated amines, alkoxylated ether amines, amine
oxides, amidoamines, nitriles, betaines, quaternary amines, imines,
amine salts, amino guanidine, alkanolamides, phosphonates,
metal-containing compounds, glycerol esters, sulfurized fatty
compounds and olefins, sunflower oil other naturally occurring
plant or animal oils, dicarboxylic acid esters, esters or partial
esters of a polyol and one or more aliphatic or aromatic carboxylic
acids, and the like.
[0245] Suitable friction modifiers may contain hydrocarbyl groups
that are selected from straight chain, branched chain, or aromatic
hydrocarbyl groups or mixtures thereof, and may be saturated or
unsaturated. The hydrocarbyl groups may be composed of carbon and
hydrogen or hetero atoms such as sulfur or oxygen. The hydrocarbyl
groups may range from about 12 to about 25 carbon atoms. In some
embodiments the friction modifier may be a long chain fatty acid
ester. In another embodiment the long chain fatty acid ester may be
a mono-ester, or a di-ester, or a (tri)glyceride. The friction
modifier may be a long chain fatty amide, a long chain fatty ester,
a long chain fatty epoxide derivative, or a long chain
imidazoline.
[0246] Other suitable friction modifiers may include organic,
ashless (metal-free), nitrogen-free organic friction modifiers.
Such friction modifiers may include esters formed by reacting
carboxylic acids and anhydrides with alkanols and generally include
a polar terminal group (e.g. carboxyl or hydroxyl) covalently
bonded to an oleophilic hydrocarbon chain. An example of an organic
ashless nitrogen-free friction modifier is known generally as
glycerol monooleate (GMO) which may contain mono-, di-, and
tri-esters of oleic acid. Other suitable friction modifiers are
described in U.S. Pat. No. 6,723,685, herein incorporated by
reference in its entirety.
[0247] Aminic friction modifiers may include amines or polyamines
Such compounds can have hydrocarbyl groups that are linear, either
saturated or unsaturated, or a mixture thereof and may contain from
about 12 to about 25 carbon atoms. Further examples of suitable
friction modifiers include alkoxylated amines and alkoxylated ether
amines Such compounds may have hydrocarbyl groups that are linear,
either saturated, unsaturated, or a mixture thereof. They may
contain from about 12 to about 25 carbon atoms. Examples include
ethoxylated amines and ethoxylated ether amines.
[0248] The amines and amides may be used as such or in the form of
an adduct or reaction product with a boron compound such as a boric
oxide, boron halide, metaborate, boric acid or a mono-, di- or
tri-alkyl borate. Other suitable friction modifiers are described
in U.S. Pat. No. 6,300,291, herein incorporated by reference in its
entirety.
[0249] A friction modifier may optionally be present in the
lubricating oil composition in ranges such as about 0 wt % to about
10 wt %, or about 0.01 wt % to about 8 wt %, or about 0.1 wt % to
about 4 wt %.
Transition Metal-Containing Compounds
[0250] In another embodiment, the oil-soluble compound may be a
transition metal containing compound or a metalloid. The transition
metals may include, but are not limited to, titanium, vanadium,
copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the
like. Suitable metalloids include, but are not limited to, boron,
silicon, antimony, tellurium, and the like.
[0251] In an embodiment, an oil-soluble transition metal-containing
compound may function as antiwear agents, friction modifiers,
antioxidants, deposit control additives, or more than one of these
functions. In an embodiment the oil-soluble transition
metal-containing compound may be an oil-soluble titanium compound,
such as a titanium (IV) alkoxide. Among the titanium containing
compounds that may be used in, or which may be used for preparation
of the oils-soluble materials of, the disclosed technology are
various Ti (IV) compounds such as titanium (IV) oxide; titanium
(IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides such
as titanium methoxide, titanium ethoxide, titanium propoxide,
titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide;
and other titanium compounds or complexes including but not limited
to titanium phenates; titanium carboxylates such as titanium (IV)
2-ethyl-1-3-hexanedioate or titanium citrate or titanium oleate;
and titanium (IV) (triethanolaminato)isopropoxide. Other forms of
titanium encompassed within the disclosed technology include
titanium phosphates such as titanium dithiophosphates (e.g.,
dialkyldithiophosphates) and titanium sulfonates (e.g.,
alkylbenzenesulfonates), or, generally, the reaction product of
titanium compounds with various acid materials to form salts, such
as oil-soluble salts. Titanium compounds can thus be derived from,
among others, organic acids, alcohols, and glycols. Ti compounds
may also exist in dimeric or oligomeric form, containing Ti--O--Ti
structures. Such titanium materials are commercially available or
can be readily prepared by appropriate synthesis techniques which
will be apparent to the person skilled in the art. They may exist
at room temperature as a solid or a liquid, depending on the
particular compound. They may also be provided in a solution form
in an appropriate inert solvent.
[0252] In one embodiment, the titanium can be supplied as a
Ti-modified dispersant, such as a succinimide dispersant. Such
materials may be prepared by forming a titanium mixed anhydride
between a titanium alkoxide and a hydrocarbyl-substituted succinic
anhydride, such as an alkenyl- (or alkyl) succinic anhydride. The
resulting titanate-succinate intermediate may be used directly or
it may be reacted with any of a number of materials, such as (a) a
polyamine-based succinimide/amide dispersant having free,
condensable --NH functionality; (b) the components of a
polyamine-based succinimide/amide dispersant, i.e., an alkenyl- (or
alkyl-) succinic anhydride and a polyamine, (c) a
hydroxy-containing polyester dispersant prepared by the reaction of
a substituted succinic anhydride with a polyol, aminoalcohol,
polyamine, or mixtures thereof. Alternatively, the
titanate-succinate intermediate may be reacted with other agents
such as alcohols, aminoalcohols, ether alcohols, polyether alcohols
or polyols, or fatty acids, and the product thereof either used
directly to impart Ti to a lubricant, or else further reacted with
the succinic dispersants as described above. As an example, 1 part
(by mole) of tetraisopropyl titanate may be reacted with about 2
parts (by mole) of a polyisobutene-substituted succinic anhydride
at 140-150.degree. C. for 5 to 6 hours to provide a titanium
modified dispersant or intermediate. The resulting material (30 g)
may be further reacted with a succinimide dispersant from
polyisobutene-substituted succinic anhydride and a
polyethylenepolyamine mixture (127 grams +diluent oil) at
150.degree. C. for 1.5 hours, to produce a titanium-modified
succinimide dispersant.
[0253] Another titanium containing compound may be a reaction
product of titanium alkoxide and C.sub.6 to C.sub.25 carboxylic
acid. The reaction product may be represented by the following
formula:
##STR00001##
wherein n is an integer selected from 2, 3 and 4, and R is a
hydrocarbyl group containing from about 5 to about 24 carbon atoms,
or by the formula:
##STR00002##
wherein m+n=4 and n ranges from 1 to 3, R.sub.4 is an alkyl moiety
with carbon atoms ranging from 1-8, Ri is selected from a
hydrocarbyl group containing from about 6 to 25 carbon atoms, and
R.sub.2 and R.sub.3 are the same or different and are selected from
a hydrocarbyl group containing from about 1 to 6 carbon atoms, or
by the formula:
##STR00003##
wherein x ranges from 0 to 3, R.sub.1 is selected from a
hydrocarbyl group containing from about 6 to 25 carbon atoms,
R.sub.2, and R.sub.3 are the same or different and are selected
from a hydrocarbyl group containing from about 1 to 6 carbon atoms,
and R.sub.4 is selected from a group consisting of either H, or
C.sub.6 to C.sub.25 carboxylic acid moiety.
[0254] Suitable carboxylic acids may include, but are not limited
to caproic acid, caprylic acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachidic acid, oleic acid, erucic
acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid,
phenylacetic acid, benzoic acid, neodecanoic acid, and the
like.
[0255] In an embodiment the oil soluble titanium compound may be
present in the lubricating oil composition in an amount to provide
from 0 to 3000 ppmw titanium or 25 to about 1500 ppmw titanium or
about 35 ppmw to 500 ppmw titanium or about 50 ppmw to about 300
ppm.
[0256] Viscosity Index Improvers
[0257] The lubricating oil compositions herein also may optionally
contain one or more viscosity index improvers. Suitable viscosity
index improvers may include polyolefins, olefin copolymers,
ethylene/propylene copolymers, polyisobutenes, hydrogenated
styrene-isoprene polymers, styrene/maleic ester copolymers,
hydrogenated styrene/butadiene copolymers, hydrogenated isoprene
polymers, alpha-olefin maleic anhydride copolymers,
polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated
alkenyl aryl conjugated diene copolymers, or mixtures thereof.
Viscosity index improvers may include star polymers and suitable
examples are described in US Publication No. 20120101017A1.
[0258] The lubricating oil compositions herein also may optionally
contain one or more dispersant viscosity index improvers in
addition to a viscosity index improver or in lieu of a viscosity
index improver. Suitable viscosity index improvers may include
functionalized polyolefins, for example, ethylene-propylene
copolymers that have been functionalized with the reaction product
of an acylating agent (such as maleic anhydride) and an amine;
polymethacrylates functionalized with an amine, or esterified
maleic anhydride-styrene copolymers reacted with an amine
[0259] The total amount of viscosity index improver and/or
dispersant viscosity index improver may be about 0 wt % to about 20
wt %, about 0.1 wt % to about 15 wt %, about 0.1 wt % to about 12
wt %, or about 0.5 wt % to about 10 wt %, of the lubricating oil
composition.
Other Optional Additives
[0260] Other additives may be selected to perform one or more
functions required of a lubricating fluid. Further, one or more of
the mentioned additives may be multi-functional and provide
functions in addition to or other than the function prescribed
herein.
[0261] A lubricating oil composition according to the present
disclosure may optionally comprise other performance additives. The
other performance additives may be in addition to specified
additives of the present disclosure and/or may comprise one or more
of metal deactivators, viscosity index improvers, detergents,
ashless TBN boosters, friction modifiers, antiwear agents,
corrosion inhibitors, rust inhibitors, dispersants, dispersant
viscosity index improvers, extreme pressure agents, antioxidants,
foam inhibitors, demulsifiers, emulsifiers, pour point depressants,
seal swelling agents and mixtures thereof. Typically,
fully-formulated lubricating oil will contain one or more of these
performance additives.
[0262] Suitable metal deactivators may include derivatives of
benzotriazoles (typically tolyltriazole), dimercaptothiadiazole
derivatives, 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam
inhibitors including copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including trialkyl phosphates, polyethylene glycols, polyethylene
oxides, polypropylene oxides and (ethylene oxide-propylene oxide)
polymers; pour point depressants including esters of maleic
anhydride-styrene, polymethacrylates, polyacrylates or
polyacrylamides.
[0263] Suitable foam inhibitors include silicon-based compounds,
such as siloxane.
[0264] Suitable pour point depressants may include a
polymethylmethacrylates or mixtures thereof. Pour point depressants
may be present in an amount sufficient to provide from about 0 wt %
to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.02
wt % to about 0.04 wt % based upon the final weight of the
lubricating oil composition.
[0265] Suitable rust inhibitors may be a single compound or a
mixture of compounds having the property of inhibiting corrosion of
ferrous metal surfaces. Non-limiting examples of rust inhibitors
useful herein include oil-soluble high molecular weight organic
acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid,
palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic
acid, and cerotic acid, as well as oil-soluble polycarboxylic acids
including dimer and trimer acids, such as those produced from tall
oil fatty acids, oleic acid, and linoleic acid. Other suitable
corrosion inhibitors include long-chain alpha, omega-dicarboxylic
acids in the molecular weight range of about 600 to about 3000 and
alkenylsuccinic acids in which the alkenyl group contains about 10
or more carbon atoms such as, tetrapropenylsuccinic acid,
tetradecenylsuccinic acid, and hexadecenylsuccinic acid. Another
useful type of acidic corrosion inhibitors are the half esters of
alkenyl succinic acids having about 8 to about 24 carbon atoms in
the alkenyl group with alcohols such as the polyglycols. The
corresponding half amides of such alkenyl succinic acids are also
useful. A useful rust inhibitor is a high molecular weight organic
acid. In some embodiments, an engine oil is devoid of a rust
inhibitor.
[0266] The rust inhibitor, if present, can be used in an amount
sufficient to provide about 0 wt % to about 5 wt %, about 0.01 wt %
to about 3 wt %, about 0.1 wt % to about 2 wt %, based upon the
final weight of the lubricating oil composition.
[0267] In general terms, a suitable lubricant may include additive
components in the ranges listed in the following table.
TABLE-US-00004 TABLE 2 Wt. % Wt. % (Suitable (Suitable Component
Embodiments) Embodiments) Dispersant(s) 0.1-20.0 1.0-10.0
Antioxidant(s) 0.1-5.0 0.01-3.0 Detergent(s) 0.1-15.0 0.2-8.0
Ashless TBN booster(s) 0.0-1.0 0.01-0.5 Corrosion inhibitor(s)
0.0-5.0 0.0-2.0 Molybdenum containing compound 0.1-1.0 0.20-0.55
Metal dihydrocarbyldithiophosphate(s) 0.1-6.0 0.1-4.0 Ash-free
phosphorus compound(s) 0.0-6.0 0.0-4.0 Antifoaming agent(s) 0.0-5.0
0.001-0.15 Antiwear agent(s) 0.0-1.0 0.0-0.8 Pour point
depressant(s) 0.0-5.0 0.01-1.5 Viscosity index improver(s) (on a
0.0-25.0 0.1-15.0 liquid/dilute basis) Dispersant viscosity index
improver(s) 0.0-10.0 0.0-5.0 Friction modifier(s) 0.01-5.0 0.05-2.0
Base oil(s) Balance Balance Total 100 100
[0268] The percentages of each component above represent the weight
percent of each component, based upon the weight of the final
lubricating oil composition. The remainder of the lubricating oil
composition consists of one or more base oils.
[0269] Additives used in formulating the compositions described
herein may be blended into the base oil individually or in various
sub-combinations. However, it may be suitable to blend all of the
components concurrently using an additive concentrate (i.e.,
additives plus a diluent, such as a hydrocarbon solvent).
EXAMPLES
[0270] The following examples are illustrative, but not limiting,
of the methods and compositions of the present disclosure. Other
suitable modifications and adaptations of the variety of conditions
and parameters normally encountered in the field, and which are
obvious to those skilled in the art, are within the spirit and
scope of the disclosure. All patents and publications cited herein
are fully incorporated by reference herein in their entirety.
[0271] Each of the lubricating oil compositions contained a major
amount of a base oil and a base conventional dispersant inhibitor
(DI) package. The DI package contained conventional amounts of
dispersant(s), antiwear additive(s), antioxidant(s), friction
modifier(s), antifoam agent(s), process oil(s), viscosity index
improver(s), and pour point depressant(s), as set forth in Table 3.
Specifically, the DI package contained a succinimide dispersant, a
molybdenum-containing compound, an antioxidant, and an antifoam
agent. The major amount of base oil was a mixture of Group III and
Group IV base oils. The components that were varied are specified
in the Tables and discussion of the Examples below. All the values
listed are states as weight percent of the component in the
lubricating oil compositions (i.e., active ingredient plus diluent
oil, if any) unless specified otherwise.
TABLE-US-00005 TABLE 3 DI Package Composition Ranges Component Wt.
% Antioxidant(s) 0.5 to 2.5 Antiwear agent(s), including any metal
dihydrocarbyl 0.5 to 1.5 dithiophosphate Antifoaming agent(s) 0.001
to 0.05 Detergent(s) 1.0-2.0 Dispersant (s) 5.0-9.0
Metal-containing friction modifier(s) 0.03-1.5 Metal free friction
modifier(s) .sup. 0 to 0.5 Pour point depressant(s) 0.05 to 0.5
Process oil 0.25 to 1.0 Viscosity Index Improver(s) 0.0 to 2.0
[0272] Sulfated ash (SASH) was calculated for total of metallic
elements that contribute to SASH in the lubricant composition
according to the following factors that were multiplied by the
amount of each metallic element in the lubricant composition
according to:
http://konnaris.com/portals/0/search/calculations.htm.
TABLE-US-00006 Element Factor Barium 1.70 Boron 3.22 Calcium 3.40
Copper 1.252 Lead 1.464 Lithium 7.92 Magnesium 4.95 Manganese 1.291
Molybdenum 1.50 Potassium 2.33 Sodium 3.09 Zinc 1.50
[0273] Reference oil R-1 was formulated from about 80.7 wt. % of a
Group III base oil, 12.1 wt. % of HiTEC.RTM. 11150 PCMO Additive
Package available from Afton Chemical Corporation and 7.2 wt. % of
a 35 SSI ethylene/propylene copolymer viscosity index improver.
HiTEC.RTM. 11150 passenger car motor oil additive package is an API
SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package. R-1 also
showed the following properties and partial elemental analysis:
TABLE-US-00007 Reference Oil R-1 10.9 Kinematic Viscosity at
100.degree. C., (mm.sup.2/sec) 3.3 HTHS at 150.degree. C., (cP)
2438 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw)
772 phosphorus (ppmw) 855 zinc (ppmw) 9.0 Total Base Number ASTM
D-2896 (mg KOH/g) 165 Viscosity Index
[0274] Low Speed Pre-Ignition (LSPI) events were measured in a GM
2.0 Liter, 4 cylinder Ecotec turbocharged gasoline direct injection
(TGDi) engine. One complete LSPI fired engine test consisted of 4
test cycles. Within a single test cycle, two operational stages or
segments are repeated in order to generate LSPI events. In stage A,
when LSPI is most likely to occur, the engine is operated at about
2000 rpm and about 1,800 kPa brake mean effective pressure (BMEP).
In stage B, when LSPI is not likely to occur, the engine is
operated at about 1500 rpm and about 1,700 kPa BMEP. For each
stage, data is collected over 25,000 engine cycles. The structure
of a test cycle is as follows: stage A stage A stage B stage B
stage A stage A. Each stage is separated by an idle period. Because
LSPI is statistically significant during stage A, the LSPI event
data that was considered in the present examples only included LSPI
events generated during stage A operation. Thus, for one complete
LSPI fired engine test, data was typically generated over a total
of 16 stages and was used to evaluate performance of comparative
and inventive oils.
[0275] LSPI events were determined by monitoring peak cylinder
pressure (PP) and when 2% of the combustible material in the
combustion chamber burns (MFB02). The threshold for peak cylinder
pressure is calculated for each cylinder and for each stage and is
typically 65,000 to 85,000 kPa. The threshold for MFB02 is
calculated for each cylinder and for each stage and typically
ranges from about 3.0 to about 7.5 Crank Angle Degree (CAD) After
Top Dead Center (ATDC). An LSPI was recorded when both the PP and
MFB02 thresholds were exceeded in a single engine cycle. LSPI
events can be reported in many ways. In order to remove ambiguity
involved with reporting counts per engine cycle, where different
fired engine tests can be conducted with a different number of
engine cycles, the relative number of LSPI events of comparative
and inventive oils were reported as an "LSPI Ratio". In this way
improvement relative to some standard response is clearly
demonstrated.
[0276] In the examples carried out in Table 4, the LSPI Ratio was
reported as a ratio of the LSPI events of a test oil relative to
the LSPI events of Reference Oil "R-1".
[0277] Considerable improvement in LSPI is recognized when there is
greater than 50% reduction in LSPI events relative to R-1 (an LSPI
Ratio of less than 0.5). A further improvement in LSPI is
recognized when there is greater than 70% reduction in LSPI events
(an LSPI Ratio of less than 0.3), an even further improvement in
LSPI is recognized when there is greater than 75% reduction in LSPI
events (an LSPI Ratio of less than 0.25), and an even further
improvement in LSPI is recognized when there is greater than 80%
reduction in LSPI events relative to R-1 (an LSPI Ratio of less
than 0 20), and an even further improvement in LSPI is recognized
when there is greater than 90% reduction in LSPI events relative to
R-1 (an LSPI Ratio of less than 0.1). The LSPI Ratio for R-1
reference oil is thus deemed to be 1.00.
[0278] In the following examples, the LSPI Ratio was reported as a
ratio of the LSPI events of a test oil relative to the LSPI events
of Reference Oil "R-1".
[0279] The following examples were prepared to demonstrate the LSPI
performance of an amount of one or more Zr containing compounds in
combination with an overbased calcium-containing detergent. Each of
the examples contained a majority of a base oil, a base oil
conventional DI package, and an overbased calcium-containing
detergent. Inventive examples, IE 1-IE 3 also included a Zr
containing compound. The LSPI results may be found in Table 4 and
FIG. 1.
TABLE-US-00008 TABLE 4 LSPI Ca Zr Zirconium Ca/Zr Zr/Ca Perfor-
(ppmw) (ppmw) type Ratio Ratio mance R-1 2438 0 N/A N/A N/A 1 IE 1
2454 926 Zirconium 2.7 0.38 0.5 2-Ethyl- hexanoate IE 2 2444 1872
Zirconium 1.3 0.77 0.23 2-Ethyl- hexanoate IE 3 2265 5245 Nano- 0.4
2.32 0.01 particles
[0280] R-1 did not include an amount of zirconium from
zirconium-containing compounds or zirconium-containing
nanoparticles. As seen from Table 4, examples IE-1 and IE-2
including 926 ppmw and 1872 ppmw of zirconium, respectively, show
that with increased zirconium a reduction in LSPI performance is
observed, relative to R-1. Furthermore, it was observed that
employing zirconium-containing nanoparticles provided a significant
reduction in LSPI events relative to R-1.
[0281] The following table shows prophetic examples according to
the present invention.
TABLE-US-00009 TABLE 5 Zr Ca Ca/Zr Zr/Ca Sulfated (ppm) (ppm) Ratio
Ratio LSPI Ash CE-1 0 ~2300 N/A N/A FAIL PASS IE-4 50 ~2300 46.00
0.02 IE-5 100 ~2300 23.00 0.04 IE-6 200 ~2300 11.50 0.09 IE-7 486
~2300 4.73 0.21 PASS PASS IE-8 926 ~2300 2.48 0.40 PASS PASS IE-9
1872 ~2300 1.23 0.81 PASS PASS CE-2 5245 ~2300 0.44 2.28 PASS
FAIL
[0282] The following table shows prophetic examples with predicted
results for LSPI and Sulfated Ash.
TABLE-US-00010 TABLE 6 CE-3 IE-10 IE-11 IE-12 CE-4 Ca 900 900 900
900 900 Mg 900 900 900 900 900 P 600 600 600 600 600 Zn 636 636 636
636 636 B 40 40 40 40 40 Mo 10 10 10 10 10 Si 5 5 5 5 5 Zr 0 50 200
500 1000 Ca/Zr Ratio 0.00 18.00 4.50 1.80 0.90 Zr/Ca Ratio 0.00
0.06 0.22 0.56 1.11 Predicted LSPI 0.35 0.31 0.21 0.01 0 Sulfated
Ash (calculated) 0.85 0.85 0.87 0.91 0.98 Relative LSPI (predicted)
1 0.89 0.60 0.03 0.00 SASH PASS PASS PASS PASS FAIL LSPI FAIL PASS
PASS PASS PASS
[0283] Other embodiments of the present disclosure will be apparent
to those skilled in the art from consideration of the specification
and practice of the embodiments disclosed herein. As used
throughout the specification and claims, "a" and/or "an" may refer
to one or more than one. Unless otherwise indicated, all numbers
expressing quantities of ingredients, properties such as molecular
weight, percent, ratio, reaction conditions, and so forth used in
the specification and claims are to be understood as being modified
in all instances by the term "about," whether or not the term
"about" is present. Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the specification and claims
are approximations that may vary depending upon the desired
properties sought to be obtained by the present disclosure. At the
very least, and not as an attempt to limit the application of the
doctrine of equivalents to the scope of the claims, each numerical
parameter should at least be construed in light of the number of
reported significant digits and by applying ordinary rounding
techniques. Notwithstanding that the numerical ranges and
parameters setting forth the broad scope of the disclosure are
approximations, the numerical values set forth in the specific
examples are reported as precisely as possible. Any numerical
value, however, inherently contains certain errors necessarily
resulting from the standard deviation found in their respective
testing measurements. It is intended that the specification and
examples be considered as exemplary only, with a true scope and
spirit of the disclosure being indicated by the following
claims.
[0284] The foregoing embodiments are susceptible to considerable
variation in practice. Accordingly, the embodiments are not
intended to be limited to the specific exemplifications set forth
hereinabove. Rather, the foregoing embodiments are within the
spirit and scope of the appended claims, including the equivalents
thereof available as a matter of law.
[0285] The patentees do not intend to dedicate any disclosed
embodiments to the public, and to the extent any disclosed
modifications or alterations may not literally fall within the
scope of the claims, they are considered to be part hereof under
the doctrine of equivalents.
[0286] It is to be understood that each component, compound,
substituent or parameter disclosed herein is to be interpreted as
being disclosed for use alone or in combination with one or more of
each and every other component, compound, substituent or parameter
disclosed herein.
[0287] It is also to be understood that each amount/value or range
of amounts/values for each component, compound, substituent or
parameter disclosed herein is to be interpreted as also being
disclosed in combination with each amount/value or range of
amounts/values disclosed for any other component(s), compounds(s),
substituent(s) or parameter(s) disclosed herein and that any
combination of amounts/values or ranges of amounts/values for two
or more component(s), compounds(s), substituent(s) or parameters
disclosed herein are thus also disclosed in combination with each
other for the purposes of this description.
[0288] It is further understood that each range disclosed herein is
to be interpreted as a disclosure of each specific value within the
disclosed range that has the same number of significant digits.
Thus, a range of from 1-4 is to be interpreted as an express
disclosure of the values 1, 2, 3 and 4.
[0289] It is further understood that each lower limit of each range
disclosed herein is to be interpreted as disclosed in combination
with each upper limit of each range and each specific value within
each range disclosed herein for the same component, compounds,
substituent or parameter. Thus, this disclosure to be interpreted
as a disclosure of all ranges derived by combining each lower limit
of each range with each upper limit of each range or with each
specific value within each range, or by combining each upper limit
of each range with each specific value within each range.
[0290] Furthermore, specific amounts/values of a component,
compound, substituent or parameter disclosed in the description or
an example is to be interpreted as a disclosure of either a lower
or an upper limit of a range and thus can be combined with any
other lower or upper limit of a range or specific amount/value for
the same component, compound, substituent or parameter disclosed
elsewhere in the application to form a range for that component,
compound, substituent or parameter.
* * * * *
References