Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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LUBRICATING OIL COMPOSITION PROVIDING WEAR PROTECTION AT LOW
VISCOSITY
FIELD OF THE INVENTION
The disclosed technology relates to lubricants for internal combustion
engines,
particularly those for spark ignition engines.
BACKGROUND OF THE INVENTION
Engine oil is blended with various additives to satisfy various performance
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
organometallic 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.
In order to improve lubricant fuel economy performance, reduction of viscosity
is
typically the best path (i.e., high temperature high- shear (HTHS) viscosity).
HTHS is the
measure of a lubricant's viscosity under severe engine conditions. Under high
temperatures and
high stress conditions viscosity index improver degradation can occur. As this
happens, the
viscosity of the oil decreases which may lead to increased engine wear.
Therefore, despite the advances in lubricant oil formulation technology, there
remains
a need for an engine oil lubricant that effectively improves fuel economy
while providing
superior anti-wear perfonnance.
RELATED ART
W02015041891 discloses a method for reducing aqueous phase separation of an
emulsion comprising ethanol-based fuel and a lubricating oil comprising
molybdenum ester
amide complex and a dispersant polyalkyl (meth) acrylate.
US 6303548 discloses an SAE OW-40 lubricant comprises the base oil and a
mixture
of polymethacylate and olefm copolymer or hydrogenated diene VI improvers.
W02014136643 discloses a polymethacrylate having amass average molecular
weight
of 30,000 to 600,000 inclusive and (B) an olefin copolymer having a 95% loss
temperature of
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-- 500T or lower as measured by a differential thermal analysis and a shear
stability index (SSI)
of 40 or less to a lubricant oil base oil.
US 20090270294 discloses a mixture of at least two polymers having a
difference of
permanent shear stability index (PSSI).
EP1436369 discloses a biodegradable lubricant that is at least 60%
biodegradable and
-- has a gelation index of about 12 or less can be formulated using a trans-
esterified triglyceride
base oil together with a synthetic ester. A combination of an ester viscosity
index improver and
an olefin copolymer viscosity index improver also can be added.
US20170088789 discloses a lubricant composition containing a (meth)-acrylate-
containing polymer comprising a multiplicity of arms containing at least 20
carbon atoms, said
-- arms being attached to a multivalent organic moiety; and an ethylene/olefin
copolymer having
a weight average molecular weight of about 10;000 to about 250;000.
SUMMARY OF THE INVENTION
In one aspect, the present disclosure provides a lubricating engine oil
composition
-- having a HTHS viscosity at 150 C in a range of about 1.3 to about 2.9 cP,
comprising:
a) a major amount of an oil of lubricating viscosity having a kinematic
viscosity
at 100 C in a range of 1.5 to 6.0 mm2/s;
b) a dispersant polymethactylate (DPMA) VII having a Mw of from 200,000
g/mol to 450,000 g/mol;
c) a non-dispersant ethylene-based olefin copolymer viscosity index improver
having a Mw of from 50,000 g/mol to 150,000 g/mol and a total ethylene
content of about 50 wt % to about 70 wt %.;
d) from about 50 to about 300 ppm of molybdenum from a molybdenum
containing compound; and
e) a minor amount of a salicylate detergent.
In another aspect, the present disclosure provides method for improving
friction and
reducing wear in an internal combustion engine comprising lubricating said
engine with a
lubricating oil composition having a HTHS viscosity at 150 C in a range of
about 1.3 to about
2.9 cP, comprising:
a) a major amount of an oil of lubricating viscosity having a kinematic
viscosity at
100 C in a range of 1.5 to 6.0 mm2/s;
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b) a dispersant polymethactylate (DPMA) VII having a Mw of from 200,000 g/mol
to 450,000 g/mol;
c) a non-dispersant ethylene-based olefin copolymer viscosity index improver
having
a Mw of from 50,000 g/mol to 150,000 g/mol and a total ethylene content of
about
50 wt % to about 70 wt %.;
d) from about 50 to about 300 ppm of molybdenum from a molybdenum containing
compound; and
e) a minor amount of a salicylate detergent.
DETAILED DESCRIPTION OF THE INVENTION
To facilitate the understanding of the subject matter disclosed herein, a
munber of
terms, abbreviations or other shorthand as used herein are defined below. Any
term,
abbreviation or shorthand not defined is understood to have the ordinary
meaning used by a
skilled artisan contemporaneous with the submission of this application.
Definitions
In this specification, the following words and expressions, if and when used,
have the
meanings given below.
A "major amount" means in excess of 50 weight % of a composition.
A "minor amount" means less than 50 weight % of a composition, expressed in
respect
of the stated additive and in respect of the total mass of all the additives
present in the
composition, reckoned as active ingredient of the additive or additives.
"Active ingredients" or "actives" refers to additive material that is not
diluent or
solvent.
All percentages reported are weight % on an active ingredient basis (i.e.,
without regard
to carrier or diluent oil) unless otherwise stated.
The abbreviation "ppm" means parts per million by weight, based on the total
weight
of the lubricating oil composition.
High temperature high shear (HTHS) viscosity at 150 C was determined in
accordance
with ASTM D4683.
Kinematic viscosity at 100 C (KV100) was determined in accordance with ASTM
D445.
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Metal ¨ The term "metal" refers to alkali metals, alkaline earth metals. or
mixtures
thereof.
Throughout the specification and claims the expression oil soluble or
dispersible is
used. By oil soluble or dispersible is meant that an amount needed to provide
the desired level
of activity or performance can be incorporated by being dissolved, dispersed
or suspended in
an oil of lubricating viscosity. Usually, this means that at least about
0.001% by weight of the
material can be incorporated in a lubricating oil composition. For a further
discussion of the
terms oil soluble and dispersible, particularly "stably dispersible", see U.S.
Pat. No. 4,320,019
which is expressly incorporated herein by reference for relevant teachings in
this regard.
The term "sulfated ash" as used herein refers to the non-combustible residue
resulting
from detergents and metallic additives in lubricating oil. Sulfated ash may be
determined using
ASTM Test D874.
The term "Total Base Number" or "TBN" as used herein refers to the amount of
base
equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN
numbers reflect
more alkaline products, and therefore a greater alkalinity. TBN was determined
using ASTM
D2896 test.
Boron, calcium, magnesium, molybdenum, phosphorus. sulfur, and zinc contents
were
determined in accordance with ASTM D5185.
Nitrogen content was determined in accordance with ASTM D4629.
All ASTM standards referred to herein are the most current versions as of the
filing
date of the present application.
Olefins ¨ The term "olefins" refers to a class of unsaturated aliphatic
hydrocarbons
having one or more carbon-carbon double bonds, obtained by a number of
processes. Those
containing one double bond are called mono-alkenes, and those with two double
bonds are
called dienes, alkyldienes, or diolefins. Alpha olefins are particularly
reactive because the
double bond is between the first and second carbons. Examples are 1-octene and
1-octadecene,
which are used as the starting point for medium-biodegradable surfactants.
Linear and branched
olefins are also included in the definition of olefins.
Normal Alpha Olefins ¨ The term "Normal Alpha Olefins" "refers to olefins
which are
straight chain, non-branched hydrocarbons with carbon-carbon double bond
present in the
alpha or primary position of the hydrocarbon chain.
Isomerized Normal Alpha Olefin. The tenn "Isomerized Normal Alpha Olefin" as
used
herein refers to an alpha olefin that has been subjected to isomerization
conditions which results
in an alteration of the distribution of the olefin species present and/or the
introduction of
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branching along the alkyl chain. The isomerized olefin product may be obtained
by isomerizing
a linear alpha olefin containing from about 10 to about 40 carbon atoms,
preferably from about
20 to about 28 carbon atoms, and preferably from about 20 to about 24 carbon
atoms.
C100 Normal Alpha Olefins ¨ This term defines a fraction of normal alpha
olefins
wherein the carbon numbers below 10 have been removed by distillation or other
fractionation
methods.
Unless otherwise specified, all percentages are in weight percent.
While the disclosure is susceptible to various modifications and alternative
forms,
specific embodiments thereof are herein described in detail. It should be
understood, however,
that the description herein of specific embodiments is not intended to limit
the disclosure to the
particular forms disclosed, but on the contrary, the intention is to cover all
modifications,
equivalents, and alternatives falling within the spirit and scope of the
disclosure as defined by
the appended claims.
Note that not all of the activities described in the general description or
the examples
are required, that a portion of a specific activity may not be required, and
that one or more
further activities may be performed in addition to those described. Still
further, the order in
which activities are listed is not necessarily the order in which they are
performed.
Benefits, other advantages, and solutions to problems have been described
herein with
regard to specific embodiments. However, the benefits, advantages, solutions
to problems, and
any feature(s) that may cause any benefit, advantage, or solution to occur or
become more
pronounced are not to be construed as a critical, required, or essential
feature of any or all the
claims.
The specification and illustrations of the embodiments described herein are
intended to
provide a general understanding of the structure of the various embodiments.
As used herein, the terms "comprises," "comprising," "includes," "including,"
"has,"
"having," or any other variation thereof, are intended to cover a non-
exclusive inclusion. For
example, a process, method, article, or apparatus that comprises a list of
features is not
necessarily limited only to those features but may include other features not
expressly listed or
other features that are inherent to such process, method, article, or
apparatus. Further, unless
expressly stated to the contrary, "or" refers to an inclusive-or and not to an
exclusive-or. For
example, a condition A or B is satisfied by any one of the following: A is
true (or present) and
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B is false (or not present), A is false (or not present) and B is true (or
present), and both A and
B are true (or present).
The use of "a" or "an" is employed to describe elements and components
described
herein. This is done merely for convenience and to give a general sense of the
scope of the
embodiments of the disclosure. This description should be read to include one
or at least one
and the singular also includes the plural, or vice versa, unless it is clear
that it is meant
otherwise. The term "averaged," when referring to a value, is intended to mean
an average, a
geometric mean, or a median value. Group numbers corresponding to columns
within the
Periodic Table of the elements use the "New Notation" convention as seen in
the CRC
Handbook of Chemistry and Physics, 81st Edition (2000-2001).
Unless otherwise defined, all technical and scientific tenns used herein have
the same
meaning as commonly understood by one of ordinary skill in the art to which
this disclosure
belongs. The materials, methods, and examples are illustrative only and not
intended to be
limiting. To the extent not described herein, many details regarding specific
materials and
processing acts are conventional and may be found in textbooks and other
sources within the
lubricants as well as the oil and gas industries.
The specification and illustrations are not intended to serve as an exhaustive
and
comprehensive description of all the elements and features of formulations,
compositions,
apparatus and systems that use the structures or methods described herein.
Separate
embodiments may also be provided in combination in a single embodiment, and
conversely,
various features that are, for brevity, described in the context of a single
embodiment, may also
be provided separately or in any sub-combination. Further, reference to values
stated in ranges
includes each and every value within that range. Many other embodiments may be
apparent to
skilled artisans only after reading this specification. Other embodiments may
be used and
derived from the disclosure, such that a structural substitution, logical
substitution, or another
change may be made without departing from the scope of the disclosure.
Accordingly, the
disclosure is to be regarded as illustrative rather than restrictive.
Oil of Lubricating viscosity/Base Oil Component
The oil of lubricating viscosity (sometimes referred to as "base stock" or
"base oil") is
the primary liquid constituent of a lubricant, into which additives and
possibly other oils are
blended, for example to produce a final lubricant (or lubricant composition).
A base oil is useful
for making concentrates as well as for making lubricating oil compositions
therefrom, and may
be selected from natural and synthetic lubricating oils and combinations
thereof.
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Natural oils include animal and vegetable oils, liquid petroleum oils and
hydrorefined,
solvent-treated mineral lubricating oils of the paraffinic, naphthenic and
mixed paraffinic-
naphthenic types. Oils of lubricating viscosity derived from coal or shale are
also useful base
oils.
Synthetic lubricating oils include hydrocarbon oils such as polymerized and
interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-
isobutylene
copolymers, chlorinated polybutylenes, poly( 1 -hexenes), poly( 1 -octenes),
poly( 1 -decenes);
alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,
di(2-
ethylhexyl)benzenes; polyphenols (e.g., biphenyls, terphenyls, alkylated
polyphenols); and
alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives,
analogues and
homologues thereof.
Another suitable class of synthetic lubricating oils comprises the esters of
dicarboxylic
acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids,
succinic acid, alkyl
succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic
acid, suberic acid,
sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with a variety
of alcohols (e.g.,
butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene
glycol, diethylene
glycol monoether, propylene glycol). Specific examples of these esters include
dibutyl adipate,
di(2-ethylhexyl) sebacate, di-n-hexyl fiunarate, dioctyl sebacate, diisooctyl
azelate, diisodecyl
azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-
ethylhexyl diester of
linoleic acid dimer, and the complex ester formed by reacting one mole of
sebacic acid with
two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12
monocarboxylic
acids and polyols, and polyol ethers such as neopentyl glycol,
trimethylolpropane,
pentaerytluitol, dipentaerythritol and tripentaerythritol.
The base oil may be derived from Fischer-Tropsch synthesized hydrocarbons.
Fischer-
Tropsch synthesized hydrocarbons are made from synthesis gas containing H2 and
CO using a
Fischer-Tropsch catalyst. Such hydrocarbons typically require further
processing in order to be
useful as the base oil. For example, the hydrocarbons may be hydroisomerized;
hydrocracked
and hydroisomerized; dewaxed; or hydroisomerized and dewaxed; using processes
known to
those skilled in the art.
Unrefined, refmed and re-refined oils can be used in the present lubricating
oil
composition. Unrefined oils are those obtained directly from a natural or
synthetic source
without further purification treatment. For example, a shale oil obtained
directly from retorting
operations, a petroleum oil obtained directly from distillation or ester oil
obtained directly from
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an esterification process and used without further treatment would be
unrefined oil. Refined
oils are similar to the unrefined oils except they have been further treated
in one or more
purification steps to improve one or more properties. Many such purification
techniques, such
as distillation, solvent extraction, acid or base extraction, filtration and
percolation are known
to those skilled in the art. Re-refined oils are obtained by processes similar
to those used to
obtain refined oils applied to refined oils which have been already used in
service. Such re-
refined oils are also known as reclaimed or reprocessed oils and often are
additionally
processed by techniques for approval of spent additive and oil breakdown
products.
Hence, the base oil which may be used to make the present lubricating oil
composition
may be selected from any of the base oils in Groups I-V as specified in the
American Petroleum
Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509).
Such base oil
groups are summarized in Table 1 below:
TABLE I
Base Oil Properties
Group Saturates, wt. % Sulfur', wt. % Viscosity Index('
Group I <90 and/or >0.03 80 to <120
Group IT >90 <0.03 80 to <120
Group III >90 <0.03 >120
Group IV Polyalphaolefins (PA0s)
Group V All other
base stocks not included in Groups 1, II, III or IV
(a) Groups 1-III are mineral oil base stocks.
(b) Determined in accordance with ASTM D2007.
(c) Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or
ASTM D4927.
4 Determined in accordance with ASTM D2270.
Base oils suitable for use herein are any of the variety corresponding to API
Group H,
Group III, Group IV, and Group V oils and combinations thereof, preferably the
Group HI to
Group V oils due to their exceptional volatility, stability, viscometric and
cleanliness features.
The base oil constitutes the major component of the present lubricating oil
composition and
is present is an amount ranging from greater than 50 to 99 wt. % (e.g., 70 to
95 wt. %, or 85 to
95 wt. %).
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The base oil may be selected from any of the synthetic or natural oils
typically used as
crankcase lubricating oils for spark-ignited internal combustion engines. The
base oil typically
has a kinematic viscosity at 100 C in a range of 1.5 to 6 mm2/s. In the case
where the kinematic
viscosity at 100 C of the lubricating base oil exceeds 6 mm2/s, low
temperature viscosity
properties may be reduced, and sufficient fuel efficiency may not be obtained.
At a kinematic
viscosity of 1.5 mm2/s or less, formation of an oil film in a lubrication
place is insufficient; for
this reason, lubrication is inferior, and the evaporation loss of the
lubricating oil composition
may be increased.
Preferably, the base oil has a viscosity index of at least 90 (e.g., at least
95, at least 105, at
least 110, at least 115, or at least 120). If the viscosity index is less than
90, not only viscosity-
temperature properties, heat and oxidation stability, and anti-volatilization
are reduced, but also
the coefficient of friction tends to be increased; and resistance against wear
tends to be reduced.
In one embodiment, the lubricating oil composition is a multi-grade oil. In
another
embodiment, the multi-grade oil is a viscosity grade SAE OW-XX oil, wherein XX
is any one
of 8, 10, 12, 16, and 20.
The lubricating oil composition has a high temperature shear (HTHS) viscosity
at 150 C
of 2.9 cP or less (e.g., 1.0 to 2.9 cP, or 1.3 to 2.9 cP) of 2.6 cP or less
(e.g., 1.0 to 2.6 cP, or 1.3
to 2.6 cP) of 2.3 cP or less (e.g., 1.0 to 2.3 cP, or 1.3 to 2.3 cP), such as
2.0 cP or less (e.g., 1.0
to 2.0 cP, or 1.3 to 2.3 cP), or even 1.7 cP or less (e.g., 1.0 to 1.7 cP, or
1.3 to 1.7 cP).
The lubricating oil composition has a viscosity index of at least 135 (e.g.,
135 to 400, or
135 to 250), at least 150 (e.g., 150 to 400, 150 to 250), at least 165 (e.g.,
165 to 400, or 165 to
250), at least 190 (e.g., 190 to 400, or 190 to 250), or at least 200 (e.g.,
200 to 400, or 200 to
250). If the viscosity index of the lubricating oil composition is less than
135, it may be difficult
to improve fuel efficiency while maintaining the HTHS viscosity at 150 C. If
the viscosity
index of the lubricating oil composition exceeds 400, evaporation properties
may be reduced,
and deficits due to insufficient solubility of the additive and matching
properties with a seal
material may be caused.
The lubricating oil composition has a kinematic viscosity at 100 C in a range
of 3 to 12
nun2/s (e.g., 3 to 8.2 mm2/s, 3.5 to 8.2 mm2/s, or 4 to 8.2 nun2/s).
In general, the level of sulfur in the lubricating oil compositions of the
present invention is
less than or equal to about 0.7 wt. %, based on the total weight of the
lubricating oil
composition, e.g., a level of sulfur of about 0.01 wt. % to about 0.70 wt. %,
0.01 to 0.6 wt.%,
0.01 to 0.5 wt.%, 0.01 to 0.4 wt.%, 0.01 to 0.3 wt.%, 0.01 to 0.2 wt.%, 0.01
wt. % to 0.10 wt.
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%. In one embodiment, the level of sulfur in the lubricating oil compositions
of the present
invention is less than or equal to about 0.60 wt. %, less than or equal to
about 0.50 wt. %, less
than or equal to about 0.40 wt. %, less than or equal to about 0.30 wt. %,
less than or equal to
about 0.20 wt. %, less than or equal to about 0.10 wt. % based on the total
weight of the
lubricating oil composition.
In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the
present invention is less than or equal to about 0.12 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.12 wt.
%. In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the
present invention is less than or equal to about 0.11 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.11 wt.
%. In
one embodiment, the levels of phosphorus in the lubricating oil compositions
of the
present invention is less than or equal to about 0.10 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.10 wt.
%. In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the
present invention is less than or equal to about 0.09 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.09 wt.
%. In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the
present invention is less than or equal to about 0.08 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.08 wt.
%. In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the
present invention is less than or equal to about 0.07 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.07 wt.
%. In one embodiment, the levels of phosphorus in the lubricating oil
compositions of the
present invention is less than or equal to about 0.05 wt. %, based on the
total weight of the
lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.05 wt.
%.
In one embodiment, the level of sulfated ash produced by the lubricating oil
compositions
of the present invention is less than or equal to about 1.60 wt. % as
determined by ASTM D
874, e.g., a level of sulfated ash of from about 0.10 to about 1.60 wt. % as
determined by ASTM
D 874. In one embodiment, the level of sulfated ash produced by the
lubricating oil
compositions of the present invention is less than or equal to about 1.00 wt.
% as determined
by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.00
wt. % as
determined by ASTM D 874. In one embodiment, the level of sulfated ash
produced by the
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lubricating oil compositions of the present invention is less than or equal to
about 0.80 wt. %
as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10
to about 0.80
wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated
ash produced
by the lubricating oil compositions of the present invention is less than or
equal to about 0.60
wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about
0.10 to about
0.60 wt. % as determined by ASTM D 874.
Suitably, the present lubricating oil composition may have a total base number
(TBN) of 4
to 15 mg KOH/g (e.g., 5 to 12 mg KOH/g, 6 to 12 mg KOH/g, or 8 to 12 mg
KOH/g).
Viscosity modifier
Viscosity modifiers (VM) or viscosity index improvers (VIIs) may be used in
the
lubricant to impart high and low temperature operability. VM may be used to
impart that sole
function or may be multifunctional. Multifunctional viscosity modifiers also
provide additional
functionality for dispersant function. Examples of Viscosity modifiers and
dispersant viscosity
modifiers are polymethacrylates, polyacrylates, polyolefins, styrene-maleic
ester copolymer
and similar polymeric substances including homopolymers, copolymers and graft
copolymers.
In one embodiment, the VIIs can be present in the lubricating oil composition
from
0.001 to 10 wt.% based on the lubricating oil composition. In other
embodiments, the VIIs can
be present from 0.01 to 8 wt.%, from 0.01 to 5 wt.%, from 0.01 to 4 wt%, from
0.01 to 3 wt.%,
from 0.01 to 2.5 wt.%, from 0.1 to 2.5 wt.% the lubricating oil composition.
Particularly useful in this disclosure is the combination of a dispersant
polymethacrylate VII and an ethylene based non-dispersant VII.
Dispersant Polymethacrylate (DPMA) VII
In one embodiment, the dispersant PMA has a weight average molecular weight of
from
200,000 g/mol to 450,000 g/mol, from 200,000 g/mol to 400.000 g/mol. from
200,000 Wino!
to 350,000 g/mol, or from 200,000 g/mol to 300,000 g/mol.
The dispersant polymethacrylate (DPMA) viscosity index modifier used in the
present
invention can be described as follows, and as set forth in WO 2013/182581, the
disclosure of
which is incorporated herein. Compounds within this defmition would include
Viscoplex
viscosity index improvers 6-054, 6-565, 6-850, 6-950 and 6-954, all available
from Evonik
RohMax Additives GmbH of Darmstadt, Germany.
The polyalkyl(meth)acrylate(s) comprise monomer units of:
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(a) 0 to 40% by weight of one or more ethylenically unsaturated ester
compounds of
the formula (I):
R2
R I
Formula I
wherein R is hydrogen or methyl, R' is a saturated or unsaturated linear or
branched alkyl
radical haying 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl
group haying 3 to
5 carbon atoms, R2 and R3 are each independently hydrogen or a group of the
formula - COOR'
wherein R' is hydrogen or a saturated or unsaturated linear or branched alkyl
group haying 1 to
5 carbon atoms;
(b) 10 to 98% by weight, preferably 20 to 95% by weight, of one or more
ethylenically
unsaturated ester compounds of the formula (II)
R5
;10
Formula II
wherein R is hydrogen or methyl, le is a saturated or unsaturated linear or
branched alkyl
radical having 6 to 15 carbon atoms or a saturated or unsaturated cycloalkyl
group haying 6
to 15 carbon atoms, R5 and R6 are each independently hydrogen or a group of
the formula -
COOR" in which R" is hydrogen or a saturated or unsaturated linear or branched
alkyl group
having 6 to 15 carbon atoms;
(c) 0 to 30% by weight, preferably 5 to 20% by weight, of one or more
ethylenically
unsaturated ester compounds of the formula (III):
R8
zo
R
7
Formula III
wherein R is hydrogen or methyl, R7 is a saturated or unsaturated linear or
branched alkyl
radical having 16 to 40 preferably 16 to 30, carbon atoms or a cycloalkyl
group haying 16 to
40, preferably 16 to 30, carbon atoms, R8 and R9 are each independently
hydrogen or a group
of the formula -COOR" in which R" is hydrogen or a saturated or unsaturated
linear or
branched alkyl group haying 16 to 40, preferably 16 to 30, carbon atoms;
(d) 0 to 30% by weight of vinyl monomers;
(e) 2 to 10% by weight of at least one N-dispersant monomer.
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The DPMA used in the present invention is believed to contain about 1 to 10
wt.%
methyl methacrylate monomer, about 0.5 to 3 wt. % N-vinyl pyrolidone as the
nitrogen-
containing monomer, and the balance longer chain alkyl methacrylate monomers,
in particular,
lauryl methacrylate, and has a MW of from 200,000 to 250,000. It has an SSI of
from about 40
to about 50.
Non-Dispersant Ethylene-based Olefin Copolymer (0CP) VII
In one embodiment, the non-dispersant ethylene-based olefin copolymer VII has
a
weight average molecular weight of from 50,000 g/mol to about 150,000 g/mol,
from about
60,000 g/mol to about 120,000 g/mol, or from about 70,000 g/mol to about
110,000 g/mol.
The ethylene-based viscosity index modifier used in the present invention can
be
described as follows, and as set forth in US20130203640, the disclosure of
which is
incorporated herein.
In one embodiment, the ethylene-based VII is an ethylene propylene copolymer.
In one embodiment, the polymer compositions typically contain about 30 wt % to
about
70 wt % of the first ethylene-a-olefin copolymer (a) and about 70 wt % to
about 30 wt % of
the second ethylene-a-olefm copolymer (b) based upon the total amount of (a)
and (b) in the
composition. In another embodiment, the polymer compositions typically contain
about 40 wt
% to about 60 wt % of the first ethylene-a-olefin copolymer (a) and about 60
wt % to about 40
wt % of the second ethylene-a-olefin copolymer (b) based upon the total amount
of (a) and (b)
in the composition. In a particular embodiment, the polymer composition
contains about 50 to
about 54 wt % of the first ethylene-a-olefin copolymer (a) and about 46 to
about 50 wt % of
the second ethylene-a-olefin copolymer (b) based upon the total amount of (a)
and (b) in the
composition.
The weight average molecular weight of the first ethylene-a-olefin copolymer
in one
embodiment is typically about 60,000 g/mol to about 120,000 g/mol. In another
embodiment,
the weight average molecular weight of the first ethylene-a-olefin copolymer
is typically about
70,000 g/mol to about 110,000 g/mol. The weight average molecular weight of
the second
ethylene-a-olefin copolymer in one embodiment is typically about 60,000 g/mol
to about
120,000 g/mol. In another embodiment, the weight average molecular weight of
the second
ethylene-a-olefin copolymer is typically about 70,000 g/mol to about 110,000
g/mol. The
weight average molecular weight of the composition of the first ethylene-a-
olefin copolymer
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and second ethylene-a-olefin copolymer in one embodiment is typically about
60,000 g/mol to
about 120,000 g/mol. In another embodiment, the weight average molecular
weight of the
composition of the first ethylene-a-olefin copolymer and second ethylene-a-
olefm copolymer
is typically about 70,000 g/mol to about 110,000 g/mol. In a still further
embodiment, the
weight average molecular weight of the composition of the first ethylene-a-
olefin copolymer
and second ethylene-a-olefin copolymer is typically about 80,000 to about
100,000 g/mol. The
molecular weight distribution of each of the ethylene-a-olefin copolymers is
typically less than
about 2.5, and more typically about 2.1 to about 2.4. The polymer distribution
as determined
by GPC is typically unimodal.
In one embodiment, the polymer compositions typically have a total ethylene
content
of about 40 wt. % to about 70 wt. %, or about 50 wt. % to about 70 wt. %. In
another
embodiment, the polymer compositions typically have a total ethylene content
of about 55 wt.
% to about 65 wt. %. In other embodiments, the polymer composition has a total
ethylene
content of about 57 wt. % to about 63 wt. %.
Organomoly bdenum Compound
The organomolybdenum compound contains at least molybdenum, carbon and
hydrogen atoms, but may also contain sulfur, phosphorus, nitrogen and/or
oxygen atoms.
Suitable organomolybdenum compounds include molybdenum dithiocarbamates,
molybdemun dithiophosphates, and various organic molybdenum complexes such as
molybdenum carboxylates, molybdenum esters, molybdenum amines, molybdenum
amides,
which can be obtained by reacting molybdenum oxide or ammonium molybdates with
fats,
glycerides or fatty acids, or fatty acid derivatives (e.g., esters, amines,
amides). The term "fatty"
means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon
chain.
Molybdate esters prepared by methods disclosed in US 4,889,647 and US
6,806,241
B2 . A commercial example is MOLYVAN 855 additive, which is manufactured by
R. T.
Vanderbilt Company, Inc.
Molybdenum dithiocarbamate (MoDTC) is an organomolybdenum compound
represented by the following structure (1):
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R1 0 0 R3
\ I I/ \
S II/S
Mo Mo _______ N (1)
R2 R4
wherein IV, R2, R3 and le are independently of each other, linear or branched
alkyl groups
having from 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).
Preparations of these compounds are well known in the literature and U.S. Pat.
Nos.
3,356,702 and 4,098,705 are incorporated herein for reference. Commercial
examples include
MOLYVAN 807, MOLYVAN 822, and MOLYVAN 2000, which are manufactured by
R. T. Vanderbilt Company Inc., SAKURA-LUBE 165 and SAKURA-LUBE 515, which
are manufactured by ADEKA CORPORATION and Naugalube MolyFM which is
manufactured by Chemtura Corporation.
Trinuclear molybdenum dialkyldithiocarbamates are also known in the art, as
taught by
U.S. Pat. Nos. 5,888,945 and 6,010,987, herein incorporated by reference.
Tiinuclear
molybdemun compounds preferably those having the formulas Mo354(dtc)4 and
Mo357(dtc)4
and mixtures thereof wherein dtc represents independently selected
diorganodithiocarbamate
ligands containing independently selected organo groups and wherein the
ligands have a
sufficient number of carbon atoms among all the organo groups of the
compound's ligands are
present to render the compound soluble or dispersible in the lubricating oil.
Molybdenum dithiophosphate (MoDTP) is an organomolybdenum compound
represented by the following structure (2):
0 0
R50 7 \ 11/S\ 11/ OR
S
P Mo Mo P (2)
R60
wherein IV, R6, R7 and R8 are independently of each other, linear or branched
alkyl groups
having from 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).
Molybdenum carboxylates are described in U.S. Pat. RE 38,929, and U.S. Pat.
No.
6,174,842 and thus are incorporated herein by reference. Molybdenum
carboxylates can be
derived from any oil soluble carboxylic acid. Typical carboxylic acids include
naphthenic acid,
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2-ethylhexanoic acid, and linolenic acid. Commercial sources of carboxylates
produce from
these particular acids are MOLYBDENUM NAP-ALL, MOLYBDENUM HEX-CEM, and
MOLYBDENUM LIN-ALL respectively. Manufacturer of these products is OMG OM
Group.
Ammonium molybdates are prepared by the acidibase reaction of acidic
molybdenum
source such as molybdenum trioxide, molybdic acid, and ammonium molybdate and
ammonitun thiomolybdates with oil-soluble amines and optionally in presence of
sulfur
sources such sulfur, inorganic sulfides and polysulfides, and carbons
disulfide to name few.
The preferred aminic compounds are polyamine dispersants that are commonly
used engine oil
compositions. Examples of such dispersants are succinimides and Mamtich type.
References
to these preparations are U.S. Pat. Nos. 4,259,194, 4,259,195, 4,265,773,
4,265,843, 4,727,387,
4,283,295, and 4,285,822.
In one embodiment, the molybdenum amine is a molybdenum-succinimide complex.
Suitable molybdenum-succinimide complexes are described, for example, in U.S.
Patent No.
8,076,275. These complexes are prepared by a process comprising reacting an
acidic
molybdenum compound with an alkyl or alkenyl succinimide of a polyamine of
structure (3)
or (4) or mixtures thereof:
0
R
N¨(R'NH)xH (3)
0
0 0
R R
N-(R'NH)yR'-N (4)
0 0
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wherein R is a C24 to C350 (e.g., C70 to C128) alkyl or alkenyl group; R. is a
straight or branched-
chain alkylene group having 2 to 3 carbon atoms; x is 1 to ii; and y is 1 to
10.
The molybdenum compounds used to prepare the molybdenum-succinimide complex
are acidic molybdenum compounds or salts of acidic molybdenum compounds. By
"acidic" is
meant that the molybdenum compounds will react with a basic nitrogen compound
as measured
by ASTM D664 or D2896. Generally, the acidic molybdenum compounds are
hexavalent.
Representative examples of suitable molybdenum compounds include molybdenum
trioxide,
molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and
other
alkaline metal molybdates and other molybdenum salts such as hydrogen salts,
(e.g., hydrogen
sodium molybdate), Mo0C14, MoO2Br2, Mo203C16, and the like.
The succinimides that can be used to prepare the molybdenum-succinimide
complex
are disclosed in numerous references and are well known in the art. Certain
fundamental types
of succinimides and the related materials encompassed by the term of art
"succinimide" are
taught in U.S. Patent Nos. 3,172,892; 3,219,666: and 3,272,746. The term
"succinimide" is
understood in the art to include many of the amide, imide, and amidine species
which may also
be formed. The predominant product however is a succinimide and this term has
been generally
accepted as meaning the product of a reaction of an alkyl or alkenyl
substituted succinic acid
or anhydride with a nitrogen-containing compound. Preferred succinimides are
those prepared
by reacting a polyisobutenyl succinic anhydride of about 70 to 128 carbon
atoms with a
polyalkylene polyamine selected from triethylenetetramine,
tetraethylenepentamine, and
mixtures thereof.
In one embodiment, the molybdenum containing compound is free of sulfur.
The molybdenum-succinimide complex may be post-treated with a sulfur source at
a
suitable pressure and a temperature not to exceed 120 C to provide a
sulfurized molybdenum-
succinimide complex. The sulfurization step may be carried out for a period of
from about 0.5
to 5 hours (e.g., 0.5 to 2 hours). Suitable sources of sulfur include
elemental sulfur, hydrogen
sulfide, phosphorus pentasulfide, organic polysulfides of formula R2Sx where R
is hydrocarbyl
(e.g., C1 to C10 alkyl) and x is at least 3, C1 to C10 mercaptans, inorganic
sulfides and
polysulfides, thioacetamide, and thiourea.
The molybdenum containing compound is used in an amount that provides from
about
50 to about 300 ppm of molybdenum, about 50 to about 275 ppm, about 50 to
about 250 ppm,
about 50 to about 200 ppm, or about 50 to about 175 ppm by weight of
molybdenum to the
lubricating oil composition.
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In some embodiments, the lubricating oil composition is substantially free of
molybdenum containing element.
Salleylate Detergent
Salicylates may be prepared by reacting a basic metal compound with at least
one
carboxylic acid and removing water from the reaction product. Detergents made
from salicylic
acid are one class of detergents prepared from carboxylic acids. Useful
salicylates include long
chain alkyl salicylates. One useful family of compositions is of the following
structure (5):
0
______________________________________ 0 ___
(5)
HO ________________________
¨2
wherein R" is a Ci to C30 (e.g., C13 to C30) alkyl group; n is an integer from
1 to 4; and M is an
alkaline earth metal (e.g., Ca or Mg).
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.
In one aspect of the present disclosure, the salicylate is derived from Cio-
Cao isomerized
NAO and is made from an alkylphenol with an alkyl group derived from an
isomerized NAO
having an isomerization level (i) from about 0.10 to about 0.40, preferably
from about 0.10 to
about 0.35, preferably from about 0.10 to about 0.30, and more preferably from
about 0.12 to
about 0.30.
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,
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carboxylic acid, phosphorous acid. phenol or mixtures thereof. The counterion
is typically an
alkaline earth or alkali metal.
Salts that contain a substantially stoichiometric amount of the metal are
described as
neutral salts and have a total base number (TBN) of from 0 to 80 mg KOH/g.
Many
compositions are overbased, containing large amounts of a metal base that is
achieved by
reacting an excess of a metal compound (e.g., a metal hydroxide or oxide) rich
an acidic gas
(e.g., carbon dioxide). Useful detergents can be neutral, mildly overbased, or
highly overbased.
It is desirable for at least some detergent used in the detergent mixture to
be overbased.
Overbased detergents help neutralize acidic impurities produced by the
combustion process
and become entrapped in the oil. Typically, the overbased material has a ratio
of metallic ion
to anionic portion of the detergent of 1.05:1 to 50:1 (e.g., 4:1 to 25:1) on
an equivalent basis.
The resulting detergent is an overbased detergent that will typically have a
TBN of 150 mg
KOH/g or higher (e.g., 250 to 450 mg KOH/g or more). A mixture of detergents
of differing
TBN can be used.
Suitable detergents include metal salts of sulfonates, phenates, carboxylates,
phosphates, and salicylates.
Sulfonates may be prepared from sulfonic acids which are typically obtained by
the
sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained
from the
fractionation of petroleum or by the alkylation of aromatic hydrocarbons.
Examples included
those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl
or their halogen
derivatives. The alkylation may be carried out in the presence of a catalyst
with alkylating
agents having from about 3 to more than 70 carbon atoms. The alkaryl
sulfonates usually
contain from about 9 to 80 or more carbon atoms (e.g., about 16 to 60 carbon
atoms) per alkyl
substituted aromatic moiety.
Phenates can be prepared by reacting an alkaline earth metal hydroxide or
oxide (e.g.,
CaO, Ca(OH)2, MgO, or Mg(OH)2) with an alkyl phenol or sulfurized alkylphenol.
Useful
alkyl groups include straight or branched chain Ci to C30 (e.g., Ca to Cm)
alkyl groups, 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
chain. 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 (e.g., elemental sulfur, sulfur halides such as sulfur
dichloride, and the like)
and then reacting the sulfurized phenol with an alkaline earth metal base.
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Magnesium Detergent
Preferred magnesium-containing detergents include magnesium sulfonates,
magnesium
phenates, and magnesium salicylates, especially magnesium sulfonates.
The magnesium-containing detergent may be used in an amount that provides at
least
250 ppm to 1000 ppm (e.g., 250 to 1000 ppm, 250 to 800 ppm, 300 to 1000 ppm,
300 to 800
ppm, 400 to 1000 ppm, or 400 to 800 ppm) by weight of magnesium to the
lubricating oil
composition.
Other Lubricating Oil Additives
In addition to the additives compound described herein, the lubricating oil
composition can comprise additional lubricating oil additives.
The lubricating oil compositions of the present disclosure may also contain
other conventional additives that can impart or improve any desirable property
of the
lubricating oil composition in which these additives are dispersed or
dissolved. Any additive
known to a person of ordinary skill in the art may be used in the lubricating
oil compositions
disclosed herein. Some suitable additives have been described in Mortier et
al., "Chemistry and
Technology of Lubricants", 2nd Edition, London, Springer, (1996); and Leslie
R. Rudnick,
"Lubricant Additives: Chemistry and Applications", New York, Marcel Dekker
(2003), both
of which are incorporated herein by reference. For example, the lubricating
oil compositions
can be blended with antioxidants, anti-wear agents, metal detergents, rust
inhibitors, dehazing
agents, demulsifying agents, metal deactivating agents, friction modifiers,
pour point
depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless
dispersants,
multifunctional agents, dyes, extreme pressure agents and the like and
mixtures thereof A
variety of the additives are known and commercially available. These
additives, or their
analogous compounds, can be employed for the preparation of the lubricating
oil compositions
of the disclosure by the usual blending procedures.
The lubricating oil composition of the present invention can contain one or
more anti-
wear agents that can reduce friction and excessive wear. Any anti-wear agent
known by a
person of ordinary skill in the art may be used in the lubricating oil
composition. Non-limiting
examples of suitable anti-wear agents include zinc dithiophosphate, metal
(e.g., Pb, Sb, Mo
and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo and the
like) salts of
dithiocarbamates, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids,
boron compounds,
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phosphate esters, phosphite esters, amine salts of phosphoric acid esters or
thiophosphoric acid
esters, reaction products of dicyclopentadiene and thiophosphoric acids and
combinations
thereof. The amount of the anti-wear agent may vary from about 0.01 wt. % to
about 5 wt. %,
from about 0.05 wt. % to about 3 wt. %, or from about 0.1 wt. % to about 1 wt.
%, based on
the total weight of the lubricating oil composition.
In certain embodiments, the anti-wear agent is or comprises a dihydrocarbyl
dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds.
The metal of the
dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth
metal, or aluminum,
lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the
metal is zinc.
In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate
metal salt has from
about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from
about 3 to
about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further
embodiments, the
alkyl group is linear or branched.
The amount of the dihydrocarbyl dithiophosphate metal salt including the zinc
dialkyl dithiophosphate salts in the lubricating oil composition disclosed
herein is measured by
its phosphorus content. In some embodiments, the phosphorus content of the
lubricating oil
composition disclosed herein is from about 0.01 wt. % to about 0.14 wt. %,
based on the total
weight of the lubricating oil composition.
The lubricating oil composition of the present invention can contain one or
more
friction modifiers that can lower the friction between moving parts. Any
friction modifier
known by a person of ordinary skill in the art may be used in the lubricating
oil composition.
Non-limiting examples of suitable friction modifiers include fatty carboxylic
acids; derivatives
(e.g., alcohol, esters, borated esters, amides, metal salts and the like) of
fatty carboxylic acid;
mono-, di- or tii-alkyl substituted phosphoric acids or phosphonic acids;
derivatives (e.g.,
esters, amides, metal salts and the like) of mono-, di- or tri-alkyl
substituted phosphoric acids
or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-
alkyl substituted
amides and combinations thereof. In some embodiments examples of friction
modifiers
include, but are not limited to, alkoxylated fatty amines; borated fatty
epoxides; fatty
phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines,
metal salts of fatty
acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty
imidazolines as
disclosed in U.S. Patent No. 6,372,696, the contents of which are incorporated
by reference
herein; friction modifiers obtained from a reaction product of a C4 to C75, or
a C6 to C24, or a
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C6 to Cm. fatty acid ester and a nitrogen-containing compound selected from
the group
consisting of ammonia, and an alkanolamine and the like and mixtures thereof.
The amount of
the friction modifier may vary from about 0.01 wt. % to about 10 wt. %, from
about 0.05 wt.
% to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. %, based on the
total weight of the
lubricating oil composition.
The lubricating oil composition of the invention preferably contains an
organic
oxidation inhibitor in an amount of 0.01-5 wt. %, preferably 0.1-3 wt. %. The
oxidation
inhibitor can be a hindered phenol oxidation inhibitor or a diarylamine
oxidation inhibitor. The
diarylamine oxidation inhibitor is advantageous in giving a base number
originating from the
nitrogen atoms. The hindered phenol oxidation inhibitor is advantageous in
producing no NOx
gas.
Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p-
cresol, 4,4' -methylenebis(2,6-di-t-butylphenol), 4,4' -methylenebis(6-t-butyl-
o-cresol), 4,4
-isopropylidenebis(2,6-di-t-butylphenol), 4,4 -bis(2,6-di-t-butylphenol),
2,2 -
methylenebis(4-methy1-6-t-butylphenol), 4,4' -thiobis(2-methyl-6-t-
butylphenol), 2,2-thio-
diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-
buty1-4-
hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate, and octyl
3-(3,54-butyl-4-hydroxy-3-methylphenyl)propionate, and commercial products
such as, but
not limited to, Irganox L1350 (BASF), Naugalube 5310 (Chemtura), and Ethanox
376* (SI
Group).
Examples of the diarylamine oxidation inhibitors include alkyldiphenylamine
having a mixture of alkyl groups of 4 to 9 carbon atoms, p,p' -
dioctAdiphenylamine, phenyl-
naphthylamine, phenyl-naphthylamine, alkylated-naphthylamine, and alkylated
phenyl-
naphthylamine.
Each of the hindered phenol oxidation inhibitor and diarylamine oxidation
inhibitor can be employed alone or in combination. If desired, other oil
soluble oxidation
In the preparation of lubricating oil formulations, it is common practice to
introduce the additives in the form of 10 to 80 wt. % active ingredient
concentrates in
hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent.
Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts
by
weight of lubricating oil per part by weight of the additive package in
fonning finished
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S lubricants, e.g. crankcase motor oils. The purpose of concentrates, of
course, is to make the
handling of the various materials less difficult and awkward as well as to
facilitate solution or
dispersion in the final blend.
Processes of Preparing Lubricating Oil Compositions
The lubricating oil compositions disclosed herein can be prepared by any
method known to a person of ordinary skill in the art for making lubricating
oils. In some
embodiments, the base oil can be blended or mixed with the zirconium-
containing compounds
described herein. Optionally, one or more other can be added. The additives
may be added to
the base oil individually or simultaneously. In some embodiments, the
additives are added to
the base oil individually in one or more additions and the additions may be in
any order. In
other embodiments, the additives are added to the base oil simultaneously,
optionally in the
form of an additive concentrate. In some embodiments, the solubilizing of the
additives in the
base oil may be assisted by heating the mixture to a temperature from about 25
C to about 200
C, from about 50 C to about 150 C or from about 75 C to about 125 C.
Any mixing or dispersing equipment known to a person of ordinary skill in the
art may be used for blending, mixing or solubilizing the ingredients. The
blending, mixing or
solubilizing may be carried out with a blender, an agitator, a disperser, a
mixer (e.g., planetary
mixers and double planetary mixers), a homogenizer (e.g., Gaulin homogenizers
and Rannie
homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any
other mixing or
dispersing equipment known in the art.
Application of the Lubricating Oil Compositions
The lubricating oil composition disclosed herein may be suitable for use as
motor oils (that is, engine oils or crankcase oils), in a spark-ignited
internal combustion engine,
particularly direct injected and boosted engines.
The following examples are presented to exemplify embodiments of the
invention but are not intended to limit the invention to the specific
embodiments set forth.
Unless indicated to the contrary, all parts and percentages are by weight. All
numerical values
are approximate. When numerical ranges are given, it should be understood that
embodiments
outside the stated ranges may still fall within the scope of the invention.
Specific details
described in each example should not be construed as necessary features of the
invention.
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EXAMPLES
The following examples are intended for illustrative puiposcs only and do not
limit in any
way the scope of the present invention.
EXAMPLE 1
A lubricating oil composition was prepared by blending together the following
components to obtain an SAE OW-20 viscosity grade fonnulation:
(a) 740 ppm, in terms of phosphorus content, of a secondary zinc
dialkyldithiophosphate;
(b) 1120 ppm, in terms of calcium content, the majority coming from an C14-
Cis normal alpha olefin derived overbased calcium salicylate and a minor
amount from a low overbased calcium sulfonate detergent;
(c) 840 ppm, in terms of magnesium of a highly overbased magnesium
sulfonate detergent;
(d) An ethylene carbonate treated and a borated succinimide dispersant;
(e) an alkylated diphenylamine antioxidant, hindered phenol antioxidant;
(f) conventional amounts of pour point depressant,
(g) a combination of viscosity index improvers which was 0.70 wt.% of a
polymer concentrate which contains an ethylene propylene derived non-
dispersant OCP (ethylene propylene based copolymer with between 55 to
65% ethylene, a weight average molecular weight of 80,000 to about
100,000 g/mol, and an SSI of about 20 to about 26) and 1.50 wt.% of
polymer concentrate which contains a dispersant type PMA (1 to 10 wt.%
methyl methacrylate monomer, about 0.5 to 3 wt. % N-vinyl pyrolidone as
the nitrogen-containing monomer, and the balance longer chain alkyl
methacrylate monomers, in particular, lauryl methacrylate, and has a MW
of from 200,000 to 250,000. It has an SSI of from about 40 to about 50, and
(h) 0.2 wt.% of a sulfur free molybdenum in an amount to provide 160 ppm of
molybdenum
(i) foam inhibitor; and
(j) the balance a mixture of Group III and Group IV PAO base oils.
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EXAMPLE 2
Example 1 was replicated except that 0.1 wt.% of a sulfur free molybdenum
compound
was added in an amount to provide 80 ppm of molybdenum to the lubricating oil
composition
and magnesium sulfonate was added in an amount to provide 240 ppm of Mg.
EXAMPLE 3
Example 1 was replicated except that 0.2 wt.% of a sulfur free molybdenum
compound
was added in an amount to provide 160 ppm of molybdenum to the lubricating oil
composition
and magnesium sulfonate was added in an amount to provide 240 ppm of Mg.
EXAMPLE 4
Example 1 was replicated except that 0.1 wt.% of a sulfur containing
molybdenum
succinimide complex was added in an amount to provide 50 ppm of molybdenum to
the
lubricating oil composition and magnesium sulfonate was added in an amount to
provide 240
ppm of Mg.
EXAMPLE 5
Example I was replicated except that 0.2 wt.% of a sulfur containing
molybdenum
succinimide complex was added in an amount to provide 100 ppm of molybdenum to
the
lubricating oil composition and magnesium sulfonate was added in an amount to
provide 240
ppm of Mg.
EXAMPLE 6
Example 1 was replicated except that 0.4 wt.% of a sulfur containing
molybdenum
succinimide complex was added in an amount to provide 200 ppm of molybdenum to
the
lubricating oil composition and magnesium sulfonate was added in an amount to
provide 240
ppm of Mg.
COMPARATIVE EXAMPLE 1
Example 1 was replicated except that the ethylene propylene derived non-
dispersant
OCP was replaced with 0.7 wt.% of polymer concentrate which contains a
hydrogenated
polyisoprene star polymer coupled with divinylbenzene with an SSI of 4 and a
molecular
weight of 35,000 and magnesium sulfonate was added in an amount to provide 240
ppm of
Mg.
COMPARATIVE EXAMPLE 2
Example 1 was replicated except that 0.4 wt.% of a sulfur free molybdenum
compound
was added in an amount to provide 320 ppm of molybdenum to the lubricating oil
composition
and magnesium sulfonate was added in an amount to provide 240 ppm of Mg.
COMPARATIVE EXAMPLE 3
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Example I was replicated except that 0.4 wt.% of a sulfur free molybdenum
compound
and 0.4 wt.% of a sulfur containing molybdenum succinimide complex was added
in an amount
to provide 490 ppm of molybdenum to the lubricating oil and magnesium
sulfonate was added
in an amount to provide 240 ppm of Mg.
COMPARATIVE EXAMPLE 4
Example 1 was replicated except that 1.0 wt.% of a sulfur free molybdenum
compound
was added in an amount to provide 780 ppm of molybdenum to the lubricating oil
and
magnesium sulfonate was added in an amount to provide 240 ppm of Mg.
COMPARATIVE EXAMPLE 5
Example 11 was replicated except the ethylene propylene derived non-dispersant
OCP
and dispersant PMA was replaced with 4.50 wt.% of polymer concentrate which
contains a
hydrogenated polyisoprene star polymer coupled with divinylbenzene with an SSI
of 4 and a
molecular weight of 35,000 and magnesium sulfonate was added in an amount to
provide 240
ppm of Mg.
COMPARATIVE EXAMPLE 6
Comparative Example 3 was replicated except the ethylene propylene derived non-
dispersant OCP and dispersant PMA was replaced with 4.50 wt.% of polymer
concentrate
which contains a hydrogenated polyisoprene star polymer coupled with
divinylbenzene with
an SSI of 4 and a molecular weight of 35,000 and magnesium sulfonate was added
in an amount
to provide 240 ppm of Mg.
COMPARATIVE EXAMPLE 7
Example 1 was replicated except that the ethylene propylene derived non-
dispersant
OCP was replaced with a 6.25 wt.% of a polymer concentrate of a dispersant OCP
and
magnesium sulfonate was added in an amount to provide 240 ppm of Mg.
The isomerization level was measured by an NMR method.
Isomerization level (1) and NMR method
The isomerization level (I) of the olefin was determined by hydrogen-1 (1H)
NMR.
The NMR spectra were obtained on a Bruker Ultrashield Plus 400 in chloroform-
dl at 400
MHz using TopSpin 3.2 spectral processing software.
The isomerization level (I) represents the relative amount of methyl groups (-
CH.3)
(chemical shift 0.30-1.01 ppm) attached to the methylene backbone groups (-CH2-
) (chemical
shift 1.01-1.38 ppm) and is defined by Fortnula (6) as shown below,
1 = m/(m+n) Formula (6)
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where m is NMR integral for methyl groups with chemical shifts between 0.30
0.03
to 1.01 0.03 ppm, and n is NMR integral for methylene groups with chemical
shifts between
1.01 0.03 to 1.38 0.10 ppm.
TESTING
Performance evaluation of the formulations is given in Table 2. The following
bench
test was performed to measure wear: FZG Wear Scuffing Load Carrying Capacity
Test. In
order to evaluate wear performance of the automotive engine oils, the load
carrying
characteristics of various engine oils having different chemistries were
evaluated on an FZG
test rig (FZG four-square test machine) using A 10 gears according to CEC-L-84-
A-02. This
method is useful for evaluating the scuffing load capacity potential of oils
typically used with
highly stressed cylindrical gearing found in many vehicle and stationary
applications. The-
minimum load stage fail was 8 for the A10 gears at 16.6 m/s and 130 C.
TABLE 2
i DPMA of OCP of Salicylate Mo (ppm)
Examples FZG Wear
disclosure disclosure Detergent
Example 1 i y Y Y 160 7
Example 2 Y Y Y 80 8
Example 3 Y Y Y 160 9
Example 4 Y Y Y 50 8
Example 5 Y Y V 100 9 .
Example 6 Y Y Y 200 8
¨
Comparative Example 1 Y N Y 0 6
¨
Comparative Example 2 Y Y Y 320 6
Comparative Example 3 Y Y V 490 6 .
Comparative Example 4 Y Y Y 780 6
Comparative Example 5 N N Y 200 6
Comparative Example 6 N N Y 490 5
Comparative Example 7 1 Y N Y 0 6
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