Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
DIESEL ENGINE LUBRICATING COMPOSITIONS AND METHODS OF USE
THEREOF
FIELD
100011 The instant disclosure provides for diesel engine
lubricating compositions
and methods of lubricating a diesel engine by supplying the engine with a
lubricating
composition as disclosed herein. The lubricating compositions disclosed herein
may
be used in diesels engines including, in particular, heavy-duty diesel engines
to
improve one or more of fuel economy and wear protection.
BACKGROUND
[0002] Lubricating oil compositions are used for the smooth
operation of internal
combustion engines. The engine oils for internal combustion engines in
particular
serve to (i) lubricate various sliding interfaces between the piston ring and
cylinder
liner, in bearings of the crank shaft and the connecting rod, and in the valve
driving
mechanism including cams and valve lifters, (ii) cool the engine, (iii) clean
and
disperse the combustion products and (iv) prevent corrosion and consequent
rust
formation. The stringent requirements for high performance engines in recent
years
has meant greater demand from lubricants used in such engines.
[0003] There is increasing interest in improving the fuel
efficiency of internal
combustion engines Vehicle manufacturers have improved fuel economy through
engine design, improvements which take advantage of advances in lubricating
oils
which provide better oxidative stability, wear protection, and reduced
friction.
Operators of heavy-duty diesel vehicles have been reluctant to adopt low
viscosity
grade engine oils to improve fuel economy; durability, i.e., the ability to
maintain
vehicles on the road for extended periods of time and mileage, has been and
remains
the primary concern. Thus, the most widely used viscosity grades for on-
highway
heavy duty diesel vehicles has been SAE 15W-40, 10W-30, and 5W-30. In recent
years, there is a growing push to improve the fuel efficiency of heavy-duty
diesel
vehicles. Consequently, there is a need to improve the fuel economy of diesel
engines
without compromising the durability of the engines or otherwise negatively
impacting the lubricant performance, including deposit and soot control and
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oxidation and corrosion resistance. This is particularly relevant for
viscosity grades
lighter than that of SAE 5W-30, especially those of OW-20, OW-16, and 0W12.
100041 There is interest, therefore, in developing a lubricating
composition that
may be used in diesel engines that may operate under severe conditions and
loads
while reducing the impact of soot and soot-related wear as well as
cleanliness,
deposits and better fuel economy
SUMMARY
100051 The present disclosure relates to diesel engine
lubricating compositions
for an internal combustion engine (typically a compression ignited engine) to
have at
least one of reduced soot, improved fuel economy, reduced deposit formation,
reduced wear and improved cleanliness.
100061 The lubricating compositions include an oil of
lubricating viscosity having
greater than 50 weight percent (sometimes referred to as "wt. %") of a Group
III base
oil, Group IV base oil, Group V base oil, or mixtures thereof. The
compositions
further include a first PIB succinimide dispersant derived from an 1800 to
2500 Mn
PIB and a second PIB succinimide dispersant derived from a PIB with an Mn less
than 1600, provided that at least one of the first PIB succinimide dispersant
and the
second PIB succinimide dispersant is boron-free; an alkaline earth metal
salicylate,
such as a calcium salicylate, detergent; an alkaline earth metal sulfonate,
where the
alkaline earth metal sulfonate is present to deliver from 0.1 wt A to 1.2 wt
% of
alkaline earth metal soap to the composition; a phosphorus antiwear agent
present in
an amount to deliver 300 to 900 ppm phosphorus to the lubricating composition
100071 The lubricating compositions can have a sulfated ash of
between 0.3 to 1.1
wt %; a kinematic viscosity at 100 C of less than 8.3 cSt; a total alkaline
earth metal
soap of from 0.6 wt % to 2.1 wt %; and a HTHS measured according to ASTM D4683
of less than 2.7 mPa= s.
DETAILED DESCRIPTION
100081 The present disclosure provides for diesel engine
lubricating compositions
and methods for using the same. The lubricating composition includes an oil of
lubricating viscosity having greater than 50 weight percent of a Group III
base oil, a
Group IV base oil, a Group V base oil, or mixtures thereof; a first PIB
succinimide
dispersant derived from an 1800 to 2500 Mn PIB; a second PIB succinimide
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dispersant derived from a PIB with an Mn less than 1600, where at least one of
the
first PIB succinimide dispersant and the second PIB succinimide dispersant is
boron-
free; a alkaline earth metal salicylate detergent; an alkaline earth metal
sulfonate
detergent present in an amount to deliver 0.1 wt % to 1.2 wt % of alkaline
earth metal
soap to the lubricating composition; and a phosphorus antiwear agent present
in an
amount to deliver 300 to 900 ppm phosphorous to the lubricating composition
The
lubricating compositions disclosed herein further include a total sulfated ash
of
between 0.3 to 0.9 wt % or 0.3 to 1.1 wt. %, a total alkaline earth metal soap
content
of from 0.6 wt % to 2.1 wt %, and an HTHS as measured according to ASTM D4683
of less than 2.7 mPa= s.
Oils of Lubricating Viscosity
100091 The lubricating compositions disclosed herein comprise an
oil of
lubricating viscosity. Such oils include natural and synthetic oils, oil
derived from
hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-
refined oils
or mixtures thereof. A more detailed description of unrefined, refined and re-
refined
oils is provided in International Publication W02008/147704, paragraphs [0054]
to
[0056] (a similar disclosure is provided in US Patent Application 2010/197536,
see
[0072] to [0073]). A more detailed description of natural and synthetic
lubricating
oils is described in paragraphs [0058] to [0059] respectively of W02008/147704
(a
similar disclosure is provided in US Patent Application 2010/197536, see
[0075] to
[0076]). Synthetic oils may also be produced by Fischer-Tropsch reactions and
typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one
embodiment, oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic
procedure as well as other gas-to-liquid oils.
100101 Oils of lubricating viscosity may also be defined as
specified in April 2008
version of "Appendix E - API Base Oil Interchangeability Guidelines for
Passenger
Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base
Stock
Categories". The API Guidelines are also summarized in US Patent US 7,285,516
(see column 11, line 64 to column 12, line 10).
100111 Group IV base oils (also known as polyalphaolefins or
PAO) are known in
the art and are prepared by oligomerization or polymerization of linear alpha
olefins.
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PAOs are characteristically water white oils with superior low temperature
viscosity
properties (as measured, as well as high viscosity index. Typical PAOs
suitable for
use in internal combustion engines include polyalphaolefins with a kinematic
viscosity of 3 to 10 m2/s, such as PA0-4 and PA0-6, i.e. approximately 4 m2/s
and 6
m2/s respectively.
100121 In addition to traditional Group III and Group IV base
oils, low levels of
some Group V base oils may be present, especially Group V ester base oils.
Ester
base fluids include esters of monocarboxylic acids with monohydric alcohols;
di-
esters of diols with monocarboxylic acids and di-esters of dicarboxylic acids
with
monohydric alcohols; polyol esters of monocarboxylic acids and polyesters of
monohydric alcohols with polycarboxylic acids; and mixtures thereof. Esters
may be
broadly grouped into two categories: synthetic and natural.
100131 Synthetic esters may comprise esters of dicarboxylic
acids (e.g., phthalic
acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic
acid,
azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer,
malonic acid, alkyl malonic acids, and alkenyl malonic acids) with any of
variety of
monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-
ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and
propylene
glycol). Specific 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 complex ester formed by reacting one mole of
sebacic
acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic
acid.
Other synthetic esters include those made from C5 to C12 monocarboxylic acids
and
polyols and polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be
monoesters of mono-carboxylic acids and monohydric alcohols.
100141 Natural (or bio-derived) esters refer to materials
derived from a renewable
biological resource, organism, or entity, distinct from materials derived from
petroleum or equivalent raw materials. Natural esters include fatty acid
triglycerides,
hydrolyzed or partially hydrolyzed triglycerides, or transesterified
triglyceride esters,
such as fatty acid methyl ester (or FAME). Suitable triglycerides include, but
are not
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limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil,
linseed oil,
and related materials. Other sources of triglycerides include, but are not
limited to,
algae, animal tallow, and zooplankton. Methods for producing biolubricants
from
natural triglycerides are described in, e.g., United States Patent Publication
2011/0009300A1.
100151
In one embodiment, the lubricant composition of the disclosure contains
0.1 to 10 weight percent of an ester base fluid, or 0.25 to 5 weight percent,
or 0.1 to
2 weight percent of an ester base fluid. In one embodiment, the lubricating
composition comprises no more than 5 weight percent of an ester base fluid, no
more
than 2.5 weight percent or no more than 1 weight percent of an ester base
fluid. In
one embodiment, the lubricant composition is free of or substantially free of,
that is
contains less than 0.2 weight percent, intentionally added ester base fluid.
100161
In one embodiment the oil of lubricating viscosity may be a base oil
including API Group I to IV oil, an ester or a synthetic oil, or mixtures
thereof. In
one embodiment the oil of lubricating viscosity may be an API Group II, Group
III,
Group IV oil, an ester or a synthetic oil, or mixtures thereof. In some
embodiments,
the oil of lubricating viscosity comprises at least 50 wt %, or at least 60 wt
%, or at
least 70 wt %, or at least 80 wt %, or at least 90 wt %, or at least 95 wt %,
or at least
100 wt % of a Group III or a Group IV base oil, or a mixture of a Group III
and Group
IV base oil.
100171
The amount of the oil of lubricating viscosity present is typically the
balance remaining after subtracting from 100 wt % the sum of the amount of the
additives of the disclosed compositions and the other performance additives.
100181
The lubricating composition may be in the form of a concentrate and/or a
fully formulated lubricant.
If the lubricating compositions described herein
(comprising the additives disclosed herein) is in the form of a concentrate
which may
be combined with additional oil to form, in whole or in part, a finished
lubricant), the
ratio of the of these additives to the oil of lubricating viscosity and/or to
diluent oil
include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
Typically,
the lubricating composition described herein include at least 50 wt %, or at
least 60
wt %, or at least 70 wt %, or at least 80 wt % of an oil of lubricating
viscosity.
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100191
In some embodiments, the oil of lubricating viscosity can include a base
oil having a kinematic viscosity measured at 100 C of 2.4 m2/s to 6.4 m2/s.
In some
embodiments, the kinematic viscosity is from 3.8 m2/s to 5.0 m2/s or from 5.2
m2/s
to 5.8 m2/s or from 6.0 m2/s to 6.5 m2/s. In other embodiments, the kinematic
viscosity of the base oil is 4.5 m2/s or 4.3 m2/s or 4.2 m2/s.
Polyisobutenyl (PIB) succinimide Dispersant(s)
100201
The lubricating compositions of the instant disclosure further include a
first polyisobutenyl succinimide dispersant and a second polyisobutenyl
succinimide
dispersant. The reference herein to a polyisobutylene succinimide dispersant
refers
to both the first polyisobutenyl succinimide dispersant as well as the second
polyisobutenyl succinimide dispersant.
The difference being that that first
polyisobutenyl succinimide dispersant is derived from a polyisobutenyl moiety
having a larger number average molecular weight (Mn) than the PIB of the
second
polyisobutenyl succinimide dispersant.
100211
The first polyisobutenyl succinimide and/or the second polyisobutenyl
succinimide dispersants can each be prepared (or, as used herein "derived")
from a
polyisobutylene ("PIB") succinimide dispersant that is either a "conventional"
PIB
or a high vinylidene PIB. The difference between a conventional polyolefin and
a
high vinylidene polyolefin can be illustrated by reference to the production
of PIB.
In a process for producing conventional PIB, isobutylene is polymerized in the
presence of A1C13 to produce a mixture of polymers comprising predominantly
trisubstituted olefin (III) and tetrasubstituted olefin (IV) end groups, with
only a very
small amount (for instance, less than 20 percent) of chains containing a
terminal
vinylidene group (I). In an alternative process, isobutylene is polymerized in
the
presence of BF3 catalyst to produce a mixture of polymers comprising
predominantly
(for instance, at least 70 percent) terminal vinylidene groups, with smaller
amounts
of tetrasubstituted end groups and other structures. The materials produced in
the
alternative method, sometimes referred to as "high vinylidene PIB," are also
described in U.S. Patent 6,165,235, which is incorporated herein by reference
in its
entirety.
In one embodiment, the polyisobutylene-derived dispersant is a
conventional polyisobutylene-derived dispersant. In another embodiment, the
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polyisobutylene-derived dispersant is a high or mid vinylidene succinimide
dispersant. The polyisobutylene-derived dispersant used herein is generally
known
in the art.
100221 The polyisobutylene-derived acylating agent may be
prepared/obtained/obtainable from reaction with maleic anhydride by an "ene"
or
"thermal" reaction, also referred to as direct alkylation. The "ene" reaction
mechanism and general reaction conditions are summarized in "Maleic
Anhydride",
pages, 147-149, Edited by B. C. Trivedi and B. C. Culbertson and Published by
Plenum Press in 1982. The polyisobutylene-derived dispersant prepared by a
process
that includes an "ene" reaction includes a dispersant having a carbocyclic
ring present
on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole
%, or
0 mole % of the dispersant molecules. The "ene" reaction may have a reaction
temperature of 180 C. to less than 300 C., or 200 C. to 250 C., or 200 C.
to 220
C.
100231 The polyisobutylene-derived acylating agent may also be
obtained/obtainable from a chlorine-assisted process, often involving Diels-
Alder
chemistry, leading to formation of carbocyclic linkages. The process is known
to a
person skilled in the art. The chlorine-assisted process may produce an
acylating
agent having a carbocyclic ring present on 50 mol % or more, or 60 to 100 mol
% of
the molecules. Both the thermal and chlorine-assisted processes are described
in
greater detail in U.S. Pat. No. 7,615,521, columns 4-5 and preparative
examples A
and B.
100241 The polyisobutylene-derived acylating agent may also be
prepared/obtained/obtainable from a free radical process, wherein the
acylating agent
is reacted with polyisobutylene in the presence of a free radical initiator.
Free radical
processes of this sort are well known in the art and may be carried out in the
presence
of an additional alpha-olefin.
100251 The polyisobutylene-derived acylating agent can be
obtained from
reacting polyisobutylene with an acylating agent, i.e., an ethylenically
unsaturated
carbonyl compound, to form an acylated polyisobutylene which may be further
functionalized with an amine or alcohol to form a suitable dispersant.
Suitable
acylating agents include maleic anhydride or a reactive equivalent thereof
(such as
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an acid or ester), i.e., succinic acid, and their reactive equivalents. In one
embodiment, polyisobutylene may be reacted with maleic anhydride to form
acylated
product with a conversion between 1 and 2. In one embodiment, the monosuccan
is
reacted with an amine so that the intended product comprises a mixture wherein
all
of the anhydride present in the acylating agent has been converted to imide.
100261 The polyisobutylene-derived dispersant may have a
carbonyl to nitrogen
ratio (CO:N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2.
In one
embodiment the dispersant may have a CO:N ratio of 2:1 to 1:10, or 2:1 to 1:5,
or 2:1
to 1:2, or 1:1.4 to 1:0.6.
100271 Polyisobutylene succinimide dispersants of the instant
disclosure may be
prepared by reaction of the acylated PIB with a suitable amine compound.
Suitable
amines include one or more hydrocarbylamines, aminoalcohols, polyetheramines,
or
combinations thereof.
100281 In one embodiment, the hydrocarbyl amine component may
comprise at
least one aliphatic amine containing at least one amino group capable of
condensing
with said acyl group to provide a pendant group and at least one additional
group
comprising at least one nitrogen, oxygen, or sulfur atom. Suitable aliphatic
amines
include polyethylene polyamines (such as tetraethylene pentamine (TEPA),
triethylene tetra amine (TETA), pentaethylene hexamine (PEHA), and polyamine
bottoms), N,N-dimethylaminopropylamine (DMAPA), N-(aminopropyl)morpholine,
N,N-diIsostearylaminopropylamine, ethanolamine, and combinations thereof.
100291 In one embodiment, the hydrocarbyl amine component may
comprise at
least one aromatic amine containing at least one amino group capable of
condensing
with said acyl group to provide a pendant group and at least one additional
group
comprising at least one nitrogen, oxygen, or sulfur atom, wherein said
aromatic amine
is selected from the group consisting of (i) a nitro-substituted aniline, (ii)
an amine
comprising two aromatic moieties linked by a C(0)NR- group, a -C(0)0- group,
an
-0- group, an N=N- group, or an -S02- group where R is hydrogen or
hydrocarbyl,
one of said aromatic moieties bearing said condensable amino group, (iii) an
aminoquinoline, (iv) an aminobenzimidazole, (v) an N,N-
dialkylphenylenediamine,
(vi), an aminodiphenylamine (also N,N-phenyldiamine), and (vii) a ring-
substituted
benzylamine.
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100301
In one embodiment, the polyetheramine compound may comprise an
amine-terminated polyether compound. Amine terminated polyether compounds may
comprise units derived from ethylene oxides, propylene oxides, butylene
oxides, or
some combination thereof. Suitable polyether compounds include Jeffamineg line
of
polyether amines available from Huntsman.
100311
In one embodiment, the first polyisobutylene succinimide dispersant may
be prepared by a thermal direct alkylation process described herein. In
another
embodiment, the second polyisobutylene succinimide dispersant may be prepared
by
a thermal direct alkylation process described herein.
100321
The polyisobutylene-derived dispersant as described herein can further be
described as having a TBN. In one embodiment, the first polyisobutylene
succinimide dispersant has a TBN of from 15 to 25. In another embodiment, the
first
polyisobutylene succinimide dispersant has a TBN of from 15 to 20. In one
embodiment, the second polyisobutylene succinimide dispersant has a TBN of
from
20 to 35. In another embodiment, the second polyisobutylene succinimide
dispersant
has a TBN of from 25 to 30. In one embodiment, the second polyisobutylene
succinimide dispersant has a TBN of from 27 to 28.
100331
In one embodiment, the first polyisobutylene succinimide dispersant is
derived from a P1B having a number average molecular weight ranging from 1720
to
2200. In another embodiment, the first polyisobutylene succinimide dispersant
is
derived from a PIB having a number average molecular weight ranging from 1800
to
2100 In one embodiment, the first polyisobutylene succinimide dispersant is
derived
from a PIB having a number average molecular weight ranging from 1850 to 2150.
100341
In one embodiment, the second polyisobutylene succinimide dispersant
is derived from a PIB having a number average molecular weight ranging from
750
to 1600. In another embodiment, the second polyisobutylene succinimide
dispersant
is derived from a PIB having a number average molecular weight ranging from
1000
to 1600. In one embodiment, the second polyisobutylene succinimide dispersant
is
derived from a PIB having a number average molecular weight ranging from 1200
to
1600. In one embodiment, the second polyisobutylene succinimide dispersant is
derived from a PIB having a number average molecular weight ranging from 800
to
1150. In another embodiment, the second polyisobutylene succinimide dispersant
is
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derived from a PIB having a number average molecular weight ranging from 900
to
1100.
[0035] In one embodiment, the first polyisobutylene succinimide
dispersant may
be present in the lubricating composition in an amount of from 0.5 wt % to 10
wt %.
In another embodiment, the first polyisobutylene succinimide dispersant may be
present in the lubricating composition in an amount of from 0S wt % to 6 wt
()/0 In
one embodiment, the first polyisobutylene succinimide dispersant may be
present in
the lubricating composition in an amount of from 1 wt % to 5 wt %. In one
embodiment, the first polyisobutylene succinimide dispersant may be present in
the
lubricating composition in an amount of from 1.1 wt % to 2.2 wt %.
[0036] In one embodiment, the second polyisobutylene succinimide
dispersant is
present in the lubricating composition in an amount of from 1 wt % to 5 wt %.
In
another embodiment, the second polyisobutylene succinimide dispersant is
present in
the lubricating composition in an amount of from 1.5 wt % to 4.8 wt %. In
another
embodiment, the second polyisobutylene succinimide dispersant is present in
the
lubricating composition in an amount of from 1.8 wt % to 4.6 wt %. In another
embodiment, the second polyisobutylene succinimide dispersant is present in
the
lubricating composition in an amount of from 1.9 wt % to 3.3 wt %.
[0037] In one embodiment, the first polyisobutylene succinimide
dispersant may
include a mixture of two or more dispersants where each of the two or more
dispersants falls within the scope, including, without limitation, the PIB Mn,
TBN,
and treat rates of the first polyisobutylene succinimide dispersant as
disclosed herein
In another embodiment, the first polyisobutylene succinimide dispersant may
include
a mixture of two dispersants where each of the two dispersants falls within
the scope,
including, without limitation, the PIB Mn, TBN, and treat rates of the first
polyisobutylene succinimide dispersant as disclosed herein.
[0038] In some embodiments, the second polyisobutylene
succinimide dispersant
may include a mixture of two or more dispersants where each of the two or more
dispersants falls within the scope, including, without limitation, the PIB Mn,
TBN,
and treat rates of the second polyisobutylene succinimide dispersant as
disclosed
herein. In another embodiment, the second polyisobutylene succinimide
dispersant
includes from 1 wt % to 5 wt % of a PIB succinimide dispersant derived from a
PIB
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having an Mn of 900 to 1100 and from 1 wt % to 5 wt % of a PIB succinimide
dispersant derived from a PIB having an Mn of from 1200 to 1600.
100391
The lubricating compositions of the instant disclosure further provide
that
at least one of the first polyisobutylene succinimide dispersant and the
second
polyisobutylene succinimide dispersant are boron free. In one embodiment, the
first
polyisobutylene succinimide dispersant is boron free and the second
polyisobutylene
succinimide dispersant is borated. In another embodiment, the first
polyisobutylene
succinimide dispersant is borated and the second polyisobutylene succinimide
dispersant is boron free.
100401
In preparing the boron-containing polyisobutylene succinimide dispersant,
the first polyisobutylene-derived succinimide dispersant or the second
polyisobutylene-derived succinimide dispersant as described herein may be post-
treated by conventional methods including a reaction with boron compounds to
generate the boron-containing polyisobutylene succinimide dispersant. Suitable
boron compounds that may be used to borate the polyisobutylene-derived
dispersant
include one or more of a variety of agents selected from the group consisting
of the
various forms of boric acid (including metaboric acid, HB02, orthoboric acid,
113B03,
and tetraboric acid, H2B407), boric oxide, boron trioxide, and alkyl borates.
In one
embodiment the borating agent is boric acid which may be used alone or in
combination with other borating agents. Methods of preparing borated
dispersants
are known in the art. The borated dispersant may be prepared in such a way
that they
contain 0.1 weight % to 2.5 weight% boron, or 0.1 weight % to 2.0 weight %
boron
or 0.2 to 1.5 weight % boron or 0.3 to 1.0 weight % boron.
100411
In some embodiments, either the borated first polyisobutylene
succinimide dispersant or the borated second polyisobutylene succinimide
dispersant
is present in an amount to deliver at least 25 ppm, or at least 50 ppm, or at
least 75
ppm boron to the lubricating composition. In another embodiment, either the
borated
first polyisobutylene succinimide dispersant or the borated second
polyisobutylene
succinimide dispersant is present in an amount to deliver from 25 ppm to 400
ppm
boron to the lubricating composition.
In another embodiment, either the borated
first polyisobutylene succinimide dispersant or the borated second
polyisobutylene
succinimide dispersant is present in an amount to deliver from 25 ppm to 400
ppm,
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or 50 ppm to 200 ppm, or 75 ppm to 150 ppm, or 78 ppm to 100 ppm boron to the
lubricating composition.
Detergents
[0042] The lubricating composition of the instant disclosure
further includes
an alkaline earth metal salicylate detergent and at least one alkaline earth
metal
sulfonate detergent as described herein. Metal-containing detergents are well
known
in the art. They are generally made up of metal salts, especially alkali
metals and
alkaline earth metals, of acidic organic substrates. Metal-containing
detergents may
be neutral, i.e. a stoichiometric salt of the metal and substrate also
referred to as
neutral soap or soap, or overbased.
[0043] Metal overbased detergents, otherwise referred to as
overbased
detergents, metal-containing overbased detergents or superbased salts, are
characterized by a metal content in excess of that which would be necessary
for
neutralization according to the stoichiometry of the metal and the particular
acidic
organic compound, i.e. the substrate, reacted with the metal. The overbased
detergent
may comprise one or more of sulfonates, salicylates, non-sulfur containing
phenates,
sulfur containing phenates, and mixtures thereof.
[0044] The amount of excess metal to substrate is commonly
expressed in
terms of metal ratio. The terminology "metal ratio" is used in the prior art
and herein
to define the ratio of the total chemical equivalents of the metal in the
overbased salt
to the chemical equivalents of the metal in the salt which would be expected
to result
from the reaction between the hydrocarbyl substituted organic acid; the
hydrocarbyl-
substituted phenol or mixtures thereof to be overbased, and the basic metal
compound
according to the known chemical reactivity and the stoichiometry of the two
reactants. Thus, in a normal or neutral salt (i.e., soap) the metal ratio is
one and, in
an overbased salt, the metal ratio is greater than one, especially greater
than 1.3. The
overbased metal detergent may have a metal ratio of 5 to 30, or a metal ratio
of 7 to
22, or a metal ratio of 11 to 18, or a metal ratio of at least 11.
[0045] The metal-containing detergent may also include
"hybrid" detergents
formed with mixed surfactant systems including phenate and/or sulfonate
components, e.g., phenate-sali cyl ates, sulfonate-phenates, sulfonate-sali
cylates,
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sulfonates-phenates-salicylates, as described, for example, in US Patents
6,429,178;
6,429,179; 6,153,565; and 6,281,179.
Where, for example, a hybrid
sulfonate/salicylate detergent is employed, the hybrid detergent would be
considered
equivalent to amounts of distinct salicylate and sulfonate detergents
introducing like
amounts of salicylate and sulfonate soaps, respectively. Overbased phenates
and
salicylates typically have a total base number of 180 to 450 TBN Overbased
sulfonates typically have a total base number of 250 to 800, or 300 to 600
Overbased
detergents are known in the art.
100461
Alkylphenols are often used as constituents in and/or building blocks
for overbased detergents. Alkylphenols may be used to prepare phenate,
salicylate,
salixarate, or saligenin detergents or mixtures thereof. Suitable alkylphenols
may
include para-substituted hydrocarbyl phenols. The hydrocarbyl group may be
linear
or branched aliphatic groups of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10
to 24
carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms. In one
embodiment,
the alkylphenol overbased detergent is prepared from an alkylphenol or mixture
thereof that is free of or substantially free of (i.e., contains less than 0.1
weight
percent) p-dodecylphenol. In one embodiment, the lubricating composition
contains
less than 0.3 weight percent of alkylphenol, less than 0.1 weight percent of
alkylphenol, or less than 0.05 weight percent of alkylphenol. In one
embodiment, the
alkylphenol detergent is a salicylate.
Alkaline Earth Metal Salicylate
100471
Salicylate detergents and overbased salicylate detergents may be
prepared in at least two different manners. Carbonyl ation (also referred to
as
carboxylation) of a p-alkylphenol is described in many references including US
Patent 8,399,388. Carbonylation may be followed by overbasing to form
overbased
salicylate detergent. Suitable p-alkylphenols include those with linear and/or
branched hydrocarbyl groups of 1 to 60 carbon atoms, 4 to 34 carbon atoms, 14
to 24
carbon atoms, and combinations thereof. Salicylate detergents may also be
prepared
by alkylation of salicylic acid, followed by overbasing, as described in US
Patent
7,009,072. Salicylate detergents prepared in this manner, may be prepared from
linear
and/or branched alkylating agents (usually 1-olefins) containing 6 to 50
carbon
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atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms. In one embodiment, the
overbased detergent is a salicylate detergent. In one embodiment, the
salicylate
detergent is free of unreacted p-alkylphenol (i.e., contains less than 0.1
weight
percent). In one embodiment, the salicylate detergent is prepared by
alkylation of
salicylic acid.
100481 In one embodiment, the alkaline earth metal salicylate
detergent has a
TBN (KOH/g) of from 200 to 575 or 200 to 500. In another embodiment, the
alkaline
earth metal salicylate detergent has a TBN (KOH/g) of from 250 to 350. In one
embodiment, the alkaline earth metal salicylate detergent has a metal ratio of
from 2
to 7, or from 2 to 4, or from 2.5 to 3.5. In one embodiment, the alkaline
earth metal
salicylate detergent is present in the lubricating composition in an amount of
from
0.1 to 5 wt %. In another embodiment, the alkaline earth metal salicylate
detergent
is present in the lubricating composition in an amount of from 0.2 to 3 wt %.
In one
embodiment, the alkaline earth metal salicylate detergent is present in the
lubricating
composition in an amount of from 0.5 to 3 wt %. In one embodiment, the
alkaline
earth metal salicylate detergent is present in the lubricating composition in
an amount
of from 0.8 to 2.5 wt %. In one embodiment, the calcium alkaline earth metal
detergent is present in the lubricating composition in an amount of from 0.9
to 2.3 wt
%.
100491 In one embodiment, the alkaline earth metal salicylate
detergent may
be a calcium salicylate, a magnesium salicylate or combinations thereof. In
one
embodiment, the alkaline earth metal salicylate is a calcium salicylate In one
embodiment, the alkaline earth metal salicylate is a magnesium salicylate. The
calcium salicylate may be present in an amount to deliver 150 to 1500 ppm
calcium
to the lubricant composition, or 250 to 1100 ppm calcium to the composition.
The
magnesium salicylate may be present in an amount to deliver 100 to 2000 ppm of
magnesium to the lubricant composition, or 250 to 1750 ppm magnesium, or 300
to
1550 ppm to the lubricant composition.
Alkaline Earth Metal Sulfonate Detergent
100501 The alkaline earth metal sulfonate may be a neutral
sulfonate salt
(metal ratio less than 1.3), a low overbased detergent (metal ration of 1.5 to
6), or a
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high overbased detergent (metal ratio of at least 8), or any combination
therein, such
that at least 0.1 weight percent of alkaline earth metal soap is present in
the lubricant
composition.
100511 Alkaline earth metal sulfonate detergents may be
linear alkylbenzene
sulfonate detergent as is described in paragraphs [0026] to [0037] of US
Patent
Publication 2005/065045 (and granted as US 7,407,919) The linear alkylbenzene
sulfonate detergent may be particularly useful for assisting in improving fuel
economy. The linear alkyl group may be attached to the benzene ring anywhere
along
the linear chain of the alkyl group, but often in the 2, 3 or 4 position of
the linear
chain, and in some instances, predominantly in the 2 position, resulting in
the linear
alkylbenzene sulfonate detergent.
100521 In one embodiment, the alkaline earth metal sulfonate
detergent of the
instant disclosure is selected from a calcium sulfonate detergent and a
magnesium
sulfonate detergent. In another embodiment, the alkaline earth metal sulfonate
detergent is a calcium sulfonate detergent. In one embodiment, the calcium
sulfonate
detergent has a TBN of less than 250 on an oil free basis. In another
embodiment,
the calcium sulfonate detergent has a TBN of less than 200, or less than 150,
or less
than 80. In one embodiment, the calcium sulfonate detergent has a TBN of from
50
to 90. In one embodiment, the calcium sulfonate has a TBN from 120 to 250 mg
KOH/g and a metal ratio of 1.5 to 5.
100531 In one embodiment, the alkaline earth metal sulfonate
detergent is a
calcium sulfonate detergent present in the lubricating composition in an
amount of
from 0.1 wt % to 2.0 wt %. In another embodiment, the calcium sulfonate
detergent
is present in the lubricating composition in an amount of from 0.3 wt % to 1.5
wt %.
100541 In one embodiment, the alkaline earth metal sulfonate
detergent is a
magnesium sulfonate detergent. The magnesium sulfonate may have a TBN (mg
KOH/g) of from 300 to 800 on an oil-free basis. In some embodiments, magnesium
sulfonate may have a TBN (mg KOH/g) of from 400 to 750. In other embodiments,
the magnesium sulfonate may have a TBN (mg KOH/g) of from 250 to 350. In other
embodiments, the magnesium sulfonate may have a TBN (mg KOH/g) of from 350
to 375. In one embodiment, the magnesium sulfonate may have a metal ratio of 8
to
30, 10 to 25, or 12 to 18.
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[0055] In one embodiment, the magnesium sulfonate detergent
is present in
the lubricating composition in an amount of from 0.05 wt % to 0.5 wt % or 0.05
to
0.2. In another embodiment, the magnesium sulfonate detergent is present in
the
lubricating composition in an amount of from 0.06 to 0.1 wt % or 0.06 wt % to
0.2
wt %.
100561 In one embodiment, the alkaline earth metal sulfonate
may be a
combination of at least one neutral or low overbased alkaline earth metal
sulfonate
(i.e., metal ratio less than 6) and at least one high overbased alkaline earth
metal
sulfonate (metal ratio of at least 8).
100571 The alkaline earth metal detergent used herein may be
sodium salts,
calcium salts, magnesium salts, or mixtures thereof of sulfonates. In one
embodiment,
the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent,
a
magnesium sulfonate detergent or mixtures thereof. In one embodiment, one or
more
of the calcium sulfonate detergent and the magnesium sulfonate detergent are
overbased. In one embodiment, the alkaline earth metal detergent is an
overbased
calcium sulfonate detergent. In another embodiment, the alkaline earth metal
detergent is an overbased magnesium sulfonate detergent. In yet another
embodiment, the alkaline earth metal detergent is mixture of an overbased
calcium
sulfonate detergent and an overbased magnesium sulfonate detergent. In one
embodiment, the alkaline earth metal sulfonate detergent is a mixture of 0.6
wt % to
1.5 wt % of a calcium sulfonate detergent having a TBN (mg KOH/g) of from 50
to
200 and 0.04 wt % to 0.1 wt % of an overbased magnesium sulfonate detergent
having
a TBN (mg KOH/g) of from 400 to 800.
100581 The detergents of the disclosed lubricating
compositions may include
alkaline earth metals contributed from the detergents. In one embodiment, the
calcium salicylate detergent is present in an amount to deliver 150 to 1500
ppm, or
250 to 1100 ppm, or 300 to 800 ppm of calcium to the lubricating composition.
In
embodiments where the alkaline earth metal detergent includes a calcium
sulfonate
detergent the calcium sulfonate detergent may be present in an amount to
deliver 100
to 1000 ppm, 150 to 800 ppm, or 250 to 650 ppm calcium to the lubricating
compositions. In embodiments where the alkaline earth metal detergent includes
a
magnesium sulfonate detergent, the magnesium sulfonate detergent may be
present
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in an amount to deliver 50 to 500, 100 to 425, or 150 to 350 ppm magnesium to
the
lubricating composition. In some embodiments, the alkaline earth metal
detergent
includes a calcium sulfonate detergent and the total amount of calcium
delivered to
the lubricating composition from the calcium salicylate detergent and the
calcium
sulfonate detergent is 800 to 2500, 900 to 1800, 950 to 1450 ppm calcium to
the
lubricating composition.
100591 Metal-containing detergents contribute sulfated ash to
a lubricating
composition. Sulfated ash may be determined by ASTM D874. In one embodiment,
the total sulfated ash delivered to the lubricating composition from the
alkaline earth
metal salicylate detergent and the alkaline earth metal detergent is from 0.25
to 0.95
weight percent. In other embodiments, the alkaline earth salicylate detergent
is
present in an amount to deliver 0.05 to 0.5 weight percent, or 0.1 to 0.35
weight
percent sulfated ash to the lubricating compositions. In another embodiment,
the
alkaline earth metal detergent is present in an amount to deliver 0.05 to
0.75, or 0.1
to 0.6 weight percent sulfated ash to the lubricating composition.
100601 In addition to ash and TBN, overbased detergents
contribute detergent
soap, also referred to as neutral detergent salt, to the lubricating
composition. Soap,
being a metal salt of the substrate, may act as a surfactant in the
lubricating
composition. In one embodiment, the alkaline earth metal sulfonate detergents
are
present in an amount to deliver 0.1 wt ()/0 to 1.5 wt %, or 0.15 to 1.2 wt
/0, or 0.2 wt
% to 0.9 wt % sulfonate soap to the lubricant composition. In one embodiment,
the
alkaline earth metal salicylate detergents are present in an amount to deliver
0.3 wt
% to 1.4 wt %, or 0.35 wt % to 1.2 wt %, or 0.4 wt % to 1.0 wt % salicylate
soap to
the lubricant composition. In one embodiment, the alkaline earth metal soap
may be
calcium, magnesium, or any mixture thereof. In one embodiment, alkaline earth
metal sulfonate soap is present in an amount 0.2 wt % to 0.8 wt % of the
lubricant
composition, and the alkaline earth metal salicylate soap is present in an
amount 0.3
wt % to 1.0 wt cYc. of the lubricant composition. The total of all alkaline
earth metal
detergent soap may be present in an amount 0.6 wt % to 2.1 wt %, or 0.7 wt %
to 1.4
wt % of the lubricant composition.
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Antiwear Agent
100611 The lubricating composition of the instant disclosure
further includes
one or more phosphorus-containing antiwear agents.
100621 Phosphorus-containing anti-wear agents are well known
to one skilled
in the art and include metal dialkyl(dithio)phosphate salts, hydrocarbyl
phosphites,
hydrocarbyl phosphines, hydrocarbyl phosphonates, alkylphosphate esters, amine
or
ammonium (alkyl)phosphate salts, and combinations thereof.
100631 In one embodiment, the phosphorus-containing ant-wear
agent may be
a metal dialkyldithiophosphate, which may include a zinc dialkyldithio-
phosphate.
Such zinc salts are often referred to as zinc dialkyldithiophosphates (ZDDP)
or
simply zinc dithiophosphates (ZDP). They are well known and readily available
to
those skilled in the art of lubricant formulation. Further zinc
dialkyldithiophosphates
may be described as primary zinc dialkyldithiophosphates or as secondary zinc
dialkyldithiophosphates, depending on the structure of the alcohol used in its
preparation. In some embodiments the instant compositions may include primary
zinc
dialkyldithiophosphates. In some embodiments, the compositions include
secondary
zinc dialkyldithiophosphates. In some embodiments, the compositions include a
mixture of primary and secondary zinc dialkyldithiophosphates. In some
embodiments component (b) is a mixture of primary and secondary zinc
dialkyldithiophosphates where the ratio of primary zinc
dialkyldithiophosphates to
secondary zinc dialkyldithiophosphates (one a weight basis) is at least 1:1,
or even at
least 1:1.2, or even at least 1:1.5 or 1:2, or 1:10.
100641 Examples of suitable metal dialkyldithiophosphate
include metal salts
of the formula:
R10 II
s _____________________________________________________ RA
R20
11
where 10 and IC are independently hydrocarbyl groups containing 3 to 24 carbon
atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms; M is a metal having a
valence
n and generally incudes zinc, copper, iron, cobalt, antimony, manganese, and
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combinations thereof. In one embodiment, R2 and R2 are secondary aliphatic
hydrocarbyl groups containing 3 to 8 carbon atoms, and M is zinc.
[0065]
In one embodiment, the phosphorus-containing anti-wear agent may be
a zinc free phosphorus compound. The zinc-free phosphorus anti-wear agent may
contain sulfur or may be sulfur-free. Sulfur-free phosphorus-containing
antiwear
agents include hydrocarbyl phosphites, hydrocarbyl phosphines, hydrocarbyl
phosphonates, alkylphosphate esters, amine or ammonium phosphate salts, or
mixtures thereof.
[0066]
In one embodiment, the phosphorus-containing antiwear agent is
present in the lubricating composition in an amount to deliver from 300 ppm to
900
ppm phosphorus to the lubricating composition. In one embodiment, the antiwear
agent is ZDDP and is present in the composition in an amount to deliver 400
ppm to
850 ppm, or 450 ppm to 800 ppm, or 500 ppm to 800 ppm, or 550 ppm to 780 ppm,
or 650 ppm to 780 ppm phosphorus to the lubricating composition.
[0067]
In one embodiment, the phosphorus-containing anti-wear agent is
present in an amount 0.2 to 2 wt %, or 0.3 to 1.3 wt %, or 0.5 to 0.95 wt % of
the
lubricant composition.
Other Performance Additives
[0068]
A lubricating composition may be prepared by blending the oil of
lubricating
viscosity, the first PIE succinimide dispersant, the second succinimide
dispersant, the
calcium salicylate detergent, the alkaline earth metal detergent, the
phosphorous antiwear
agent and, optionally one or more performance additives (as described herein
below).
[0069]
The other performance additives include at least one of metal
deactivators,
viscosity modifiers, friction modifiers, antiwear agents, corrosion
inhibitors, extreme
pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point
depressants,
seal swelling agents and mixtures thereof. Typically, fully formulated
lubricating oil
will contain one or more of these performance additives.
[0070]
The lubricating composition in a further embodiment comprises an
antioxidant, wherein the antioxidant comprises a phenolic or an aminic
antioxidant
or mixtures thereof. The antioxidants include diarylamines, alkylated
diarylamines,
hindered phenols, or mixtures thereof. When present the individual
antioxidants are
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independently present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt
% to
2.5 wt % of the lubricating composition.
100711
The diarylamine or alkylated diarylamine may be a phenyl-a-naphthylamine
(PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or
mixtures
thereof. The alkylated diphenylamine may include di-nonylated diphenylamine,
nonyl
diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated
diphenylamine, decyl diphenylamine and mixtures thereof. In one embodiment the
diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl
diphenylamine, dioctyl diphenylamine, or mixtures thereof. In another
embodiment
the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl
diphenylamine. The alkylated diarylamine may include octyl, di-octyl, nonyl,
di-nonyl,
decyl or di-decyl phenylnapthylamines.
100721
The hindered phenol antioxidant often contains a secondary butyl and/or a
tertiary butyl group as a sterically hindering group. The phenol group may be
further
substituted with a hydrocarbyl group (typically linear or branched alkyl)
and/or a
bridging group linking to a second aromatic group. Examples of suitable
hindered
phenol antioxidants include 2,6-di-tert-butylphenol, 4-methy1-2,6-di-tert-
butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-butylphenol
or 4-
buty1-2,6-di-tert-butylphenol, or 4-dodecy1-2,6-di-tert-butylphenol.
In one
embodiment, the hindered phenol antioxidant may be an ester and may include,
e.g.,
IrganoxTm L-135 from Ciba. Suitable hindered phenol esters include hydrocarbyl
esters of 3-(3,5-di-tert-buty1-4-hydroxyphenyl)propanoic acid, such as
hydrocarbyl
esters containing 3 to 18 carbon atoms, or 4 to 12 carbon atoms, or 6 to 10
carbon
atoms. A more detailed description of suitable ester-containing hindered
phenol
antioxidant chemistry is found in US Patent 6,559,105.
100731
In one embodiment, the lubricating compositions contains a friction
modifier. The friction modifier may be chosen from long chain fatty acid
derivatives
of amines, long chain fatty esters, or derivatives of long chain fatty
epoxides; fatty
imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates;
fatty alkyl
tartrimides; fatty alkyl tartramides; fatty glycolates; fatty glycolamides;
and
combinations thereof.
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[0074] As used herein, the term "fatty alkyl" or "fatty" in
relation to friction
modifiers means a carbon chain having 10 to 24 carbon atoms, typically a
straight
carbon chain, which may be saturated or unsaturated.
100751 Examples of suitable friction modifiers include long
chain fatty acid
derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines
such as
condensation products of carboxylic acids and polyalkylene-pc)lyamines; amine
salts
of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides;
fatty alkyl
tartramides; fatty phosphonates; fatty phosphites; borated phospholipids,
borated
fatty epoxides; glycerol esters; borated glycerol esters; fatty amines;
alkoxylated fatty
amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty
amines
including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of
fatty
acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated
alcohols;
condensation products of carboxylic acids and polyalkylene polyamines; or
reaction
products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or
thiourea and salts thereof.
100761 Friction modifiers may also encompass materials such as
sulfurized fatty
compounds and olefins, molybdenum compounds such as molybdenum
dialkyldithiophosphates, molybdenum dithiocarbamates, amine salted molybdenum
acid compounds, and molybdenum post-treated succinimide dispersants.
Molybdenum dithiocarbamates may be mono-nuclear, di-nuclear, or even tri-
nuclear
complexes. Suitable molybdenum compounds may be present as Mo(IV) complexes,
or Mo(V) complexes, or Mo(VI) complexes, or combinations thereof and include
commercial materials such as Sakura-lube 525 from Adeka Co. Ltd and Molyvan
855 from Vanderbilt Chemicals LLC.
100771 In another embodiment, the friction modifier may be a
long chain fatty
acid ester. In another embodiment, the long chain fatty acid ester may be a
mono-
ester and in another embodiment the long chain fatty acid ester may be a
triglyceride.
Suitable triglycerides include vegetable oils, such as soybean oil or
sunflower oil.
100781 The ashless friction modifier may be present in the
lubricating composition
in an amount of from 0.01 to 2.5 wt %, or 0.1 to 0.5 wt %, or 0.3 to 2.0 wt %,
or 0.5
to 0.9 wt %.
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100791
The lubricating composition optionally further includes at least one
antiwear agent other than the phosphorus-containing antiwear agent described
above.
Examples of suitable antiwear agents include titanium compounds, tartaric acid
esters, tartrimides, thiocarbamate- containing compounds, such as
thiocarbamate
esters, thiocarbamate amides, thiocarbamic ethers, alkyl ene-coupled
thiocarbamates,
and bis(S-alkyldithiocarbamyl) disulphides
The antiwear agent may in one
embodiment include a tartrate, or tartrimide as disclosed in International
Publication
WO 2006/044411 or Canadian Patent CA 1 183 125. The tartrate or tartrimide may
contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups
is at
least 8. The antiwear agent may in one embodiment include a citrate as is
disclosed
in US Patent Application 20050198894.
100801
Another class of additives includes oil-soluble titanium compounds as
disclosed in US 7,727,943 and US2006/0014651.
The oil-soluble titanium
compounds may function as antiwear agents, friction modifiers, antioxidants,
deposit
control additives, or more than one of these functions. In one embodiment, the
oil
soluble titanium compound is a titanium (IV) alkoxide. The titanium alkoxide
is
formed from a monohydric alcohol, a polyol or mixtures thereof. The monohydric
alkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the
titanium
alkoxide is titanium (IV) isopropoxide. In one embodiment, the titanium
alkoxide is
titanium (IV) 2-ethylhexoxide. In one embodiment, the titanium compound
comprises the alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the
1,2-
vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty
acid is oleic
acid.
100811
In one embodiment, the oil soluble titanium compound is a titanium
carboxylate. In a further embodiment the titanium (IV) carboxylate is titanium
neodecanoate.
100821
Extreme Pressure (EP) agents that are soluble in the oil include sulfur-
and
chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2 derivatives of
dispersants (typically succinimi de dispersants), derivative of chlorinated
hydrocarbon EP agents and phosphorus EP agents. Examples of such EP agents
include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene),
a
hydrocarbyl-substituted 2,5-dimercapto-I,3,4-thiadiazole, or oligomers
thereof,
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organic sulphides and polysulphides such as dibenzyldisulphide,
bis¨(chlorobenzyl)
disulphide, dibutyl tetrasulphide, sulfurized methyl ester of oleic acid,
sulfurized
alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-
Alder
adducts; phosphosulfurized hydrocarbons such as the reaction product of
phosphorus
sulphide with turpentine or methyl oleate; phosphorus esters such as the
dihydrocarbon and trihydrocarbon phosphites, e g dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl
phosphite, tridecyl phosphite, distearyl phosphite and polypropylene
substituted
phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and
barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids
or
derivatives including, for example, the amine salt of a reaction product of a
dialkyl-
dithiophosphoric acid with propylene oxide and subsequently followed by a
further
reaction with P205; and mixtures thereof (as described in US 3,197,405).
100831 Foam inhibitors that may be useful in the instant
compositions and include
polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and
optionally
vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl
phosphates,
polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene
oxide-
propylene oxide) polymers.
100841 Polymeric viscosity index improvers, also referred to as
viscosity
modifiers (VM) or dispersant viscosity modifiers (DVM, may be useful in the
compositions disclosed herein. The dispersant viscosity modifier may be
generally
understood to be a functionalized, i e derivatized, form of a polymer similar
to that
of the polymeric viscosity modifier. The polymeric viscosity modifier may be
an
olefin (co)polymer, a poly(meth)acrylate (PMA), or mixtures thereof. In one
embodiment, the polymeric viscosity modifier is an olefin (co)polymer or
dispersant
viscosity modifier derived therefrom.
100851 The olefin polymer may be derived from isobutylene or
isoprene. In one
embodiment, the olefin polymer is prepared from ethylene and a higher olefin
within
the range of C3-C10 alpha-mono-olefins, for example, the olefin polymer may be
prepared from ethylene and propylene.
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[0086] Useful olefin polymers, in particular, ethylene-a-olefin
copolymers have a
number average molecular weight ranging from 4500 to 500,000, for example,
5000
to 100,000, or 7500 to 60,000, or 8000 to 45,000.
100871 The formation of functionalized ethylene-a-olefin
copolymer is well
known in the art, for instance those described in U.S. Patent US 7,790,661
column 2,
line 48 to column 10, line 38 Additional detailed descriptions of similar
functionalized ethylene-a-olefin copolymers are found in International
Publication
W02006/015130 or U.S. Patents 4,863,623; 6, 107,257; 6,107,258; 6,117,825; and
US 7,790,661. In one embodiment, the functionalized ethylene-a-olefin
copolymer
may include those described in U.S. Patent 4,863,623 (see column 2, line 15 to
column 3, line 52) or in International Publication W02006/015130 (see page 2,
paragraph [0008] and preparative examples are described paragraphs [0065] to
[0073]).
100881 In one embodiment, the lubricating composition comprises
a dispersant
viscosity modifier (DVM). The DVM may comprise an olefin polymer that has been
modified by the addition of a polar moiety.
100891 The olefin polymers are functionalized by modifying the
polymer by the
addition of a polar moiety. In one useful embodiment, the functionalized
copolymer
is the reaction product of an olefin polymer grafted with an acylating agent.
In one
embodiment, the acylating agent may be an ethylenically unsaturated acylating
agent.
Useful acylating agents are typically a,3-unsaturated compounds having at
least one
ethylenic bond (prior to reaction) and at least one, for example two,
carboxylic acid
(or its anhydride) groups or a polar group which is convertible into said
carboxyl
groups by oxidation or hydrolysis. The acylating agent grafts onto the olefin
polymer
to give two carboxylic acid functionalities. Examples of useful acylating
agents
include maleic anhydride, chlormaleic anhydride, itaconic anhydride, or the
reactive
equivalents thereof, for example, the corresponding dicarboxylic acids, such
as
maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, the esters of
these
compounds and the acid chlorides of these compounds.
100901 In one embodiment, the functionalized ethylene-cc-olefin
copolymer
comprises an olefin copolymer grafted with the acyl group, which is further
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functionalized with a hydrocarbyl amine, a hydrocarbyl alcohol group, amino-
or
hydroxy- terminated polyether compounds, and mixtures thereof.
100911 In one embodiment, the hydrocarbyl amine may be selected
from aromatic
amines, aliphatic amines, and mixtures thereof. In one embodiment, the
hydrocarbyl
amine component may comprise at least one aromatic amine containing at least
one
amino group capable of condensing with said acyl group to provide a pendant
group
and at least one additional group comprising at least one nitrogen, oxygen, or
sulfur
atom, wherein said aromatic amine is selected from the group consisting of (i)
a nitro-
substituted aniline, (ii) an amine comprising two aromatic moieties linked by
a
C(0)NR- group, a -C(0)0- group, an -0- group, an N=N- group, or an -802- group
where R is hydrogen or hydrocarbyl, one of said aromatic moieties bearing said
condensable amino group, (iii) an aminoquinoline, (iv) an aminobenzimidazole,
(v)
an N,N- dialkylphenylenediamine, (vi), an aminodiphenyl amine (also N-
phenylphenylenediamine), (vii) a ring-substituted benzyl amine, and (viii) a
methylene-coupled dimer of aminodiphenyl amine.
100921 In one embodiment, lubricating composition may comprise a
poly(meth)acrylate polymeric viscosity modifier. As used herein, the term
"(meth)acrylate" and its cognates means either methacrylate or acrylate, as
will be
readily understood.
100931 In one embodiment, the poly(meth)acrylate polymer is
prepared from a
monomer mixture comprising (meth)acrylate monomers having alkyl groups of
varying length The (meth)acrylate monomers may contain alkyl groups that are
straight chain or branched chain groups. The alkyl groups may contain 1 to 24
carbon
atoms, for example, 1 to 20 carbon atoms.
100941 In one embodiment, the poly(meth)acrylate polymer
comprises a
dispersant monomer; dispersant monomers include those monomers which may
copolymerize with (meth)acrylate monomers and contain one or more heteroatoms
in
addition to the carbonyl group of the (meth)acrylate. The dispersant monomer
may
contain a nitrogen-containing group, an oxygen-containing group, or mixtures
thereof.
100951 Dispersant monomers may be present in an amount up to 5
mol percent of
the monomer composition of the (meth)acrylate polymer. In one embodiment, the
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poly(meth)acrylate is present in an amount 0 to 5 mol percent, 0.5 to 4 mol
percent,
or 0.8 to 3 mol percent of the polymer composition. In one embodiment, the
poly(meth)acrylate is free of or substantially free of dispersant monomers.
100961 In one embodiment, the poly(meth)acrylate polymer (P) is
a block or
tapered block copolymer that comprises at least one polymer block (Bi) that is
insoluble or substantially insoluble in the base oil and a second polymer
block (B2)
that is soluble or substantially soluble in the base oil
100971 In one embodiment, the poly(meth)acrylate polymers may
have an
architecture selected from linear, branched, hyper-branched, cross-linked,
star (also
referred to as "radial"), or combinations thereof. Star or radial refers to
multi -armed
polymers. Such polymers include (meth)acrylate-containing polymers comprising
3
or more arms or branches, which, in some embodiments, contain at least about
20, or
at least 50 or 100 or 200 or 350 or 500 or 1000 carbon atoms. The arms are
generally
attached to a multivalent organic moiety which acts as a "core" or "coupling
agent."
The multi-armed polymer may be referred to as a radial or star polymer, or
even a
"comb" polymer, or a polymer otherwise having multiple arms or branches as
described herein.
100981 Linear poly(meth)acrylates, random, block or otherwise,
may have weight
average molecular weight (Mw) of 1000 to 400,000 Daltons, 1000 to 150,000
Daltons, or 15,000 to 100,000 Daltons. In one embodiment, the
poly(meth)acrylate
may be a linear block copolymer with a Mw of 5,000 to 40,000 Daltons, or
10,000 to
30,000 Daltons Radial, cross-linked or star copolymers may be derived from
linear
random or di-block copolymers with molecular weights as described above. A
star
polymer may have a weight average molecular weight of 10,000 to 1,500,000
Daltons, or 40,000 to 1,000,000 Daltons, or 300,000 to 850,000 Daltons.
100991 Another class of polymeric viscosity modifiers is styrene-
diene (SD)
copolymers, such as styrene isoprene (SI) and styrene butadiene (SBR). Styrene-
diene copolymers may be linear or radial (star-shaped), and generally contain
one or
more distinct blocks of styrene attached to one or more distinct blocks of
hydrogenated diene.
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[00100] The lubricating compositions may comprise 0.05 weight % to 2 weight %,
or 0.08 weight % to 1.2 weight %, or 0.1 to 0.8 weight % of the one or more
polymeric
viscosity modifiers and/or dispersant viscosity modifiers.
[00101] Pour point depressants that may be useful in the compositions
disclosed
herein include polyalphaolefins, esters of maleic anhydride-styrene
copolymers,
poly(meth)acrylates, polyacrylates or polyacryl amides
[00102] Demulsifiers include trialkyl phosphates, and various polymers and
copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof.
[00103] Metal deactivators include derivatives of benzotriazoles (typically
tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles
or 2-
alkyldithiobenzothiazoles. The metal deactivators may also be described as
corrosion
inhibitors.
[00104] Seal swell agents include sulfolene derivatives Exxon Necton-37Tm (FN
1380) and Exxon Mineral Seal OilTM (FN 3200).
[00105] The lubricating composition may further include one or more
dispersants
different from that of the first PIB succinimide dispersant and the second PIB
succinimide dispersant of the compositions disclosed herein. Such dispersants
include succinimide dispersants different from that of described compositions,
Mannich dispersants, polyolefin succinic acid esters, amides, or ester-amides,
or
mixtures thereof.
[00106] The additional dispersant may be a PIBsuccinimide similar to the
dispersants of the described compositions, derived from polyisobutylene with a
number average molecular weight of 800 Daltons to 2600 Daltons. Additional
dispersants may be present to provide a boost to soot handling or as sources
of ashless
TBN. Soot dispersants may be functionalized with an aromatic (poly)amine.
Dispersants used as TBN boosters typically have high TBN, such as greater than
80
mg KOH/g, greater than 95 mg KOH/g, or even greater than 110 mg KOH/g.
[00107] The additional dispersant may be present in an amount 0.05 to 2 wt %,
or
0.1 to 1.1 wt %, or 0.2 to 0.8 wt % of the lubricant composition.
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Industrial Application
[00108] The lubricating compositions disclosed herein are suitable for use in
diesel
engines. Diesel engines are classified by their Gross Vehicle Weight Rating
(GVWR). The GVWR includes the maximum rated weight of the vehicle and cargo,
including passengers. The GVWR is applied to trucks or trailers, but not the
two
combined, which is a separate rating referred to as the Gross Combined Weight
Rating (GCWR). The GVWR's for various classes of diesel engines are set forth
in
the table below:
Class GVWR (lbs)
Class 1 0-6,000 lbs
Class 2 6,001-10,000 lbs
(divided into 2 classes Class 2A & 2B, see
below)
Class 2A 6,001-8,500 lbs
Class 2B 8,501-10,000 lbs
Class 3 10,001-14,000 lbs
Class 4 14,001-16,000 lbs
Class 5 16,001-19,500 lbs
Class 6 19,5001-26,000 lbs
Class 7 26,001-33,000 lbs
Class 8 Over 33,000 lbs
[00109] Light duty vehicles are classified as those falling in Class 1 to 3.
Class 2A
vehicles are typically called "light duty" and class 2B vehicles are often
called "light
heavy duty" vehicles.
[00110] Medium duty vehicles refer to those falling into Classes 4 to 6. Heavy-
Duty vehicles are those classified in Class 7 and Class 8.
[00111] There is a distinct difference between the class of vehicles as they
relate
to operating conditions. The difference in size means that higher classified
vehicles
have engines that will experience significantly different operating conditions
such as
load, oil temperatures, duty cycle and engine speeds. Heavy-duty diesel
engines are
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designed to maximize torque for hauling payloads at maximum fuel economy while
passenger car (lower class vehicles) are designed for commuting people and
acceleration at maximum fuel economy. The designed purpose of the engine
hauling
versus communing results in different hardware designs and resulting stresses
imparted to lubricant designed to protect and lubricate the engine. Another
distinct
design difference is the operating revolution per minute (RPM) that each
engine
operates at to haul versus commute. A heavy-duty diesel engine such as a
typical 12-
13 liter truck engine would typically not exceed 2200 rpm while a passenger
car
engine can go up to 4500 rpm.
[00112] In one embodiment, the internal combustion engine is a heavy-duty
diesel
compression ignited (or spark assisted compression ignited) internal
combustion
engine.
[00113] The sulfur content of the lubricating composition may be 1 wt % or
less,
or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one
embodiment, the
sulfur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to
0.3 wt
%. The phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or
0.1 wt
% or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or
less,
0.055 wt % or less, or 0.05 wt % or less. In one embodiment, the phosphorus
content
may be 0.04 wt % to 0.12 wt %. In one embodiment, the phosphorus content may
be
100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content may
be 0.3 wt % to 1.2 wt %, or 0.5 wt % to 1.1 wt % of the lubricating
composition.
[00114] In one embodiment, the sulfated ash content may be 0.2 to 1.2 wt % of
the
lubricating composition. The lubricating compositions disclosed herein may
have a
sulfated ash content of from 0.2 to 1.2 wt %, or from 0.3 to 1.1 wt %, or 0.4
to 0.8 wt
%.
[00115] As used herein, TBN values are (total base number) measured by the
methodology described in ASTM D4739 (buffer).
[00116] The lubricating composition may be characterized as having a total
base
number (TBN) content of at least 3, or at least 4, or at least 5 mg KOH/g.
[00117] The lubricating composition may be characterized as having a total
base
number (TBN) content of 5 to 10 mg KOH/g, or 5 to 8.5 mg KOH/g.
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[00118] The lubricating compositions disclosed herein have a kinematic
viscosity
as measured by ASTM D-445 at 100 C of from 2.5 to 8.3, or 3.5 to 6.5 cSt
(mm2/s)
and a kinematic viscosity at 40 C of from 15 to 30 cSt (mm2/s). In another
embodiment, the lubricating composition has a kinematic viscosity at 100 C of
from
2.5 to 6.5 or 3 to 5.5 cSt (mm2/s) and a kinematic viscosity at 40 C of from
15 to 25
cSt (mm2/s)
[00119] The lubricating composition disclosed herein have a high temperature,
high shear viscosity (HTHS) as measured by ASTM D4683 at 150 C of less than
2.6
mPa-s, or less than 2.5 mPa-s, or less than 2.3 mPa-s, or less than 2.1 mPa-s.
In
another embodiment, the HTHS of the lubricating composition is from 1.4 to 2.5
mPa-s, or from 1.6 to 2.1 mPa-s, or from 1.8 to 2.1 mPa-s, or from 1.9 to 2.0
mPa-s.
[00120] The lubricating composition may have a SAE viscosity grade of OW-Y,
wherein Y may be 12, 16, or 20. In one embodiment, the lubricating composition
has
an SAE viscosity grade of OW-12.
[00121] The internal combustion engine disclosed herein may have a steel
surface
on a cylinder bore, cylinder block, or piston ring.
[00122] The internal combustion engine may have a surface of steel, or an
aluminum alloy, or an aluminum composite.
[00123] Typically, the compression-ignition internal combustion engine has a
maximum laden mass over 3,500 kg.
[00124] The instant disclosure is further directed to a method of lubricating
a diesel
engine by supplying to the diesel engine any one of the lubricating
compositions
disclosed herein. In one embodiment, the method includes lubricating a diesel
engine
by supplying to said engine a lubricating composition having an oil of
lubricating
viscosity having greater than 50 weight percent of a Group III base oil, a
Group IV
base oil, or mixtures thereof; a first PIB succinimide dispersant derived from
an 1800
to 2500 Mn PIB; a second PIB succinimide dispersant derived from a PIB with an
Mn less than 1600, where at least one of the first PIB succinimide dispersant
and the
second PIB succinimide dispersant is boron-free; a calcium salicylate
detergent; an
alkaline earth metal sulfonate detergent present in an amount to deliver 0.3
wt % to
2.1 wt % of alkaline earth metal soap to the lubricating composition; and a
phosphorus antiwear agent present in an amount to deliver 300 to 900 ppm
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phosphorous to the lubricating composition, wherein the lubricating
compositions
further include a total sulfated ash of between 0.3 to 0.9 wt. % and an HTHS
as
measured according to ASTM D4683 of less than 2.7 mPa= s.
[00125] Another embodiment provides for the use of any one of the lubricating
compositions disclosed herein to improve at least one of wear protection and
fuel
economy in a compression ignited internal combustion engine (typically a heavy-
duty diesel internal combustion engine).
[00126] In different embodiments, the lubricating composition disclosed herein
may have a composition as described in the following table:
Additive Embodiments (wt %)
A
PIB succinimide Dispersant 1 0.5 to 10 0.8 to 5
1.1 to 2.2
PIB succinimide Dispersant 2 0.5 to 8 1 to 5
1.4 to 2.6
Alkaline Earth Salicylate
0.2 to 3 0.3 to 2
0.4 to 1.2
Detergent(s)
Alkaline Earth Metal Sulfonate
0.1 to 2 0.3 to 1.2
0.4 to 0.8
Detergent(s)
Phosphorous Antiwear Agent 0.2 to 2 0.3 to 1.3
0.5 to 0.95
Ashless Antioxidants 0 to 6 1.2 to 5
1.8 to 4.2
Friction Modifier 0 to 2 0.05 to 1.2
0.1 to 0.85
or
Additional Dispersant 0 to 2 0.1 to 1.1 0
0.2
to 0.8
0 or 0.1
Additional Detergent 0 to 1 0.05 to 0.7
to 0.5
Polymeric VM or DVM 0 to 5 0.05 to 1.8
0.1 to 0.6
Any Other Performance Additive 0 to 1 0.01 to 0.5 0
or 0.1
to 0.3
Group III and/or Group IV Base
50 to98 75 to 95
80 to 90
Oil
Other oil of lubricating viscosity Balance to 100 %
[00127] The following examples provide illustrations of the described
compositions. These examples are non-exhaustive and are not intended to limit
the
scope of the invention.
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EXAMPLES
1001281 A series of OW-12 engine lubricants in Group III base oil of
lubricating
viscosity are prepared containing the additives described above as well as
conventional additives including polymeric viscosity modifiers, corrosion
inhibitors,
pourpoint depressants, as well as other performance additives as follows
(Table 1).
El em ental s are included to demonstrate relative equivalence of
compositions.
Table 1 - Lubricating compositions'
EX1 EX2 EX3 EX4 EX5 EX6 EX7 EX8
OW-12 OW-12 OW-12 OW-12 OW-12 OW-12 OW-12 5W-30
4.2 cSt Group III
86.3 82.6 87.5 85.8 85.2 86.4
86.4 38
Oil
6.3 cSt Group III 0 0 0 0 0 0 0
36
Oil
Conventional 0 0 0 0 0 0 0
2.0
PIBsuccinimide2
Borated
0 0 0 0 0 0 0
1.0
Dispersant3
Soot Dispersant4 0 0 0 0 0 0 0
0.73
succinimide from
1.22 1.83 1.16 1.16 0.67 1.04
1.16 0
2000 Mn PIB5
PIBSuccinimide
from 980 Mn 1.68 2.52 0 0 0 0 0
0
PIB6
PIBsuceinimide
from 1550 Mn 0 0 1.49 1.49 1.42 1.42
1.49 0
PIB-2
Ashless TBN 0 0 0 0 0 0 0
0.13
Booster
Overbased
Calcium 0 0 0 0 0 0 0
0.22
sulfonates
S-free Magnesium 0 0 0 0 0 0 0
0.37
phenate
Calcium
0.56 0.84 0.67 0.84 0.84 1.12
0.56 0
Salicylate 9
T,ow 'MN
Calcium 0.4 0.6 0.5 0.55 0.55 0.15
0.50 0
Sulfonatel
Overbased
Magnesium 0.04 0.06 0.12 0.18 0.18
0.18 0.06 0.38
Sulfonate
C3/6 mixed 0 0 0 0 0 0 0
0.78
ZDDP
C6 Secondary
0.82 0.82 0.82 0.82 0.82 0.82
0.82 0
ZDDP
Ashless
3.2 3.2 3.2 4.2 4.2 4.2 4.2
3.5
Antioxidant'l
DVM12 0.3 0.35 0.13 0.13 0.13 0.13
0.13 0.6
Styrene diene VI 0 0 0 0 0 0 0
0.4
Improver
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Olcyl
0.5 0.5
glycolamide
G1V10 0.25
0.50
Oleyl amide 0.1 0.1
Ta rtrimide
1.8
Additive"
Molybdenum
0.16
Additive"
Other Additives15 0.24 0.24 0.24 0.24 0.24
0.24 0.24 0.24
Diluent Oil Balance to 100%
Calcium (ppm) 1000 1500 1220 1450 1450
1370 1090 1290
Magnesium (ppm) 70 100 190 280 280 280 90
720
Phosphorus (ppm) 760 790 760 760 730 740 720
760
Zinc (ppm) 820 900 820 870 820 820 800
820
Sulfur (ppm) 2100 2400 2200 2400 2200
2200 2100 2700
Boron (ppm) 0 0 0 0 80 0 0
100
Molybdenum 0 0 0 0 0 310 0
0
(ppm)
Sulfated Ash
0.5 0.7 0.6 0.8 0.8 0.8 0.5
1.0
(wt%)
1. All treat rates presented are oil free, unless otherwise noted
2. Polyisobutenyl succinimide dispersant prepared from 2300 Mn low
vinylidene PIB via chlorine
Diels-Alder process (TBN 54 mg KOH/g)
3. Borated analog of above dispersant (1% boron by weight)
4. PIBsuccinimide aromatic amine soot dispersant
5. Polyisobutenyl succinimicle dispersant prepared from high vinylidene
2000 Mn PIB via thermal
ene alkylation (TBN 26 mg KOH/g)
6. Polyisobutenyl succinimicle dispersant prepared from 980 Mn PIB (TBN 25
mg KOH/g)
7. Polyisobutenyl succinimicle dispersant prepared from high vinylidene
1550 Mn FIB Oa thermal
ene alkylation (TBN 17 mg KOH/g)
8. Overbased calcium alkylbenzene sulfimate (TBN 520 mg KOH/g; 48%
substrate)
9. Calcium overba,sed alkylsalicylate detergent (TBN 300 mg KOH/g; metal
ratio 2.8)
10. Low TBN calcium alkylbenzene sulfonate detergent (TBN 170 mg KOH/g; 84%
subs/rate; metal
ratio 2.7)
11. Combination of diary/amine, hindered phenol, and sulfiirized olefin.
12. Combination of low Mn (10 kDa) and high Mn (60 kDa) substituted ethylene-
propylene co-
polymers, finictionalized with aromatic amines
13. Pre-mixture of oleyl tartrimide (44 wt%), borating agent, basic nitrogen,
and compatibilizer (0.46
wt % Boron; TBN 17 mg KOH/g)
14. Sulfur-bridged Molybdenum (V) dimer, dithiocarbamate complex (commercially
available as
Sakuralube 525 from Adeka)
15. Other Additives include pourpoint depressant, foam inhibitor, and low
levels of corrosion
inhibitors and compatibilizers.
[00129] Lubricating examples of Table 1 are evaluated for fuel economy
improvement and ability to prevent/reduce wear. Results are summarized, along
with
other chemical and physical properties related to performance (Table 2). Fuel
economy improvement is measured according to the Volvo D 13TC fuel economy
test.
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In this test, improvement is determined relative to a pre-selected reference
oil; in
these data, Example 8 (EX8) was selected as the reference oil.
[00130] Resistance to wear (also called durability) was determined on a high
frequency reciprocating rig (HFRR) available from PCS Instruments. HFRR
conditions for the evaluations were 500 g load, 75minute duration, 1000
micrometer
stroke, 20 Hertz frequency, and at a temperature of 105 C. The wear and
contact
potential are then measured.
Table 2
EX1 EX2 EX3 EX4 EX5 EX6 EX7 EX8
Alkaline earth metal
0.8 1.2 1.0 1.2 1.2 1.1
0.9 1.3
soap
Alkaline earth metal
0.35 0.53 0.47 0.54 0.54
0.20 0.44 1.0
sulfonate soap
Alkaline earth metal
0.44 0.66 0.53 0.66 0.66
0.88 0.44 0
salicylate soap
Kinematic Viscosity at
5.7 6.3 5.7 5.7 5.6 5.6
5.7 9.9
100 C (D445) (m2/s)
HTHS (D4683)
2.05 2.24 2.06 2.08 2.06
2.04 2.06 3.08
(mPas s)
Base Oil viscosity at
4.2 4.2 4.2 4.2 4.2 4.2
4.2 5.2
100 C (D445)
% Fuel Economy
Improvement Volvo 1.41 0.78 1.11 1.11 1.46
1.41 1.08 REF
D13TC
HERR Wear Scar (p.m) 166 212 230 220 261 215
218 257
[00131] The results obtained indicate that the lubricant compositions are
capable
of providing improved fuel economy, while maintaining and even improving wear
control.
[00132] Lubricant compositions of the described herein also provide
cleanliness,
deposit control, and oxidation control in suitable bench tests. Deposit
performance
can be measured according to the Thermo-Oxidation Engine Oil Simulation Test
(TEOST 33) as presented in ASTM D6335. The results of the TEOST 33 test show
the milligrams of deposit after an engine oil is run at elevated temperatures.
Lower
TEOST 33 results are indicative of improved resistance to deposit formation.
The
lubricating compositions can be tested for deposit control in a Panel Coker
heated to
325 C., with a sump temperature of 105 C., and a splash/bake cycle of 120
s/45 s.
The airflow is 350 ml/min, with a spindle speed of 1000 rpm and the test lasts
for 4
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hours. The oil is splashed onto an aluminum panel which is then optically
rated by
computer. Performance ranges from 0% (black panel) to 100% (clean panel).
[00133] Fuel economy of the disclosed lubricating compositions can be tested
and
may have improvements pursuant to any one of the M111 Fuel Economy Test (CEC
L-54-96), Daimler 0M501LA Fuel Economy Test, NEDC MB Fuel Economy Tests,
and ILSAC Sequence VI Engine Test_ Friction performance may also be evaluated
in
any of several high frequency reciprocating rig (HFRR) bench test, e.g., ASTM
D6079.
[00134] Unless otherwise stated herein, reference to treat rates or amounts of
components present in the lubricating compositions disclosed herein are quoted
on
an oil free basis, i.e., amount of active.
[00135] As used herein, the term "hydrocarbyl sub stituent" or "hydrocarbyl
group"
is used in its ordinary sense, which is well-known to those skilled in the
art.
Specifically, it refers to a group having a carbon atom directly attached to
the
remainder of the molecule and having predominantly hydrocarbon character
including one or more double bonds. Examples of hydrocarbyl groups include:
hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g.,
cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and
alicyclic-
substituted aromatic substituents, as well as cyclic substituents wherein the
ring is
completed through another portion of the molecule (e.g., two substituents
together
form a ring); substituted hydrocarbon substituents, that is, substituents
containing
non- hydrocarbon groups which, in the context of this invention, do not alter
the
predominantly hydrocarbon nature of the substituent (e.g., halo (especially
chloro
and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and
sulfoxy);
hetero substituents, that is, substituents which, while having a predominantly
hydrocarbon character, in the context of this invention, contain other than
carbon in
a ring or chain otherwise composed of carbon atoms and encompass substituents
as
pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen,
and
nitrogen. In general, no more than two, or no more than one, non- hydrocarbon
substituent will be present for every ten carbon atoms in the hydrocarbyl
group;
alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl
group.
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[00136] The present disclosure is not to be limited in terms of the particular
embodiments described in this application, which are intended as illustrations
of
various aspects. Many modifications and variations can be made without
departing
from its spirit and scope, as will be apparent to those skilled in the art.
Functionally
equivalent methods and components within the scope of the disclosure, in
addition to
those enumerated herein, will be apparent to those skilled in the art from the
foregoing descriptions. Such modifications and variations are intended to fall
within
the scope of the appended claims. The present disclosure is to be limited only
by the
terms of the appended claims, along with the full scope of equivalents to
which such
claims are entitled. It is to be understood that this disclosure is not
limited to
particular methods, reagents, compounds, or compositions, which can, of
course,
vary. It is also to be understood that the terminology used herein is for the
purpose
of describing particular embodiments only and is not intended to be limiting.
[00137] As used in this document, the singular forms "a," "an," and "the"
include
plural references unless the context clearly dictates otherwise. Unless
defined
otherwise, all technical and scientific terms used herein have the same
meanings as
commonly understood by one of ordinary skill in the art. Nothing in this
disclosure
is to be construed as an admission that the embodiments described in this
disclosure
are not entitled to antedate such disclosure by virtue of prior invention. As
used in
this document, the term "comprising" means "including, but not limited to."
[00138] While various compositions, methods, and devices are described in
terms
of "comprising" various components or steps (interpreted as meaning
"including, but
not limited to"), the compositions, methods, and devices can also "consist
essentially
of" or "consist of" the various components and steps, and such terminology
should
be interpreted as defining essentially closed-member groups.
[00139] With respect to the use of substantially any plural and/or singular
terms
herein, those having skill in the art can translate from the plural to the
singular and/or
from the singular to the plural as is appropriate to the context and/or
application. The
various singular/plural permutations may be expressly set forth herein for
sake of
clarity.
[00140] It will be understood by those within the art that, in general, terms
used
herein, and especially in the appended claims (e.g., bodies of the appended
claims)
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are generally intended as "open" terms (e.g., the term "including" should be
interpreted as "including but not limited to," the term "having" should be
interpreted
as "having at least," the term "includes" should be interpreted as "includes
but is not
limited to," etc.). It will be further understood by those within the art that
if a specific
number of an introduced claim recitation is intended, such an intent will be
explicitly
recited in the claim, and in the absence of such recitation, no such intent is
present
For example, as an aid to understanding, the following appended claims may
contain
usage of the introductory phrases "at least one" and "one or more" to
introduce claim
recitations. However, the use of such phrases should not be construed to imply
that
the introduction of a claim recitation by the indefinite articles "a" or "an"
limits any
particular claim containing such introduced claim recitation to embodiments
containing only one such recitation, even when the same claim includes the
introductory phrases "one or more" or "at least one" and indefinite articles
such as
"a" or "an" (e.g., "a" and/or "an" should be interpreted to mean "at least
one" or "one
or more"); the same holds true for the use of definite articles used to
introduce claim
recitations. In addition, even if a specific number of an introduced claim
recitation is
explicitly recited, those skilled in the art will recognize that such
recitation should be
interpreted to mean at least the recited number (e.g., the bare recitation of
"two
recitations," without other modifiers, means at least two recitations, or two
or more
recitations). Furthermore, in those instances where a convention analogous to
"at
least one of A, B, and C, etc." is used, in general, such a construction is
intended in
the sense one having skill in the art would understand the convention (e g ,
"a system
having at least one of A, B, and C" would include but not be limited to
systems that
have A alone, B alone, C alone, A and B together, A and C together, B and C
together,
and/or A, B, and C together, etc.). In those instances where a convention
analogous
to "at least one of A, B, or C, etc." is used, in general, such a construction
is intended
in the sense one having skill in the art would understand the convention
(e.g., "a
system having at least one of A, B, or C" would include but not be limited to
systems
that have A alone, B alone, C alone, A and B together, A and C together, B and
C
together, and/or A, B, and C together, etc.). It will be further understood by
those
within the art that virtually any disjunctive word and/or phrase presenting
two or
more alternative terms, whether in the description, claims, or drawings,
should be
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understood to contemplate the possibilities of including one of the terms,
either of
the terms, or both terms. For example, the phrase "A or B" will be understood
to
include the possibilities of "A" or "B" or "A and B."
[00141] In addition, where features or aspects of the disclosure may be
described
in terms of Markush groups, those skilled in the art will recognize that the
disclosure
is also thereby described in terms of any individual member or subgroup of
members
of the Markush group.
[00142] As will be understood by one skilled in the art, for any and all
purposes,
such as in terms of providing a written description, all ranges disclosed
herein also
encompass any and all possible subranges and combinations of subranges
thereof.
Any listed range can be easily recognized as sufficiently describing and
enabling the
same range being broken down into at least equal halves, thirds, quarters,
fifths,
tenths, etc. As a non-limiting example, each range discussed herein can be
readily
broken down into a lower third, middle third and upper third, etc. As will
also be
understood by one skilled in the art all language such as "up to," "at least,"
and the
like include the number recited and refer to ranges which can be subsequently
broken
down into subranges as discussed above. Finally, as will be understood by one
skilled
in the art, a range includes each individual member. Thus, for example, a
group
having 1-3 wt. % refers to groups having 1, 2, or 3 wt.%. Similarly, a group
having
1-5 wt. % refers to groups having 1, 2, 3, 4, or 5 wt. %, and so forth,
including all
points therebetween.
[00143] Moreover, where a recited range for a treat rate is provided, it is
contemplated that such range shall include treat rates for individual
components
and/or a mixture of components. Thus, for example, a range of 1 to 3 wt %
contemplates that a given component may be present in a range of 1 to 3 wt %
or that
a mixture of similar components can be present in a range from 1 to 3 wt %.
[00144] As used herein, the term "about" means that a value of a given
quantity is
within +20% of the stated value. In other embodiments, the value is within
+15% of
the stated value. In other embodiments, the value is within +10% of the stated
value. In other embodiments, the value is within +5% of the stated value. In
other
embodiments, the value is within +2.5% of the stated value. In other
embodiments,
the value is within +1% of the stated value.
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[00145] Unless otherwise stated, "wt %" as used herein shall refer to the
weight
percent based on the total weight of the composition on an oil-free basis.
[00146] As described hereinafter the number average molecular weight of the
dispersant viscosity modifier and viscosity modifier has been determined using
known methods, such as GPC analysis using polystyrene standards. Methods for
determining molecular weights of polymers are well known. The methods are
described
for instance: (i) P.J. Flory, "Principles of Polymer Chemistry", Cornell
University Press
91953), Chapter VII, pp 266-315; or (ii) "Macromolecules, an Introduction to
Polymer
Science", F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp
296-312.
[00147] While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the specification.
Therefore, it is to
be understood that the invention disclosed herein is intended to cover such
modifications as fall within the scope of the appended claims.
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