Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Fuel Efficient Lubricating Composition
BACKGROUND
[0001] There is increasing interest in improving the
fuel efficiency of internal combustion
engines. Vehicle manufacturers have improved fuel economy through engine
design,
improvements which take advantage of advances in lubricating oils which
provide better oxidative
stability, wear protection, and reduced friction.
[0002] Lubricant viscosity and base oil viscosity are
two of the primary drivers of lubricant
mediated fuel economy. Lower lubricant viscosity often translates into
improved fuel efficiency
for internal combustion engines. However, there are practical limits that
govern the available
viscosity ranges available for lubricant compositions.
[0003] Lubricant life is limited by many factors,
including exposure to combustion gases,
high temperatures, and pressures. In addition, oil consumption, that is the
loss of lubricant from
the crankcase during normal operation of the engine, is a major factor
impacting low viscosity
fluids While base oil volatility may be one of many factors governing oil
consumption, the move
to lower viscosity lubricants to achieve improvements in fuel economy may
result in significant
reduction in oil life.
[0004] The instant disclosure relates to lubricants for
internal combustion engines, that
may, at least, provide improved fuel economy without reducing the effective
life of the lubricant
and/or impacting the cleanliness and durability performance of the engine.
This may be achieved
through the use of low viscosity, low volatility base oils in combination with
ashless succinimide
dispersants
SUMMARY
[0005] The instant disclosure is directed to low
viscosity, low volatility lubricating
compositions having an oil of lubricating viscosity that includes a
lubricating base oil and a
hydrocarbon oil, the hydrocarbon oil being at least 20 wt % of the oil of
lubricating viscosity and
has a kinematic viscosity of less than 3.7 cSt at 100 C and a NOACK volatility
(measured by
ASTM D5800) of less than 25 wt %; and from 1.2 to 4 wt % of a polyalkenyl
succinimide
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dispersant where the lubricating composition is a OW-)0C multi-grade
composition according to
SAE J300 and )0C is selected from 8, 12, 16, and 20.
100061 In another embodiment, the instant disclosure
relates to a low viscosity, low
volatility lubricating compositions having an oil of lubricating viscosity
that includes a lubricating
base oil and a hydrocarbon oil, the hydrocarbon oil being from 20 to 95 wt %
of the oil of
lubricating viscosity and has a kinematic viscosity of less than 3.7 cSt at
100 C and a NOACK
volatility (measured by ASTM D5800) of less than 20 wt %; and from 1.2 to 4 wt
% of a
polyalkenyl succinimide dispersant where the lubricating composition is a OW-
XX multi-grade
composition according to SAE 1300 and XX is selected from 8, 12, 16, and 20.
100071 In another embodiment, the instant disclosure
relates to a low viscosity, low
volatility lubricating compositions having an oil of lubricating viscosity
that includes a lubricating
base oil and a hydrocarbon oil, the hydrocarbon oil being at least 20 wt % of
the oil of lubricating
viscosity and has a kinematic viscosity of less than 3.7 cSt at 100 C and a
NOACK volatility
(measured by ASTM D5800) of less than 25 wt %; from 1.2 to 4 wt % of a
polyisobutylene
succinimide dispersant; from 0.1 to 3 wt % of an antiwear agent, such as zinc
dialkyldithiophosphate; from 0.5 to 3 wt % of a metal-containing detergent
selected from one or
more of an overbased calcium salicylate detergent and a magnesium salicylate
detergent; and from
0.08 to 1.2 wt % of a polymeric viscosity modifier; where the lubricating
composition is a OW-
)0C multi-grade composition according to SAE J300 and )0C is selected from 8,
12, 16, and 20.
100081 The instant disclosure further relates to
methods of lubricating an internal
combustion engine where the method includes supplying a composition as
described herein to at
least one lubricating system within the internal combustion engine.
100091 The instant disclosure also relates to the use
of any one of the lubricating
compositions described herein to improve fuel economy in an internal
combustion engine without
reducing the effective life of the lubricating composition and/or impacting
the cleanliness and
durability performance of the engine.
DETAILED DESCRIPTION
100101 Various features and embodiments will be
described below by way of non-limiting
illustration. The instant disclosure relates to methods for lubricating an
internal combustion
engine.
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[0011] The disclosed technology provides a low
volatility lubricating composition, a
method for lubricating an internal combustion engine with a low volatility
lubricating composition,
and the use as disclosed above. The term "low volatility" when used in
reference to a hydrocarbon
oil means that the hydrocarbon oil has an evaporative loss of less than 25 wt
A as measured by
ASTM D5800 Noack test. The lubricating composition disclosed herein includes
an oil of
lubricating viscosity that includes a lubricating base oil and a hydrocarbon
oil, the hydrocarbon oil
being at least 20 wt % of the oil of lubricating viscosity and having a
kinematic viscosity measured
at 100 C of no more than 17 cSt and an evaporative loss of less than 25 wt %
as measured by
ASTM D5800 Noack test. The oil of lubricating viscosity may further include
one or more suitable
lubricating base oils, different from that of the hydrocarbon oil.
Lubricating Base Oil
[0012] Lubricating base oils (in addition to and
different from the hydrocarbon oil) include
natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and
hydrofinishing,
unrefined, refined, re-refined oils or mixtures thereof. A more detailed
description of unrefined,
refined and re-refined oils is provided in International Publication
W02008/147704, paragraphs
[0054] to [0056] (a similar disclosure is provided in US Patent Publication
2010/0197536, see
[0072] to [00731). A more detailed description of natural and synthetic
lubricating oils is described
in paragraphs [0058] to [0059] respectively of W02008/147704 (a similar
disclosure is provided
in US Patent Publication 2010/0197536, see [0075] to [0076]). Synthetic oils
may also be
produced by Fischer-Tropsch reactions and typically may be hydroisomerised
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
[0013] Lubricating base oils may also be defined as
specified in the April 2008 version of
"Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car
Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 13. "Base Stock Categories". The
API Guidelines
are also summarized in US Patent US 7,285,516 (see column 11, line 64 to
column 12, line 10).
In one embodiment, the lubricating base oil may be an API Group 11, Group III,
or Group IV oil,
or mixtures thereof. The five base oil groups are as follows:
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Base Oil Category Sulfur (%)
Saturates (%) Viscosity Index
Group I >0.03 and/or
<90 80 to 120
Group II <0.03 and
>90 80 to 120
Group III <0,03 and
>90 >120
Group IV All polyalphaolefins (PAO)
Group V All others not included in Groups
I, II, III, or IV
100141 The amount of the oil of lubricating base oil
present in the lubricating composition
is typically the balance remaining after subtracting from 100 weight % (wt %)
the sum of the
amount of instantly disclosed hydrocarbon oil and the other performance
additives.
100151 In one embodiment, the lubricating base oil
comprises at least 30 wt % of Group II
or Group BI base oil. In another embodiment, the base oil comprises at least
60 weight % of Group
II or Group III base oil, or at least 80 wt % of Group II or Group III base
oil. In one embodiment,
the lubricant composition comprises less than 20 wt % of Group IV (i.e.
polyalphaoleftn) base oil.
In another embodiment, the lubricant composition comprises less than 10 wt %
of Group IV base
oil. In one embodiment, the lubricating composition is substantially free of
(i.e. contains less than
0.5 wt %) of Group IV base oil.
100161 Ester base fluids, which are characterized as
Group V oils, have high levels of
solvency as a result of their polar nature. Addition of low levels (typically
less than 10 wt %) of
ester to a lubricating composition may significantly increase the resulting
solvency of the base oil.
Esters may be broadly grouped into two categories: synthetic and natural. An
ester base fluid would
have a kinematic viscosity at 100 C suitable for use in an engine oil
lubricant, such as between 2
cSt and 30 cSt, or from 3 cSt to 20 cSt, or even from 4 cSt to 12 cSt. In one
embodiment, the
lubricating composition comprises at least 2 weight % of an ester base fluid.
In one embodiment
the lubricating composition comprises at least 4 weight % of an ester base
fluid, or at least 7 weight
% of an ester base fluid, or even at least 10 weight % of an ester base fluid.
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Hydrocarbon Oil
100171 The hydrocarbon oil of the invention comprises
one or more saturated hydrocarbons
containing at least one hydrocarbyl branch, sufficient to provide fluidity to
both very low and high
temperatures. Hydrocarbons of the invention may include natural and synthetic
oils, oil derived
from hydrocrackingõ hydrogenation, and hydrofinishing,, refined, bio-derived,
re-refined oils or
combinations or mixtures thereof.
[0018] Synthetic hydrocarbon oils may be produced by
isomerization of predominantly
linear hydrocarbons to product branched hydrocarbons. Linear hydrocarbons may
be naturally
sourced, synthetically prepared, or derived from Fischer-Tropsch reactions or
similar processes.
Hydrocarbon oil may be derived from hydro-isomerized wax and typically may be
hydroisomerised 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.
[0019] Suitable hydrocarbon oils may also be obtained
from natural, renewable, sources.
Natural (or bio-derived) oils refer to materials derived from a renewable
biological resource,
organism, or entity, distinct from materials derived from petroleum or
equivalent raw materials.
Natural sources of hydrocarbon oil include fatty acid triglycerides,
hydrolyzed or partially
hydrolyzed triglycerides, or transesterified triglyceride esters, such as
fatty acid methyl ester (or
FAME). Suitable triglycerides include, but are not limited to, palm oil,
soybean oil, sunflower oil,
rapeseed oil, olive oil, linseed oil, and related materials. Other sources of
triglycerides include, but
are not limited to algae, animal tallow, and zooplankton. Linear and branched
hydrocarbons may
be rendered or extracted from vegetable oils and hydrorefined and/or
hydroisomerized in a manner
similar to synthetic oils to produce hydrocarbon oil. In some embodiments, at
least 50 wt % of the
hydrocarbon oil is bio-derived. In other embodiments, at least 55 wt %, or at
least 60 wt %, or at
least 65 wt %, or at least 70 wt %, or at least 80 wt % or at least 90 wt % of
the hydrocarbon oil is
bio-derived. In one embodiment, the hydrocarbon oil is bio-derived and is
substantially free, i.e.,
less than 0.5 wt % based on the weight of the hydrocarbon oil, of ester
functionality.
100201 Hydrocarbons are generally understood to consist
essentially of carbon and
hydrogen atoms but may often contain low amounts of heteroatoms. The
hydrocarbon oil of the
invention is free of or substantially free of heteroatoms, except for
impurities and contaminants
that may carry over from processing or manufacture.
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[0021] The hydrocarbon oil of the invention comprises a
hydrocarbon compound
containing 16 carbon atoms up to a maximum of 60 carbon atoms and at least one
hydrocarbyl
branch containing at least one carbon atom. In one embodiment, the hydrocarbon
compound
comprises at least 18 or at least 22 carbon atoms with the proviso that the
longest continuous chain
of carbon atoms is no more than 24 carbons in length. In one embodiment, the
hydrocarbon oil
comprises a hydrocarbon compound containing 22 to 38 carbon atoms with the
proviso that the
longest continuous chain of carbon atoms is no more than 24 carbons in length.
In one
embodiment, the hydrocarbon oil is bio-derived and includes a hydrocarbon
compound having a
continuous chain of no more than 24 carbon atoms and at least 30 total carbon
atoms.
[0022] Alternatively, the hydrocarbon oil may be
described as a paraffinic or iso-paraffinic
compound.
[0023] Mineral oils often contain cyclic structures,
i.e., aromatics or cycloparaffins also
called naphthenes. In one embodiment, the hydrocarbon oil comprises a
saturated hydrocarbon
compound free of or substantially free of cyclic structures. In one
embodiment, the hydrocarbon
oil is substantially aliphatic (95 wt % and greater) and contains less than 5
wt % of cyclic
hydrocarbons.
[0024] In one embodiment, the hydrocarbon oil has a
kinematic viscosity, measured at 100
C, of at least 0.7 cSt, or at least about 0.9 cSt, or at least about 1.1 cSt.
In one embodiment, the
hydrocarbon oil has a kinematic viscosity less than 3.7 cSt at 100 C, or less
than 3.6 cSt at 100
C, or less than 3.5 cSt at 100 C, or less than 3.4 cSt, or less than 3.2 cSt
at 100 C. In a further
embodiment, the hydrocarbon oil has a closed cup flash point of at least 50
C, or at least 60 C,
or at least 75 C, or at least 100 'C.
[0025] In one embodiment, the hydrocarbon oil has an
evaporative loss (also called Noack
volatility) of less than 25 wt %wt %, as measured by ASTM D5800. In one
embodiment the
evaporative loss is less than 20 wt %wt % or less than 18 wt %wt %, or less
than 15 wt %. In one
embodiment, the hydrocarbon oil has a kinematic viscosity of less than 3.7 cSt
at 100 C and an
evaporative loss of less than 25 wt %.
[0026] The lubricating composition comprises oil of
lubricating viscosity that includes at
least 20 wt % of the hydrocarbon oil based on the weight of the oil of
lubricating viscosity. In one
embodiment, the oil of lubricating viscosity may comprise at least 30 wt % of
the hydrocarbon oil,
or at least 35 wt %, or at least 40 wt %, or at least 50 wt %, or at least 60
wt %, or at least 70 wt %
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of the hydrocarbon oil. In another embodiment, the oil of lubricating
viscosity is at least 90 wt %
of the hydrocarbon oil, based on the weight of the oil of lubricating
viscosity. In one embodiment,
the oil of lubricating viscosity is 100 wt % of the hydrocarbon oil, based on
the weight of the oil
of lubricating viscosity.
[0027] In some embodiments, the oil of lubricating
viscosity may include at least 20 wt %
of the hydrocarbon oil, based on the weight of the oil of lubricating
viscosity. In another
embodiment, the oil of lubricating viscosity may comprise 20 wt % to 95 wt %
of the hydrocarbon
oil, or 25 wt % to 75 wt %, or 30 wt % to 60 wt % of the hydrocarbon oil.
[0028] The oil of lubricating viscosity containing the
lubricating base oil and hydrocarbon
oil can have a viscosity index of greater than 100. In some embodiments, the
viscosity index is
greater than 115, or greater than 125. In other embodiments, the viscosity
index is from 110 to
130, or 115 to 125, or from 117 to 122,
Polyalkenyl Suceinimide Dispersant
100291 The lubricating composition of the instant
disclosure further includes a polyalkenyl
succinimide dispersant. Dispersants, generally, are well known in the field of
lubricants and
include primarily what is known as ashless dispersants and polymeric
dispersants. Ashless
dispersants are so-called because, as supplied, they do not contain metal and
thus do not normally
contribute to sulfated ash when added to a lubricant. However, they may,
interact with ambient
metals once they are added to a lubricant which includes a metal-containing
species. Ashless
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, having a variety of chemical structures, including those
represented by Formula (I)
0
0
N
[122 -NHL - -N
0
0
Formula (I)
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where each IV is independently an alkyl group, frequently a polyisobutylene
group with a
molecular weight (Me) of 500-5000 based on the polyisobutylene precursor, and
R2 are alkylene
groups, commonly ethylene (C2H4) groups.
[0030] Such molecules are commonly derived from
reaction of an alkenyl acylating agent
with a polyamine, and a wide variety of linkages between the two moieties is
possible beside the
simple imide structure shown above, including a variety of amides and
quaternary ammonium
salts. In the above Formula (I), the amine portion is shown as an alkylene
polyamine, although
other aliphatic and aromatic mono- and polyamines may also be used. Also, a
variety of modes of
linkage of the 11.1- groups onto the imide structure are possible, including
various cyclic linkages.
The ratio of the carbonyl groups of the acylating agent to the nitrogen atoms
of the amine may be
1:0,5 to 1:3, and in other instances 1:1 to 1:2.75 or 1:1.510 1:2.5.
Succinimide dispersants are more
fully described in U.S. Pat, Nos, 4,234,435 and 3,172,892 and in EP 0355895.
[0031] In certain embodiments, the dispersant is
prepared by a process that involves the
presence of small amounts of chlorine or other halogen, as described in U.S.
Pat. No. 7,615,521
(see, e.g., col. 4, lines 18-60 and preparative example A). Such dispersants
typically have some
carbocyclic structures in the attachment of the hydrocarbyl substituent to the
acidic or amidic
"head" group. In other embodiments, the dispersant is prepared by a thermal
process involving an
"ene" reaction, without the use of any chlorine or other halogen, as described
in U.S. Pat. No.
7,615,521; dispersants made in this manner are often derived from high
vinylidene (i.e. greater
than 50 4 terminal vinylidene) polyisobutylene (See col. 4, line 61 to col. 5,
line 30 and preparative
example B). Such dispersants typically do not contain the above-described
carbocyclic structures
at the point of attachment. In certain embodiments, the dispersant is prepared
by free radical
catalyzed polymerization of high-vinylidene polyisobutylene with an
ethylenically unsaturated
acylating agent, as described in U.S. Pat. No. 8,067,347.
[0032] Some dispersants for use in the instant
lubricating compositions may be derived
from, as the polyolefin, high vinylidene polyisobutylene, that is, having
greater than 50, 70, or
75% terminal vinylidene groups (alpha. and .beta. isomers). In certain
embodiments, the
succinimide dispersant may be prepared by the direct alkylation route. In
other embodiments, it
may comprise a mixture of direct alkylation and chlorine-route dispersants.
100331 Suitable dispersants for use in the instant
lubricating compositions include
succinimide dispersants. In one embodiment, the dispersant may be present as a
single dispersant.
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In one embodiment, the dispersant may be present as a mixture of two or three
different
dispersants, wherein at least one may be a succinimide dispersant.
100341 The succinimide dispersant may be a derivative
of an aliphatic polyamine, or
mixtures thereof. The aliphatic polyamine may be aliphatic polyamine such as
an
ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures
thereof. In one
embodiment, the aliphatic polyamine may be ethylenepolyamine. In one
embodiment, the aliphatic
polyamine may be selected from the group consisting of ethylenediamine,
diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine
still bottoms,
and mixtures thereof
100351 The succinimide dispersant may be a derivative
of an aromatic amine, an aromatic
polyamine, or mixtures thereof The aromatic amine may be 4-aminodiphenylamine
(ADPA) (also
known as N-phenylphenylenediamine), derivatives of ADPA (as described in
United States Patent
Publications 2011/0306528 and 2010/0298185), a nitroaniline, an
aminocarbazole, an amino-
indazolinone, an aminopyrimidine, 4-(4-nitrophenylazo)aniline, or combinations
thereof In one
embodiment, the dispersant is derivative of an aromatic amine wherein the
aromatic amine has at
least three non-continuous aromatic rings
100361 The succinimide dispersant may be a derivative
of a polyether amine or polyether
polyamine. Typical polyether amine compounds contain at least one ether unit
and will be chain
terminated with at least one amine moiety. The polyether polyamines can be
based on polymers
derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and
butylene oxide.
Examples of polyether polyamines are sold under the Jeffamine brand and are
commercially
available from Hunstman Corporation located in Houston, Texas.
100371 The dispersant may also be post-treated by
conventional methods by a reaction with
any of a variety of agents. Among these are boron compounds, urea, thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic
acids, hydrocarbon-
substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and
phosphorus compounds.
In one embodiment, the succinimide dispersant may be post-treated with boron,
resulting in a
borated dispersant. In one embodiment, the succinimide dispersant comprises at
least one boron-
containing dispersant and at least one boron-free dispersant. In one
embodiment, the lubricating
composition is free of or substantially free of a boron-containing succinimide
dispersant.
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100381 The polyalkenyl succinimide dispersant may be
present in an amount of from 1.2
wt % to 4 wt % of the lubricating composition, or 1.5 wt % to 3.8 wt % of the
composition, or 1.2
wt % to 3 wt %, or 2.0 wt % to 3.5 wt % of the composition. It is understood
that if a mixture of
two or more dispersants comprises the succinimide dispersant, each of those
dispersants may be
independently present in the composition at 0.01 wt % to 4 wt %, or 0.1 wt %
to 3.5 wt %, or 0.5
wt % to 3.5 wt %, or 1.0 wt % to 3.0 wt %, or 0.5 wt % to 2.2 wt % of the
lubricating composition,
with the proviso that the total amount of dispersant is as described above. In
one embodiment, the
polyalkenyl succinimide dispersant is a polyisobutylene succinimide. In
another embodiment, the
polyalkenyl succinimide dispersant is a polyisobutylene succinimide and is
present in the
lubricating composition in an amount of from 1.2 to 4 wt %.
100391 In one embodiment, the polyalkenyl succinimide
dispersant is a boron-containing
succinimide dispersant in an amount of from 1.2 to 4 wt % of the lubricating
composition. In
another embodiment, the polyalkenyl succinimide dispersant is a mixture of
boron-free and boron-
containing succinimide dispersants. When both boron-containing dispersants and
boron-free
dispersants are present, the ratio of the one or more boron-containing
dispersants to the one or
more boron-free dispersants may be 4:1 to 1:4 on a weight basis, or 3:1 to
1:3, or 2:1 to 1:3, or 1:1
to 1:4 on a weight basis. In another embodiment, one or more boron-containing
dispersants is
present in an amount 0.8 wt% up to 2.1 wt% and one or more boron-free
dispersants is present in
an amount 0.8 wt% up to 4 wt% of the lubricating composition.
Other Performance Additives
100401 The compositions of the invention may optionally
comprise one or more additional
performance additives. These additional performance additives may include one
or more metal
deactivators, viscosity modifiers, detergents, friction modifiers, antiwear
agents, corrosion
inhibitors, dispersants (other than those of the invention), dispersant
viscosity modifiers, extreme
pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point
depressants, seal swelling
agents, and any combination or mixture thereof. Typically, fully-formulated
lubricating oil will
contain one or more of these performance additives, and often a package of
multiple performance
additives.
100411 In one embodiment, the invention provides a
lubricating composition further
comprising an anti-wear agent, a dispersant viscosity modifier, a friction
modifier, a viscosity
modifier, an antioxidant, an overbased detergent, a dispersant (different from
that of the invention),
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or a combination thereof, where each of the additives listed may be a mixture
of two or more of
that type of additive. In one embodiment, the invention provides a lubricating
composition further
comprising an anti-wear agent, a dispersant viscosity modifier, a friction
modifier, a viscosity
modifier (typically an olefin copolymer such as an ethylene-propylene
copolymer), an antioxidant
(including phenolic and aminic antioxidants), an overbased detergent
(including overbased
sulfonates and phenates), or a combination thereof, where each of the
additives listed may be a
mixture of two or more of that type of additive.
100421 Another additive is an anti-wear agent. Examples
of anti-wear agents include
phosphorus-containing anti-wear/extreme pressure agents such as metal
thiophosphates,
phosphoric acid esters and salts thereof, phosphorus-containing carboxylic
acids, esters, ethers,
and amides, and phosphites. In certain embodiments a phosphorus antiwear agent
may be present
in an amount to deliver 0.01 to 0.2, 010.015 to 0.15, or 0.02 to 0.1, or 0.025
to 0.08, or 0.01 to
0.05 percent phosphorus. Often the anti-wear agent is a zinc
dialkyldithiophosphate (ZDDP or
ZDP).
100431 Zinc dialkyldithiophosphates may be described as
primary zinc
dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates,
depending on the structure
of the alcohol used in its preparation. In some embodiments the compositions
of the invention
include primary zinc dialkyldithiophosphates. In some embodiments the
compositions of the
invention include secondary zinc dialkyldithiophosphates. In some embodiments
the compositions
of the invention include a mixture of primary and secondary zinc
dialkyldithiophosphates. In some
embodiments component (b) is a mixture of primary and secondary zinc
dialkyldithiophosphates
where the ratio of primary zinc dialkyldithiophosphates to secondary zinc
dialkyldithiophosphates
(one a weight basis) is at least 1.1, or even at least 1:1.2, or even at least
1:1.5 or 1:2, or 1:10. In
some embodiments, component (b) is a mixture of primary and secondary zinc
dialkyldithiophosphates that is at least 50 percent by weight primary, or even
at least 60, 70, 80,
or even 90 percent by weight primary. In some embodiments component (b) is
free of primary zinc
dialkyldithiophosphates.
100441 The phosphorus anti wear agent may be present at
0 weight % to 3 weight %, 01 0,1
to 3 wt % or 0.1 weight % to 1.5 weight %, or 0.5 weight % to 0.9 weight % of
the lubricating
composition.
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100451 In one embodiment, the invention provides a
lubricating composition which further
comprises ashless antioxidant. Ashless antioxidants may comprise one or more
of arylamines,
diarylamines, alkylated arylamines, alkylated diaryl amines, phenols, hindered
phenols, sulfurized
olefins, or mixtures thereof. In one embodiment, the lubricating composition
includes an
antioxidant, or mixtures thereof The antioxidant may be present at 0 weight %
to 15 weight %, or
0.1 weight % to 10 weight %, or 0.5 weight % to 5 weight %, or 0.5 weight % to
3 weight %, or
0.3 weight % to 1.5 weight % of the lubricating composition.
[0046] The diarylamine or alkylated diarylamine may be
a phenyl-a-naphthylamine
(PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or
mixtures thereof.
The alkylated diphenylamine may include di-nonylated diphenylamine, nonyl
diphenylamine,
octyl diphenylamine, di -octylated diphenylamine, di-decylated diphenylamine,
decyl
diphenylamine and mixtures thereof In one embodiment, the diphenylamine may
include nonyl
diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl
diphenylamine, or mixtures
thereof. In one embodiment, the alkylated diphenylamine may include nonyl
diphenylamine, or
dinonyl diphenylamine. The alkylated diarylamine may include octyl, di-octyl,
nonyl, di-nonyl,
decyl or di-decyl phenylnapthylamines.
[0047] The diarylamine antioxidant of the invention may
be present on a weight basis of
the lubrication composition at 0.1% to 10%, 0.35% to 5%, 0.4% to 1.2%, or even
0.5% to 2%.
[0048] The phenolic antioxidant may be a simple alkyl
phenol, a hindered phenol, or
coupled phenolic compounds.
[0049] The hindered phenol antioxidant often contains 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 (typically linear or branched alkyl) 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-ethy1-2,6-di4ert-butylphenol,
4-propy1-2,6-di-
tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, 4-dodecy1-2,6-di-tert-
butylphenol, or butyl 3-
(3,5-ditert-buty1-4-hydroxyphenyl)propanoate. In one embodiment, the hindered
phenol
antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from BASF.
In one
embodiment, the phenolic antioxidant comprises a hindered phenol. In another
embodiment the
hindered phenol is derived from 2,6-ditertbutyl phenol.
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100501 In one embodiment, the lubricating composition
of the invention comprises a
phenolic antioxidant in a range of 0.01 weight % to 5 weight %, or 0.1 weight
% to 4 weight %,
or 0.2 weight % to 3 weight %, or 0.5 weight % to 2 weight % of the
lubricating composition.
100511 Sulfurized olefins are well known commercial
materials, and those which are
substantially nitrogen-free, that is, not containing nitrogen functionality,
are readily available. The
olefinic compounds which may be sulfurized are diverse in nature. They contain
at least one
olefinic double bond, which is defined as a non-aromatic double bond; that is,
one connecting two
aliphatic carbon atoms. These materials generally have sulfide linkages having
1 to 10 sulfur
atoms, for instance, 1 to 4, or 1 or 2.
100521 Ashless antioxidants may be used separately or
in combination. In one embodiment
of the invention, two or more different antioxidants are used in combination,
such that there is at
least 0.1 wt % of each of the at least two antioxidants and wherein the
combined amount of the
ashless antioxidants is 0.5 to 5 wt %. In one embodiment, there may be at
least 0.25 to 3 wt % of
each ashless antioxidant.
100531 In one embodiment, the invention provides a
lubricating composition further
comprising a molybdenum compound. The molybdenum compound may be selected from
the
group consisting of molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates, amine
salts of molybdenum compounds, and mixtures thereof. The molybdenum compound
may provide
the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750
ppm, or 5 ppm to
300 ppm, or 20 ppm to 250 ppm of molybdenum, or 350 ppm to 900 ppm.
100541 In one embodiment, the lubricating composition
of the invention further comprises
a dispersant viscosity modifier. The dispersant viscosity modifier may be
present at 0 weight % to
weight %, or 0 weight % to 4 weight %, or 0.05 weight % to 2 weight % of the
lubricating
composition.
100551 Suitable dispersant viscosity modifiers include
functionalized polyolefins, for
example, ethylene-propylene copolymers that have been functionalized with an
acylating agent
such as maleic anhydride and an amine; polymethacrylates fimaionalized with an
amine, or
esterified styrene-maleic anhydride copolymers reacted with an amine. More
detailed description
of dispersant viscosity modifiers are disclosed in International Publication
W02006/015130 or
U.S. Pat. Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In one
embodiment, the dispersant
viscosity modifier may include those described in U.S. Pat. No. 4,863,623 (see
column 2, line 15
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to column 3, line 52) or in International Publication W02006/015130 (see page
2, paragraph
[0008] and preparative examples are described at paragraphs [0065] to [0073]).
100561 In one embodiment, the invention provides a
lubricating composition further
comprising a metal-containing detergent. The metal-containing detergent may be
an overbased
detergent. Overbased detergents otherwise referred to as overbased or
superbased salts are
characterized by a metal content in excess of that which would be necessary
for neutralization
according to the stoichiometry of the metal and the particular acidic organic
compound reacted
with the metal. The overbased detergent may be selected from the group
consisting of non-sulfur
containing phenates, sulfur containing phenates, sulfonates, salixarates,
salicylates, and mixtures
thereof.
100571 The overbased metal-containing detergent may be
sodium salts, calcium salts,
magnesium salts, or mixtures thereof of the phenates, sulfur-containing
phenates, sulfonates,
salixarates and salicylates. Overbased phenates and salicylates typically have
a total base number
of 180 to 450 TBN. Overbased sulfonates typically have a total base number of
250 to 600, or 300
to 500. Overbased detergents are known in the art. In one embodiment, the
sulfonate detergent
may be predominantly a linear alkylbenzene sulfonate detergent having a metal
ratio of at least 8
as is described in paragraphs [0026] to [0037] of US Patent Publication
2005065045 (and granted
as U.S. Pat. No. 7,407,919). The linear alkylbenzene sulfonate detergent may
be particularly useful
for assisting in improving fuel economy. The linear alkyl group may be
attached to the benzene
ring anywhere along the linear chain of the alkyl group, but often in the 2, 3
or 4 position of the
linear chain, and in some instances, predominantly in the 2 position,
resulting in the linear
alkylbenzene sulfonate detergent. Overbased detergents are known in the art.
The overbased
detergent may be present at 0 weight % to 15 weight %, or 0.1 weight % to 10
weight %, or 0.2
weight % to 8 weight %, or 0.5 to 3 weight %, or 0.2 weight % to 3 weight %.
For example, in a
heavy-duty diesel engine, the detergent may be present at 2 weight % to 3
weight % of the
lubricating composition. For a passenger car engine, the detergent may be
present at 0.2 weight %
to 1 weight % of the lubricating composition.
100581 Metal-containing detergents contribute sulfated
ash to a lubricating composition.
Sulfated ash may be determined by ASTM D874. In one embodiment, the
lubricating composition
of the invention comprises a metal-containing detergent in an amount to
deliver at least 0.4 wt %
sulfated ash to the total composition. In another embodiment, the metal-
containing detergent is
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present in an amount to deliver at least 0.6 wt % sulfated ash, or at least
0.75 wt % sulfated ash, or
even at least 0.9 wt % sulfated ash to the lubricating composition.
100591 The lubricating composition may contain a
polymeric viscosity modifier or
mixtures thereof The polymeric viscosity modifier may be an olefin
(co)polymer, a
poly(meth)acrylate (PMA), or mixtures thereof. In one embodiment, the
polymeric viscosity
modifier is an olefin (co)polymer.
100601 The olefin polymer may be derived from
isobutylene or isoprene. In one
embodiment, the olefin polymer is prepared from ethylene and a higher olefin
within the range of
C3-C10 alpha-mono-olefins, for example, the olefin polymer may be prepared
from ethylene and
propylene.
100611 In one embodiment, the olefin polymer may be a
polymer of 15 to 80 mole percent
of ethylene, for example, 30 mol percent to 70 mol percent ethylene and from
and from 20 to 85
mole percent of C3 to C10 mono-olefins, such as propylene, for example, 30 to
70 mol percent
propylene or higher mono-olefins. Terpolymer variations of the olefin
copolymer may also be used
and may contain up to 15 mol percent of a non-conjugated diene or triene. Non-
conjugated dienes
or trienes may have 5 to about 14 carbon atoms. The non-conjugated diene or
triene monomers
may be characterized by the presence of a vinyl group in the structure and can
include cyclic and
bicycle compounds. Representative dienes include 1,4-hexadiene, 1,4-
cyclohexadiene,
dicyclopentadiene, 5-ethyldiene-2-norbomene, 5-methylene-2-norbomene, 1,5-
heptadiene, and
1,6-octadiene.
100621 In one embodiment, the olefin copolymer may be a
copolymer of ethylene,
propylene, and butylene. The polymer may be prepared by polymerizing a mixture
of monomers
comprising ethylene, propylene and butylene. These polymers may be referred to
as copolymers
or terpolymers. The terpolymer may comprise from about 5 mol % to about 20 mol
%, or from
about 5 mol % to about 10 mol % structural units derived from ethylene; from
about 60 mol % to
about 90 mol %, or from about 60 mol % to about 75 mot structural units
derived from propylene;
and from about 5 mol % to about 30 mol %, or from about 15 mol % to about 30
mot % structural
units derived from butylene. The butylene may comprise any isomers or mixtures
thereof, such as
n-butylene, iso-butylene, or a mixture thereof. The butylene may comprise
butene-1. Commercial
sources of butylene may comprise butene-1 as well as butene-2 and butadiene.
The butylene may
comprise a mixture of butene-1 and isobutylene wherein the weight ratio of
butene-1 to isobutylene
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is about 1:0.1 or less. The butylene may comprise butene-1 and be free of or
essentially free of
isobutylene.
[0063] In one embodiment, the olefin copolymer may be a
copolymer of ethylene and
butylene. The polymer may be prepared by polymerizing a mixture of monomers
comprising
ethylene and butylene wherein, the monomer composition is free of or
substantially free of
propylene monomers (i.e., contains less than 1 wt % of intentionally added
monomer). The
copolymer may comprise 30 to 50 mol percent structural units derived from
butylene; and from
about 50 mol percent to 70 mol percent structural units derived from ethylene.
The butylene may
comprise a mixture of butene-1 and isobutylene wherein the weight ratio of
butene-1 to isobutylene
is about 1:0.1 or less. The butylene may comprise butene-1 and be free of or
essentially free of
isobutylene.
[0064] Useful olefin polymers, in particular, ethylene-
a-olefin copolymers have a number
average molecular weight ranging from 4500 to 500,000, for example, 5000 to
100,000, or 7500
to 60,000, or 8000 to 45,000.
100651 hi one embodiment, lubricating composition may
comprise a poly(meth)acrylate
polymeric viscosity modifier. As used herein, the term "(meth)acrylate" and
its cognates means
either methacrylate or acrylate, as will be readily understood.
100661 In one embodiment, the poly(meth)acrylate
polymer is prepared from a monomer
mixture comprising (meth)acrylate monomers having alkyl groups of varying
length. The
(meth)acrylate monomers may contain alkyl groups that are straight chain or
branched chain
groups. The alkyl groups may contain 1 to 24 carbon atoms, for example 1 to 20
carbon atoms.
100671 The poly(meth)acrylate polymers described herein
are formed from monomers
derived from saturated alcohols, such as methyl (meth)acrylate, ethyl
(meth)acrylate, propyl
(meth)acrylate, butyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 2-
propylheptyl
(meth)acrylate, 2-butyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
octyl (meth)acrylate,
nonyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-tert-
butylheptyl
(meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate,
undecyl (meth)acrylate,
5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl
(meth)acrylate,
tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl
(meth)acrylate, pentadecyl
(meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate,
heptadecyl
(meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl
(meth)acrylate,
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5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl-(meth)acrylate,
octadecyl (meth)acrylate,
nonadecyl (meth)acrylate, eicosyl (meth)acrylate, (meth)acrylates derived from
unsaturated
alcohols, such as oleyl (meth)acrylate; and cycloalkyl (meth)acrylates, such
as 3-viny1-2-
butylcyclohexyl (meth)acrylate or bornyl (meth)acrylate.
100681
Other examples of monomers
include alkyl (meth)acrylates with long-chain
alcohol-derived groups which may be obtained, for example, by reaction of a
(meth)acrylic acid
(by direct esterification) or methyl (meth)acrylate (by transesterification)
with long-chain fatty
alcohols, in which reaction a mixture of esters such as (meth)acrylate with
alcohol groups of
various chain lengths is generally obtained. These fatty alcohols include Oxo
Alcohol 7911, Oxo
Alcohol 7900 and Oxo Alcohol 1100 of Monsanto; Alphanol 79 of ICI; Nafol
1620, Alfol
610 and Alfol 810 of Condea (now Sasol); Epal 610 and Epal 810 of Ethyl
Corporation;
Linevol 79, Linevol 911 and Dobanol 25 L of Shell AG; Lial 125 of Condea
Augusta,
Milan; Dehydad and Lorol of Henkel KGaA (now Cognis) as well as Linopol 7-
11 and
Acropol 91 of Ugine Kuhlmann.
100691
In one embodiment, the
poly(meth)acrylate polymer comprises a dispersant
monomer; dispersant monomers include those monomers which may copolymerize
with
(meth)acrylate monomers and contain one or more heteroatoms in addition to the
carbonyl group
of the (meth)acrylate The dispersant monomer may contain a nitrogen-containing
group, an
oxygen-containing group, or mixtures thereof.
100701
The nitrogen-containing
compound may be a (meth)acrylamide or a nitrogen
containing (meth)acrylate monomer. Examples of a suitable nitrogen-containing
compound
include N,N-climethylacrylamide, N-vinyl carbonamides such as N-vinyl-
forrnamide, vinyl
pyridine, N-vinylacetoamide, N-vinyl propionamides, N-vinyl hydroxy-
acetoamide, N-vinyl
imidazole, N-vinyl pyrrolidinone, N-vinyl caprolactam, dimethylaminoethyl
acrylate (DMAEA),
dimethylaminoethyl methacrylate (DMAEMA),
di methylaminobutyl acrylamide,
dimethylaminopropyl meth-acrylate (DMAPMA), dimethylaminopropyl acrylamide,
dimethyl-
aminopropyl methacrylamide, dimethylaminoethyl acrylamide or mixtures thereof.
100711
Dispersant monomers may be
present in an amount up to 5 mol percent of the
monomer composition of the (meth)acrylate polymer. In one embodiment, the
poly(meth)acrylate
is present in an amount 0 to 5 mol percent, 0.5 to 4 mol percent, or 0.8 to 3
mol percent of the
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polymer composition. In one embodiment, the poly(meth)acrylate is free of or
substantially free
of dispersant monomers.
[0072] In one embodiment, the poly(meth)acrylate
comprises a block copolymer or
tapered block copolymer. Block copolymers are formed from a monomer mixture
comprising one
or more (meth)acrylate monomers, wherein, for example, a first (meth)acrylate
monomer forms a
discrete block of the polymer joined to a second discrete block of the polymer
formed from a
second (meth)acrylate monomer. While block copolymers have substantially
discrete blocks
formed from the monomers in the monomer mixture, a tapered block copolymer may
be composed
of, at one end, a relatively pure first monomer and, at the other end, a
relatively pure second
monomer. The middle of the tapered block copolymer is more of a gradient
composition of the
two monomers.
[0073] In one embodiment, the poly(meth)acrylate
polymer (P) is a block or tapered block
copolymer that comprises at least one polymer block (B1) that is insoluble or
substantially
insoluble in the base oil and a second polymer block (B2) that is soluble or
substantially soluble in
the base oil.
100741 In one embodiment, the poly(meth)acrylate
polymers may have an architecture
selected from linear, branched, hyper-branched, cross-linked, star (also
referred to as "radial"), or
combinations thereof. Star or radial refers to multi-armed polymers. Such
polymers include
(meth)acrylate-containing polymers comprising 3 or more arms or branches,
which, in some
embodiments, contain at least about 20, or at least 50 or 100 or 200 or 350 or
500 or 1000 carbon
atoms. The arms are generally attached to a multivalent organic moiety which
acts as a "core" or
"coupling agent." The multi-armed polymer may be referred to as a radial or
star polymer, or even
a "comb" polymer, or a polymer otherwise having multiple arms or branches as
described herein.
[0075] Linear poly(meth)acrylates, random, block or
otherwise, may have weight average
molecular weight (Ms) of 1000 to 400,000 Daltons, 1000 to 150,000 Daltons, or
15,000 to 100,000
Daltons. In one embodiment, the poly(meth)acrylate may be a linear block
copolymer with a Mw
of 5,000 to 40,000 Daltons, or 10,000 to 30,000 Daltons.
100761 Radial, cross-linked or star copolymers may be
derived from linear random or di-
block copolymers with molecular weights as described above. A star polymer may
have a weight
average molecular weight of 10,000 to 1,500,000 Daltons, or 40,000 to
1,000,000 Daltons, or
300,000 to 850,000 Dalton&
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100771 The lubricating compositions may comprise 0.05
weight % to 2 weight %, or 0.08
weight % to 1.8 weight %, or 0.1 to 1.2 weight % of the one or more polymeric
viscosity modifiers
as described herein.
[0078] In one embodiment, the invention provides a
lubricating composition further
comprising a friction modifier. Examples of friction modifiers include long
chain fatty acid
derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as
condensation products
of carboxylic acids and polyalkylene-polyamines; amine salts of
alkylphosphoric acids; fatty alkyl
tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides. The term
fatty, as used herein, can mean
having a C8-22 linear alkyl group.
[0079] Friction modifiers may also encompass materials
such as sulfurized fatty
compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum
dithioearbamates,
sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
[0080] In one embodiment the friction modifier may be
selected from the group consisting
of long chain fatty acid derivatives of amines, long chain fatty esters, or
long chain fatty epoxides;
fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl
tartrates; fatty alkyl
tartrimides; and fatty alkyl tartramides. The friction modifier may be present
at 0 weight % to 6
weight %, or 0.05 weight % to 4 weight %, or 0.1 weight % to 2 weight % of the
lubricating
composition.
[0081] In one embodiment, 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
diester or a mixture
thereof, and in another embodiment the long chain fatty acid ester may be a
triglyceride.
[0082] Other performance additives such as corrosion
inhibitors include those described
in paragraphs 5 to 8 of US Application US05/038319, published as
W02006/047486, octyl
octanamide, condensation products of dodecenyl succinic acid or anhydride and
a fatty acid such
as oleic acid with a polyamine. In one embodiment, the corrosion inhibitors
include the Synalox '
(a registered trademark of The Dow Chemical Company) corrosion inhibitor. The
Synalox
corrosion inhibitor may be a homopolymer or copolymer of propylene oxide. The
Synalox.
corrosion inhibitor is described in more detail in a product brochure with
Form No. 118-01453-
0702 AMS, published by The Dow Chemical Company. The product brochure is
entitled
"SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications."
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100831 The lubricating composition may further include
metal deactivators, including
derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole
derivatives, 1,2,4-
triazoles, benzi midazol es, 2-al kyl dithi obenzimi dazol es, or 2-alkyl
dithi obenzothi azol es; foam
inhibitors, including copolymers of ethyl acrylate and 2-ethylhexylacrylate
and copolymers of
ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers
including triallcyl
phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides
and (ethylene oxide-
propylene oxide) polymers; and pour point depressants, including esters of
maleic anhydride-
styrene, polymethacrylates, polyacrylates or polyacrylamides.
[0084] Pour point depressants that may be useful in the
compositions of the invention
further include polyalphaolefins, esters of maleic anhydride-styrene,
poly(meth)acrylates,
polyacrylates or polyacrylamides.
100851 In different embodiments, the lubricating
composition may have a composition as
described in the following table:
Additive
Embodiments (wt
A
Low volatility Hydrocarbon Base Oil 20
to 95 30 to 85 40 to 65
Polyalkenyl Succinimide Dispersant
1.2 to 4 1.5 to 3.6 2 to 3.4
Anti-wear Agents 0.15 to 4
0.2 to 2 0.5 to 1,5
Ashless Antioxidants 0 to 6
0.6 to 3 0.8 to 2.5
Metal Detergents 0 to 5
0.45 to 2.5 0.8 to 2
O
or 0,1 0,5 to 3 0,8 to 1.8
Viscosity Modifier
to 4.5
O
or 0.1 0 or 0.1 0.5 to 1.6
Dispersant Viscosity Modifier
to 4.5
to 2.5
O
or 0.05 0.05 to 1.6 0.1 to 1.2
Friction Modifier
to 2
O
or 0.05 0 or 0.05 0 or 0.05
Any Other Performance Additive
to 6
to 3 to 1.8
Other Oil of Lubricating Viscosity
Balance to 100 %
[0086] The present invention provides a surprising
ability to provide engine durability (i.e.
resistance to wear) and increased fuel economy, without increasing oil
consumption.
INDUSTRIAL APPLICATION
[0087] As described above, the invention provides for a
method of lubricating an internal
combustion engine comprising supplying to the internal combustion engine a
lubricating
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composition as disclosed herein. Generally, the lubricant is added to the
lubricating system of the
internal combustion engine, which then delivers the lubricating composition to
the critical parts of
the engine, during its operation, that require lubrication. Further, the
instant disclosure relates to
use of the described lubricant composition in an internal combustion engine
for improving the fuel
economy thereof.
[0088] The lubricating compositions described above may
be utilized in an internal
combustion engine. The engine components may have a surface of steel or
aluminum (typically a
surface of steel) and may also be coated for example with a diamond-like
carbon (DLC) coating.
[0089] The internal combustion engine may be fitted
with an emission control system or a
turbocharger. Examples of the emission control system include diesel
particulate filters (DPF),
Gasoline Particulate Filters (GPF), three-way catalysts, or systems employing
selective catalytic
reduction (SCR).
[0090] The internal combustion engine may be spark
ignited or compression ignited and
would utilize fuels appropriate to the ignition sequence. A spark ignited
internal combustion
engine may be port fuel injected (PFI) or direct injected.
100911 The internal combustion engine may be fueled by
a normally liquid or gaseous fuel
or combinations thereof. The liquid fuel is normally a liquid at ambient
conditions e.g., room
temperature (20 to 30 C.). The fuel can be a hydrocarbon fuel, a
nonhydrocarbon fuel, or a mixture
thereof. The hydrocarbon fuel may be a gasoline as defined by ASTM
specification D4814. In an
embodiment of the invention the fuel is a gasoline, and in other embodiments
the fuel is a leaded
gasoline, or a nonleaded gasoline.
[0092] The internal engine may be operated at a brake
mean effective pressure (BMEP) of
at least at least 12 bars, or at least 20 bars, or at least 22 bars, or at
least 24 bars, or at least 26 bars.
In one embodiment, high BlVIEP is achieved through operating the engine with
one or more
features comprising gasoline direct injection (GDI), turbochargers,
superchargers, variable valve
timing, homogeneous charge compression ignition (HCCI), lean burn, or
combinations thereof.
[0093] The nonhydrocarbon fuel can be an oxygen
containing composition, often referred
to as an oxygenate, to include an alcohol, an ether, a ketone, an ester of a
carboxylic acid, a
nitroalkane, or a mixture thereof. The nonhydrocarbon fuel can include for
example methanol,
ethanol, methyl t-butyl ether, methyl ethyl ketone, transestetified oils
and/or fats from plants and
animals such as rapeseed methyl ester and soybean methyl ester, and
nitromethane. Mixtures of
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hydrocarbon and nonhydrocarbon fuels can include, for example, gasoline and
methanol and/or
ethanol. In an embodiment of the invention, the liquid fuel is a mixture of
gasoline and ethanol,
wherein the ethanol content is at least 5 volume percent of the fuel
composition, or at least 10
volume percent of the composition, or at least 15 volume percent, or 15 to 85
volume percent of
the composition. In one embodiment, the liquid fuel contains less than 15% by
volume ethanol
content, less than 10% by volume ethanol content, less than 5% ethanol content
by volume, or is
substantially free of (i.e. less than 0.5% by volume) of ethanol.
100941 The gaseous fuel is normally a gas at ambient
conditions e.g., room temperature
(20 to 30 C.). Suitable gas fuels include natural gas, liquefied petroleum gas
(LPG), compressed
natural gas, or mixtures thereof. In one embodiment, the engine is fueled with
natural gas.
100951 The lubricant composition may be an engine oil
having a kinematic viscosity of up
to about 32.5 cSt at 100 C, or from about 4.5 to about 18.5 cSt at 100 C.,
or from about 5.3 to
about 13.5 cSt at 100 C, or from about 6 to about 10.5 cSt at 100 C as
measured by AST/vI D445.
100961 High temp high shear (HTHS) are viscosity
measurements and represent a fluid's
resistance to flow under conditions resembling highly-loaded journal bearings
in internal
combustion engines. The HTHS value of an oil andlor lubricating composition
directly correlates
to the oil film thickness in a bearing. HTHS values of a fluid may be obtained
by using ASTM
D4683 at 150° C. The lubricating compositions of this invention may
have a HTHS of
between 1.8 cP and 3.2 cP, or between 2.3 cP and 2.6 cP, or less than 2.3 cP.
100971 In one embodiment, the lubricating composition
may be an engine oil, wherein the
lubricating composition may be characterized as having at least one of (i) a
sulfur content of 0.5
wt % or less, (ii) a phosphorus content of 0.1 wt % or less, (iii) a sulfated
ash content of 1.5 wt %
or less, or combinations thereof
EXAMPLES
100981 The invention will be further illustrated by the
following examples, which set forth
particularly advantageous embodiments. While the examples are provided to
illustrate the
invention, they are not intended to limit it.
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Lubricating Base Oils
[0099] A series of fluids are evaluated as base fluids
for preparing lubricants suitable for
internal combustion engines. Materials include conventional mineral oils,
polyalphaolefins, and
bio-engineered hydrocarbon oils, as described in Table 1 below.
Kinematic Viscosity
100 C
Noack Volatility
at
Base Fluid Type (D5800)
(D/115 100)
(wt %)
(m Is)
4 cSt Group III Mineral Oil
4.2 14
PAO-41
Polyalphaolefin 3.8 13
3 cSt Group III Mineral Oil
3.0 42
PAO-22
Polyalphaolefin 1.7 75
3
Branched
HC-A 3.2 24
hydrocarbon
4
Bmached
HC-B 2.8 28
hydrocarbon
1. Polyalpha olefin available from Chevron Phillips Chemical Company as
Synfluicr PAO 4 cSt
2. Polyalpha olefm available as Durasyn- 162 from INFOS
3. Rio-derived branched hydrocarbon with average carbon no. of 28-34, with
at least 30 mol% carbons on one or
more branches
4. Bio-derived branched hydrocarbon with average carbon no. of 24-28, with
at least 30 mol% carbons on one or
more branches
Lubricating Compositions
[00100] A series of OW-16 engine lubricants are prepared
containing the base fluids
described above as well as conventional additives including ashless
succinimide dispersant,
overbased detergents, antioxidants (combination of phenolic ester,
diarylamine, and sulfinized
olefin), zinc dialkyldithiophosphate (ZDDP), polymeric viscosity modifier, as
well as other
performance additives. All of the lubricants are prepared based on a common
formulation as
follows in Table 2.
Table 2¨ Lubricating Oil Composition Formulations'
EX1 EX2 E3 EX4 EX5 EX6 EX7
4 cSt Gp III 85 65 65
65 55 65 65
3 cSt Gp III 0 20 0
0 0 0 0
HC-A 0 0 0
20 30 20 20
PAO-2 0 0 20
0 0 0 0
Pffisuccinimide dispersant2 2 2 2
2 3 2 2
C3/6 Secondary? ZDDP 0.8 0.8 0.8
0.8 0.8 0.8 0.8
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EX1 EX2 EX3 EX4 EX5 EX6 EX7
Ovetbased Calcium Sulfonate 1.2 1.2 1.2
1.2 1.2 0 0.2
Calcium Salicylate4 0 0 0
0 0 0.6 0
Ashless Antioxidant' 1.2 1.2 1.2
1.2 1.2 1.2 1.2
Overbased Mg Sulfonate 0 0 0
0 0 0 1.0
E-P VI Improvee 0_7 0.6 0.6
0.45 0.6 0.45 0.45
Additional Additives' 0.25 0.25 0.25
0.25 0.25 0.25 0.25
Noack (D5800)8 14 24 35
18 20 18 18
Cakium (ppm) (calculated) 2300 2300 2300
2300 2300 1060 450
Magnesium (ppm) (calculated) 0 0 0
0 0 0 1400
Phosphorus (ppm) (calculated) 0.075 0.075
01)75 0.075 0.075 0.075 0.075
I ¨ All amounts shown above are in wt % and are on an oil-free basis unless
otherwise noted
2¨ NB Fsuccinimide prepared from 2000 Mn PIB with oil five TBN of 27 mg KOH/g
3 ¨500 TBN (oil five) overbased calcium sulfonate
4¨ 400 TBN overb axed calcium alkylsalicylate
¨ Combination of alkylated diatylamine, hindered phenol, and sulfurized olefin
antioxidants
6¨ Ethylene-propylene copolymer
7¨ The Additional Additives used in the examples include friction modifier,
pourpoint depressants, anti-foam
agents, emulsifier, titanium alkoxide, and includes some amount of diluent oil
that may be present in additives as
manufactured
8¨ Calculated amount
Testing
1001011 The lubricants are evaluated for wear
performance, fuel economy, friction
reduction performance, and oil consumption. Many industry standard engine
tests are used to
evaluate engine lubricant performance and often have an oil consumption
measurement. Engine
tests include the BMW N20 Endurance Engine Oil Test, The N20 test is a 395-
hour test that is
used to evaluate the lubricating composition for piston cleanliness, engine
sludge, turbocharger
deposits, and wear iron; the New European Drive Cycle (NEDC) in two Mercedes
Benz vehicles,
OM 271FE and 0M642FE; the API Sequence UM for measuring oxidation deposit
control; the
API Sequence IVB for measuring engine durability; and many others as part of
the API SN plus
gasoline engine approval and the API CK-4 diesel engine approval.
1001021 The lubricants are evaluated for wear
performance in a programmed temperature
high frequency reciprocating rig (HERR) available from PCS Instruments. HERR
conditions for
the evaluations are 200 g load, 75-minute duration, 1000 micrometer stroke, 20
hertz frequency,
and temperature profile of 15 minutes at 40 C. followed by an increase in
temperature to 1600 C.
at a rate of 2 C. per minute. Wear scar in micrometers and film formation as
percent film thickness
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are then measured with lower wear scar values and higher film formation values
indicating
improved wear performance.
[00103] The percent film thickness is based on the
measurement of electrical potential
between an upper and a lower metal test plate in the HERR. When the film
thickness is 100%,
there is a high electrical potential for the full length of the 1000
micrometer stroke, suggesting no
metal to metal contact. Conversely for a film thickness of 0% there is no
electrical potential
suggesting continual metal to metal contact between the plates. For
intermediate film thicknesses,
there is an electrical potential suggesting the upper and lower metal test
plate have a degree of
metal to metal contact as well as other areas with no metal to metal contact.
[00104] The lubricating compositions are tested for
deposit control in a Panel Coker heated
to 325 C., with a sump temperature of 105 C., and a splash/bake cycle of 120
s/45 s. The airflow
is 350 ml/min, with a spindle speed of 1000 rpm and the test lasts for 4
hours. The oil is splashed
onto an aluminum panel which is then optically rated by computer. Performance
ranges from 0%
(black panel) to 100% (clean panel).
[00105] The propensity for a lubricating composition to
resist deposit formation is evaluated
in the Komatsu Hot Tube (KHT) test. This is an industry test used to evaluate
performance of
engine oils based on their deposit-forming tendencies by circulating a sample
of the engine oil at
0.31 mL per hour and air at 10 mL per minute through a glass tube for 16 hours
at a specified
temperature, usually from 270 C. up to 310 C. After the test, the tubes are
visually rated, with a
higher number being a better rating: 10 representing a clean tube and 0 (zero)
representing a tube
with heavy deposits.
[00106] Deposit performance can be measured according to
the Thermo-Oxidation Engine
Oil Simulation Test (TEOST 33) as presented in ASTM D6335. The results of the
TEOST 33 test
show the milligrams of deposit after an engine oil is run at elevated
temperatures. Lower TEOST
33 results are indicative of improved resistance to deposit formation
[00107] It is known that some of the materials described
above may interact in the final
formulation, so that the components of the final formulation may be different
from those that are
initially added. The products formed thereby, including the products formed
upon employing
lubricant composition of the present invention in its intended use, may not be
susceptible of easy
description. Nevertheless, all such modifications and reaction products are
included within the
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scope of the present invention; the present invention encompasses lubricant
composition prepared
by admixing the components described above.
[00108] Each of the documents referred to above is
incorporated herein by reference, as is
the priority document and all related applications, if any, which this
application claims the benefit
of Except in the Examples, or where otherwise explicitly indicated, all
numerical quantities in this
description specifying amounts of materials, reaction conditions, molecular
weights, number of
carbon atoms, and the like, are to be understood as modified by the word
"about." Unless otherwise
indicated, each chemical or composition referred to herein should be
interpreted as being a
commercial grade material which may contain the isomers, by-products,
derivatives, and other
such materials which are normally understood to be present in the commercial
grade. However,
the amount of each chemical component is presented exclusive of any solvent or
diluent oil, which
may be customarily present in the commercial material, unless otherwise
indicated. It is to be
understood that the upper and lower amount, range, and ratio limits set forth
herein may be
independently combined. Similarly, the ranges and amounts for each element of
the invention may
be used together with ranges or amounts for any of the other elements.
[00109] 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
predominantly hydrocarbon character. Examples of hydrocarbyl groups include
hydrocarbon
substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g.,
cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic
substituents, as well as
cyclic substituents wherein the ring is completed through another portion of
the molecule (e.g.,
two substituents together form a ring); (ii) substituted hydrocarbon
substituents, that is,
substituents containing non-hydrocarbon groups which, in the context of this
invention, do not
alter the predominantly hydrocarbon nature of the substituent (e.g., halo
(especially chloro and
fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and
sulfoxy); (iii) hetero
substituents, that is, substituents which, while having a predominantly
hydrocarbon character, in
the context of this invention, contain other than carbon in a ring or chain
otherwise composed of
carbon atoms.
[00110] Heteroatoms include sulfur, oxygen, nitrogen,
and encompass substituents as
pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,
preferably no more than one,
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non-hydrocarbon substituent will be present for every ten carbon atoms in the
hydrocarbyl group;
typically, there will be no non-hydrocarbon substituents in the hydrocarbyl
group.
1001111 As used in this document, the singular forms
"a," "an," and "the" include plural
references unless the context clearly dictates otherwise. Unless defined
otherwise, all technical and
scientific terms used herein have the same meanings as commonly understood by
one of ordinary
skill in the art. Nothing in this disclosure is to be construed as an
admission that the embodiments
described in this disclosure are not entitled to antedate such disclosure by
virtue of prior invention.
As used in this document, the term "comprising" means "including, but not
limited to."
1001121 While various compositions, methods, and devices
are described in terms of
"comprising" various components or steps (interpreted as meaning "including,
but not limited to"),
the compositions, methods, and devices can also "consist essentially of' or
"consist of' the various
components and steps, and such terminology should be interpreted as defining
essentially closed-
member groups.
1001131 While various compositions, methods, and devices
are described in terms of
"comprising" various components or steps (interpreted as meaning "including,
but not limited to"),
the compositions, methods, and devices can also "consist essentially of' or
"consist of' the various
components and steps, and such terminology should be interpreted as defining
essentially closed-
member groups.
1001141 It will be understood by those within the art
that, in general, terms used herein, and
especially in the appended claims (e.g., bodies of the appended claims) are
generally intended as
"open" terms (e.g., the term "including" should be interpreted as "including
but not limited to," the
term "having" should be interpreted as "having at least," the term "includes"
should be interpreted
as "includes but is not limited to," etc.). It will be further understood by
those within the art that if
a specific number of an introduced claim recitation is intended, such an
intent will be explicitly
recited in the claim, and in the absence of such recitation, no such intent is
present. For example,
as an aid to understanding, the following appended claims may contain usage of
the introductory
phrases "at least one" and "one or more" to introduce claim recitations.
However, the use of such
phrases should not be construed to imply that the introduction of a claim
recitation by the indefinite
articles "a" or "an" limits any particular claim containing such introduced
claim recitation to
embodiments containing only one such recitation, even when the same claim
includes the
introductory phrases "one or more" or "at least one" and indefinite articles
such as "a" or "an" (e.g.,
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"a" and/or "an" should be interpreted to mean "at least one" or "one or
more"); the same holds true
for the use of definite articles used to introduce claim recitations. In
addition, even if a specific
number of an introduced claim recitation is explicitly recited, those skilled
in the art will recognize
that such recitation should be interpreted to mean at least the recited number
(e.g., the bare
recitation of "two recitations," without other modifiers, means at least two
recitations, or two or
more recitations). Furthermore, in those instances where a convention
analogous to "at least one
of A, B, and C, etc." is used, in general, such a construction is intended in
the sense one having
skill in the art would understand the convention (e.g., "a system having at
least one of A, B, and
C" would include but not be limited to systems that have A alone, B alone, C
alone, A and B
together, A and C together, B and C together, and/or A, B, and C together,
etc.). In those instances
where a convention analogous to "at least one of A, B, or C, etc." is used, in
general, such a
construction is intended in the sense one having skill in the art would
understand the convention
(e.g., "a system having at least one of A, B, or C" would include but not be
limited to systems that
have A alone, B alone, C alone, A and B together, A and C together, B and C
together, and/or A,
B, and C together, etc.). It will be further understood by those within the
art that virtually any
disjunctive word and/or phrase presenting two or more alternative terms,
whether in the
description, claims, or drawings, should be understood to contemplate the
possibilities of including
one of the terms, either of the terms, or both terms. For example, the phrase
"A or B" will be
understood to include the possibilities of "A" or "B" or "A and B."
[00115] In addition, where features or aspects of the
disclosure may be described in terms
of Markush groups, those skilled in the art will recognize that the disclosure
is also thereby
described in terms of any individual member or subgroup of members of the
Marlcush group.
[00116] As will be understood by one skilled in the art,
for any and all purposes, such as in
terms of providing a written description, all ranges disclosed herein also
encompass any and all
possible subranges and combinations of subranges thereof. Any listed range can
be easily
recognized as sufficiently describing and enabling the same range being broken
down into at least
equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting
example, each range discussed
herein can be readily broken down into a lower third, middle third and upper
third, etc. As will
also be understood by one skilled in the art all language such as "up to," "at
least," and the like
include the number recited and refer to ranges which can be subsequently
broken down into
subranges as discussed above. Finally, as will be understood by one skilled in
the art, a range
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includes each individual member. Thus, for example, a group having 1-3 wt %
refers to groups
having 1, 2, or 3 wt.%. Similarly, a group having 1-5 wt % refers to groups
having 1, 2, 3, 4, or 5
wt %, and so forth, including all points therebetween.
[00117] As used herein, the term "about" means that a
value of a given quantity is within
20% of the stated value. In other embodiments, the value is within +15% of the
stated value. In
other embodiments, the value is within th10% of the stated value. In other
embodiments, the value
is within +5% of the stated value. In other embodiments, the value is within
2.5% of the stated
value. In other embodiments, the value is within 1% of the stated value.
[00118] Unless otherwise stated, "wt %" as used herein
shall refer to the wt % (weight
percent) based on the total weight of the lubricating composition.
[00119] While the invention has been explained in
relation to its preferred embodiments, it
is to be understood that various modifications thereof will become apparent to
those skilled in the
art upon reading the specification. Therefore, it is to be understood that the
invention disclosed
herein is intended to cover such modifications as fall within the scope of the
appended claims.
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