Note: Descriptions are shown in the official language in which they were submitted.
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TITLE: METHOD OF OPERATING INTERNAL COMBUSTION ENGINE BY
INTRODUCING DETERGENT INTO COMBUSTION CHAMBER
This application claims the benefit of U.S. Provisional Application Nos.
60/368354 filed
28 March 2002 and 60/441012 filed 17 January 2003.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention comprises a method of operating an internal combustion
engine that comprises introducing a nitrogen-containing detergent composition
into a
combustion chamber during the operation of the engine. The method results in
improved
performance of a lubricating oil of the engine and also improves performance
of a fuel
composition when the detergent composition is present in the fuel composition.
2. Description of the Related Art
Current and future performance requirements and exhaust emission requirements
for internal combustion engines are necessitating new and improved lubricating
oil
formulations and methods of lubrication for engines.
Longer intervals between engine oil drains lessen demands for disposal and
effects
on the environment, but increase performance requirements for oxidation, wear,
detergency, dispersancy, viscosity stability and friction durability.
Compression-ignited
diesel engines and spark-ignited direct injection engines have exhaust gas
recirculation
(EGR) systems that reduce generation of nitrogen oxides (NOx), by reducing the
oxygen
concentration and consequently the combustion temperature, but that increase
the
generation of soot in the lubricating oil. This increased soot requires
increased
dispersancy, detergency and wear performance or more frequent oil drains to
avoid severe
problems of wear, deposits and exhaust emissions. Formulating an engine
lubricating oil
with increased amounts of additives to meet increased performance requirements
is not
always possible due to limitations such as allowable sulfur, phosphorus and
metal content
as well as performance issues from high levels of additives such as seal
compatibility with
high levels of dispersants. '
Spark-ignited gasoline engines and compression-ignited diesel engines have
various exhaust treatment devices to reduce emissions of carbon monoxide,
hydrocarbons,
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nitrogen oxides and particulates. Since it is believed that sulfur, phosphorus
and metals
can adversely affect engine exhaust treatment devices such as catalytic
converters, a
gradual reduction in the level of sulfur, phosphorus and metals in engine
lubricating oils is
being implemented. This reduction in sulfur, phosphorus and metals
consequently
requires increased detergency, oxidation and wear performance from additives
that do not
contain sulfur, phosphorus or metals.
Fuels with reduced levels of sulfur for both spark-ignited and compression-
ignited
engines are also being introduced that are more compatible with exhaust
treatment devices
for reducing air pollutants. However, this reduction of sulfur levels in fuels
can require
increased oxidation performance in lubricating oils.
U.S. Application No. 60/368,354 filed on March 28, 2002, discloses
introduction
of nitrogen-containing detergents including polyetheramines into the
combustion chamber
of an internal combustion engine to improve the performance of the lubricating
oil.
U.S. Application No. 60/374,640 filed on April 23, 2002, discloses use of an
antioxidant in the fuel of an internal combustion engine to improve the
performance of the
lubricating oil.
European Publication No. EP1132455 A1 discloses a fuel additive composition of
a Mannich condensation product and a hydrocarbyl-substituted polyoxyallcylene
amine
that controls engine oil screen plugging.
U.S. Patent No. 6,224,642 discloses the combination of a polyetheramine
RO(Cd H80)n CHZCHZCH2NH2 and a second compound that is a fatty acid,
derivative of a
fatty acid, or a succinic acid or anhydride where the combination is useful in
fuels to
reduce engine wear.
International Publication No. WO 01/88069 A1 discloses entrainment of metal
detergents and nonmetal detergents in the combustion chamber during operation
of the
engine to improve engine operation.
International Publication No. WO 97/44414 discloses the addition of a
detergent
and combustion improver to a fuel to reduce liner lacquering in a marine
diesel engine.
International Publication No. WO 02/18521 A2 discloses that a lubricating oil
can
have a phosphorus level of 0.05% by weight and satisfactory wear performance
in
conjunction with a gasoline fuel having a sulfur content below 10 ppm by
weight.
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International Publication No. WO 021079353 discloses a) a gasoline additive
concentrate composition containing a solvent, an alkoxylated fatty amine, and
a partial
ester having at least one free hydroxyl group and formed by reacting a fatty
carboxylic
acid and a polyol, b) a fuel composition containing gasoline and the
concentrate
composition, and c) a method of operating a gasoline internal combustion
engine by
fueling the engine with the fuel composition which reduces fuel consumption.
It has now been found that the introduction of a nitrogen-containing detergent
composition into a combustion chamber of an internal combustion engine
improves the
performance of a lubricating oil of the engine and also of a fuel composition
when the
detergent composition is present in the fuel composition.
SUMMARY OF THE INVENTION
It is an object of the present invention to improve the performance of both a
fuel
composition and a lubricating oil of an internal combustion engine.
Another object of this invention is to improve the performance a fuel
composition
and a lubricating oil of a compression-ignited or spark-ignited direct
injection internal
combustion engine having an exhaust gas recirculation system.
A further object of the invention is to improve the performance of a fuel
composition and a lubricating oil of a spark-ignited or compression-ignited
internal
combustion engine having an exhaust treatment device and a lubricating oil
that has at
least one of the properties selected from the group consisting of a phosphorus
content
below 0.1% by weight, a sulfur content below 0.5% by weight, and a sulfated
ash content
below 1.5% by weight.
An additional object of the present invention is to improve the performance of
a
fuel composition and a lubricating oil of a spark-ignited or compression-
ignited internal
combustion engine having an exhaust treatment device and where a fuel of the
fuel
composition has a sulfur content below 80 ppm by weight.
Yet another object of this invention is to improve the performance of a fuel
composition and a lubricating oil of a spark-ignited or compression-ignited
internal
combustion engine that is installed in a motor vehicle and has a recommended
drain
interval for the lubricating oil of the engine of greater than 6,000 miles.
Yet a further object of the invention is to improve the performance of a fuel
composition and a lubricating oil of a spark-ignited or compression-ignited
internal
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combustion engine that is a stationary engine having a recommended drain
interval for the
lubricating oil of the engine of greater than 150 operational hours.
Additional objects and advantages of the present invention will be set forth
in the
Detailed Description that follows and, in part, will be obvious from the
Detailed
Description or may be learned by the practice of the invention. The objects
and
advantages of the invention may be realized by means of the instrumentalities
and
combinations pointed out in the appended claims.
To achieve the foregoing objects in accordance with the invention, as
described
and claimed herein, a method of operating an internal combustion engine
comprises
introducing a nitrogen-containing detergent composition that comprises (A) a
reaction
product of a hydrocarbyl-substituted acylating agent and an amine; (B) a
hydrocarbyl-
substituted amine; (C) a Mannich reaction product of a hydrocarbyl-substituted
hydroxy-
containing aromatic compound, an aldehyde, and an amine; (D) a high molecular
weight
polyetheramine prepared by reacting one unit of a hydroxy-containing
hydrocarbyl
compound with two or more units of butylene oxide to form a polyether
intermediate, and
aminating the polyether intermediate by reacting the polyether intermediate
with an amine
or with acrylonitrile and hydrogenating the reaction product of the polyether
intermediate
and acrylonitrile; or (E) a mixture thereof into a combustion chamber of the
engine during
the operation of the engine wherein the detergent composition improves the
performance
of a lubricating oil of the engine.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows end of test total base number retention for OW30 oil from VW
fleet
trial.
Figure 2 shows end of test total base number retention for 5W40 oil from VW
fleet
trial.
Figure 3 shows average piston ratings for engine oils from VW fleet trial.
Figure 4 shows change in particulate emissions from VW fleet trial.
Figure 5 shows total base number retention for engine oils from Ford Crown
Victoria fleet trial.
Figure 6 shows distance accumulated for TBN-TAN cross-over for engine oils
from Ford direct injection fleet trial.
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Figure 7 shows particulate emissions for IS08178 test cycle from Liebherr 914T
engine test.
Figure 8 shows particulate emissions in 20-200 nm size spectrum for IS08178
test
cycle from Liebherr 914T engine test.
Figure 9 shows engine oil sludge ratings from M-B M111E engine test.
DETAILED DESCRIPTION OF THE INVENTION
A method of the present invention of operating an internal combustion engine
comprises introducing a nitrogen-containing detergent composition that
comprises (A) a
reaction product of a hydrocarbyl-substituted acylating agent and an amine;
(B) a
hydrocarbyl-substituted amine; (C) a Mannich reaction product of a hydrocarbyl-
substituted hydroxy-containing aromatic compound, an aldehyde, and an amine;
(D) a
high molecular weight polyetheramine prepared by reacting one unit of a
hydroxy-
containing hydrocarbyl compound with two or more units of butylene oxide to
form a
polyether intermediate, and aminating the polyether intermediate by reacting
the polyether
intermediate with an amine or with acrylonitrile and hydrogenating the
reaction product of
the polyether intermediate and acrylonitrile; or (E) a mixture thereof into a
combustion
chamber of the engine during the operation of the engine wherein the detergent
composition improves the performance of a lubricating oil of the engine.
The internal combustion engine of the present invention includes all types of
spark-ignited and compression-ignited engines to include those that can
operate on a two-
stroke or a four-stroke cycle. These internal combustion engines can be used
in various
types of motor vehicles and stationary and mobile or transportable equipment
to include
automobiles, trucks, off-highway vehicles and equipment, boats and ships,
railroad
engines, airplanes, recreational vehicles, generators, pumps, compressors,
chain saws,
? 5 mowers, and farm vehicles and equipment.
The method of the present invention of operating an internal combustion engine
involves introducing a detergent composition into a combustion chamber of the
engine. In
one embodiment the detergent composition is introduced into the combustion
chamber by
injection from a dosing system. The injection from the dosing system can be
directly into
the combustion chamber or into a fuel system of the engine such as a fuel
storage tank of
the fuel system so that the detergent composition enters the combustion
chamber as a
component of a fuel composition. In other embodiments of the invention the
detergent
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composition is introduced into the combustion chamber as a component of the
fuel
composition where the detergent composition is added to-a fuel in a bulk
treatment at a
refinery or storage facility or is added to a fuel in an aftermarket treatment
such as adding
the detergent composition to a fuel in a fuel tank of a motor vehicle.
The introduction of the detergent composition into a combustion chamber of an
internal combustion engine improves the performance of a lubricating oil of
the engine
and also the performance of a fuel composition when the detergent composition
is a
component of the fuel composition. Improving the performance of the fuel
composition
can include deposit control in keeping clean or cleaning up deposits
throughout the fuel
system to include intake valves, fuel injectors and combustion chambers;
enhancing
lubricity so that wear is reduced of fuel system components such as fuel pumps
and fuel
injectors; and reduction of particulate emissions. Improving the performance
of the
lubricating oil can include detergency such as acid neutralization or TBN
(total base
number) retention, dispersancy to include control of engine sludge and piston
cleanliness,
antioxidation, antiwear, viscosity control and friction durability.
In one embodiment of the invention the detergent composition is (A) a reaction
product of a hydrocarbyl-substituted acylating agent and an amine. Throughout
this
application the term hydrocarbyl represents a univalent group of one or more
carbon atoms
that is predominately hydrocarbon in nature, but can contain heteroatoms such
as oxygen
in the carbon chain and can have nonhydrocarbon and heteroatom-containing
groups such
as hydroxy, halo, nitro and alkoxy attached to a the carbon chain. The
hydrocarbyl
substituent of the acylating agent can be a hydrocarbon group having a number
average
molecular weight of 150 to 5000 and in other instances of 175 to 3000 and 200
to 1500.
The hydrocarbon group can be derived from an olefin or polyolefin. Virtually
any
compound containing an olefinic bond may be used to react with a
monounsaturated
carboxylic acid reactant or equivalent thereof. The polyolefin can be derived
from olefin
monomers to include CZ to Cao monoolefins and in another instance C2 to CS
monoolefins.
Useful monoolefins include ethylene, propylene, butenes such as isobutylene
and 1-
butene, pentenes, hexenes octenes and decenes. The polyolefin can be a
homopolymer
prepared from a single olefin monomer such as a polyisobutylene or a copolymer
prepared
from a mixture of two or more olefin monomers such as copolymers of ethylene
and
propylene, 1-butene and isobutylene, and propylene and isobutylene. In an
embodiment
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of the invention the polyolefin is a polyisobutylene having a vinylidene
double bond
content of 50 to 70% and in another instance of 50 to 95%. Polyolefins can be
prepared
from olefin monomers by well known polymerization methods and are also
commercially
available.
The acylating agent can be derived from a monounsaturated monocarboxylic or
polycarboxylic acid or reactive equivalent thereof. Reactive equivalents
include acid
anhydrides, esters, and acid halides. Useful monounsaturated monocarboxylic
acids or
reactive equivalents thereof include C3 to C1o acids and reactive equivalents
such as
acrylic acid, methacrylic acid and methyl acrylate. Useful monounsaturated
polycarboxylic acids and reactive equivalents thereof include C4 to Clo acids
and reactive
equivalents such as malefic acid, malefic anhydride, fumaric acid and dimethyl
fumarate.
The hydrocarbyl-substituted acylating agent can be prepared by reacting a
polyolefin and a monounsaturated monocarboxylic and/or polycarboxylic acid or
reactive
equivalent thereof by well known methods such as the thermal reaction of a
polyisobutylene and malefic anhydride with or without chlorination as
described in U.S.
Patent No. 4,234,435.
The amine of the detergent composition (A) can be any compound that contains a
reactive nitrogen to hydrogen or N-H bond. The amine can be ammonia, a
monoamine, a
polyamine, or a mixture thereof. The monoamine and polyamine and ammonia also
include alkanolamines having one or more hydroxyl groups. In another
embodiment of the
invention an alcohol can also be present with the amine in a reaction with the
hydrocarbyl-
substituted acylating agent. The alcohol can be a monohydric alcohol such as
butanol or a
polyhydric alcohol such as ethylene glycol or pentaerythritol. Useful amines
include
hydroxylamine, ethanolamine, diethanolamine, butylamine, ethylenediamine,
hydrazines,
polyethylenepolyamines such as tetraethylenepentamine, and
polyethylenepolyamine
bottoms. The amines are generally commercially available.
The detergent composition (A) can be prepared by reacting the hydrocarbyl-
substituted acylating agent and the amine at elevated temperatures such as the
reaction of a
polyisobutenylsuccinic acylating agent and a polyethylenepolyamine, for
example,
polyisobutenylsuccinic anhydride and tetraethylenepentamine, at 100 to
200°C as
described in U.S. Patent No. 4,234,435. In an embodiment of the invention the
detergent
composition (A) is a reaction product of a polyisobutenylsuccinic anhydride
prepared from
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a high vinylidene content polyisobutylene and a polyethylenepolyamine such as
tetraethylenepentamine where the reaction product has a high imide content as
described
in International Publication No. W002/102942. In another embodiment of the
invention
the detergent composition (A) is a reaction product of a hydrocarbyl-
substituted acylating
agent and a polyamine where the hydrocarbyl-substituted acylating agent is
prepared from
a reaction of an oxoalkanoic acid or reactive equivalent thereof such as
glyoxylic acid or
glyoxylic acid methyl ester methyl hemiacetal or pyruvic acid and a polyolefin
such as a
polyisobutylene as described in U.S. Patent No. 5,696,067. In a further
embodiment of
this invention the detergent composition (A) is a reaction product of a
hydrocarbyl-
substituted acylating agent and a polyamine where the hydrocarbyl-substituted
acylating
agent is prepared from a reaction of an oxoallcanoic acid or reactive
equivalent thereof as
just described above and a C4 to C145 alkylphenol as described in U.S. Patent
No.
5,336,278. In still another embodiment of the invention the detergent
composition (A) is
the reaction product of a C12 to C2o alkenylsuccinic anhydride such as
hexadecenylsuccinic
anhydride and an alkanolamine such as N,N-diethylethanolamine. In yet a
further
embodiment of the invention the detergent composition (A) is a product of a
mixture of a
first and second polyisobutenylsuccinic anhydride, where the polyisobutenyl
substituents
have respectively number average molecular weights of 2300 and 1000, reacted
with
ethylene glycol and then reacted with N,N-dimethylethanolamine in a mole ratio
of
respectively 2:1:2.
The detergent composition of the present invention can be (B) a hydrocarbyl-
substituted amine. The hydrocarbyl substituent of the amine can have a number
average
molecular weight of 150 to 5000 and in other instances of 175 to 3000 and 200
to 1500.
The hydrocarbyl substituent can be derived from an olefin or a polyolefin as
described
above for the hydrocarbyl-substituent of the detergent composition (A). Useful
polyolefins include polyisobutylenes. The amine of the hydrocarbyl-substituted
amine can
be derived from ammonia, a monoamine, a polyamine, or a mixture thereof. The
monoamine or polyamine can be an alkanolamine having one or more hydroxyl
groups.
Useful amines include polyamines such as ethylenediamine and
diethylenetriamine and
alkanolamines such as 2-(2-aminoethylamino)ethanol. The detergent composition
(B) can
be prepared by several methods. In one embodiment of the invention
polyisobutylene is
chlorinated and the chlorinated polyisobutylene is reacted with an amine such
as
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ethylenediamine in the presence of a base such as sodium carbonate as
described in U.S.
Patent No. 5,407,453. In another embodiment of the invention a polyisobutylene
is
hydroformylated, for example, via the Oxo process, with carbon monoxide and
hydrogen
using a metal catalyst at an elevated temperature and pressure, and the
product from the
hydroformylation is aminated optionally in the presence of hydrogen as
described in U.S.
Patent No. 5,496,383. In a further embodiment of the invention a
polyisobutylene is
oxidized to an epoxide by one of several known methods such as oxidation with
a
peroxycarboxylic acid, and the epoxide is aminated generally with an excess of
an amine
as described in European Publication No. EP-B-573578. In still another
embodiment of
the invention the detergent composition (B) is a hydroxyalkyl-substituted
fatty amine
which can be represented by the formula RN[(A10)XH][(AZO)yH]. R can be a C1z
to C;n
hydrocarbyl group and in other instances can be a C14 to CZ~ and a C1~ to C22
hydrocarbyl
group. The hydrocarbyl group can be a straight chain, a branched chain, or a
mixture
thereof. The hydrocarbyl group can be saturated, unsaturated, or a mixture
thereof. A1 and
A2 are independently CZ to C18 alkylene groups and in other instances are C2
to C1z and CZ
to C8 alleylene groups where x and y are independently integers having a value
of 0 or
higher and x + y is at least 1 and in other instances x + y is 2 or greater
than 2. The
hydroxyalkyl-substituted fatty amine can be prepared by reacting one unit of a
fatty amine
with one or more units of an alkylene oxide to produce a monoallcoxylated
andlor
20~ polyalkoxylated fatty amine. The alkylene oxide can be a C2 to C18
alkylene oxide or a
mixture of two or more CZ to C1g allcylene oxides. Useful alkylene oxides
include ethylene
oxide, propylene oxide, butylene oxide, or a mixture thereof. Useful
hydroxyalkyl-
substituted fatty amines include diethoxylated tallowamine, diethoxylated
oleylamine,
diethoxylated stearylamine and diethoxylated amines from soybean oil fatty
acids which
are commercially available such as the Ethomeen~ series from Akzo Nobel.
The detergent composition of the present invention can be (C) a Mannich
reaction
product of a hydrocarbyl-substituted hydroxy-containing aromatic compound, an
aldehyde, and an amine. The hydrocarbyl substituent of the aromatic compound
can have
a number average molecular weight of 120 to 3000 and in other instances the
number
average molecular weight can be 130 to 2300, 140 to 1500, 140 to 950, and 1000
to 2300.
The hydrocarbyl substituent can be derived from an olefin or polyolefin as
described
above for the hydrocarbyl substituent of the acylating agent of detergent
composition (A).
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Useful polyolefins for the hydrocarbyl substituent of detergent composition
(C) include a
polyisobutylene, a polyisobutylene having a vinylidene double bond content of
50% or
greater, and a polypropylene such as a C12 polypropylene. The hydroxy-
containing
aromatic compound of the Mannich reaction product can include phenol, a
polyhydroxy-
containing aromatic compound such as resorcinol and catechol, a Ci to C$
allcyl-
substituted hydroxy-containing aromatic compound such as ortho-cresol, or a
mixture
thereof. The hydrocarbyl-substituted hydroxy-containing aromatic compounds can
be
prepared by well known methods such as for example a Lewis acid catalyzed
alkylation of
phenol with a polyisobutylene. The aldehyde of the Mannich reaction product
can be a Ci
to C~ aldehyde to include formaldehyde in one of its reactive forms such as
formalin and
paraformaldehyde. The amine used to prepare the Mannich reaction product
contains at
least one reactive nitrogen to hydrogen or N-H bond and can be ammonia, a
monoamine, a
polyamine, or a mixture thereof. The amine can be an allcanolamine containing
one or
more hydroxyl groups. Useful amines include ammonia, hydroxylamine,
ethylamine,
dimethylamine, ethanolamine, diethanolamine, ethylenediamine,
dimethylaminopropylamine, and polyethylenepolyamines. The Mannich reaction
product
can be prepared by reacting a hydrocarbyl-substituted hydroxy-containing
aromatic
compound, an aldehyde, and an amine at an elevated temperature such as for
example an
alkylphenol derived from a high vinylidene polyisobutylene, formaldehyde and
ethylenediamine as described in U.S. Patent No. 5,697,988.
The detergent composition of the present invention can be (D) a high molecular
weight polyetheramine. This polyetheramine can contain two or more ether units
and is
generally prepared from a polyether intermediate. The polyether intermediate
can be a
reaction product of one unit of a hydroxy-containing hydrocarbyl compound with
two or
more units of butylene oxide. The hydroxy-containing hydrocarbyl compound can
be an
alcohol or an alkyl-substituted phenol where the alcohol or alkyl substituent
of the phenol
can have 1 to 50 carbon atoms, 6 to 30 carbon atoms in a second instance, and
8 to 24
carbon atoms in a third instance. The alcohol or alkyl substituent of the
phenol can have a
straight carbon chain, branched carbon chain, or a mixture thereof. The
hydroxy-
containing hydrocarbyl compound can contain one or more hydroxyl groups.
The polyether intermediate from the reaction of a hydroxy-containing
hydrocarbyl
compound and butylene oxide can have 2 to 100 repeating butylene oxide units,
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repeating butylene oxide units in a second embodiment, and 151 to 30 repeating
butylene
oxide units in a third embodiment. U.S. Patent No. 5,094,667 provides reaction
conditions
for preparing a polyether intermediate.
The high molecular weight polyetheramine of the present invention can be
prepared from the above described polyether intermediate that is prepared from
butylene
oxide.
In one embodiment of the invention the polyetheramine is prepared by reacting
the
polyether intermediate derived from butylene oxide with acrylonitrile to form
a nitrile that
is then hydrogenated to form a 3-aminopropyl terminated polyether as described
in U.S.
Patent No. 5,094,667.
In another embodiment of the invention the polyetheramine is prepared by
reacting
the polyether intermediate derived from butylene oxide with an amine in an
amination
reaction to give an aminated polyether as described in European Publication
No.
EP310875. The amine can be a primary or secondary monoamine, a polyamine
containing
an amino group with a reactive N-H bond, or ammonia.
The high molecular weight polyetheramine of the present invention can have a
number average molecular weight of 300 or 350 to 5000, in another instance of
400 to
3500, and in further instances of 450 to 2500 and 1000 to 2000.
In another embodiment of the invention the high molecular weight
polyetheramine
of the present invention can be represented by the formula R(OCHZCHRI)XA where
R is a
C~ to C3o alkyl group or a CG to C3o alkyl-substituted phenyl group; R1 is
ethyl; x is a
number from 5 to 50; and A is OCH2CHZCHZNH2 or -NR2 R3 wherein R2 and R3 are
independently hydrogen, a hydrocarbyl group, or -(R4 NRS)yR~ wherein R4 is an
allcylene
group having 2 to 10 carbon atoms, RS and R~ are independently hydrogen or a
hydrocarbyl group, and y is a number from 1 to 7. Throughout this application
an
allcylene group is a divalent alkane group. In a further embodiment of the
polyetheramine
of the invention, R is a C8 to C24 alkyl group, x is a number from 15 to 30,
and A is
-OCH2 CHZ CH2 NH2.
The detergent composition of this invention can be (E) a mixture of detergent
compositions (A), (B), (C) and (D). In an embodiment of the invention the
mixture (E)
includes two or more components taken from a single detergent composition type
such as
a mixture of two components taken from detergent composition (A). In another
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embodiment of this invention the mixture (E) includes one or more components
taken
from a detergent type and one or more components taken from one or more of the
other
three detergent types such as a mixture of a component taken from detergent
composition
(B) and a component taleen from detergent composition (D).
The method of the present invention improves the performance of a lubricating
oil
of an internal combustion engine. The lubricating oil comprises an oil of
lubricating
viscosity, which can be a natural oil, a synthetic oil, or mixtures thereof.
Natural oils
include various refined mineral oils, animal oils, and vegetable oils.
Synthetic oils include
hydrogenated poly(alpha-olefins), poly(alkylene glycol)s, and esters of
carboxylic acids.
In an embodiment of the invention the lubricating oil can be an American
Petroleum
Institute Group I-V base oil or a mixture thereof. The lubricating oil of the
present
invention can further comprise one or more lubricating oil additives to
include nitrogen-
containing dispersants such as polyisobutenylsuccinimides, metal-containing
detergents
such as alkali and alkaline earth metal neutral and overbased salts of
alkylaryl sulfonates,
antioxidants such as sulfurized olefins which can be sulfides or polysulfides
or mixtures
thereof, antiwear agents such as zinc dialkyl dithiophosphates and organic
molybdenum
compositions, corrosion inhibitors such as tolyltriazole, viscosity modifiers
to include
viscosity index improvers and pour point depressants such as various
polyolefins and
polymethacrylates, friction modifiers such as glycerol mono- and dioleate, and
antifoam
agents such as silicones. Lubricating oil additives can be present in a
lubricating oil and at
a level to provide the required performance for an internal combustion engine.
The level
of the lubricating oil additive in the lubricating oil can range from about
0.1 ppm by
weight to about 20% by weight.
In the method of the present invention a detergent composition can be
introduced
into a combustion chamber of an internal combustion engine as a component of a
fuel
composition. The fuel composition comprises a normally liquid fuel. The
normally liquid .
fuel can include a hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture
thereof. The
hydrocarbon fuel can be a petroleum distillate to include a gasoline as
defined by ASTM
specification D4814 or a diesel fuel as defined by ASTM specification D975.
The
nonhydrocarbon fuel can be an oxygen-containing composition to include an
alcohol, an
ether, a nitroalkane, an ester of a vegetable oil, or a mixture thereof.
Useful
nonhydrocarbon fuels include methanol, ethanol, diethyl ether, methyl t-butyl
ether,
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nitromethane, and methyl esters of vegetable oils such as the methyl ester of
rapeseed oil.
Useful mixtures of a hydrocarbon and nonhydrocarbon fuel include a mixture of
gasoline
and ethanol and a mixture of a diesel fuel and a biodiesel fuel such as the
methyl ester of
rapeseed oil. In an embodiment of the invention the fuel composition comprises
an
emulsified water in oil composition that contains the normally liquid fuel as
described
above which can be a hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture
thereof. This
emulsified water in oil composition can be prepared by a mechanical mixing, by
including
one or more emulsifiers andlor surfactants in the composition, or by a
combination of
mechanical mixing and inclusion of emulsifiers and/or surfactants.
The fuel composition of the present invention can further comprise one or more
fuel additives to include nitrogen-containing detergents, amine-containing
polyethers,
metal-containing detergents, antioxidants such as hindered phenols, rust
inhibitors such as
alkenylsuccinic acids, corrosion inhibitors, combustion improvers such as
nitroallcanes,
demulsifiers, antifoaming agents, valve seat recession additives, metal
deactivators,
lubricity agents, bacteriostatic agents, gum inhibitors, anti-icing agents,
anti-static agents,
organometallic fuel-borne catalysts for improved combustion performance, low
temperature flow improvers, and fluidizers such as mineral oils, polyolefins
and
polyethers.
In an embodiment of the invention the fuel additive can be a partial ester
having at
least one free hydroxyl group and formed by reacting at least one fatty
carboxylic acid or
reactive equivalent thereof, such as an anhydride or an ester or an acid
halide, and a
polyol. The fatty carboxylic acid can have 4 to 40 carbon atoms and in other
instances 8
to 26 and 12 to 24 carbon atoms. The fatty carboxylic acid can be a
monocarboxylic acid
or polycarboxylic acid or a mixture thereof; can have a straight chain or
branched chain or
be a mixture thereof; and can be saturated or unsaturated or a mixture
thereof. Saturated
and unsaturated mono- and dicarboxylic acids are useful and include capric,
lauric,
myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic,
palmitoleic, linoleic,
linolenic, erucic, and octadecenylsuccinic acid. The polyol can have two or
more
hydroxyl groups. Polyols useful in this invention include alkylene glycols,
polyalkylene
glycols, diols, triols and polyols having four or more hydroxyl groups.
Examples of useful
polyols are ethylene glycol, neopentyl glycol, diethylene glycol, glycerol,
trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. Partial
esters of the
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present invention are commercially available or can be prepared by reacting a
fatty
carboxylic acid or reactive equivalent thereof and a polyol by methods well
known in the
art. The partial esters can be prepared from a fatty carboxylic acid and a
polyol or from
mixtures thereof. In another embodiment of the invention two or more partial
esters are
prepared separately from one another and then mixed. An example of a useful
partial ester
is a mixture of glycerol monooleate and glycerol dioleate.
In another embodiment of the invention the fuel additive can be an amine-
containing polyether. The amine-containing polyether can contain two or more
ether units
and is generally prepared from a polyether intermediate. The polyether
intermediate can
be the reaction product of one unit of a hydroxy-containing hydrocarbyl
compound and
two or more units of a) an alkylene oxide other than butylene oxide or b) two
or more
different allcylene oxides that can include butylene oxide. The hydroxy-
containing
hydrocarbyl compound can be an alcohol or an alkyl-substituted phenol where
the alcohol
or alkyl substituent of the phenol can have 1 to 50 carbom atoms, 6 to 30
carbon atoms in a
second instance, and 8 to 24 carbon atoms in a third instance. The alcohol or
alkyl
substituent of the phenol can have a straight carbon chain, branched carbon
chain, or a
mixture thereof. The alkylene oxide can have 2 to 18 carbon atoms, 2 to 12
carbon atoms
in another instance, and 2 to 8 carbon atoms in a further instance. Two or
more different
allcylene oxides can be reacted with the hydroxy-containing hydrocarbyl
compound as a
mixture or in a sequential fashion to form the polyether intermediate. The
polyether
intermediate can have 2 to 100 repeating allcylene oxide units, in another
embodiment 5 to
50 alkylene oxide units, and in an additional embodiment 15 to 30 alkylene
oxide units.
U.S. Patent No. 5,094,667 provides reaction conditions for preparing the
polyether
intermediate. The amine-containing polyether can include a reaction product of
a) the
polyether intermediate derived from an alkylene oxide or two or more different
alleylene
oxides and b) an amine to include ammonia, a primary or secondary monoamine,
or a
polyamine. The amine-containing polyether can include a reaction product of a)
the
polyether intermediate from one or more alkylene oxides and b) acrylonitrile
to form a
nitrite product that is hydrogenated to form an aminopropyl terminated
polyether. The
amine-containing polyether can include a reaction product of a) the above
described
aminopropyl terminated polyether derived from one or more alkylene oxides and
b) an
aldehyde such as formaldehyde to form a product that can include a heterocycle
that is a
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N-substituted perhydro-S-triazine as described in U.S. Patent No. 5,830,243.
This reaction
product of an aminopropyl terminated polyether and an aldehyde can also be
prepared
from an aminopropyl terminated polyether derived from a polyether intermediate
that is
prepared from butylene oxide. The amine-containing polyether can include a
reaction
product of a) the polyether intermediate from one or more alkylene oxides and
b) a
carbonylating reagent such as phosgene to form in the case of phosgene a
chloroformate
ester that is then reacted with a polyamine to form a polyether-containing,
amine-
containing carbamate as described in U.S. Patent No. 5,503,644. The polyether-
containing, amine-containing carbamate can also be prepared from a polyether
intermediate that is prepared from butylene oxide.
In an additional embodiment of the invention the fuel additive can be a
polyether.
The polyether can contain two or more ether units. The polyether can be
prepared from
the reaction of a hydroxy-containing hydrocarbyl compound and an allcylene
oxide or two
or more different alkylene oxides. The hydroxy-containing hydrocarbyl compound
can be
an alcohol or an alkyl-substituted phenol where the alcohol or alkyl
substituent of the
phenol can have 1 to 50 carbon atoms, 6 to 30 carbon atoms in a second
instance, and 8 to
24 carbon atoms in a third instance. The alcohol or alkyl substituent of the
phenol can
have a straight carbon chain, branched carbon chain, or a mixture thereof. The
alkylene
oxide can have 2 to 18 carbon atoms, 2 to 12 carbon atoms in another instance,
and 2 to 8
carbon atoms in a further instance. Useful alkylene oxides include ethylene
oxide,
propylene oxide, butylene oxide, and mixtures thereof. Two or more different
allcylene
oxides can be reacted with the hydroxy-containing hydrocarbyl compound as a
mixture or
in a sequential fashion to form the polyether. The polyether can have 2 to 100
repeating
alkylene oxide units, in another embodiment 5 to 50 alkylene oxide units, and
in an
additional embodiment 15 to 30 alkylene oxide units. U.S. Patent No. 5,094,667
provides
reaction conditions for preparing the polyether.
The fuel composition can also include the nitrogen-containing detergent
composition comprising (A), (B), (C), (D) or (E) as described above. The
nitrogen-
containing detergent composition can be present in the fuel composition at 10
to 20,000
ppm by weight and in other instances at 0.1 to 10,000 and 50 to 2000 and 75 to
1200 and
100 to 900 ppm by weight. The nitrogen-containing detergent composition can be
introduced into the fuel composition alone or in combination with one or more
of the
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above described fuel additives as a bulk treatment at a refinery or storage
terminal, as an
aftermarlcet treatment for example by addition to a fuel in a fuel storage
tank of a
motorized vehicle, or via a dosing system into a fuel system of an internal
combustion
engine. Alternatively the nitrogen-containing detergent composition alone or
in
combination with one or more of the above described fuel additives can be
introduced
from a dosing system directly into a combustion chamber of an internal
combustion engine
at a rate that is equivalent to the treatment levels of the detergent
composition and fuel
additives used in the fuel composition. In an embodiment of the invention the
detergent
composition further comprises a fuel additive or a mixture of fuel additives
as described
hereinabove. In another embodiment of the invention the detergent composition
comprises a combination of a hydroxyalkyl-substituted fatty amine represented
by the
formula RN[(A10)XH][(A20)yH] as described above for detergent composition (B)
and a
partial ester of a fatty carboxylic acid and a polyol where the ester has at
least one free
hydroxyl group as described above for fuel additives that can be present in a
fuel
composition. The combination of the partial ester and the hydroxyallcyl-
substituted fatty
amine can be in a weight ratio of respectively 0.25-1:0.25-1 and in other
instances of 0.5-
1:0.5-1 and 0.75-1: 0.75-1 and 1:1.
The above described fuel additives can be included in the fuel composition of
the
present invention for fuel and lubricating oil performance requirements
depending on the
type of internal combustion engine and the characteristics of the fuel being
used. In
general the fuel additives can be used in the fuel composition at 10 to 20,000
ppm by
weight and in other instances at 0.1 to 10,000 and 0.3 to 1000 and 0.5 to 700
ppm by
weight.
Detergent compositions and fuel compositions of the present invention
containing
two or more components can generally be prepared by admixing the components.
Their
preparation can include the use of hydrocarbon solvents, mineral oils and
synthetic base
oils to facilitate the admixing, and mixing via a mechanical means at room or
elevated
temperatures can also be employed.
Both recent and future lubricating oil performance requirements and exhaust
emission requirements for internal combustion engines are placing additional
performance
demands on the lubricating oil. The method of the present invention provides a
way to
improve performance of the lubricating oil by meeting these additional
performance
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demands. These lubricating oil performance requirements and exhaust emission
requirements for internal combustion engines include a) extended intervals
between
lubricating oil changes or drains, b) internal combustion engines containing
an exhaust gas
recirculation system, c) internal combustion engines having an exhaust
treatment device
' and run on a low sulfur content fuel, d) internal combustion engines having
an exhaust
treatment device and a lubricating oil that has a reduced level of sulfur,
phosphorus and/or
sulfated ash where sulfated ash is a measure of the metal content in the oil,
and e) various
combinations thereof. Exhaust treatment devices can include three-way
catalytic
converters, NOX traps, oxidation catalysts, reduction catalysts and diesel
particulate filters.
In an embodiment of the method of the present invention the inteunal
combustion engine is
a compression-ignited engine having an exhaust gas recirculation system. In an
additional
embodiment of the method of the invention the internal combustion engine is a
sparlc-
ignited direct injection engine having an exhaust gas recirculation system. In
another
embodiment of the method of the invention the engine is a spark-ignited or
compression-
ignited engine having an exhaust treatment device, and the lubricating oil has
at least one
of the properties selected from the group consisting of a phosphorus content
below 0.1 %
by weight, a sulfur content below 0.5% by weight, and a sulfated ash content
below 1.5%
by weight. In other instances the phosphorus content of the lubricating oil
can be below
0.08 or 0.05% by weight, the sulfur content of the lubricating oil can be
below 0.3 or 0.2%
by weight, and the sulfated ash content of the lubricating oil can be below
1.2 or 1% by
weight. In still other instances the phosphorus content of the lubricating oil
can be 0.02 to
0.06% by weight, the sulfur content of the lubricating oil can be 0.1 to 0.4%
by weight,
and the sulfated ash content of the lubricating oil can be 0.1 to 0.9% by
weight. In a
further embodiment of the method of the present invention the engine is a
spark-ignited or
compression-ignited engine having an exhaust treatment device, and a fuel of a
fuel
composition has a sulfur content below 80 ppm by weight. In other instances
the sulfur
content of the fuel can be below 50, 15 or 10 ppm by weight. In still a
further embodiment
of the method of the invention an engine is installed in a motor vehicle and
has a
recommended drain interval for a lubricating oil of the engine of greater than
6,000 miles
and in other instances of greater than 8,000 or 10,000 miles. In another
embodiment of the
method of the present invention a stationary engine has a recommended drain
interval for
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a lubricating oil of the engine of greater than 150 operational hours and in
other instances
of greater than 200 or 250 operational hours.
The following examples demonstrate the method of the present invention where
the introduction of the detergent composition into a combustion chamber of an
internal
combustion engine results in improvement in the performance of a lubricating
oil of the
engine. The examples are provided for illustrative purposes only and are not
intended to
limit the scope of the invention.
VW Fleet Trial
A fleet of six, identical vehicles was used to investigate fuel additive and
lubricant
interactions. The vehicles were model year 2000 Volkswagen Passats equipped
with 1.9L
turbo, direct injection engines. This modern engine design is equipped with
exhaust gas
recirculation (EGR) and meets Euro 3 emissions standards. Fuel is injected
through high-
pressure unit injectors directly into the combustion chamber.
The test program involved two separate phases, each operated for 50,000
ltilometers. Mileage accumulation followed a driving cycle that included
urban, suburban
and motorway conditions. During each phase of the test, vehicles were assigned
to a
specific combination of fuel and lubricant as outlined in Table 1. The test
fuels varied by
additive including; no additive, additive of Example A, and additive of
Example B.
Example A was the reaction product of a polyisobutenylsuccinic anhydride
derived from
1000 molecular wt. high vinylidene polyisobutylene and tetraethylenepentamine
in a mole
ratio of 1:0.87. Example B was the reaction product of an alkylphenol derived
from 1000
molecular wt. high vinylidene polyisobutylene, 37 wt.% aqueous formaldehyde
and
ethylenediamine in a mole ratio of 1:1.15:1.1. Diesel fuel A was procured from
a
commercial source in the United Kingdom. The fuel did not contain
dispersant/detergent
additives and met the EN590 specifications. Analysis of the fuel is shown in
Table 2.
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Table 1: Test Matrix Design
Vehicle Phase 1 Phase 2
Oil Fuel AdditiveOil Fuel Additive
1 OW-30 None . OW30 Example A
2 5W-40 None 5W40 Example B
3 OW-30 Example A OW30 Example B
4 5W-40 Example A 5W40 None
OW-30 ' Example B OW30 None
G 5W-40 Example B 5W40 Example A
Table 2: Test Fuel Properties
Property Result
Fuel A
Specific Gravity 0.8399
@ 15 C
T95 334 C
Final Boiling Pint 349 C
Cetane Number 49.3
Sulfur Content 34 ppm mass
Water Content 72 ppm
Oxidation Stability0.2mg/100
ml
Lubricity by HF'RR 277 ~,m
(wear scar diameter)
Olefins 2 volume
%
5 Two different lubricant formulations were used during the test program: a OW-
30,
fully synthetic lubricating oil having 0.1040 %wt P, 0.53%wt S, TBN = 11.0,
TAN= 2.8,
and 1.61 % sulfated ash; and a 5W-40 partially synthetic oil having 0.085%wt
P,
0.4600%wt S, TBN = 9.3, TAN = 2.8, and 1.24%wt sulfated ash.
During each phase of testing, the crankcase was filled only once. Interim
samples
were taken from each vehicle every 10,000 kilometers for used oil analysis.
Each group of
three vehicles using a particular lubricant was treated as a set. For each set
of vehicles the
interim samples were removed from the crankcase, then the amount of "top up"
oil needed
for each vehicle was calculated. The vehicle needing the most "top up" oil was
treated as
the baseline and some lubricant was removed from the other two vehicles in the
set to
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achieve the same cranlccase level. Then all three vehicles were given the same
amount of
"top up" oil. In this manner, all vehicles operating on the same lubricant
always received
the same amount of additional oil and the crankcase oil of all three vehicles
aged at the
same rate.
Plots of the TBN (total base number in mg equivalents of KOH per gram of
sample) and percent change in TBN for the end of test (EOT) used OW30 and 5W40
oil
samples are provided in Figures 1 and 2. Used oil samples from vehicles using
a fuel that
contained a dispersant/detergent showed higher end of test TBN levels compared
to
vehicles using a fuel that contained no dispersant/detergent indicating that
the oil for
vehicles using a fuel containing dispersants/detergents retained more TBN
compared to
the start of test TBN. The amount of TBN remaining in engine oil is a measure
of the
effectiveness of the lubricating oil to protect the engine from the acidic
materials, such as
soot, generated by the incomplete combustion of fuel. The higher the TBN of
the oil at
end of test, the better the oil is performing. Figures 1 and 2 indicate a
significant
improvement for those oils coming from engines operated on fuels comprising
dispersants/detergents.
Plots of the average piston ratings for the engines from the ends of each
phase are
provided in Figure 3. Engines operated on fuels comprising a
dispersant/detergent showed
cleaner pistons. Engine cleanliness is a direct measure of the effectiveness
of a lubricating
?0 oil to protect key engine parts such as the piston. Figure 3 indicates that
the performance
of the lubricant oils in those engines operated on fuels comprising a
dispersant or
detergent were significantly enhanced.
Engine out and tail pipe emissions were measured using both the ECE and the
ELTDC driving cycle. Emission measurements were obtained at three points
during each
test phase. The first emissions test points were taken at the start of test
with fresh
lubricant in the crankcase. The second emissions test points were taken after
the mileage
accumulation with the used lubricant. Finally, the third emissions test points
for each
phase were taken after the mileage accumulation with a fresh charge of
lubricant in the
crankcase. This test design gives the ability to determine the different
effects that occur
during mileage accumulation, making it possible to separate the effect of used
lubricant on
emissions and the effect of the engine deposits on emissions. Plots of the
particulate
emissions for the two driving cycles are provided in Figure 4. As indicated by
Figure 4,
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the particulate emissions for vehicles using a fuel containing the
dispersant/detergent of
Example A were significantly lower in both emissions driving cycles.
Ford Crown Victoria Fleet Trial
Four vehicles were used to investigate fuel additive and lubricant
interactions. The
vehicles were 1991-1992 Ford Crown Victorias equipped with 4.6L engines and
automatic
transmissions. The test program consisted of evaluating two fuels, one
baseline fuel with
no additive, and the same baseline fuel additized with a combination of
dispersants/detergents of Examples C and D. Example C was the reaction product
of a
chlorinated 1300 molecular wt. polyisobutylene, ethylenediamine and sodium
hydroxide.
Example D was a polyetheramine prepared by reacting a Ci2-is alcohol with an
average of
24 units of propylene oxide, reacting the propoxylated alcohol with
acrylonitrile to form a
nitrile and hydrogenating the nitrile. Mileage accumulation followed a driving
cycle that
consisted of 70% highway driving and 30% city driving. Two vehicles, one on
base fuel
and one on additized fuel, were driven for 30,000 miles. Intermediate
inspection and oil
change were done at 15,000 miles and at end of test (30,000 miles). The
remaining two
vehicles, one on base fuel and one on additized fuel, were run for 15,000
miles with only a
final inspection at the end of test. All four vehicles were run using a 5W-30
lubricating oil
meeting the SG American Petroleum Institute automotive gasoline engine service
category. The performance of the two fuels were comparatively evaluated by
used oil
analysis, especially TBN retention.
Plots of the TBN for used oil samples at 15,000 miles and 30,000 miles are
provided in Figure 5. Used oil samples from vehicles using
dispersant/detergent showed
higher end of test TBN levels compared to vehicles using no
dispersant/detergent,
indicating that the oil for vehicles using a fuel that contained
dispersants/detergents
retained more of its original TBN. The amount of TBN remaining in engine oil
is a
measure of the effectiveness of the lubricating oil to protect the engine from
the acidic
materials generated from the combustion of fuel. The higher the TBN of the
used oil, the
better the oil is performing. Figure 5 indicates a significant improvement for
those oils
coming from engines operated on fuels comprising dispersants/detergents.
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Ford Direct Injection Fleet Trial
Three identical vehicles were used to investigate fuel additive and lubricant
interactions. The vehicles were Ford pre-production 3 cylinder direct
injection spark
ignited 1.125L engines equipped with EGR.
The test program, as outlined in Table 3, involved operating each vehicle for
30,000 km. Mileage accumulation followed a driving cycle that included urban,
suburban,
and motorway conditions. The vehicles were assigned to specific combinations
of fuel
and lubricant as outlined in Table 3. The test fuel varied by additive
including: no additive
and additive of Example B which was a Mannich reaction product as described
above for
the VW fleet trial. The fuel was procured from a commercial source in the
United
Kingdom. The fuel did not contain dispersant/detergent additives except for
those added
in the study.
Table 3
Vehicle Oil Fuel Additive
1 Normal Ash None
2 Reduced Ash None
3 Normal Ash Example B
Two different lubricant formulations were used during the test program: a
lubricating oil having Ford M2C913A approval and containing 1.2%wt sulfated
ash; and a
reduced ash (0.8%wt sulfated ash) lubricating oil capable of meeting ACEA AlBl
criteria.
Plots of the TBN for the used oil samples are provided in Figure 6. Used oil
samples from vehicle 2 containing the reduced ash lubricating oil showed an
earlier
TBN:TAN (total acid number in mg equivalents KOH per gram of sample) cross-
over
(10,000 km) than the used oil samples from vehicle 1 containing the normal ash
lubricating oil (14,000 km). The TBN:TAN cross-over is an indication of the
effectiveness of the lubricating oil to protect the engine from the acidic by-
products of the
combustion process. The higher the distance accumulated before TBN:TAN cross-
over,
the better the oil is performing. As Figure 6 indicates, the addition of a
dispersant/detergent to the fuel in vehicle 3 increased the distance
accumulated prior to
TBN:TAN cross-over from 14,000 km of vehicle 1 to 18,000 km.
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Liebherr 914T Engine Test
Emissions data for a base fuel and base fuel plus a mixture of
dispersant/detergent
were obtained on a Liebherr 914T engine using 4 points of the IS08178 off-road
test
cycle. These data points vary in the speed and load conditions that the engine
is run at.
Plots of the total particulate emissions for the base fuel and the base fuel
containing an
additive package comprising the three dispersants/detergents of Examples E, F
and G are
provided in Figure 7. Example E was the reaction product of
hexadecenylsuccinic
anhydride and diethylethanolamine in a mole ratio of 1:1.35. Example F was the
reaction
product of a 60 wt.% and 40 wt.% mixture of polyisobutenylsuccinic anhydrides
derived
from respectively 2300 and 1000 molecular wt. high vinylidene polyisobutylene,
ethylene
glycol, and dimethylaminoethanol. Example G was the reaction product of a
polyisobu-
tenylsuccinic anhydride derived from a 2300 molecular wt. high vinylidene
polyisobutylene and heavy polyethylenepolyamines. Plots of the particulate
emissions in
the 20-200 nm size spectrum for the base fuel and the base fuel containing an
additive
package comprising the three dispersants/detergents of Example E, F and G are
provided
in Figure 8. Surprisingly, both plots of Figures 7 and 8 indicate that the use
of the
dispersant/detergent can lower the particulate emissions of an internal
combustion engine.
Of significant importance, Figure 8 indicates that the use of the
dispersant/detergent
lowers the ultra fine particulates by 8%.
M-B M111E Engine Test
A baseline fuel (no additive) and the same fuel additized with dispersant
/detergent
of Example B, the Mannich reaction product described above in the VW fleet
trial, were
evaluated in the Mercedes-Benz or M-B M111E (Test Method CEC-L-53-T-95) engine
test. This engine test is part of the ACEA A1, A2, and A3 test specifications.
The test
evaluates engine sludge and cam wear performance of a lubricating oil. Each
fuel,
baseline and additized, was evaluated in the M111E engine test at two
independent testing
facilities. The sludge ratings for the baseline fuel and the additized fuel
are provided in
Figure 9. As the data indicates, significant improvements in the sludge rating
of the
M111E engine test were achieved with the fuel additized with dispersant of
Example B
versus the non-additized baseline fuel.
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ASTM Sequence VE Engine Test
TABLE 4
ASTM
Sequence
VE Engine
Wear
Example Fuel Treatment Max Cam Lobe Iron in oil,
Wear, micrometersppm"
H None 192 717
I 600 ppm PEA-1~ 95 407
J 420 ppm PIBEDA +282 161 788
ppm
PEA-23
K 600 ppm [PEA- 273 1219
2/formalydehyde]4
L 600 ppm PEA carbamate'262 801
1 ASTM Sequence VE engine test was run using a Phillips J unleaded reference
fuel and
the Reference Oil #1002, a GF-2 ILEAC service category gasoline engine oil.
Z PEA-1 is a polyetheramine prepared by reacting C13 alcohol with butylene
oxide in
respectively a 1:20 mole ratio to form a polyether, condensing the polyether
with
acrylonitrile to form a nitrite, and hydrogenating the nitrite to form the
polyetheramine.
PIBEDA contains as 65% by weight actives the reaction product of a chlorinated
1300 molecular weight polyisobutylene reacted with ethylenediamine; PEA-2 is
an amine
containing polyether prepared as described above for PEA-1 except that the
polyether is
prepared by reacting CI~-is alcohol and propylene oxide in respectively a 1:24
mole ratio.
4 [PEA-2/formaldehyde] is the reaction product of the amine-containing
polyether PEA-2
described above reacted with formaldehyde in a 1:1 mole ratio.
5 PEA carbamate is a polyether-containing, amine-containing carbamate derived
from (a)
the polyether prepared by reacting dodecylphenol and butylene oxide in
respectively a
1:20 mole ratio and (b) a polyethylenepolyamine.
G The amount of iron metal in the oil at the end of test after 288 hours.
25
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Ford Crown Victoria Engine Test
TABLE 5
1992/1994
Ford 4.61
Crown Victoria
Vehicle
Engine Wear
Example Fuel Treatment Iron in oil,
ppm"
M None' 86
N 700 ppm [PEA-2/formaldehyde] 168
'
O 400 ppm Mannich +312 ppm PEA-2'65
P 125 ppm ETA + 125 ppmGM04 49
360 ppm PEA-1 +190 ppm PE-1' 53
' 1992/1994 Ford 4.61 Crown Victoria vehicle engine test was run over 7,500
miles using
an unleaded regular fuel and a lOW-30 SH oil.
2 [PEA-2/formaldehyde] is the same as the [PEA-2/formaldehyde] reaction
product
described above in Table 1.
The Mannich is 65% by weight actives of the reaction product prepared by
reacting
1000 molecular weight polyisobutylene allcylated phenol, formaldehyde and
ethylenediamine; PEA-2 is the same as the PEA-2 amine-containing polyether
described
above in Table 1.
4 ETA is a diethoxylated tallowamine; GMO is glycerol monooleate.
5 PEA-1 is the same as the PEA-1 polyetheramine described above in Table 1; PE-
1 is a
polyether formed by reacting C13 alcohol and butylene oxide in respectively a
1:20 mole
ratio.
~ Iron wear metal in the oil as an average of the top and bottom drain.
Each of the documents referred to in this Detailed Description of the
Invention
section is incorporated herein by reference. All numerical quantities in this
application
used to describe or claim the present invention are understood to be modified
by the word
"about" except for the examples or where explicitly indicated otherwise. All
chemical
treatments or contents throughout this application regarding the present
invention are
understood to be as actives unless indicated otherwise even though solvents or
diluents
may be present.
