FIELD
[0001] This disclosure relates to improving fuel efficiency and friction reduction properties,
while maintaining or improving deposit control, in an engine lubricated with a lubricating
oil by including a friction modifier mixture, in the lubricating oil.
BACKGROUND
[0002] Fuel efficiency requirements for passenger vehicles are becoming increasingly more
stringent. New legislation in the United States and European Union within the past
few years has set fuel economy and emissions targets not readily achievable with today's
vehicle and lubricant technology.
[0003] To address these increasing standards, automotive original equipment manufacturers
are demanding better fuel economy as a lubricant-related performance characteristic,
while maintaining deposit control and oxidative stability requirements. One well known
way to increase fuel economy is to decrease the viscosity of the lubricating oil.
However, this approach is now reaching the limits of current equipment capabilities
and specifications. At a given viscosity, it is well known that adding organic or
organic metallic friction modifiers reduces the surface friction of the lubricating
oil and allows for better fuel economy. However these additives often bring with them
detrimental effects such as increased deposit formation, seals impacts, or they out-compete
the anti-wear components for limited surface sites, thereby not allowing the formation
of an anti-wear film, causing increased wear.
[0004] Contemporary lubricants such as engine oils use mixtures of additives such as dispersants,
detergents, inhibitors, viscosity index improvers and the like to provide engine cleanliness
and durability under a wide range of performance conditions of temperature, pressure,
and lubricant service life.
[0005] Lubricant-related performance characteristics such as high temperature deposit control
and fuel economy are extremely advantageous attributes as measured by a variety of
bench and engine tests. As indicated above, it is known that adding organic friction
modifiers to a lubricant formulation imparts frictional benefits at low temperatures,
consequently improving the lubricant fuel economy performance. At high temperatures,
however, adding increased levels of organic friction modifier can invite high temperature
performance issues. For example, engine deposits are undesirable consequences of high
levels of friction modifier in an engine oil formulation at high temperature engine
operation.
[0006] A major challenge in engine oil formulation is simultaneously achieving high temperature
deposit control while also achieving improved fuel economy.
[0007] Despite the advances in lubricant oil formulation technology, there exists a need
for an engine oil lubricant that effectively improves fuel economy while maintaining
or improving friction reduction properties and deposit control.
SUMMARY
[0008] This disclosure relates in part to the use of a friction modifier mixture for improving
fuel efficiency and reducing frictional properties, while maintaining or improving
deposit control, in an engine lubricated with a lubricating oil having a composition
comprising from 50 to 99 weight % based on the total weight of the lubricating oil
of a lubricating oil base stock as a major component wherein the friction modifier
mixture comprises an ethoxylated fatty acid ester and a glycerol fatty acid ester
in a weight ratio of from 0.1:1 to 1:0.1 and is present in a range of from 0.1 to
1.5 weight % based on the total weight of the lubricating oil and wherein fuel efficiency
and friction reduction properties are improved and deposit control is maintained or
improved as compared to friction reduction properties and deposit control achieved
using a lubricating engine oil containing a minor component other than the friction
modifier mixture. The lubricating oils of this disclosure are useful in internal combustion
engines including direct injection, gasoline and diesel engines.
[0009] Fuel efficiency and friction reduction properties are improved and deposit control
is maintained or improved as compared to friction reduction properties and deposit
control achieved using a lubricating engine oil containing a minor component other
than the friction modifier mixture.
[0010] This disclosure further relates in part to a lubricating engine oil having a composition
comprising from 50 to 99 weight % based on the total weight of the lubricating oil
of a lubricating oil base stock as a major component; and a friction modifier mixture
comprising an ethoxylated fatty acid ester and a glycerol fatty acid ester in a weight
ratio of from 0.1:1 to 1:0.1 said friction modifier mixture being present in a range
of from 0.1 to 1.0 weight % based on the total weight of the lubricating oil; and
wherein fuel efficiency and friction reduction properties are improved and deposit
control is maintained or improved as compared to friction reduction properties and
deposit control achieved using a lubricating engine oil containing a minor component
other than the friction modifier mixture.
[0011] It has been surprisingly found that, in accordance with this disclosure, improvements
in fuel economy and friction reduction properties are obtained without sacrificing
engine cleanliness (e.g., while maintaining or improving deposit control) in an engine
lubricated with a lubricating oil, by including a friction modifier mixture in the
lubricating oil.
[0012] Other objects and advantages of the present disclosure will become apparent from
the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
Fig. 1 shows a comparison of testing results of three 0W-20 oils for cleanliness and
friction in accordance with embodiments of this disclosure.
Fig. 2 graphically shows average integrated Stribeck friction coefficients from mini-traction
machine (MTM) measurements performed at 140°C as a function of ethoxylated fatty ester
treat rate and other friction modifier treat variations.
Fig. 3 graphically shows MTM Stribeck friction coefficient plots showing 0W-20 baseline
reference (in light blue at top) and traces 1-10 of the same formulation containing
only ethoxylated fatty ester as a friction modifier.
Fig. 4 shows formulation embodiments of this disclosure (e.g., organic friction modifier
boost and combo boost). Formulation details are shown in weight percent based on the
total weight percent of the formulation, of various formulations. Fig. 4 also shows
the results of bench testing of the formulations using thermo-oxidation engine oil
simulation (TEOST 33C) measured by ASTM D6335.
Fig. 5 shows formulation details in weight percent based on the total weight percent
of the formulation, of various formulations. Fig. 5 also shows the results of bench
testing of the formulations using thermo-oxidation engine oil simulation TEOST 33C
and MTM friction.
Fig. 6 shows formulation details in weight percent based on the total weight percent
of the formulation, of various formulations. Fig. 6 also shows the results of bench
testing of the formulations using thermo-oxidation engine oil simulation TEOST 33C
and MTM friction.
Fig. 7 depicts other exemplary lubricant formulations of the present disclosure with
individual contributions of components used in such formulations.
Fig. 8 depicts still other exemplary formulations of the present disclosure with individual
contributions of components used in such formulations.
Fig. 9 depicts still yet other exemplary formulations of the present disclosure with
individual contributions of components used in such formulations.
DETAILED DESCRIPTION
[0014] It has now been found that improved fuel efficiency and friction reduction properties
can be attained, while deposit control is unexpectedly maintained or improved, in
an engine lubricated with a lubricating oil by using as the lubricating oil a formulated
oil that has a friction modifier mixture. The formulated oil preferably comprises
a lubricating oil base stock as a major component, and a friction modifier mixture,
a metal dialkyl dithio phosphate, and a viscosity index improver, as minor components.
The lubricating oils of this disclosure are particularly advantageous as passenger
vehicle engine oil (PVEO) products.
[0015] The lubricating oils of this disclosure provide excellent engine protection including
friction reduction and anti-wear performance. This benefit has been demonstrated for
the lubricating oils of this disclosure in the Sequence VID (ASTM D7589) engine tests.
The lubricating oils of this disclosure provide improved fuel efficiency. A lower
HTHS viscosity engine oil generally provides superior fuel economy to a higher HTHS
viscosity product. This benefit has been demonstrated for the lubricating oils of
this disclosure in the Sequence VID Fuel Economy (ASTM D7589) engine test.
[0016] The lubricating engine oils of this disclosure have a composition sufficient to pass
wear protection requirements of one or more engine tests selected from Sequence VID
and others.
[0017] In comparison with fuel efficiency achieved using a lubricating engine oil containing
a minor component other than the friction modifier mixture, the lubricating engine
oils containing the friction modifier mixture of this disclosure can exhibit a fuel
efficiency improvement preferably greater than 10%, as determined by the Sequence
VID Fuel Economy (ASTM D7589) engine test.
Lubricating Oil Base Stocks
[0018] A wide range of lubricating base oils is known in the art. Lubricating base oils
that are useful in the present disclosure are both natural oils, and synthetic oils,
and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefined
(the latter is also known as reclaimed or reprocessed oil). Unrefined oils are those
obtained directly from a natural or synthetic source and used without added purification.
These include shale oil obtained directly from retorting operations, petroleum oil
obtained directly from primary distillation, and ester oil obtained directly from
an esterification process. Refined oils are similar to the oils discussed for unrefined
oils except refined oils are subjected to one or more purification steps to improve
at least one lubricating oil property. One skilled in the art is familiar with many
purification processes. These processes include solvent extraction, secondary distillation,
acid extraction, base extraction, filtration, and percolation. Rerefined oils are
obtained by processes analogous to refined oils but using an oil that has been previously
used as a feed stock.
[0019] Groups I, II, III, IV and V are broad base oil stock categories developed and defined
by the American Petroleum Institute (API Publication 1509;
www.API.org) to create guidelines for lubricant base oils. Group I base stocks have a viscosity
index of between 80 to 120 and contain greater than 0.03% sulfur and/or less than
90% saturates. Group II base stocks have a viscosity index of between 80 to 120, and
contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
Group III stocks have a viscosity index greater than 120 and contain less than or
equal to 0.03 % sulfur and greater than 90% saturates. Group IV includes polyalphaolefins
(PAO). Group V base stock includes base stocks not included in Groups I-IV. The table
below summarizes properties of each of these five groups.
| |
Base Oil Properties |
| |
Saturates |
Sulfur |
Viscosity Index |
| Group I |
<90 and/or |
>0.03% and |
≥80 and <120 |
| Group II |
≥90 and |
≤0.03% and |
≥80 and <120 |
| Group III |
≥90 and |
≤0.03% and |
≥120 |
| Group IV |
Polyalphaolefins (PAO) |
| Group V |
All other base oil stocks not included in Groups I, II, III or IV |
[0020] Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example),
and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative
stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils
vary widely as to their crude source, for example, as to whether they are paraffinic,
naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also
useful. Natural oils vary also as to the method used for their production and purification,
for example, their distillation range and whether they are straight run or cracked,
hydrorefined, or solvent extracted.
[0021] Group II and/or Group III hydroprocessed or hydrocracked basestocks, including synthetic
oils such as polyalphaolefins, alkyl aromatics and synthetic esters are also well
known basestock oils.
[0022] Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oils such as polymerized
and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene
copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example).
Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
By way of example, PAOs derived from C
6, C
8, C
10, C
12, C
14 olefins or mixtures thereof may be utilized. See
U.S. Patent Nos. 4,956,122;
4,827,064; and
4,827,073.
[0023] The number average molecular weights of the PAOs, which are known materials and generally
available on a major commercial scale from suppliers such as ExxonMobil Chemical Company,
Chevron Phillips Chemical Company, BP, and others, typically vary from 250 to 3,000,
although PAO's may be made in viscosities up to 100 cSt (100°C). The PAOs are typically
comprised of relatively low molecular weight hydrogenated polymers or oligomers of
alphaolefins which include, but are not limited to, C
2 to C
32 alphaolefins with the C
8 to C
16 alphaolefins, such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like, being
preferred. The preferred polyalphaolefins are poly-1-hexene, poly-1-octene, poly-1-decene
and poly-1-dodecene and mixtures thereof and mixed olefin-derived polyolefins. However,
the dimers of higher olefins in the range of C
14 to C
18 may be used to provide low viscosity base stocks of acceptably low volatility. Depending
on the viscosity grade and the starting oligomer, the PAOs may be predominantly trimers
and tetramers of the starting olefins, with minor amounts of the higher oligomers,
having a viscosity range of 1.5 to 12 cSt. PAO fluids of particular use may include
3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof. Bi-modal mixtures of PAO
fluids having a viscosity range of 1.5 to 100 cSt may be used if desired.
[0024] The PAO fluids may be conveniently made by the polymerization of an alphaolefin in
the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including,
for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride
with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters
such as ethyl acetate or ethyl propionate. For example the methods disclosed by
U.S. Patent Nos. 4,149,178 or
3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis are found in
the following
U.S. Patent Nos. 3,742,082;
3,769,363;
3,876,720;
4,239,930;
4,367,352;
4,413,156;
4,434,408;
4,910,355;
4,956,122; and
5,068,487. The dimers of the C
14 to C
18 olefins are described in
U.S. Patent No. 4,218,330.
[0025] Other useful lubricant oil base stocks include wax isomerate base stocks and base
oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack
waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids
(GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks
and base oils, or mixtures thereof Fischer-Tropsch waxes, the high boiling point residues
of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur
content. The hydroprocessing used for the production of such base stocks may use an
amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized
lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization
catalyst, preferably a zeolitic catalyst. For example, one useful catalyst is ZSM-48
as described in
U.S. Patent No. 5,075,269. Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized
waxes are described, for example, in
U.S. Patent Nos. 2,817,693;
4,975,177;
4,921,594 and
4,897,178 as well as in British Patent Nos.
1,429,494;
1,350,257;
1,440,230 and
1,390,359. Particularly favorable processes are described in European Patent Application Nos.
464546 and
464547. Processes using Fischer-Tropsch wax feeds are described in
U.S. Patent Nos. 4,594,172 and
4,943, 672.
[0026] Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other
wax-derived hydroisomerized (wax isomerate) base oils be advantageously used in the
instant disclosure, and may have useful kinematic viscosities at 100°C of 3 cSt to
50 cSt, preferably 3 cSt to 30 cSt, more preferably 3.5 cSt to 25 cSt, as exemplified
by GTL 4 with kinematic viscosity of 4.0 cSt at 100°C and a viscosity index of 141.
These Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other
wax-derived hydroisomerized base oils may have useful pour points of -20°C or lower,
and under some conditions may have advantageous pour points of -25°C or lower, with
useful pour points of -30°C to -40°C or lower. Useful compositions of Gas-to-Liquids
(GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized
base oils are recited in
U.S. Patent Nos. 6,080,301;
6,090,989, and
6,165,949 for example.
[0027] The hydrocarbyl aromatics can be used as base oil or base oil component and can be
any hydrocarbyl molecule that contains at least 5% of its weight derived from an aromatic
moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives. These
hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides,
alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol,
and the like. The aromatic can be mono-alkylated, dialkylated, polyalkylated, and
the like. The aromatic can be mono- or poly-functionalized. The hydrocarbyl groups
can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl
groups, cycloalkenyl groups and other related hydrocarbyl groups. The hydrocarbyl
groups can range from C
6 up to C
60 with a range of C
8 to C
20 often being preferred. A mixture of hydrocarbyl groups is often preferred, and up
to three such substituents may be present. The hydrocarbyl group can optionally contain
sulfur, oxygen, and/or nitrogen containing substituents. The aromatic group can also
be derived from natural (petroleum) sources, provided at least 5% of the molecule
is comprised of an above-type aromatic moiety. Viscosities at 100°C of approximately
3 cSt to 50 cSt are preferred, with viscosities of approximately 3.4 cSt to 20 cSt
often being more preferred for the hydrocarbyl aromatic component. In one embodiment,
an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene
is used. Other alkylates of aromatics can be advantageously used. Naphthalene or methyl
naphthalene, for example, can be alkylated with olefins such as octene, decene, dodecene,
tetradecene or higher, mixtures of similar olefins, and the like. Useful concentrations
of hydrocarbyl aromatic in a lubricant oil composition can be 2% to 25%, preferably
4% to 20%, and more preferably 4% to 15%, depending on the application.
[0028] Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may
be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See
Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Interscience Publishers,
New York, 1963. For example, an aromatic compound, such as benzene or naphthalene, is alkylated
by an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst.
See
Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Interscience Publishers, New York, 1964. Many homogeneous
or heterogeneous, solid catalysts are known to one skilled in the art. The choice
of catalyst depends on the reactivity of the starting materials and product quality
requirements. For example, strong acids such as AlCl
3, BF
3, or HF may be used. In some cases, milder catalysts such as FeCl
3 or SnCl
4 are preferred. Newer alkylation technology uses zeolites or solid super acids.
[0029] Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics
may be secured by the use of esters such as the esters of dibasic acids with monoalkanols
and the polyol esters of monocarboxylic acids. Esters of the former type include,
for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid,
alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid,
sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl
malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl
alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specific examples
of these types of esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl
fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,
didecyl phthalate, dieicosyl sebacate, etc.
[0030] Particularly useful synthetic esters are those which are obtained by reacting one
or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl
polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol,
trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing
at least 4 carbon atoms, preferably C
5 to C
30 acids such as saturated straight chain fatty acids including caprylic acid, capric
acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic
acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such
as oleic acid, or mixtures of any of these materials.
[0031] Suitable synthetic ester components include the esters of trimethylol propane, trimethylol
butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more
monocarboxylic acids containing from 5 to 10 carbon atoms. These esters are widely
available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil
Chemical Company.
[0032] Also useful are esters derived from renewable material such as coconut, palm, rapeseed,
soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters,
complex esters, or mixtures thereof. These esters are widely available commercially,
for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
[0033] Engine oil formulations containing renewable esters are included in this disclosure.
For such formulations, the renewable content of the ester is typically greater than
70 weight percent, preferably more than 80 weight percent and most preferably more
than 90 weight percent. Renewable esters can be preferred in combination with the
friction modifier mixture.
[0034] Other useful fluids of lubricating viscosity include non-conventional or unconventional
base stocks that have been processed, preferably catalytically, or synthesized to
provide high performance lubrication characteristics.
[0035] Non-conventional or unconventional base stocks/base oils include one or more of a
mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials,
as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds,
mineral and or non-mineral oil waxy feed stocks such as slack waxes, natural waxes,
and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate,
hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum
oil derived waxy materials such as waxy materials received from coal liquefaction
or shale oil, and mixtures of such base stocks.
[0036] GTL materials are materials that are derived via one or more synthesis, combination,
transformation, rearrangement, and/or degradation/deconstructive processes from gaseous
carbon-containing compounds, hydrogen-containing compounds and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane,
ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are
generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that
are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing
compounds and/or elements as feed stocks. GTL base stock(s) and/or base oil(s) include
oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized
GTL materials such as, for example, by distillation and subsequently subjected to
a final wax processing step which involves either or both of a catalytic dewaxing
process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point;
(2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized
cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed
or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e.,
hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably
hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T
waxy hydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (or solvent)
dewaxing dewaxed, F-T waxes, or mixtures thereof.
[0037] GTL base stock(s) and/or base oil(s) derived from GTL materials, especially, hydrodewaxed
or hydroisomerized/followed by cat and/or solvent dewaxed wax or waxy feed, preferably
F-T material derived base stock(s) and/or base oil(s), are characterized typically
as having kinematic viscosities at 100°C of from 2 mm
2/s to 50 mm
2/s (ASTM D445). They are further characterized typically as having pour points of
-5°C to -40°C or lower (ASTM D97). They are also characterized typically as having
viscosity indices of 80 to 140 or greater (ASTM D2270).
[0038] In addition, the GTL base stock(s) and/or base oil(s) are typically highly paraffinic
(>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins
in combination with non-cyclic isoparaffins. The ratio of the naphthenic (i.e., cycloparaffin)
content in such combinations varies with the catalyst and temperature used. Further,
GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content,
generally containing less than 10 ppm, and more typically less than 5 ppm of each
of these elements. The sulfur and nitrogen content of GTL base stock(s) and/or base
oil(s) obtained from F-T material, especially F-T wax, is essentially nil. In addition,
the absence of phosphorous and aromatics make this materially especially suitable
for the formulation of low SAP products.
[0039] The term GTL base stock and/or base oil and/or wax isomerate base stock and/or base
oil is to be understood as embracing individual fractions of such materials of wide
viscosity range as recovered in the production process, mixtures of two or more of
such fractions, as well as mixtures of one or two or more low viscosity fractions
with one, two or more higher viscosity fractions to produce a blend wherein the blend
exhibits a target kinematic viscosity.
[0040] The GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived
is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
[0041] In addition, the GTL base stock(s) and/or base oil(s) are typically highly paraffinic
(>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins
in combination with non-cyclic isoparaffins. The ratio of the naphthenic (i.e., cycloparaffin)
content in such combinations varies with the catalyst and temperature used. Further,
GTL base stock(s) and/or base oil(s) and hydrodewaxed, or hydroisomerized/cat (and/or
solvent) dewaxed base stock(s) and/or base oil(s) typically have very low sulfur and
nitrogen content, generally containing less than 10 ppm, and more typically less than
5 ppm of each of these elements. The sulfur and nitrogen content of GTL base stock(s)
and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially
nil. In addition, the absence of phosphorous and aromatics make this material especially
suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP)
products.
[0042] Base oils for use in the formulated lubricating oils useful in the present disclosure
are any of the variety of oils corresponding to API Group I, Group II, Group III,
Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III,
Group IV, and Group V oils and mixtures thereof, more preferably the Group III to
Group V base oils due to their exceptional volatility, stability, viscometric and
cleanliness features. Minor quantities of Group I stock, such as the amount used to
dilute additives for blending into formulated lube oil products, can be tolerated
but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier
oil for additives used on an "as-received" basis. Even in regard to the Group II stocks,
it is preferred that the Group II stock be in the higher quality range associated
with that stock, i.e. a Group II stock having a viscosity index in the range 100 <
VI < 120.
[0043] The base oil constitutes the major component of the engine oil lubricant composition
of the present disclosure and is present in an amount ranging from 50 to 99 weight
percent, preferably from 70 to 95 weight percent, and more preferably from 85 to 95
weight percent, based on the total weight of the composition. The base oil may be
selected from any of the synthetic or natural oils typically used as crankcase lubricating
oils for spark-ignited and compression-ignited engines. The base oil conveniently
has a kinematic viscosity, according to ASTM standards, of 2.5 cSt to 12 cSt (or mm
2 /s) at 100°C and preferably of 2.5 cSt to 9 cSt (or mm
2/s) at 100° C. Mixtures of synthetic and natural base oils may be used if desired.
Mixtures of Group III, IV, V may be preferable.
Friction Modifier Mixtures
[0044] Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene
stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene
stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate,
polyoxyethylene palmitate.
[0045] Illustrative glycerol fatty acid esters include, for example, glycerol mono-oleate,
saturated mono-, di, and tri- glyceride esters, glycerol monostearate, and the like.
Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates,
glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding
glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the
respective isostearates, linoleates, and the like. On occasion the glycerol esters
can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated,
butoxylated fatty acid esters of glycerol can be preferred.
[0046] Illustrative borated glycerol fatty acid esters include, for example, borated glycerol
mono-oleate, borated saturated mono-, di, and tri- glyceride esters, borated glycerol
mono-sterate, and the like.
[0047] The friction modifier mixture of this disclosure comprises an ethoxylated fatty acid
ester and a glycerol fatty acid ester. A preferred formulation of this disclosure
comprises a lubricating oil base stock that includes a Group I, Group II, Group III,
Group IV and/or Group V base oil and a friction modifier mixture that includes an
ethoxylated fatty acid ester and a glycerol fatty acid ester.
[0048] Useful concentrations of friction modifier mixtures ranges from 0.1 weight percent
to 1.5 weight percent, or 0.1 weight percent to 1 weight percent. The weight ratio
of the first friction modifier to the other friction modifier can range from 0.1:1
to 1:0.1.
Other Additives
[0049] The formulated lubricating oil useful in the present disclosure may additionally
contain one or more of the other commonly used lubricating oil performance additives
including but not limited to antiwear agents, dispersants, other detergents, corrosion
inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure
agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss
additives, seal compatibility agents, organic metallic friction modifiers, lubricity
agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers,
densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
For a review of many commonly used additives, see
Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN
0-89573-177-0. Reference is also made to "
Lubricant Additives" by M. W. Ranney, published by Noyes Data Corporation of Parkridge,
NJ (1973); see also
U.S. Patent No. 7,704,930.
[0050] The types and quantities of performance additives used in combination with the instant
disclosure in lubricant compositions are not limited by the examples shown herein
as illustrations.
Antiwear Additive
[0051] A metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate
in which the metal constituent is zinc, or zinc dialkyl dithio phosphate (ZDDP) is
a useful component of the lubricating oils of this disclosure. ZDDP can be derived
from primary alcohols, secondary alcohols or mixtures thereof. ZDDP compounds generally
are of the formula Zn[SP(S)(OR
1)(OR
2)]
2 where R
1 and R
2 are C
1-C
18 alkyl groups, preferably C
2-C
12 alkyl groups. These alkyl groups may be straight chain or branched. Alcohols used
in the ZDDP can be 2-propanol, butanol, secondary butanol, pentanols, hexanols such
as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols,
and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can
be preferred. Alkyl aryl groups may also be used.
[0052] Preferable zinc dithiophosphates which are commercially available include secondary
zinc dithiophosphates such as those available from for example, The Lubrizol Corporation
under the trade designations "LZ 677A", "LZ 1095" and "LZ 1371", from for example
Chevron Oronite under the trade designation "OLOA 262" and from for example Afton
Chemical under the trade designation "HITEC 7169".
[0053] The ZDDP is typically used in amounts of from 0.4 weight percent to 1.2 weight percent,
preferably from 0.5 weight percent to 1.0 weight percent, and more preferably from
0.6 weight percent to 0.8 weight percent, based on the total weight of the lubricating
oil, although more or less can often be used advantageously. Preferably, the ZDDP
is a secondary ZDDP and present in an amount of from 0.6 to 1.0 weight percent of
the total weight of the lubricating oil.
[0054] Low phosphorus engine oil formulations are included in this disclosure. For such
formulations, the phosphorus content is typically less than 0.12 weight percent preferably
less than 0.10 weight percent and most preferably less than 0.085 weight percent.
Low phosphorus can be preferred in combination with the friction modifier mixture.
Viscosity Index Improvers
[0055] Viscosity index improvers (also known as VI improvers, viscosity modifiers, and viscosity
improvers) can be included in the lubricant compositions of this disclosure.
[0056] Viscosity index improvers provide lubricants with high and low temperature operability.
These additives impart shear stability at elevated temperatures and acceptable viscosity
at low temperatures.
[0057] Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters
and viscosity index improver dispersants that function as both a viscosity index improver
and a dispersant. Typical molecular weights of these polymers are between 10,000 to
1,500,000, more typically 20,000 to 1,200,000, and even more typically between 50,000
and 1,000,000.
[0058] Examples of suitable viscosity index improvers are linear or star-shaped polymers
and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutylene
is a commonly used viscosity index improver. Another suitable viscosity index improver
is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example),
some formulations of which also serve as pour point depressants. Other suitable viscosity
index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers
of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates,
for example). Specific examples include styrene-isoprene or styrene-butadiene based
polymers of 50,000 to 200,000 molecular weight.
[0059] Olefin copolymers, are commercially available from Chevron Oronite Company LLC under
the trade designation "PARATONE®" (such as "PARATONE® 8921" and "PARATONE® 8941");
from Afton Chemical Corporation under the trade designation "HiTEC®" (such as "HiTEC®
5850B"; and from The Lubrizol Corporation under the trade designation "Lubrizol® 7067C".
Polyisoprene polymers are commercially available from Infineum International Limited,
e.g. under the trade designation "SV200"; diene-styrene copolymers are commercially
available from Infineum International Limited, e.g. under the trade designation "SV
260".
[0060] In an embodiment of this disclosure, the viscosity index improvers may be used in
an amount of less than 2.0 weight percent, preferably less than 1.0 weight percent,
and more preferably less than 0.5 weight percent, based on the total weight of the
formulated oil or lubricating engine oil. Viscosity improvers are typically added
as concentrates, in large amounts of diluent oil.
[0061] In another embodiment of this disclosure, the viscosity index improvers may be used
in an amount of from 0.25 to 2.0 weight percent, preferably 0.15 to 1.0 weight percent,
and more preferably 0.05 to 0.5 weight percent, based on the total weight of the formulated
oil or lubricating engine oil.
Detergents
[0062] Illustrative detergents useful in this disclosure include, for example, alkali metal
detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal
detergents and one or more alkaline earth metal detergents. A typical detergent is
an anionic material that contains a long chain hydrophobic portion of the molecule
and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic
portion of the detergent is typically derived from an organic acid such as a sulfur
acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof. The counterion
is typically an alkaline earth or alkali metal.
[0063] Salts that contain a substantially stochiometric amount of the metal are described
as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of
from 0 to 80. Many compositions are overbased, containing large amounts of a metal
base that is achieved by reacting an excess of a metal compound (a metal hydroxide
or oxide, for example) with an acidic gas (such as carbon dioxide). Useful detergents
can be neutral, mildly overbased, or highly overbased. These detergents can be used
in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates,
phenates and/or magnesium salicylate, sulfonates, phenates. The TBN ranges can vary
from low, medium to high TBN products, including as low as 0 to as high as 600. Mixtures
of low, medium, high TBN can be used, along with mixtures of calcium and magnesium
metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates.
A detergent mixture with a metal ratio of 1, in conjunction of a detergent with a
metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used.
Borated detergents can also be used.
[0064] Alkaline earth phenates are another useful class of detergent. These detergents can
be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH)
2, BaO, Ba(OH)
2, MgO, Mg(OH)
2, for example) with an alkyl phenol or sulfurized alkylphenol. Useful alkyl groups
include straight chain or branched C
1-C
30 alkyl groups, preferably, C
4-C
20 or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol,
nonylphenol, dodecyl phenol, and the like. It should be noted that starting alkylphenols
may contain more than one alkyl substituent that are each independently straight chain
or branched and can be used from 0.5 to 6 weight percent. When a non-sulfurized alkylphenol
is used, the sulfurized product may be obtained by methods well known in the art.
These methods include heating a mixture of alkylphenol and sulfurizing agent (including
elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then
reacting the sulfurized phenol with an alkaline earth metal base.
[0065] Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid
detergents may be prepared by reacting a basic metal compound with at least one carboxylic
acid and removing free water from the reaction product. These compounds may be overbased
to produce the desired TBN level. Detergents made from salicylic acid are one preferred
class of detergents derived from carboxylic acids. Useful salicylates include long
chain alkyl salicylates. One useful family of compositions is of the formula

where R is an alkyl group having 1 to 30 carbon atoms, n is an integer from 1 to 4,
and M is an alkaline earth metal. Preferred R groups are alkyl chains of at least
C
11, preferably C
13 or greater. R may be optionally substituted with substituents that do not interfere
with the detergent's function. M is preferably, calcium, magnesium, or barium. More
preferably, M is calcium.
[0066] Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe
reaction (see
U.S. Patent No. 3,595,791). The metal salts of the hydrocarbyl-substituted salicylic acids may be prepared
by double decomposition of a metal salt in a polar solvent such as water or alcohol.
[0067] Alkaline earth metal phosphates are also used as detergents and are known in the
art.
[0068] Detergents may be simple detergents or what is known as hybrid or complex detergents.
The latter detergents can provide the properties of two detergents without the need
to blend separate materials. See
U.S. Patent No. 6,034,039.
[0069] Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates,
magnesium phenates, magnesium sulfonates, magnesium salicylates and other related
components (including borated detergents), and mixtures thereof. Preferred mixtures
of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate
and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and
calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium
salicylate, calcium phenate and magnesium phenate.
[0070] The detergent concentration in the lubricating oils of this disclosure can range
from 1.0 to 6.0 weight percent, preferably 2.0 to 5.0 weight percent, and more preferably
from 2.0 weight percent to 4.0 weight percent, based on the total weight of the lubricating
oil.
[0071] As used herein, the detergent concentrations are given on an "as delivered" basis.
Typically, the active detergent is delivered with a process oil. The "as delivered"
detergent typically contains from 20 weight percent to 80 weight percent, or from
40 weight percent to 60 weight percent, of active detergent in the "as delivered"
detergent product.
Dispersants
[0072] During engine operation, oil-insoluble oxidation byproducts are produced. Dispersants
help keep these byproducts in solution, thus diminishing their deposition on metal
surfaces. Dispersants used in the formulation of the lubricating oil may be ashless
or ash-forming in nature. Preferably, the dispersant is ashless. So called ashless
dispersants are organic materials that form substantially no ash upon combustion.
For example, non-metal-containing or borated metal-free dispersants are considered
ashless. In contrast, metal-containing detergents discussed above form ash upon combustion.
[0073] Suitable dispersants typically contain a polar group attached to a relatively high
molecular weight hydrocarbon chain. The polar group typically contains at least one
element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 50
to 400 carbon atoms.
[0074] A particularly useful class of dispersants are the alkenylsuccinic derivatives, typically
produced by the reaction of a long chain hydrocarbyl substituted succinic compound,
usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino
compound. The long chain hydrocarbyl group constituting the oleophilic portion of
the molecule which confers solubility in the oil, is normally a polyisobutylene group.
Many examples of this type of dispersant are well known commercially and in the literature.
Exemplary U.S. patents describing such dispersants are
U.S. Patent Nos. 3,172,892;
3,215,707;
3,219,666;
3,316,177;
3,341,542;
3,444,170;
3,454,607;
3,541,012;
3,630,904;
3,632,511;
3,787,374 and
4,234,435. Other types of dispersant are described in
U.S. Patent Nos. 3,036,003;
3,200,107;
3,254,025;
3,275,554;
3,438,757;
3,454,555;
3,565,804;
3,413,347;
3,697,574;
3,725,277;
3,725,480;
3,726,882;
4,454,059;
3,329,658;
3,449,250;
3,519,565;
3,666,730;
3,687,849;
3,702,300;
4,100,082;
5,705,458. A further description of dispersants may be found, for example, in European Patent
Application No.
471 071, to which reference is made for this purpose.
[0075] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride
derivatives are useful dispersants. In particular, succinimide, succinate esters,
or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic
acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent,
with at least one equivalent of an alkylene amine are particularly useful, although
on occasion, having a hydrocarbon substituent between 20-50 carbon atoms can be useful.
[0076] Succinimides are formed by the condensation reaction between hydrocarbyl substituted
succinic anhydrides and amines. Molar ratios can vary depending on the polyamine.
For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA
can vary from 1:1 to 5:1. Representative examples are shown in
U.S. Patent Nos. 3,087,936;
3,172,892;
3,219,666;
3,272,746;
3,322,670; and
3,652,616,
3,948,800; and Canada Patent No.
1,094,044.
[0077] Succinate esters are formed by the condensation reaction between hydrocarbyl substituted
succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the
alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted
succinic anhydride and pentaerythritol is a useful dispersant.
[0078] Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted
succinic anhydrides and alkanol amines. For example, suitable alkanol amines include
ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines
such as polyethylene polyamines. One example is propoxylated hexamethylenediamine.
Representative examples are shown in
U.S. Patent No. 4,426,305.
[0079] The molecular weight of the hydrocarbyl substituted succinic anhydrides used in the
preceding paragraphs will typically range between 800 and 2,500 or more. The above
products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde,
carboxylic acids such as oleic acid. The above products can also be post reacted with
boron compounds such as boric acid, borate esters or highly borated dispersants, to
form borated dispersants generally having from 0.1 to 5 moles of boron per mole of
dispersant reaction product.
[0080] Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde,
and amines. See
U.S. Patent No. 4,767,551. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part
of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500.
Representative examples are shown in
U.S. Patent Nos. 3,697,574;
3,703,536;
3,704,308;
3,751,365;
3,756,953;
3,798,165; and
3,803,039.
[0081] Typical high molecular weight aliphatic acid modified Mannich condensation products
useful in this disclosure can be prepared from high molecular weight alkyl-substituted
hydroxyaromatics or HNR
2 group-containing reactants.
[0082] Hydrocarbyl substituted amine ashless dispersant additives are well known to one
skilled in the art; see, for example,
U.S. Patent Nos. 3,275,554;
3,438,757;
3,565,804;
3,755,433,
3,822,209, and
5,084,197.
[0083] Preferred dispersants include borated and non-borated succinimides, including those
derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and
bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene
group such as polyisobutylene having a Mn of from 500 to 5000, or from 1000 to 3000,
or 1000 to 2000, or a mixture of such hydrocarbylene groups, often with high terminal
vinylic groups. Other preferred dispersants include succinic acid-esters and amides,
alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other
related components. Such additives may be used in an amount of 0.1 to 20 weight percent,
preferably 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. On
an active ingredient basis, such additives may be used in an amount of 0.06 to 14
weight percent, preferably 0.3 to 6 weight percent. The hydrocarbon portion of the
dispersant atoms can range from C60 to C400, or from C70 to C300, or from C70 to C200.
These dispersants may contain both neutral and basic nitrogen, and mixtures of both.
Dispersants can be end-capped by borates and/or cyclic carbonates.
[0084] As used herein, the dispersant concentrations are given on an "as delivered" basis.
Typically, the active dispersant is delivered with a process oil. The "as delivered"
dispersant typically contains from 20 weight percent to 80 weight percent, or from
40 weight percent to 60 weight percent, of active dispersant in the "as delivered"
dispersant product.
Antioxidants
[0085] Antioxidants retard the oxidative degradation of base oils during service. Such degradation
may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase
in the lubricant. One skilled in the art knows a wide variety of oxidation inhibitors
that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related
Products, op cite, and
U.S. Patent Nos. 4,798,684 and
5,084,197, for example.
[0086] Useful antioxidants include hindered phenols. These phenolic antioxidants may be
ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain
phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics
which are the ones which contain a sterically hindered hydroxyl group, and these include
those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in
the o- or p-position to each other. Typical phenolic antioxidants include the hindered
phenols substituted with C
6+ alkyl groups and the alkylene coupled derivatives of these hindered phenols. Examples
of phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol;
2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl
phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
Other useful hindered mono-phenolic antioxidants may include for example hindered
2,6-di-alkyl-phenolic proprionic ester derivatives. Bis-phenolic antioxidants may
also be advantageously used in combination with the instant disclosure. Examples of
ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol); 2,2'-bis(4-octyl-6-t-butyl-phenol);
and 2,2'-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols include for example
4,4'-bis(2,6-di-t-butyl phenol) and 4,4'-methylene-bis(2,6-di-t-butyl phenol).
[0087] Effective amounts of one or more catalytic antioxidants may also be used. The catalytic
antioxidants comprise an effective amount of a) one or more oil soluble polymetal
organic compounds; and, effective amounts of b) one or more substituted N,N'-diaryl-o-phenylenediamine
compounds or c) one or more hindered phenol compounds; or a combination of both b)
and c). Catalytic antioxidants are more fully described in
U.S. Patent No. 8, 048,833.
[0088] Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants
and these may be used either as such or in combination with phenolics. Typical examples
of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines
such as aromatic monoamines of the formula R
8R
9R
10N where R
8 is an aliphatic, aromatic or substituted aromatic group, R
9 is an aromatic or a substituted aromatic group, and R
10 is H, alkyl, aryl or R
11S(O)
XR
12 where R
11 is an alkylene, alkenylene, or aralkylene group, R
12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or
2. The aliphatic group R
8 may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon
atoms. The aliphatic group is a saturated aliphatic group. Preferably, both R
8 and R
9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused
ring aromatic group such as naphthyl. Aromatic groups R
8 and R
9 may be joined together with other groups such as S.
[0089] Typical aromatic amines antioxidants have alkyl substituent groups of at least 6
carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and
decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms.
The general types of amine antioxidants useful in the present compositions include
diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl
phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric
amine antioxidants can also be used. Particular examples of aromatic amine antioxidants
useful in the present disclosure include: p,p'-dioctyldiphenylamine; t-octylphenyl-alphanaphthylamine;
phenyl-alphanaphthylamine; and p-octylphenyl-alphanaphthylamine.
[0090] Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are
useful antioxidants.
[0091] Preferred antioxidants include hindered phenols, arylamines. These antioxidants may
be used individually by type or in combination with one another. Such additives may
be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent,
more preferably zero to less than 1.5 weight percent, more preferably zero to less
than 1 weight percent.
Pour Point Depressants (PPDs)
[0092] Conventional pour point depressants (also known as lube oil flow improvers) may be
added to the compositions of the present disclosure if desired. These pour point depressant
may be added to lubricating compositions of the present disclosure to lower the minimum
temperature at which the fluid will flow or can be poured. Examples of suitable pour
point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation
products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers,
and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
U.S. Patent Nos. 1,815,022;
2,015,748;
2,191,498;
2,387,501;
2,655, 479;
2,666,746;
2,721,877;
2,721,878; and
3,250,715 describe useful pour point depressants and/or the preparation thereof. Such additives
may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight
percent.
Seal Compatibility Agents
[0093] Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction
in the fluid or physical change in the elastomer. Suitable seal compatibility agents
for lubricating oils include organic phosphates, alkoxysulfonlanes (C
10 alcohol, for example), aromatic esters, aromatic hydrocarbons, esters (butylbenzyl
phthalate, for example), and polybutenyl succinic anhydride. Such additives may be
used in an amount of 0.01 to 3 weight percent, preferably 0.01 to 2 weight percent.
Antifoam Agents
[0094] Anti-foam agents may advantageously be added to lubricant compositions. These agents
retard the formation of stable foams. Silicones and organic polymers are typical anti-foam
agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane,
provide antifoam properties. Anti-foam agents are commercially available and may be
used in conventional minor amounts along with other additives such as demulsifiers;
usually the amount of these additives combined is less than 1 weight percent and often
less than 0.1 weight percent.
Inhibitors and Antirust Additives
[0095] Antirust additives (or corrosion inhibitors) are additives that protect lubricated
metal surfaces against chemical attack by water or other contaminants. A wide variety
of these are commercially available.
[0096] One type of antirust additive is a polar compound that wets the metal surface preferentially,
protecting it with a film of oil. Another type of antirust additive absorbs water
by incorporating it in a water-in-oil emulsion so that only the oil touches the metal
surface. Yet another type of antirust additive chemically adheres to the metal to
produce a non-reactive surface. Examples of suitable additives include zinc dithiophosphates,
metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may
be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent.
Organic Metallic Friction Modifiers
[0097] In addition to the friction modifier mixtures used in the lubricating engine oil
formulations of this disclosure, organic metallic friction modifiers may also be used.
Organic metallic friction modifiers useful in this disclosure are any materials that
can alter the coefficient of friction of a surface lubricated by any lubricant or
fluid containing such material(s). Organic metallic friction modifiers, also known
as friction reducers, or lubricity agents or oiliness agents, and other such agents
that change the ability of base oils, formulated lubricant compositions, or functional
fluids, to modify the coefficient of friction of a lubricated surface can be effectively
used in combination with the base oils or lubricant compositions of the present disclosure.
Organic metallic friction modifiers that lower the coefficient of friction are particularly
advantageous in combination with the base oils and lube compositions of this disclosure.
[0098] Illustrative organic metallic friction modifiers useful in the lubricating engine
oil formulations of this disclosure include, for example, molybdenum amine, molybdenum
diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates,
molybdenum amine complexes, molybdenum carboxylates, and the like. Similar tungsten
based compounds may be preferable. Useful concentrations of the organic metallic friction
modifiers may range from 0.01 weight percent to 5 weight percent, or 0.1 weight percent
to 2.5 weight percent. Useful concentration of molybdenum can range from 25 to 700
ppm, or more preferably from 50 to 200 ppm.
[0099] When lubricating oil compositions contain one or more of the additives discussed
above, the additive(s) are blended into the composition in an amount sufficient for
it to perform its intended function. Typical amounts of such additives useful in the
present disclosure are shown in Table 1 below.
[0100] It is noted that many of the additives are shipped from the additive manufacturer
as a concentrate, containing one or more additives together, with a certain amount
of base oil diluents. Accordingly, the weight amounts in the table below, as well
as other amounts mentioned herein, are directed to the amount of active ingredient
(that is the non-diluent portion of the ingredient). The weight percent (wt%) indicated
below is based on the total weight of the lubricating oil composition.
TABLE 1
| Typical Amounts of Other Lubricating Oil Components |
| Compound |
Approximate wt% (Useful) |
Approximate wt% (Preferred) |
| Dispersant |
0.1-20 |
0.1-8 |
| Detergent |
0.1-20 |
0.1-8 |
| Friction Modifier |
0.01-5 |
0.01-1.5 |
| Antioxidant |
0.1-5 |
0.1-1.5 |
| Pour Point Depressant (PPD) |
0.0-5 |
0.01-1.5 |
| Anti-foam Agent |
0.001-3 |
0.001-0.15 |
| Viscosity Index Improver (solid polymer basis) |
0.1-2 |
0.1-1 |
| Anti-wear |
0.1-2 |
0.5-1 |
| Inhibitor and Antirust |
0.01-5 |
0.01-1.5 |
[0101] The foregoing additives are all commercially available materials. These additives
may be added independently but are usually precombined in packages which can be obtained
from suppliers of lubricant oil additives. Additive packages with a variety of ingredients,
proportions and characteristics are available and selection of the appropriate package
will take the requisite use of the ultimate composition into account.
[0102] The following non-limiting examples are provided to illustrate the disclosure.
EXAMPLES
[0103] The detergents used in the formulations were a petroleum derived calcium sulfonate,
a synthetic calcium sulfonate, a neutral calcium salicylate, an overbased calcium
salicylate, a mixed calcium salicylate, and a magnesium sulfonate.
[0104] The friction modifiers used in the formulations included organic friction modifiers
and organic metallic friction modifiers. The organic friction modifiers were an ethoxylated
fatty ester and a mixed glyceride ester (mono, di and tri glyceride), mostly C14,
C16, & C18, saturated. The organic metallic friction modifier was a molybdenum dithiocarbamate
that was held constant for a majority of the formulations.
[0105] The antioxidants used in the formulations were a methylene bridged bis-hindered phenol
and a alkylated diphenyl amine.
[0106] Bench testing was conducted for formulations of this disclosure. The bench testing
included the following: kinematic viscosity (KV) at 100°C measured by ASTM D445; integrated
mini traction machine (MTM) friction at 140°C measured as described below; and thermo-oxidation
engine oil simulation (TEOST 33C) measured by ASTM D6335. For the formulations identified
in FIG. 1, the bench testing also included high temperature high shear (HTHS) viscosity
at 150°C measured by ASTM D4683.
[0107] The Mini Traction Machine (MTM) is a fully automated instrument manufactured by PCS
Instruments and identified as Model MTM. The test specimens and apparatus configuration
are such that realistic pressure, temperature and speed can be attained without requiring
very large loads, motors or structures. A small sample of fluid (50 milliliters) is
placed in a test cell and the machine automatically runs either through a range of
speeds, slide-to-roll ratios, temperatures and loads, or at specifically set temperature,
slide-to-roll ratio and speed range to generate information regarding the friction
performance of a test fluid without further operator intervention. The working of
the MTM is known and familiar to those of skill in the art.
[0108] PCMO (passenger car motor oil) formulations were prepared. Fig. 1 provides formulation
details in weight percent based on the total weight percent of the formulation. A
synthetic oil was used as baseline and contained both organic metallic and organic
friction modifiers to allow for comparison of the different chemistries. Additional
cleanliness and average integrated MTM Stribeck friction data were also collected
on oil containing only organic metallic friction modifier, Comparative Example 3,
as well as no friction modifier, Comparative Example 2, to provide a reference. All
other components were the same across all three blends with the differences being
made up by base oil. Fig. 1 summarizes the three oils considered baseline comparison
oils for the 0W-20 oils of this disclosure and their respective TEOST 33C and average
integrated friction coefficient from MTM Stribeck measurements at 140°C.
[0109] In order to allow for numerical comparison of the MTM Stribeck traces, an integration
method (the trapezoidal rule) was employed for each curve individually and an average
integrated Stribeck friction coefficient and standard deviation for all 4 traces,
run back-to-back, was calculated. The average integrated Stribeck friction coefficient
provides a measure of the friction an engine will see during operation (albeit at
different ratios to those calculated). The MTM integrated area value listed in this
disclosure has been calculated using this method.
Combination of Ethoxylated Fatty Ester and Mixed Glyceride Ester
[0110] A MTM Stribeck friction treat rate study was undertaken and the results are shown
in Fig. 2, indicating that the lowest MTM friction observed was achieved using only
ethoxylated fatty ester (red diamonds) in the formulation. Use of ethoxylated fatty
ester as a toptreat (blue diamonds) to the baseline formulation also decreased MTM
friction versus the baseline formulations, but not as much as for the blends with
only ethoxylated fatty ester. The total deposits formed also increased.
[0111] Additionally, to highlight the reduction in friction performance with ethoxylated
fatty ester, Fig. 3 shows a comparison of the MTM performance for the baseline oil
with mixed glyceride ester and an organic metallic friction modifier versus that of
a blend with a 1% treat of ethoxylated fatty ester and no mixed glyceride ester or
an organic metallic friction modifier. Several unexpected performance features are
displayed in Figure 3. First, the average Stribeck friction coefficient for the first
four traces is 1/6
th of the 0W-20 baseline comparison (4
th trace of baseline oil shown in light blue). Second, the very low first trace indicate
that ethoxylated fatty ester is fast-acting. Third, over 10 MTM traces, the ethoxylated
fatty ester containing oil continues to build friction, whereas the baseline oil stabilizes
after 4-6 traces (not shown), albeit at a significantly higher coefficient of friction.
Finally, the ethoxylated fatty ester traces have a defined coefficient of friction
structure as a function of speed, confirming the unexpected friction benefits. The
addition of ethoxylated fatty ester is clearly shown to have significant friction
benefits compared to the baseline with mixed glyceride ester and metal containing
organic complex.
[0112] Building from the above bench scale work, an engine test oil was developed with 1%
ethoxylated fatty ester and an organic metallic friction modifier, but no other friction
modifier, and run in the Sequence VID Fuel Economy (ASTM D7589) engine test. The FEI
sum for the test oil was 2.9%, an increase over the Sequence VID result for the baseline
formulation of 2.6%, showing that the reduced friction seen in the MTM can be translated
in an engine test.
[0113] While ethoxylated fatty ester has reduced the MTM friction and increased the Sequence
VID FEI sum, there is an increase in deposits with ethoxylated fatty ester. Fig. 4
shows the TEOST 33C performance for a number of blends with ethoxylated fatty ester,
mixed glyceride ester, or a combination of both. The formulation with only ethoxylated
fatty ester, Comparative Example 5, had 43 mg of deposit, which is unacceptable versus
the GF-5 limit of 30 mg and versus the 28 mg result for oil with only mixed glyceride
ester, Comparative Example 4.
[0114] Fig. 4 shows multiple formulation changes which were made to reduce the TEOST 33C
deposits with minimal impact on the friction reduction benefit for ethoxylated fatty
ester. Mixing 0.2% mixed glyceride ester with ethoxylated fatty ester at an unchanged
treat, Inventive Example 1, the friction surprising improves, while the TEOST 33C
result reduces to 30 mg, which is at the industry limit and can be considered equivalent
to Comparative Example 4. The MTM results show that the friction is reduced with the
combination of ethoxylated fatty ester and mixed glyceride ester versus the performance
of the baseline formulation. Inventive Example 1 thus shows that the use of mixed
friction modifier chemistries is unexpectedly used to improve deposits, while maintaining
or reducing friction.
[0115] Other modifications shown in Fig. 4, Inventive Example 2, improve TEOST 33C performance
compared to Comparative Example 4 and Comparative Example 5. While these modifications,
such as an increase in overbased detergent or dispersant, are expected to have a significant
detrimental impact on MTM friction performance, Inventive Example 2 shows that they
surprisingly maintain the same level of friction benefit obtained in Inventive Example
1.
[0116] The above results show that the combination of ethoxylated fatty ester and mixed
glyceride ester can provide improved fuel economy performance by reducing friction
with no debit in deposit control.
[0117] Fig. 5 shows formulation details in weight percent based on the total weight percent
of the formulation, of various formulations. Fig. 5 also shows the results of bench
testing of the formulations using thermo-oxidation engine oil simulation TEOST 33C
and MTM friction coefficient. As can be seen in Fig. 5, the concentrations in weight
percent of the friction modifiers (ethoxylated fatty ester and mixed glyceride ester)
vary from blend to blend while the weight percent of the remaining ingredients remains
the same. The results show that formulations with ethoxylated fatty ester and mixed
glyceride ester concentrations ranging from 0.1 wt% to 1.0 wt% (while the other is
being held constant), exhibit good friction reduction and deposit control properties,
as shown in Inventive Example 3 through Inventive Example 18. Additionally, Inventive
Examples 19 and Inventive Example 20 highlight the impact of using Group I and Group
II base stocks, with Group I being more beneficial, instead of a mixture of Group
II, III, IV, V, on the friction and deposit bench test results.
[0118] The components and base stocks used in the exemplary formulations of Fig. 6 are set
forth therein. All of the ingredients are commercially available.
[0119] The detergent used in the formulations was an overbased calcium salicylate.
[0120] The friction modifiers used in the formulations included organic friction modifiers.
The organic friction modifiers were an ethoxylated fatty ester and a mixed glyceride
ester. An organic metallic friction modifier (i.e., molybdenum dithiocarbamate) was
also used in the formulations.
[0121] PIB dispersants, antioxidants, antiwear agents, and pour point depressants were also
used in the formulations.
[0122] Fig. 6 shows formulation details in weight percent based on the total weight percent
of the formulation, of various formulations. Fig. 6 also shows the results of bench
testing of the formulations using thermo-oxidation engine oil simulation (TEOST 33C)
measured by ASTM D6335 and MTM friction. As can be seen in Fig. 6, the concentrations
in weight percent of the PIB dispersant and detergent vary from blend to blend while
the weight percent of the remaining ingredients remains the same. Inventive Examples
21 through Inventive Example 28 demonstrate that a treatment of overbased calcium
salicylate detergent of from 0.5 wt% to 2.5 wt%, and a treatment of PIB dispersant
of from 2.0 wt% to 5.0 wt% may be used in combination with the mixed friction modifier
chemistries to achieve deposit and/or friction benefits.
[0123] The components and base stocks used in the exemplary formulations of Fig. 6 are set
forth therein and are the same as in Fig. 5. All of the ingredients are commercially
available.
Other Exemplary Formulations
[0124] The lubricating engine oil formulations in Figure 7 are combinations of additives
and base stocks and are expected to have kinematic viscosity at 100°C around 6 cSt
and high temperature high shear (10
-6 s
-1) viscosity at 150°C around 2.0 cP. The lubricating engine oil formulations of Examples
1, 2, 3, 4, and 5 are expected to have phosphorus levels around 650 ppm, while Example
6 will have around 350 ppm phosphorus and Example 7 will have around 1300 ppm phosphorus.
The lubricating engine oil formulations of Examples 1, 4, 5, 6, 7 are expected to
have molybdenum levels around 800 ppm while Example 2 will have around 0 ppm of molybdenum
and Example 3 will have around 275 ppm of molybdenum. The lubricant formulations of
Examples 1, 2, 3, 6, 7 are expected to have TBN values around 9 while Example 4 will
have a TBN value of around 6 and Example 5 will have a TBN value of around 15. The
lubricant formulations of Examples 1, 2, 3, 6, 7 are expected to have ash levels around
0.95% while the formulations in example 5 will have around 0.6% ash and example 6
will have around 1.6% ash.
[0125] The lubricating engine oil formulations in Figure 8 are combinations of additives
and base stocks and are expected to have kinematic viscosities at 100°C of around
8 cSt and high temperature high shear (10
-6 s
-1) viscosity at 150°C of around 2.6 cP. The lubricating engine oil formulations of
Examples 8, 9, 10, 11, 12 are expected to have phosphorus levels of around 650ppm
while Example 13 will have around 350 ppm Phosphorus and Example 14 will have around
1300 ppm Phosphorus. The lubricating engine oil formulations of Examples 8, 11, 12,
13, 14 are expected to have molybdenum levels of around 800 ppm while Example 9 will
have around 0 ppm of molybdenum and Example 10 will have around 275 ppm of molybdenum.
The lubricant formulations of Examples 8, 9, 10, 13, 14 are expected to have TBN values
of around 9 while Example 11 will have a TBN value of around 6 and Example 12 will
have a TBN value of around 15. The lubricant formulations of Examples 8, 9, 10, 13,
14 are expected to have ash levels of around 0.95% while the formulations in example
11 will have around 0.6% ash and example 12 will have around 1.6% ash.
[0126] The lubricating engine oil formulations in Figure 9 are combinations of additives
and base stocks and are expected to have kinematic viscosity at 100°C around 10 cSt
and high temperature high shear (10
-6 s
-1) viscosity at 150°C of around 3.0 cP. The lubricating engine oil formulations of
Examples 15, 16, 17, 18, 19 are expected to have phosphorus levels of around 650 ppm
while Example 20 will have around 350 ppm phosphorus and Example 21 will have around
1300 ppm phosphorus. The lubricating engine oil formulations of Examples 15, 18, 19,
20, 21 are expected to have molybdenum levels of around 800 ppm while Example 16 will
have around 0 ppm of molybdenum and Example 17 will have around 275 ppm of molybdenum.
The lubricant formulations of Examples 15, 16, 17, 20, 21 are expected to have TBN
values of around 9 while Example 18 will have a TBN value of around 6 and Example
19 will have a TBN value of around 15. The lubricant formulations of Examples 15,
16, 17, 20, 21 are expected to have ash levels of around 0.95% while the formulations
in example 18 will have around 0.6% ash and example 19 will have around 1.6% ash.
[0127] When numerical lower limits and numerical upper limits are listed herein, ranges
from any lower limit to any upper limit are contemplated.