Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DESCRIPTION
TITLE OF INVENTION
LUBRICATING OIL COMPOSITIONS FOR MOTORCYCLES
FIELD OF THE INVENTION
The present invention generally relates to lubricating oil compositions useful
for motorcycles.
BACKGROUND OF THE INVENTION
Lubricants for motorcycles typically provide lubrication for the engine (a
crankcase) and a
wet clutch. These two devices, although often lubricated by the same fluid,
often have
different lubrication requirements. For example, the lubrication of the engine
desirably
provides low "metal-on-metal" friction interface to promote good fuel economy.
Typically,
the "metal" referred to is steel. However, the friction coefficient for the
"metal-on-
composition" interface, which occurs within the wet clutch, is typically
desired to be
relatively high, to assure good engagement and power transmission.
Additionally, motorcycle
lubricants also lubricate other devices such as gears or bearings, each having
their own
lubrication requirement.
Many lubricants have been designed over the years for lubrication of
motorcycles (also
known as motorbikes or motorscooters). One such lubricant is described in U.S.
Patent
Publication 2008-0096778, Breon et al., April 24, 2008.
Four-stroke motorcycle engine lubricants may appear to be similar to passenger
car engine
lubricants. However, there are several key engineering design features of
motorcycles, such
as integration of clutch and gearbox, high speed of operation, high specific
power output, low
sump volumes, and lightweight engine construction, all of which require
additional
consideration when formulating motorcycle oils. Because of the varied and
demanding
lubrication performance required, motorcycle lubricants are typically designed
specifically
for use in motorcycles. That is, typical lubricants as used in lubricating
passenger car engines
are not normally used for motorcycles.
Nevertheless, there are a certain number of motorcycles which do not employ a
wet clutch,
but, rather, "dry" or non-lubricated clutches or clutch plates. Likewise,
there might be
motorcycles for which a wet clutch is lubricated by a separate lubricant from
that used to
lubricate the engine. For those motorcycles, the high metal-on-composition
friction is of no
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benefit to the engine and is indeed undesirable to the extent that it may
interfere with the
provision of the lowest possible friction in the metal-on-metal interfaces.
While one possible
approach to solving this problem would be to remove from the lubricant those
components
that provide high metal-on-composition friction, this is not necessarily
desirable. The
additives within such lubricants are usually carefully balanced, so that the
removal of one
component may affect the performance of the lubricant in unintended ways.
Furthermore, it
may be undesirable, from a commercial standpoint, to stock multiple complete
motorcycle
lubricants: some for motorcycles with a wet clutch, and some for motorcycles
with a dry
clutch.
JASO (Japanese Automobile Standard Organization) MB oils are being widely used
in the
world for four cycle gasoline engine of motorcycles with a dry clutch, e.g.
scooter. The MB
oils have been formulated with MoDTC since it is essential to meet OEM's
requirement of
friction characteristics and fuel economy. One such lubricant is described in
JP2004099676.
SUMMARY OF THE INVENTION
In accordance with one embodiment of the present invention, there is provided
a
MoDTC-free lubricating oil composition for motorcycles which comprises an
engine and a
clutch,
wherein the composition comprises:
(a) a major amount of an oil of lubricating viscosity,
(b) a molybdenum compound, and
(c) a salicylate detergent having a TBN 100-450 on active basis,
wherein the composition lubricates the engine but not the clutch.
In another embodiment, provided is a method for lubricating the engine of a
motorcycle which comprises an engine and a clutch, with a MoDTC-free
lubricating oil
composition,
wherein the composition comprises:
(a) a major amount of an oil of lubricating viscosity,
(b) a molybdenum compound, and
(c) a salicylate detergent having a TBN 100-450 on active basis, and
wherein the composition lubricates the engine but not the clutch.
2
In a further embodiment, disclosed is the use of a lubricating oil composition
to
lubricate the engine of a motorcycle which comprises an engine and a clutch,
with a MoDTC-
free lubricating oil composition,
wherein the composition comprises:
a. a major amount of an oil of lubricating viscosity,
b. a molybdenum compound, and
c. a salicylate detergent having a TBN 100-450 on active basis, and
wherein the composition lubricates the engine but not the clutch.
In another embodiment, disclosed is the use of the lubricating oil
compositions above
to lubricate four cycle gasoline engines of motorcycles equipped with a dry
clutch.
In accordance with another embodiment, there is a MoDTC-free lubricating oil
composition for motorcycles which comprise an engine and a dry clutch, wherein
the
composition comprises:
a. at least 40 wt. % of an oil of lubricating viscosity based on the weight
of the
lubricating oil composition,
b. a molybdenum compound, and
c. a salicylate detergent having a Total Base Number (TBN) 100 - 450 on
active
basis in accordance with ASTM Standard No. D2896,
wherein the salicylate detergent is a calcium alkylsalicylate detergent
derived from
C14-18 normal alpha olefins, and wherein the calcium alkylsalicylate detergent
is
present in an amount of from 0.1 - 10 wt. % based on the weight of the
lubricating oil
composition.
In accordance with a further embodiment, there is a method for lubricating the
engine
of a motorcycle which comprises an engine and a clutch, with a MoDTC-free
lubricating oil
composition, wherein the composition comprises:
a. at least 40 wt. % of an oil of lubricating viscosity based on the weight
of the
lubricating oil composition,
b. a molybdenum compound, and
c. a salicylate detergent having a Total Base Number (TBN) 100 - 450 on
active
basis in accordance with ASTM Standard No. D2896, and
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wherein the composition lubricates the engine but not the clutch; wherein the
salicylate
detergent is a calcium alkylsalicylate detergent derived from CI4-18 nomial
alpha olefins, and
wherein the calcium alkylsalicylate detergent is present in an amount of from
0.1 - 10 wt. %
based on the weight of the lubricating oil composition.
Definitions:
The following terms will be used throughout the specification and will have
the
following meanings unless otherwise indicated.
The temi "a major amount" of a base oil refers to where the amount of the base
oil is
at least 40 wt. % of the lubricating oil composition. In some embodiments, "a
major amount"
of a base oil refers to an amount of the base oil more than 50 wt.%, more than
60 wt.%, more
than 70 wt.%, more than 80 wt.%, or more than 90 wt.% of the lubricating oil
composition.
In the following description, all numbers disclosed herein are approximate
values,
regardless whether the word "about" or "approximate" is used in connection
therewith. They
may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent.
The temi "Total Base Number" or "'MN" refers to the level of alkalinity in an
oil
sample, which indicates the ability of the composition to continue to
neutralize corrosive
acids, in accordance with ASTM Standard No. D2896 or equivalent procedure. The
test
measures the change in electrical conductivity, and the results are expressed
as mgKOH/g
(the equivalent number of milligrams of KOH needed to neutralize 1 gram of a
product).
Therefore, a high TBN reflects strongly overbased products and, as a result, a
higher base
reserve for neutralizing acids.
The teun "NAO" refers to Normal Alpha Olefins.
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Date Recue/Date Received 2023-01-23
The term "on an actives basis" indicates that only the active component(s) of
a
particular additive are considered when determining the concentration or
amount of that
particular additive within the overall motorcycle lubricating oil composition.
Diluent oil in
the additive is excluded.
DETAILED DESCRIPTION OF THE INVENTION
Provided herein are lubricating oil compositions suitable for motorcycles that
do not
have a clutch lubricated by the same lubricant, e.g., with non- lubricated
("dry") clutch plates.
The compositions are MoDTC-free, but give low friction properties and show
good fuel
economy performance.
Molybdenum Succinimide
The unsulfurized or sulfurized oxymolybdenum-containing compounds employed in
the present invention ([component (b)1 may be generally characterized as an
oxymolybdenum
complex of a basic nitrogen compound. Such molybdenum/sulfur complexes are
known in
the art and are described, for example, in U.S. Pat. No. 4,263,152 to King et
al.
The structure of the molybdenum compound employed in this invention are not
known with certainty; however, they are believed to be compounds in which
molybdenum,
whose valences are satisfied with atoms of oxygen or sulfur, is either
complexed by, or the
salt of, one or more nitrogen atoms of the basic nitrogen containing compound
used in the
preparation of these compositions.
The molybdenum compounds used to prepare the oxymolybdenum and
oxymolybdenum/sulfur complexes employed in the present invention are acidic
molybdenum
compounds. By acidic is meant that the molybdenum compounds will react with a
basic
nitrogen compound as measured by ASTM test D-664 or D-2896 titration
procedure.
Typically, these molybdenum compounds are hexavalent and are represented by
the
following compounds: 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, Mo20306,
molybdenum trioxide or similar acidic molybdenum compounds. Preferred acidic
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Date Recue/Date Received 2023-01-23
molybdenum compounds are molybdic acid, ammonium molybdate, and alkali metal
molybdates. Particularly preferred are molybdic acid and ammonium molybdate.
The basic nitrogen compound used to prepare the oxymolybdenum complexes have
at
least one basic nitrogen and are preferably oil-soluble. Typical examples of
such compound
.. are succinimides, carboxylic acid amides, hydrocarbyl monoamines,
hydrocarbon
polyamines, Mannich bases, phosphoramides, thiophosphoramides, phosphonamides,
dispersant viscosity index improvers, and mixtures thereof. Any of the
nitrogen-containing
compounds may be after-treated with, e.g., boron, using procedures well known
in the art so
long as the compounds continue to contain basic nitrogen. These after-
treatments are
particularly applicable to succinimides and Mannich base compositions.
The mono and polysuccinimides that can be used to prepare the molybdenum
complexes described herein are disclosed in numerous references and are well
known in the
art. Certain fundamental types of succinimides and the related materials
encompassed by the
tetra of art "succinimide" are taught in U.S. Pat. Nos. 3,219,666; 3,172,892;
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 alkenyl substituted succinic acid or anhydride with a nitrogen-
containing compound.
Preferred succinimides, because of their commercial availability, are those
succinimides
prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbyl group
contains
from about 24 to about 350 carbon atoms, and an ethylene amine, said ethylene
amines being
especially characterized by ethylene diamine, diethylene triamine, triethylene
tetramine, and
tetraethylene pentamine. Particularly preferred are those succinimides
prepared from
polyisobutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene
pentamine or
.. triethylene tetramine or mixtures thereof.
Also included within the term "succinimide" are the cooligomers of a
hydrocarbyl
succinic acid or anhydride and a poly secondary amine containing at least one
tertiary amino
nitrogen in addition to two or more secondary amino groups. Ordinarily this
composition has
between 1500 and 50000 average molecular weight. A typical compound would be
that
prepared by reacting polyisobutenyl succinic anhydride and ethylene
dipiperazine.
Carboxylic acid amide compounds are also suitable starting materials for
preparing
the oxymolybdenum complexes employed in this invention. Typical of such
compounds are
those disclosed in U.S. Pat. No. 3,405,064. These compounds are ordinarily
prepared by
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Date Recue/Date Received 2023-01-23
reacting a carboxylic acid or anhydride or ester thereof, having at least 12
to about 350
aliphatic carbon atoms in the principal aliphatic chain and, if desired,
having sufficient
pendant aliphatic groups to render the molecule oil soluble with an amine or a
hydrocarbyl
polyamine, such as an ethylene amine, to give a mono or polycarboxylic acid
amide.
Preferred are those amides prepared from (1) a carboxylic acid of the formula
R'COOH,
where R' is C12-2oalkyl or a mixture of this acid with a polyisobutenyl
carboxylic acid in
which the polyisobutenyl group contains from about 72 to 128 carbon atoms and
(2) an
ethylene amine, especially triethylene tetramine or tetraethylene pentamine or
mixtures
thereof.
Another class of compounds which are useful in this invention are hydrocarbyl
monoamines and hydrocarbyl polyamines, preferably of the type disclosed in
U.S. Pat. No.
3,574,576. The hydrocarbyl group, which is preferably alkyl, or olefinic
having one or two
sites of unsaturation, usually contains from about 9 to 350, preferably from
about 20 to 200
carbon atoms. Particularly preferred hydrocarbyl polyamines are those which
are derived,
e.g., by reacting polyisobutenyl chloride and a polyalkylene polyamine, such
as an ethylene
amine, e.g., ethylene diamine, diethylene triamine, tetraethylene pentamine, 2-
aminoethylpiperazine, 1,3-propylene diamine, 1,2-propylenediamine, and the
like.
Another class of compounds useful for supplying basic nitrogen are the Mannich
base
compounds. These compounds are prepared from a phenol or C9-200 alkylphenol,
an aldehyde,
such as formaldehyde or formaldehyde precursor such as paraformaldehyde, and
an amine
compound. The amine may be a mono or poly amine and typical compounds are
prepared
from an alkylamine, such as methylamine or an ethylene amine, such as,
diethylene triamine,
or tetraethylene pentamine, and the like. The phenolic material may be
sulfurized and
preferably is dodecylphenol or a Cso-thoalkylphenol. Typical Mannich bases
which can be
used in this invention are disclosed in U.S. Pat. Nos. 4,157,309 and
3,649,229; 3,368,972;
and 3,539,663. The last referenced patent discloses Mannich bases prepared by
reacting an
alkylphenol having at least 50 carbon atoms, preferably 50 to 200 carbon atoms
with
formaldehyde and an alkylene polyamine HN(ANH).H where A is a saturated
divalent alkyl
hydrocarbon of from about 2 to 6 carbon atoms and n is from about 1-10 and
where the
condensation product of said alkylene polyamine may be further reacted with
urea or
thiourea. The utility of these Mannich bases as starting materials for
preparing lubricating oil
additives can often be significantly improved
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by treating the Mannich base using conventional techniques to introduce boron
into the
composition.
Another class of compounds useful for preparing the oxymolybdenum complexes
employed in this invention are the phosphoramides and phosphonamides such as
those
disclosed in U.S. Pat. Nos. 3,909,430 and 3,968,157. These compounds may be
prepared by
fonning a phosphorus compound having at least one P N bond. They can be
prepared, for
example, by reacting phosphorus oxychloride with a hydrocarbyl diol in the
presence of a
monoamine or by reacting phosphorus oxychloride with a difimctional secondary
amine and a
mono-functional amine. Thiophosphoramides can be prepared by reacting an
unsaturated
hydrocarbon compound containing from about 2 to 450 or more carbon atoms, such
as
polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-
hexadiene,
isobutylene, 4-methyl-l-pentene, and the like, with phosphorus pentasulfide
and a nitrogen-
containing compound as defined above, particularly an alkylamine,
alkyldiamine,
alkylpolyamine, or an alkyleneamine, such as ethylene diamine,
diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, and the like.
Another class of nitrogen-containing compounds useful in preparing the
molybdenum
complexes employed in this invention includes the so-called dispersant
viscosity index
improvers (VI improvers). These VI improvers are commonly prepared by
functionalizing a
hydrocarbon polymer, especially a polymer derived from ethylene and/or
propylene,
optionally containing additional units derived from one or more co-monomers
such as
alicyclic or aliphatic olefins or diolefins. The functionalization may be
carried out by a
variety of processes which introduce a reactive site or sites which usually
has at least one
oxygen atom on the polymer. The polymer is then contacted with a nitrogen-
containing
source to introduce nitrogen-containing functional groups on the polymer
backbone.
Commonly used nitrogen sources include any basic nitrogen compound especially
those
nitrogen-containing compounds and compositions described herein. Preferred
nitrogen
sources are alkylene amines, such as ethylene amines, alkyl amines, and
Mannich bases.
Preferred basic nitrogen compounds for use in this invention are succinimides,
carboxylic acid amides, and Mannich bases. More preferred are succinimides
having an
average molecular weight of 1000 or 1300 or 2300 and mixtures thereof. Such
succinimides
can be post treated with boron or ethylene carbonate as known in the art.
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The oxymolybdenum complexes of this invention can also be sulfurized.
Representative sulfur sources for preparing the oxymolybdenum/sulfur complexes
used in
this invention are sulfur, hydrogen sulfide, sulfur monochloride, sulfur
dichloride,
phosphorus pentasulfide, R"2-Sõ where R" is hydrocarbyl, preferably CI-40
alkyl, and x is at
least 2, inorganic sulfides and polysulfides such as (NH4)2S, where y is at
least 1,
thioacetarnide, thiourea, and mercaptans of the formula R"SH where R" is as
defined above.
Also useful as sulfurizing agents are traditional sulfur-containing
antioxidants such as wax
sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic and
esters and sulfurized
ester-olefins, and sulfurized alkylphenols and the metal salts thereof.
The sulfurized fatty acid esters are prepared by reacting sulfur, sulfur
monochloride,
and/or sulfur dichloride with an unsaturated fatty ester under elevated
temperatures. Typical
esters include C1-C20 alkyl esters of C8-C24 unsaturated fatty acids, such as
palmitoleic, oleic,
ricinoleic, petroselinic, vaccenic, linoleic, linolenic, oleostearic, licanic,
paranaric, tariric,
gadoleic, arachidonic, cetoleic, etc. Particularly good results have been
obtained with mixed
unsaturated fatty acid esters, such as are obtained from animal fats and
vegetable oils, such as
tall oil, linseed oil, olive oil, castor oil, peanut oil, rape oil, fish oil,
sperm oil, and so forth.
Exemplary fatty esters include lauryl tallate, methyl oleate, ethyl oleate,
lauryl oleate,
cetyl oleate, cetyl linoleate, lauryl ricinoleate, ()ley' linoleate, oleyl
stearate, and alkyl
glycerides.
Cross-sulfurized ester olefins, such as a sulfurized mixture of C10-C25
olefins with
fatty acid esters of C10-C25 fatty acids and C10-C25 alkyl or alkenyl
alcohols, wherein the fatty
acid and/or the alcohol is unsaturated may also be used.
Sulfurized olefins are prepared by the reaction of the C3-C6 olefin or a low-
molecular-
weight polyolefin derived therefrom with a sulfur-containing compound such as
sulfur, sulfur
monochloride, and/or sulfur dichloride.
Also useful are the aromatic and alkyl sulfides, such as dibenzyl sulfide,
dixylyl
sulfide, dicetyl sulfide, diparaffin wax sulfide and polysulfide, cracked wax-
olefin sulfides
and so forth. They can be prepared by treating the starting material, e.g.,
olefinically
unsaturated compounds, with sulfur, sulfur monochloride, and sulfur
dichloride. Particularly
preferred are the paraffin wax thiomers described in U.S. Pat. No. 2,346,156.
Sulfurized alkyl phenols and the metal salts thereof include compositions such
as
sulfurized dodecylphenol and the calcium salts thereof. The alkyl group
ordinarily contains
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from about 9 to 300 carbon atoms. The metal salt may be preferably, a Group I
or Group II
salt, especially sodium, calcium, magnesium, or barium.
Preferred sulfur sources are sulfur, hydrogen sulfide, phosphorus
pentasulfide, R'"2Sz
where R" is hydrocarbyl, preferably C i-C 10 alkyl, and z is at least 3,
mercaptans wherein R"
is C1-C10 alkyl, inorganic sulfides and polysulfides, thioacetamide, and
thiourea. Most
preferred sulfur sources are sulfur, hydrogen sulfide, phosphorus
pentasulfide, and inorganic
sulfides and polysulfides.
The polar promoter used in the preparation of the molybdenum complexes
employed
in this invention is one which facilitates the interaction between the acidic
molybdenum
compound and the basic nitrogen compound. A wide variety of such promoters are
well
known to those skilled in the art. Typical promoters are 1,3-propanediol, 1,4-
butane-diol,
diethylene glycol, butyl cellosolve, propylene glycol, 1,4-butyleneglycol,
methyl carbitol,
ethanolamine, diethanolamine, N-methyl-diethanol-amine, dimethyl formamide, N-
methyl
acetamide, dimethyl acetamide, methanol, ethylene glycol, dimethyl sulfoxide,
hexamethyl
phosphoramide, tetrahydrofuran and water. Preferred are water and ethylene
glycol.
Particularly preferred is water.
While ordinarily the polar promoter is separately added to the reaction
mixture, it may
also be present, particularly in the case of water, as a component of non-
anhydrous starting
materials or as waters of hydration in the acidic molybdenum compound, such as
(N114)6M07024.H20. Water may also be added as ammonium hydroxide.
A method for preparing the oxymolybdenum complexes used in this invention is
to
prepare a solution of the acidic molybdenum precursor and a polar promoter
with a basic
nitrogen-containing compound with or without diluent. The diluent is used, if
necessary, to
provide a suitable viscosity for easy stirring. Typical diluents are
lubricating oils and liquid
compounds containing only carbon and hydrogen. If desired, ammonium hydroxide
may also
be added to the reaction mixture to provide a solution of ammonium molybdate.
This reaction
is carried out at a variety of temperatures, typically at or below the melting
point of the
mixture to reflux temperature. It is ordinarily carried out at atmospheric
pressure although
higher or lower pressures may be used if desired. This reaction mixture may
optionally be
treated with a sulfur source as defined above at a suitable pressure and
temperature for the
sulfur source to react with the acidic molybdenum and basic nitrogen
compounds. In some
cases, removal of water from the reaction mixture may be desirable prior to
completion of
reaction with the sulfur source.
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In a preferred and improved method for preparing the oxymolybdenum complexes,
the reactor is agitated and heated at a temperature less than or equal to
about 120 C.,
preferably from about 70 C. to about 90 C. Molybdic oxide or other suitable
molybdenum
source is then charged to the reactor and the temperature is maintained at a
temperature less
than or equal to about 120 C., preferably at about 70 C. to about 90 C.,
until the
molybdenum is sufficiently reacted. Excess water is removed from the reaction
mixture.
Removal methods include but are not limited to vacuum distillation or nitrogen
stripping
while maintaining the temperature of the reactor at a temperature less than or
equal to about
120 C., preferably between about 70 C. to about 90 C. The temperature
during the
stripping process is held at a temperature less than or equal to about 120 C.
to maintain the
low color intensity of the molybdenum-containing composition. It is ordinarily
carried out at
atmospheric pressure although higher or lower pressures may be used. The
stripping step is
typically carried out for a period of about 0.5 to about 5 hours.
If desired, this product can be sulfurized by treating this reaction mixture
with a sulfur
source as defined above at a suitable pressure and temperature, not to exceed
about 120 C.
for the sulfur source to react with the acidic molybdenum and basic nitrogen
compounds. The
sulfurization step is typically carried out for a period of from about 0.5 to
about 5 hours and
preferably from about 0.5 to about 2 hours. In some cases, removal of the
polar promoter
(water) from the reaction mixture may be desirable prior to completion of
reaction with the
sulfur source.
The oxymolybdenum complex and oxymolybdenum/sulfur complex produced by such
method is lighter in color (when compared to complexes prepared at higher
temperatures)
while maintaining good fuel economy, excellent oxidation inhibition, and anti-
wear
performance qualities. Color in this instance can be more visibly or more
quantifiably using a
UV spectrophotometer such as a Perkin-Elmer Lambda 18 UV-Visible Double-Beam
Spectrophotometer. As used herein, this test recorded the visible spectra of
molybdenum
compositions at a constant concentration in an isooctane solvent. The spectra
represent the
absorbance intensity plotted versus the wavelength in nanometers. The spectra
extend from
the visible region into the near infrared region of the electromagnetic
radiation (350
nanometers to 900 nanometers). In this test, the highly colored samples showed
increasingly
higher absorbance at increasingly higher wavelengths at a constant molybdenum
concentration. The preparation of the sample for color measurement comprises
diluting the
molybdenum-containing composition with isooctane to achieve a constant
molybdenum
concentration of 0.00025 g molybdenum per gram of the molybdenum-containing
composition/isooctane mixture. Prior to sample measurement the
spectrophotometer is
referenced by scanning air versus air. The UV visible spectrum from 350
nanometers to 900
milometers is obtained using a one centimeter path-length quartz cell versus
an air reference.
The spectra are offset corrected by setting the 867 nanometer absorbance to
zero. Then the
absorbance of the sample is determined at 350 nanometers wavelength.
Characteristics of these new oxymolybdenum/sulfur complexes are disclosed in
U.S.
patent application Ser. No. 10/159,446 filed May 31, 2002, entitled REDUCED
COLOR
MOLYBDENUM-CONTAINING COMPITION AND A METHOD OF MAKING SAME.
In the reaction mixture, the ratio of molybdenum compound to basic nitrogen
compound is not critical; however, as the amount of molybdenum with respect to
basic
nitrogen increases, the filtration of the product becomes more difficult.
Since the
molybdenum component probably oligomerizes, it is advantageous to add as much
molybdenum as can easily be maintained in the composition. Usually, the
reaction mixture
will have charged to it from about 0.01 to 2.00 atoms of molybdenum per basic
nitrogen
atom. Preferably from about 0.3 to 1.0, and most preferably from about 0.4 to
0.7, atoms of
molybdenum per atom of basic nitrogen is added to the reaction mixture.
When optionally sulfurized, the sulfurized oxymolybdenum containing
compositions
may be generally characterized as a sulfur/molybdenum complex of a basic
nitrogen
dispersant compound preferably with a sulfur to molybdenum weight ratio of
from about
(0.01 to 1.0) to 1 and more preferably from about (0.05 to 0.5) to 1 and a
nitrogen to
molybdenum weight ratio of from about (1 to 10) to 1 and more preferably from
about (2 to
5) to 1. For extremely low sulfur incorporation the sulfur to molybdenum
weight ratio can be
from about (0.01 to 0.08) to 1.
The oxymolybdenum-containing complex comprises from about 0.02 to 10 wt % and
preferably from about 0.1 to 2.0 wt %, based on the total weight of the
lubricating oil
composition.
In one embodiment, the molybdenum succinimide present in the lubrication oil
is 0.1
- 5 wt%. In another embodiment, the molybdenum succinimide present in the
lubrication oil
is 0.1 ¨2 wt%. In another embodiment, the molybdenum succinimide present in
the
lubrication oil is 0.1 ¨ 1 wt%. In another embodiment, the molybdenum
succinimide present
in the lubrication oil is 0.5 ¨2 wt%. In another embodiment, the molybdenum
succinimide
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present in the lubrication oil is 0.1 ¨2 wt%. In another embodiment, the
molybdenum
succinimide present in the lubrication oil is 0.5 ¨ 1 wt%.
Salicylate
In one embodiment, the lubricating oil composition disclosed herein comprises
a
salicylate compound [component (c)]. In one embodiment, the salicylate
compound is a
calcium alkylsalicylate detergent. The calcium alkylsalicylate detergent
necessarily contained
in the lubricating oil composition of the invention contains an organic acid
calcium salt to
give the lubricating oil composition containing the organic acid calcium salt
in an amount of
0.1 to 10 wt. %, preferably 0.2 to 7 wt. %, more preferably 1.0 to 6 wt. %,
and comprises an
unsulfurized calcium alkylsalicylate detergent having a TBN of 100-450 on
active basis. In
one embodiment, the calcium alkylsalicylate detergent has a TBN 100-400 on
active basis.
In one embodiment, the calcium alkylsalicyalte detergent has a TBN 100-350 on
active basis.
In one embodiment, the calcium alkylsalicylate detergent has a TBN 150-400 on
active basis.
In one embodiment, the calcium alkylsalicylate detergent has a TBN 150-350 on
active basis.
In one embodiment, the calcium alkylsalicylate detergent has a TBN 200-400 on
active basis.
In one embodiment, the calcium alkylsalicylate detergent has a TBN 200-350 on
active basis.
In one embodiment, the calcium alkylsalicylate detergent has a TBN 250-400 on
active basis. ,
In one embodiment, the calcium alkylsalicylate detergent has a TBN 250-350 on
active basis.
The calcium alkylsalicylate detergent may have an alkyl group having 10-40
carbon
atoms, and the alkyl group may be derived from normal-alpha-olefins (NAO) or
isomerized
normal-alpha-olefins (NAO). In one embodiment, the calcium alkylsalicylate
detergent may
be derived from a C14-18 NAO. In another embodiment, the calcium
alkylsalicylate
detergent is derived from a C20-28 NAO. In another embodiment, the calcium
alkylsalicylate detergent is derived from a C20-24 isomerized NAO.
The unsulfurized calcium alkylsalicylate detergent preferably is a calcium
alkylsalicylate prepared from an alkyl phenol (which is prepared from a-olefin
having the
desired carbon atom number and phenol) by way of Kolbe-Schmitt reaction.
Generally, an
overbased calcium salicylate which is obtained by way of the carbonation
process using
slaked lime and carbon dioxide gas for overbasing is used as the calcium
salicylate detergent.
12
Otherwise, the calcium alkylsalicylate can be directly produced by carbonizing
an
alkylphenol calcium salt obtained by direct neutralization.
In addition to the heretofore described metal-containing detergents, a small
amount of
sulfonates such as alkali metal salts or alkaline earth metal salts of
petroleum sulfonic acid,
alkylbenzenesulfonic acid or alkyltoluenesulfonic acid can be employed in
combination with
the alkylsalicylate detergent.
A sulfurized phenate which has been used for the conventionalengine oils is an
alkali
metal salt or an alkaline earth metal salt of a sulfurized alkylphenol.
Typically, calcium salt
and magnesium salt are employed. The sulfurized phenate shows high thermal
stability but
generally has a high sulfur content such as approx. 3 wt. % or more, which is
brought about
by the sulfurization reaction. In the invention, a small amount of the
sulfurized phenate may
be employed in combination with the alkylsalicylate detergent.
In one embodiment, the calcium alkylsalicylate is 0.1 ¨ lOwt%. In another
embodiment, the calcium alkylsalicylate is 0.5 ¨ lOwt%. In another embodiment,
the calcium
alkylsalicylate is 1 ¨ lOwt%. In another embodiment, the calcium
alkylsalicylate is 2 ¨10wt%. In another embodiment, the calcium
alkylsalicylate is 2¨ 6wt%.
The Oil of Lubricating Viscosity
The lubricating oil compositions disclosed herein generally comprise at least
one oil
of lubricating viscosity. Any base oil known to a skilled artisan can be used
as the oil of
lubricating viscosity disclosed herein. Some base oils suitable for preparing
the lubricating oil
compositions have been described in Mortier et al., "Chemistry and Technology
of
Lubricants," 2nd Edition, London, Springer, Chapters 1 and 2 (1996); and A.
Sequeria, Jr.,
"Lubricant Base Oil and Wax Processing," New York, Marcel Decker, Chapter 6,
(1994);
and D. V. Brock, Lubrication Engineering, Vol. 43, pages 184-5, (1987).
Generally, the
amount of the base oil in the lubricating oil composition may be from about 70
to about 99.5
wt. %, based on the total weight of the lubricating oil composition. In some
embodiments, the
amount of the base oil in the lubricating oil composition is from about 75 to
about 99 wt. %,
from about 80 to about 98.5
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Date Recue/Date Received 2023-01-23
wt. %, or from about 80 to about 98 wt. %, based on the total weight of the
lubricating oil composition.
In certain embodiments, the base oil is or comprises any natural or synthetic
lubricating base oil fraction. Some non-limiting examples of synthetic oils
include oils, such
as polyalphaolefins or PA0s, prepared from the polymerization of at least one
alpha-olefin,
such as ethylene, or from hydrocarbon synthesis procedures using carbon
monoxide and
hydrogen gases, such as the Fisher-Tropsch process. In certain embodiments,
the base oil
comprises less than about 10 wt. % of one or more heavy fractions, based on
the total weight
of the base oil. A heavy fraction refers to a lube oil fraction having a
viscosity of at least
about 20 cSt at 100 C. In certain embodiments, the heavy fraction has a
viscosity of at least
about 25 cSt or at least about 30 cSt at 100 C. In further embodiments, the
amount of the one
or more heavy fractions in the base oil is less than about 10 wt. %, less than
about 5 wt. %,
less than about 2.5 wt. %, less than about 1 wt. %, or less than about 0.1 wt.
%, based on the
total weight of the base oil. In still further embodiments, the base oil
comprises no heavy
fraction.
In certain embodiments, the lubricating oil compositions comprise a major
amount of
a base oil of lubricating viscosity. In some embodiments, the base oil has a
kinematic
viscosity at 100 C. from about 2.5 centistokes (cSt) to about 20 cSt, from
about 4 centistokes
(cSt) to about 20 cSt, or from about 5 cSt to about 16 cSt. The kinematic
viscosity of the base
oils or the lubricating oil compositions disclosed herein can be measured
according to ASTM
D445.
In other embodiments, the base oil is or comprises a base stock or blend of
base
stocks. In further embodiments, the base stocks are manufactured using a
variety of different
processes including, but not limited to, distillation, solvent refining,
hydrogen processing,
oligomerization, esterification, and rerefining. In some embodiments, the base
stocks
comprise a rerefined stock. In further embodiments, the rerefined stock shall
be substantially
free from materials introduced through manufacturing, contamination, or
previous use.
In some embodiments, the base oil comprises one or more of the base stocks in
one or
more of Groups I-V as specified in the American Petroleum Institute (API)
Publication 1509,
Fourteen Edition, December 1996 (i.e., API Base Oil Interchangeability
Guidelines for
Passenger Car Motor Oils and Diesel Engine Oils). The API guideline defines a
base stock as
a lubricant component that may be manufactured using a variety of different
processes.
Groups I, II and III base stocks are mineral oils, each
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with specific ranges of the amount of saturates, sulfur content and viscosity
index. Group IV
base stocks are polyalphaolefins (PAO). Group V base stocks include all other
base stocks
not included in Group I, II, III, or IV.
In some embodiments, the base oil comprises one or more of the base stocks in
Group
I, II, III, IV, V or a combination thereof. In other embodiments, the base oil
comprises one or
more of the base stocks in Group II, III, IV or a combination thereof. In
further embodiments,
the base oil comprises one or more of the base stocks in Group II, III, IV or
a combination
thereof wherein the base oil has a kinematic viscosity from about 2.5
centistokes (cSt) to
about 20 cSt, from about 4 cSt to about 20 cSt, or from about 5 cSt to about
16 cSt at 100 C.
The base oil may be selected from the group consisting of natural oils of
lubricating
viscosity, synthetic oils of lubricating viscosity and mixtures thereof. In
some embodiments,
the base oil includes base stocks obtained by isomerization of synthetic wax
and slack wax,
as well as hydrocrackate base stocks produced by hydrocracking (rather than
solvent
extracting) the aromatic and polar components of the crude. In other
embodiments, the base
oil of lubricating viscosity includes natural oils, such as animal oils,
vegetable oils, mineral
oils (e.g., liquid petroleum oils and solvent treated or acid-treated mineral
oils of the
paraffinic, naphthenic or mixed paraffinic-naphthenic types), oils derived
from coal or shale,
and combinations thereof. Some non-limiting examples of animal oils include
bone oil,
lanolin, fish oil, lard oil, dolphin oil, seal oil, shark oil, tallow oil, and
whale oil. Some non-
limiting examples of vegetable oils include castor oil, olive oil, peanut oil,
rapeseed oil, corn
oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil,
hemp oil, linseed oil,
tung oil, oiticica oil, jojoba oil, and meadow foam oil. Such oils may be
partially or fully
hydrogenated.
In some embodiments, the synthetic oils of lubricating viscosity include
hydrocarbon
.. oils and halo-substituted hydrocarbon oils such as polymerized and inter-
polymerized olefins,
alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl
sulfides, as well as
their derivatives, analogues and homologues thereof, and the like. In other
embodiments, the
synthetic oils include alkylene oxide polymers, interpolymers, copolymers and
derivatives
thereof wherein the terminal hydroxyl groups can be modified by
esterification, etherification,
and the like. In further embodiments, the synthetic oils include the esters of
dicarboxylic
acids with a variety of alcohols. In certain embodiments, the synthetic oils
include esters
made from C5 to C12 monocarboxylic acids and polyols and polyol ethers. In
further
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embodiments, the synthetic oils include tri-alkyl phosphate ester oils, such
as tri-n-butyl
phosphate and tri-iso-butyl phosphate.
In some embodiments, the synthetic oils of lubricating viscosity include
silicon-based
oils (such as the polyakyl-, polyaryl-, polyalkoxy-, polyaryloxy-siloxane oils
and silicate oils).
In other embodiments, the synthetic oils include liquid esters of phosphorus-
containing acids,
polymeric tetrahydrofurans, polyalphaolefins, and the like.
Base oil derived from the hydroisomerization of wax may also be used, either
alone or
in combination with the aforesaid natural and/or synthetic base oil. Such wax
isomerate oil is
produced by the hydroisomerization of natural or synthetic waxes or mixtures
thereof over a
hydroisomerization catalyst.
In further embodiments, the base oil comprises a poly-alpha-olefin (PAO). In
general,
the poly-alpha-olefins may be derived from an alpha-olefin having from about 2
to about 30,
from about 4 to about 20, or from about 6 to about 16 carbon atoms. Non-
limiting examples
of suitable poly-alpha-olefins include those derived from octene, decene,
mixtures thereof,
and the like. These poly-alpha-olefins may have a viscosity from about 2 to
about 15, from
about 3 to about 12, or from about 4 to about 8 centistokes at 100 C. In some
instances, the
poly-alpha-olefins may be used together with other base oils such as mineral
oils.
In further embodiments, the base oil comprises a polyalkylene glycol or a
polyalkylene glycol derivative, where the terminal hydroxyl groups of the
polyalkylene
glycol may be modified by esterification, etherification, acetylation and the
like. Non-limiting
examples of suitable polyalkylene glycols include polyethylene glycol,
polypropylene glycol,
polyisopropylene glycol, and combinations thereof. Non-limiting examples of
suitable
polyalkylene glycol derivatives include ethers of polyalkylene glycols (e.g.,
methyl ether of
polyisopropylene glycol, diphenyl ether, of polyethylene glycol, diethyl ether
of
polypropylene glycol, etc.), mono- and polycarboxylic esters of polyalkylene
glycols, and
combinations thereof. In some instances, the polyalkylene glycol or
polyalkylene glycol
derivative may be used together with other base oils such as poly-alpha-
olefins and mineral
oils.
In further embodiments, the base oil comprises any of the esters of
dicarboxylic acids
(e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic
acids, maleic acid,
azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, malonic
acid, alkyl malonic acids, alkenyl malonic acids, and the like) with a variety
of alcohols (e.g.,
butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene
glycol,
16
diethylene glycol monoether, propylene glycol, and the like). Non-limiting
examples of these
esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl
fumarate, dioctyl
sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl
sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the like.
In further embodiments, the base oil comprises a hydrocarbon prepared by the
Fischer-Tropsch process. The Fischer-Tropsch process prepares hydrocarbons
from gases
containing hydrogen and carbon monoxide using a Fischer-Tropsch catalyst.
These
hydrocarbons may require further processing in order to be useful as base
oils. For example,
the hydrocarbons may be dewaxed, hydroisomerized, and/or hydrocracked using
processes
known to a person of ordinary skill in the art.
In further embodiments, the base oil comprises an unrefined oil, a refined
oil, a
rerefined oil, or a mixture thereof. Unrefined oils are those obtained
directly from a natural or
synthetic source without further purification treatment. Non-limiting examples
of unrefined
oils include shale oils obtained directly from retorting operations, petroleum
oils obtained
directly from primary distillation, and ester oils obtained directly from an
esterification
process and used without further treatment. Refined oils are similar to the
unrefined oils
except the founer have been further treated by one or more purification
processes to improve
one or more properties. Many such purification processes are known to those
skilled in the art
such as solvent extraction, secondary distillation, acid or base extraction,
filtration,
percolation, and the like. Rerefined oils are obtained by applying to refined
oils processes
similar to those used to obtain refined oils. Such rerefined oils are also
known as reclaimed or
reprocessed oils and often are additionally treated by processes directed to
removal of spent
additives and oil breakdown products.
Other additives
Optionally, the lubricating oil composition may further comprise at least an
additive
or a modifier (hereinafter designated as "additive") that can impart or
improve any desirable
property of the lubricating oil composition. 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). In some
embodiments, the
17
Date Recue/Date Received 2023-01-23
additive can be selected from the group consisting of antioxidants, antiwear
agents,
detergents, rust inhibitors, demulsifiers, friction modifiers, multi-
functional additives,
viscosity index improvers, pour point depressants, foam inhibitors, metal
deactivators,
dispersants, corrosion inhibitors, lubricity improvers, thellnal stability
improvers, anti-haze
additives, icing inhibitors, dyes, markers, static dissipaters, biocides and
combinations
thereof. In general, the concentration of each of the additives in the
lubricating oil
composition, when used, may range from about 0.001 wt. % to about 10 wt. %,
from about
0.01 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 2.5 wt. %, based
on the total
weight of the lubricating oil composition. Further, the total amount of the
additives in the
lubricating oil composition may range from about 0.001 wt. % to about 20 wt.
%, from about
0.01 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 5 wt. %, based
on the total
weight of the lubricating oil composition.
Dispersants
In one embodiment, the lubricating oil composition disclosed herein comprises
an
ashless dispersant which can be an alkenyl succinimide, an alkyl succinimide,
or a derivative
thereof, in which the alkenyl group and alkyl group can be derived from
polyolefin. The
ashless dispersant is incorporated into the lubricating oil composition in an
amount of 0.01 to
0.3 wt. % in terms of the nitrogen content. The percent is given per the
amount of the
lubricating oil composition. A representative succinimide can be obtained by
the reaction
between succinic anhydride having a substituent group of a high molecular
weight alkenyl or
alkyl with a polyalkylene polyamine having a mean nitrogen atom number of 4 to
10,
preferably 5 to 7. The high molecular weight alkenyl or alkyl is preferably
derived from
polybutene having a number average molecular weight of approximately 900 to
3,000, 900 to
2300, 900 to 1100, or 1100 to 2300.
In the process for producing a polybutenyl succinic anhydride by the reaction
of
polybutene and maleic anhydride, a chlorination procedure is generally
employed. However,
the chlorination procedure gives remaining chlorine in the product, and hence
the finally
produced succinimide inevitably contains a large amount (such as approximately
2,000 to
3,000 ppm) of the emigrated chlorine. In contrast, the thermal reaction using
no chlorine
gives a final product having an extremely small chlorine content (such as 0 to
30 ppm).
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Therefore, the succinimide derived from a polyisobutenyl succinimide obtained
by the
thermal reaction can be favorably employed for formulating a lubricating oil
composition
having low chlorine content such as 0 to 30 wt. ppm. The succinimide can be
post-treated
with boric acid, a boron-containing compound, alcohol, aldehyde, ketone,
alkylphenol, cyclic
carbonate or an organic acid. Preferred is a borated alkenyl- (or alkyl-)
succinimide which is
obtained by post-treatment with boric acid or a boron-containing compound, and
which
shows high thermal stability and high oxidation stability.
In one embodiment, the lubricating oil composition comprises a succinimide. In
another embodiment, the lubricating oil composition comprises a bissucinimide.
In another
embodiment, the lubricating oil composition comprises a borated
bissuccinimide. In another
embodiment, the lubricating oil composition comprises a mixture of borated and
non-borated
bissucinimide.
Antioxidants
The lubricating oil composition of the present invention can contain one or
more antioxidants that can reduce or prevent the oxidation of the base oil.
Any antioxidant
known by a person of ordinary skill in the art may be used in the lubricating
oil composition.
Non-limiting examples of suitable antioxidants include amine-based
antioxidants (e.g., alkyl
diphenylamines such as bis-nonylated diphenylamine, bis-octylated
diphenylamine, and
octylated/butylated diphenylamine, phenyl-a-naphthylamine, alkyl or arylalkyl
substituted
phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl-
diaminodiphenylamine and the like), phenolic antioxidants (e.g., 2-tert-
butylphenol, 4-
methy1-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-
p-cresol, 2,6-di-
tert-butylphenol, 4,4'-methylenebis-(2,6-di-tert-butylphenol), 4,4'-thiobis(6-
di-tert-butyl-o-
cresol) and the like), sulfur-based antioxidants (e.g., dilaury1-3,3'-
thiodipropionate, sulfurized
phenolic antioxidants and the like), phosphorous-based antioxidants (e.g.,
phosphites and the
like), zinc dithiophosphate, oil-soluble copper compounds and combinations
thereof. The
amount of the antioxidant 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.
Wear Inhibitors
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
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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, 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.
Foam Inhibitors
The lubricating oil composition of the present invention can contain one or
more foam inhibitors or anti-foam inhibitors that can break up foams in oils.
Any foam
inhibitor or anti-foam known by a person of ordinary skill in the art may be
used in the
lubricating oil composition. Non-limiting examples of suitable foam inhibitors
or anti-foam
inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones,
alkoxylated
aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl
ethers, alkyl
acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines and
combinations thereof
In some embodiments, the foam inhibitors or anti-foam inhibitors comprises
glycerol
monostearate, polyglycol palmitate, a trialkyl monothiophosphate, an ester of
sulfonated
ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or
glycerol dioleate.
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The amount of the foam inhibitors or anti-foam inhibitors may vary from about
0.001 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.
Pour Point Depressants
The lubricating oil composition of the present invention can contain one or
more pour point depressants that can lower the pour point of the lubricating
oil composition.
Any pour point depressant known by a person of ordinary skill in the art may
be used in the
lubricating oil composition. Non-limiting examples of suitable pour point
depressants
include polymethacrylates, alkyl acrylate polymers, alkyl methacrylate
polymers, di(tetra-
paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates
of a chlorinated
paraffin with naphthalene and combinations thereof. In some embodiments, the
pour point
depressant comprises an ethylene-vinyl acetate copolymer, a condensate of
chlorinated
paraffin and phenol, polyalkyl styrene or the like. The amount of the pour
point depressant
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.
Demulsifiers
In one embodiment, the lubricating oil composition of the present invention
does not contain one or more demulsifiers. In another embodiment, the
lubricating oil
composition of the present invention can contain one or more demulsifiers that
can promote
oil-water separation in lubricating oil compositions that are exposed to water
or steam. Any
demulsifier known by a person of ordinary skill in the art may be used in the
lubricating oil
composition. Non-limiting examples of suitable demulsifiers include anionic
surfactants (e.g.,
alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like), nonionic
alkoxylated
alkyl phenol resins, polymers of alkylene oxides (e.g., polyethylene oxide,
polypropylene
oxide, block copolymers of ethylene oxide, propylene oxide and the like),
esters of oil soluble
acids, polyoxyethylene sorbitan ester and combinations thereof. The amount of
the
demulsifier 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.
Corrosion Inhibitors
The lubricating oil composition of the present invention can contain one or
more corrosion inhibitors that can reduce corrosion. Any corrosion inhibitor
known by a
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=
person of ordinary skill in the art may be used in the lubricating oil
composition. Non-
limiting examples of suitable corrosion inhibitor include half esters or
amides of
dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines,
sarcosines and
combinations thereof. The amount of the corrosion inhibitor 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.
Extreme Pressure Agents
The lubricating oil composition of the present invention can contain one or
more extreme pressure (EP) agents that can prevent sliding metal surfaces from
seizing under
conditions of extreme pressure. Any extreme pressure agent known by a person
of ordinary
skill in the art may be used in the lubricating oil composition. Generally,
the extreme
pressure agent is a compound that can combine chemically with a metal to form
a surface
film that prevents the welding of asperities in opposing metal surfaces under
high loads.
Non-limiting examples of suitable extreme pressure agents include sulfurized
animal or
vegetable fats or oils, sulfurized animal or vegetable fatty acid esters,
fully or partially
esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized
olefins,
dihydrocarbyl polysulfides, sulfurized Diets-Alder adducts, sulfurized
dicyclopentadiene,
sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated
olefins, co-
sulfurized blends of fatty acid, fatty acid ester and alpha-olefin,
functionally-substituted
dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds,
sulfur-
containing acetal derivatives, co-sulfurized blends of terpene and acyclic
olefins, and
polysulfide olefin products, amine salts of phosphoric acid esters or
thiophosphoric acid
esters and combinations thereof. The amount of the extreme pressure 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.
Rust Inhibitors
The lubricating oil composition of the present invention can contain one or
more rust inhibitors that can inhibit the corrosion of ferrous metal surfaces.
Any rust
inhibitor known by a person of ordinary skill in the art may be used in the
lubricating oil
composition. Non-limiting examples of suitable rust inhibitors include
nonionic
polyoxyalkylene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene
higher alcohol
ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether,
polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether,
polyoxyethylene sorbitol
22
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monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol
monooleate;
stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty
acid amine salts;
metal salts of heavy sulfonic acid; partial carboxylic acid ester of
polyhydric alcohol;
phosphoric esters; (short-chain) alkenyl succinic acids; partial esters
thereof and nitrogen-
containing derivatives thereof; synthetic alkarylsulfonates, e.g., metal
dinonylnaphthalene
sulfonates; and the like and mixtures thereof The amount of the rust inhibitor
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 present invention can contain one or
= 10 more metal deactivators. Non-limiting examples of suitable
metal deactivators include
disalicylidene propylenediamine, triazole derivatives, thiadiazole
derivatives, and
mercaptobenzimidazoles.
VII
. 15
The lubricating oil composition of the present . invention can contain
one or
more viscosity index improvers. Non-limiting examples of suitable viscosity
index
improvers include, but are not limited to, olefin copolymers, such as ethylene-
propylene
copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers,
polybutene,
polyisobutylene, polymethacrylates, vinylpyrrolidone and methacrylate
copolymers and
20
dispersant type viscosity index improvers. These viscosity modifiers can
optionally be
grafted with grafting materials such as, for example, maleic anhydride, and
the grafted
material can be reacted with, for example, amines, amides, nitrogen-containing
heterocyclic
compounds or alcohol, to form multifunctional viscosity modifiers (dispersant-
viscosity
modifiers). Other examples of viscosity modifiers include star polymers (e.g.,
a star polymer
25
comprising isoprene/styrene/isoprene triblock). Yet other examples of
viscosity modifiers
include poly alkyl(meth)acrylates of low Brookfield viscosity and high shear
stability,
functionalized poly alkyl(meth)acrylates with dispersant properties of high
Brookfield
viscosity and high shear stability, polyisobutylene having a weight average
molecular weight
ranging from 700 to 2,500 Daltons and mixtures thereof The amount of the
viscosity index
30
improvers may vary from about 0.01 wt. % to about 25 wt. %, from about 0.05
wt. % to
about 20 wt. %, or from about 0.3 wt. % to about 15 wt. %, based on the total
weight of the
lubricating oil composition.
23
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Metal Deactivators
In some embodiments, the lubricating oil composition comprises at least a
metal deactivator.
Some non-limiting examples of suitable metal deactivators include
disalicylidene
propylenediamine, triazole derivatives, thiadiazole derivatives, and
mercaptobenzimidazoles.
The additives disclosed herein may be in the form of an additive concentrate
having
more than one additive. The additive concentrate may comprise a suitable
diluent, such as a
hydrocarbon oil of suitable viscosity. Such diluent can be selected from the
group consisting
of natural oils (e.g., mineral oils), synthetic oils and combinations thereof.
Some non-limiting
examples of the mineral oils include paraffin-based oils, naphthenic-based
oils, asphaltic-
based oils and combinations thereof Some non-limiting examples of the
synthetic base oils
include polyolefin oils (especially hydrogenated alpha-olefin oligomers),
alkylated aromatic,
polyalkylene oxides, aromatic ethers, and carboxylate esters (especially
diester oils) and
combinations thereof. In some embodiments, the diluent is a light hydrocarbon
oil, both
natural or synthetic. Generally, the diluent oil can have a viscosity from
about 13 centistokes
to about 35 centistokes at 40 C.
Generally, it is desired that the diluent readily solubilizes the lubricating
oil soluble
additive of the invention and provides an oil additive concentrate that is
readily soluble in the
lubricant base oil stocks or fuels. In addition, it is desired that the
diluent not introduce any
undesirable characteristics, including, for example, high volatility, high
viscosity, and
impurities such as heteroatoms, to the lubricant base oil stocks and thus,
ultimately to the
finished lubricant or fuel.
The present invention further provides an oil soluble additive concentrate
composition
comprising an inert diluent and from 2.0 % to 90% by weight, preferably 10% to
50% by
weight based on the total concentrate, of an oil soluble additive composition
according to the
present invention.
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
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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.
EXAMPLES
The following examples are intended for illustrative purposes only and do not
limit in
any way the scope of the present invention.
The lubricating oil compositions for evaluating their performances were
prepared from the
below-mentioned additives. All the lubricating oil compositions were prepared
to have a
viscosity grade (SAE viscosity grade) of 10W-30.
Salicylate A: Ca salicylate having TBN of 280 on an active basis.
Salicylate B: Ca salicylate having TBN of 300 on an active basis.
Sulfonate: An oil concentrate of Ca sulfonate.
Phenate: An oil concentrate of Ca phenate.
Additionally, each of the examples contain 7.1 wt. % primary ZnDTP, 7.1 wt. %
secondary
ZnDTP, 0.5 wt. % amine antioxidant, and 50 wt. ppm of foam inhibitor.
The lubricating oil compositions were evaluated according to the High
Frequency
Reciprocating Rig (HFRR) Evaluation and JASCO T903:2011 as described below.
Friction Performance
[High Frequency Reciprocating Rig (HE RR) Evaluation]
The friction coefficient was determined in terms of a metal-metal friction
coefficient.
The HFRR test rig is an industry recognized test for determining lubricant
performance using
a tribometer. The PCS instrument uses an electromagnetic vibrator to oscillate
a specimen
(the ball) over a small amplitude while pressing it against a fixed specimen
(a flat disk). The
amplitude and frequency of the oscillation and the load are variable. The
frictional force
between the ball and flat disk and the electrical contact resistance (ECR) are
measured. The
flat, stationary specimen is held in a bath to which the lubricating oil is
added, and can be
heated. For this test, the tribometer was set up to run at >50 Hz for >60
minutes, using 6 mm
.. ball on flat specimens of 52100 steel. The load was 1.0 kg and the
temperature was 100 C. In
this test, a smaller coefficient of friction corresponds to a more effective
lubricating friction
modifier additive. The HFRR friction performance data are presented in Table
2.
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JASO T903:2011 Procedure:
The lubricant compositions were subjected to a clutch system friction test as
described in
JASO 1903:2011. The test evaluates three main clutch parameters: static
friction, relating to
clutch-slip; dynamic friction, relating to clutch feel/uptake; and stop time,
relating to
synchronization time. A clutch performance index is then assigned to the
lubricating
composition, which can be classified as JASO MA, JASO MA1, or JASO MA2 (high
friction,
suitable for wet clutch applications), or JASO MB (low friction, more suitable
for dry clutch
applications).
For a lubricating composition to claim JASO MB performance, all three indices
must fall
within the values specified for the MB category, or two indices must fall
within the values
specified for the MB category and one within the values specified for the MA
category, or
one index must fall within the values specified for the MB category and two
within the values
specified for the MA category, as set forth below in Table 1.
Table 1
Parameter Index JASO MA JASO MA2 JASO MA1 JASO MB
Dynamic DFI 1.30<DFI<2.50 1.85<DFI<2.50 1.30<DFI<1.85
0.5<DFI<1.30
Friction
Index
Static SFI 1.25<SFI<2.50 1.70<SFI<2.50 1.25<SFI<1.70
0.5<SFI<1.25
Friction
Index
Stop Time STI 1.45<STI<2.50 1.85<STI<2.50 1.45<STI<1.85
0.5<STI<1.45
Index=
The JASO T903:2011 clutch performance data are presented in Table 2.
26
. .
=
Table 2
Examples> 1 2 3 4 5 6 7 8
Comp A B C D 0
t4
0
=i
=i
CZ
Dispersant A 1.25 1.25 1.25 1.25 1.25 - 1.25
1.25 - - _
1.25
,..
ts)
00
1..)
Dispersant B 1.25 1.25 1.25 1.25 1.25 - 1.25
1.25 2.5 2.5 2.5 1.25
Salicylate A 2.88 ' - 2.88 2.88 - - 2.88
5.76 - - - -
Salicylate B - 2.88 - - 3.52 3.52 - -
- -
Molybdenum 0.8 0.8 0.5 1.0 0.8 0.8 0.8 0.8 -
- . 0.8 0.8
Succinimide
0
Phenate 0.42 0.42 0.42 0.42 - 2.3 -
0.21 2.3 - 2.3 2.3 .
ow
N) Sulfonate - 0.25 -
- ' 1.37 -
.,1
.
HFRR Friction 0.062 0.062 0.071 0.062 0.059 0.098
0.079 0.107 0.151 0.136 0.113 0.09 ,9
1
L.,
Coefficient
,
6-`
JASO MB MB MB MB MB MB MB MB MA/ MA MA/ MA/
Classification
MA2 MA2 MA2
DFI 1.71 1.63 1.97 . 1.83 1.79 1.47 1.87
1.77 2.06 2.00 2.10 2.00
SFI 0.50 0.50 1.16 1.16 0.53 0.80 0.91
0.69 2.27 1.45 2.38 2.27
ti
STI 1.57 1.48 1.87 1.81 1.71 1.41 1.77
1.65 2.13 2.03 2.11 2.08 n
-.t
t.)
-1
,
c,
.6.
IQ
--I
0
4=.
=
. .
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Examples 1-8 all qualified as MB oils whereas comparative examples A to D
failed to
qualify as MB oils. Examples1-8 has lower friction coefficients (<0.1), which
means the
compositions have improved friction benefits over comparative examples A to D.
The MB
oils all meet OEM requirements for friction and fuel economy performance in
four cycle
gasoline engines of motorcycles equipped with a dry clutch.
It will be understood that various modifications may be made to the
embodiments
disclosed herein. Therefore, the above description should not be construed as
limiting, but
merely as exemplifications of preferred embodiments. For example, the
functions described
above and implemented as the best mode for operating the present invention are
for
illustration purposes only. Other arrangements and methods may be implemented
by those
skilled in the art without departing from the scope and spirit of this
invention. Moreover,
those skilled in the art will envision other modifications within the scope
and spirit of the
claims appended hereto.
28
