Note: Descriptions are shown in the official language in which they were submitted.
TITLE
METHOD OF LUBRICATING AN END-PIVOT FINGER FOLLOWER VALVE TRAIN LASH ADJUSTER
FIELD OF INVENTION
[0001] The invention provides a method of lubricating an end-pivot finger
follower valve train lash adjuster of a passenger car compression ignition
internal combustion engine having a reference mass not exceeding 2610 kg
comprising supplying to the internal combustion engine a lubricating
composition comprising an oil of lubricating viscosity 0.01 wt % to 3 wt % of
a
dispersant viscosity modifier, and 0.01 wt % to 3 wt % of a zinc free sulphur-
containing antiwear agent, wherein the lubricating composition has a sulphur-
content of less than 5000 ppm, a phosphorus content of 1000 ppm or less, and a
sulphated ash content of 12,000 ppm or less, or 10,000 ppm or less.
BACKGROUND OF THE INVENTION
[0002] The valve train of internal combustion engines is known to vary in
both the design and with fuel type. For example the fuel type may be gasoline
or
diesel; and the valve train may have general types of configuration such as a
direct acting cam and bucket, an end-pivot finger follower, a push rod or a
rocker
arm.
When considering valve-train designs from a tribological standpoint as it
interacts with a lubricant, the specific type of valve-train, the slide to
roll ratio
between contacts and the metallurgy can all affect the lubrication regime
differently, meaning that engine metallurgy, contact pressure, speed of
contact,
surface finish, sliding versus rolling contact (or slide to roll ratio) all
affect the
way in which lubricant additives interact and contribute towards reducing
wear,
corrosion, or fatigue of engine components.
[0003] For example, the differences in engine design allow for
different types
of valve train design. Valve-train designs are selected by original equipment
manufacturer (OEM) depending upon design requirements for their engine and
whilst there is no "best" design for an engine, the OEM considers design
factors
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including valve-train design in combination other factors such as different
fuel
types and engine size.
[0004] Heavy duty diesel engines are noted to be limited to all motor
vehicles
with a "technically permissible maximum laden mass" over 3,500 kg, equipped
with compression ignition engines or positive ignition natural gas (NG) or LPG
engines. In contrast, the European Union indicates that for new light duty
vehicles (passenger cars and light commercial vehicles) included within the
scope of ACEA testing section "C" have a "technically permissible maximum
laden mass" not exceeding 2610 kg.
[0005] There is a distinct difference between passenger car, and heavy duty
diesel engines. The difference in size from over 3,500 kg to not more than
2610
kg means that engines of both types will experience significantly different
operating conditions such as load, oil temperatures, duty cycle and engine
speeds. Heavy duty diesel engines are designed to maximize torque for hauling
payloads at maximum fuel economy while passenger car diesels are designed for
commuting people and acceleration at maximum fuel economy. The designed
purpose of the engine hauling versus commuting 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 litre truck engine
would typically not exceed 2200 rpm while a passenger car engine can go up to
4500 rpm. The difference in rpm between a heavy duty diesel engine and a
passenger car means that because of the more extreme operating conditions a
passenger car lubricant will be exposed to higher operating temperatures,
higher
shear, increased oxidation and deposit rates.
[0006] For many years engine design has focused on heavy duty diesel
and
gasoline engines that have a valve train comprising a direct acting cam and
bucket, or a rocker arm. The prior art references summarised below emphasizes
the efforts undertaken to improve engine lubricant design to enhance soot
handling for heavy duty diesel engines such as Mac0 T-10 or T-11, or
minimisation of wear or sludge formation in gasoline engines such as those
TM
required for GF-3 approval or Sequence IIIF approval, or Peugeot TU3M
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engine. Efforts have been made to reduce deposit formation in cam- and bucket
valve train TDi Volkswagon engines.
[0007] US 2013/0143781 (Barton et al., published 20 May 2013)
discloses a
method of lubricating an internal combustion engine and a lubricating
composition comprising an oil of lubricating viscosity and 0.1 wt % to 70 wt %
of a copolymer comprising units derived from monomers (i) an a-olefin and (ii)
an ethylenically unsaturated carboxylic acid or derivatives thereof,
esterified and
ami dated with an alcohol and an aromatic amine respectively,
wherein the copolymer is obtained by a process comprising: (1) reacting
monomers (i) an a-olefin and (ii) an ethylenically unsaturated carboxylic acid
or
derivatives thereof to form a copolymer; (2) reacting the product of step (1)
with
an aromatic amine; and (3) reacting the copolymer of step (2) with an alcohol,
to
form a copolymer that is amidated and esterified.
[0008] US 2013/0143780 (Gieselman et al, published 20 May 2013)
discloses
a lubricating composition comprising an oil of lubricating viscosity and a
compound comprising the reaction product of a polyolefin, an ethylenically
unsaturated aromatic acylating agent (or carboxylic reactant), and an amine.
In
one embidimen the amine is an acyclic polyamine, the polyolefin is a
polybutene, and the lubricating composition has a sulphated ash content of 0.3
wt % to 1.2 wt % of the lubricating composition. The lubricating composition
is
disclosed for use in an internal combustion engine having a surface of steel
or
aluminium (typically a surface of steel).
[0009] US 2012/0184473 (Boffa et al., published 20 December 2012)
discloses a lubricating oil composition comprising: i) a major amount of a
base
oil, ii) at least one oil-soluble molybdenum compound and iii) a zinc
dialkyldithiophosphate compound, wherein the molybdenum content derived
from the molybdenum compound is at least 10 ppm Molybdenum based on the
total weight of the lubricating oil composition and the phosphorus content
derived from the zinc dialkyldithiophosphate compound is about 200 ppm to 500
ppm based on the total weight of the lubricating oil composition. The method
of lubricating a motor engine comprising the step of operating the engine with
the lubricating oil composition is also disclosed.
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[0010] US
2012/0046206 (Gieselman et al., published 23 February 2012)
discloses a lubricating composition comprising an oil of lubricating
viscosity, a
dispersant and an amine-functionalised additive, wherein the amine-
functionalised additive is derived from an amine having at least 3 or 4
aromatic
groups, wherein the amine-functionalised additive is a product
obtained/obtainable by reacting the amine having at least 3 aromatic groups
with
a carboxylic functionalised polymer. . The lubricants are used in a Mack T 11
test, and further exemplify the use of sulphurised olefin antioxidant in an
unspecified amount.
[0011] US 2009/0325831
(Mathur et al., published 30 June 2008) discloses a
lubricating composition comprising: a major amount of an oil of lubricating
viscosity; and a minor amount of an additive concentrate comprising a
viscosity
index modifying copolymer comprising the reaction product of an acylated
ethylene-olefin copolymer and a polyamine, wherein the polyamine comprises at
least two primary or secondary amine functional group. The lubricating
composition is disclosed as useful for a method of lubricating an automotive
engine.
[0012] US
2009/0305923 (Visger et al., published 10 December 2009)
discloses in a lubricant a composition comprising a major amount of an oil of
lubricating viscosity and a minor amount of the an esterified, nitrogen-
functionalized interpolymer composition derived from monomers comprising (i)
at least one monomer selected from (a) vinyl aromatic monomers, and (ii) at
least one a,13-unsaturated acylating agent; wherein a portion of said
acylating
agent-derived units is esterified and wherein a portion of said acylating
agent-
derived units is condensed with at least one aromatic amine containing at
least
one N-H group capable of condensing with the acylating agent monomer-derived
unit, the amine being selected from the group consisting of 4-
aminodiphenylamine, 4-phenylazoaniline, 2-aminobenzimidazole, and 3-
nitroaniline. The lubricant is disclosed as useful for reducing soot-induced
viscosity increase in heavy duty diesel engines and exemplified in Mack T-11
test.
[0013] US
2008/182768 (Devlin et al., published 31 July 2008) discloses
improved lubricant compositions for bio-diesel fuel engine. The bio diesel
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engine operate on a fuel containing from about 5 to about 100 wt. % bio-diesel
components and is lubricated with a lubricating oil composition comprising a
major amount of oil of lubricating viscosity, and a minor amount of at least
one
highly grafted, multi-functional olefin copolymer made by reacting an
acylating
agent with an olefin copolymer having a number average molecular weight
greater than about 1,000 in the presence of a free radical initiator to
provide an
acylated olefin copolymer having a degree of grafting (DOG) of the acylating
agent on the olefin copolymer of at least 0.5 wt. %, and reacting the acylated
olefin copolymer with an amine to provide the highly grafted, multi-functional
olefin copolymer, wherein the highly grafted, multi-functional olefin
copolymer
is effective to reduce a viscosity increase in the lubricating oil composition
for
the engine to less than or equal to a viscosity increase in a lubrication oil
composition for an engine operating on a fuel devoid of the bio-diesel
components. The lubricant performs in the T-11 soot deposit test.
[0014] US 2007/0111904
(Van Dam, published 17 May, 2007) discloses a
low sulfur and low phosphorus lubricating oil composition comprising: (a) a
major amount of an oil of lubricating viscosity; (b) one or more dispersants;
(c)
one or more anti-oxidants; and (d) one or more detergents; wherein the
lubricating oil composition is essentially free of zinc di-alkyl di-
thiophosphates
and contains no more than 0.1 weight percent sulfur and provided the
lubricating
oil composition does not contain alkylated and non-alkylated aromatic amines
and tri-nuclear molybdenum compounds. The lubricant is evaluated in a Mack
T-10 diesel engine cylinder liner wear test.
[0015] US
2006/0264342 (Shaw et al, published 23 November 2006)
discloses a method of lubricating an internal combustion engine having a cam
and a rotating tappet, the method comprising employing as the lubricant for
the
engine a lubricating composition comprising a base oil of lubricating
viscosity,
phosphorus in an amount of from 50 to 900 ppm by mass, sulfur in an amount of
from 1500 to 3000 ppm by mass, boron in an amount of from 0.0 to 100 ppm,
sulphated ash in an amount not exceeding 1.0 mass %, and friction modifier in
an
amount of from 0.0 to 0.1 mass %, said amounts being based on the mass of
fully
formulated lubricating oil composition. Preferred lubricating compositions
also
contain a viscosity index improver dispersant. Examples of viscosity index
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improver dispersants include reaction products of amines, for example
polyamines, with a hydrocarbyl-substituted mono -or dicarboxylic acid in which
the hydrocarbyl substituent comprises a chain of sufficient length to impart
viscosity index improving properties to the compounds. In general, the
viscosity
index improver dispersant may be, for example, a polymer of a C4 to C24
unsaturated ester of vinyl alcohol or a C3 to CIO unsaturated mono-carboxylic
acid or a C4 to C10 di-carboxylic acid with an unsaturated nitrogen-containing
monomer having 4 to 20 carbon atoms; a polymer of a C2 to C20 olefin with an
unsaturated C3 to C10 mono- or di-carboxylic acid neutralised with an amine,
hydroxyamine or an alcohol; or a polymer of ethylene with a C3 to C20 olefin
further reacted either by grafting a C4 to C20 unsaturated nitrogen-containing
monomer thereon or by grafting an unsaturated acid onto the polymer backbone
and then reacting carboxylic acid groups of the grafted acid with an amine,
hydroxy amine or alcohol.
[0016] US 2003/0148895
(Robson et al., published 9 November 2001)
discloses a lubricating oil compositions intended to reduce wear in the
Peugeot
TU3M gasoline Scuffing Test. This test is intended to investigate wear on the
cam and tappets of an internal combustion engine. The disclosures of this
document show that relatively high levels of boron (derived from borated
dispersant) and preferably augmented with significant amount of molybdenum
(derived from, e.g., a trinuclear molybdenum additive) are required to reduce
cam and tappet wear to acceptable levels.
[0017] US
2006/0205614 (Artman et al., published 14 September 2006)
discloses a low-sulfur, low-phosphorus composition suitable for lubricating a
compression ignited internal combustion engine, comprising: (a) an oil of
lubricating viscosity; (b) a substantially nitrogen-free sulfurized olefin
antiwear
agent, in an amount sufficient to provide improved antiwear performance to the
composition; (c) about 1 to about 10 percent by weight of a nitrogen-
containing
dispersant; and (d) an overbased detergent selected from the group consisting
of
salixarates, saligenins, salicylates, glyoxylates, and mixtures thereof; said
composition containing less than about 0.1 percent by weight phosphorus, less
than about 0.4 percent by weight sulfur, and having less than about 1.2%
sulfated
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ash. The internal combustion engine exemplified is an API CH-4 Cummins Mll
heavy duty diesel engine.
[0018] US
8,420,583 (Boegner et al., published 22 May, 2003) discloses a
lubricating oil composition comprising: a major amount of oil of lubricating
viscosity; and a minor amount of at least one highly grafted, multi-functional
olefin copolymer made by reacting an acylating agent with an olefin copolymer
having a number average molecular weight greater than about 10,000 up to about
50,000 in the presence of a free radical initiator to provide an acylated
olefin
copolymer having a degree of grafting (DOG) of the acylating agent on the
olefin copolymer of from above about 1.5 to about 3.0 wt. %, and reacting the
acylated olefin copolymer with an amine to provide the highly grafted, multi-
functional olefin copolymer. The lubricating compositions are disclosed for
lubricating compression ignited internal combustion engines for reducing soot
deposits.
[0019] US 8,168,574
(Visger et al., published 10 December 2009) discloses
reducing soot-induced viscosity increase in heavy duty diesel engines. The
lubricating composition disclosed therein comprises an oil of lubricating
viscosity and an esterified, nitrogen-functionalized interpolymer composition
derived from monomers comprising (i) at least one monomer selected from (a)
vinyl aromatic monomers, and (ii) at least one a,P-unsaturated acylating
agent;
wherein a portion of said acylating agent-derived units is esterified and
wherein
a portion of said acylating agent-derived units is condensed with at least one
aromatic amine containing at least one N-H group capable of condensing with
said acylating agent monomer-derived unit, said amine being selected from the
group consisting of 4-aminodiphenylamine, 4-phenylazoaniline, 2-
aminobenzimidazole, and 3-nitroaniline.
[0020] US
8,093,189 (Devlin et al., published 13 March, 2008) discloses a
low SAP lubricating oil composition for heavy-duty diesel engines, and
particularly CJ-4, CI-4 PLUS or CI-4 engines comprising a major amount of oil
of lubricating viscosity and a minor amount of an amine-functionalized olefin
copolymer dispersant viscosity index improver comprising the reaction product
of an acylated olefin copolymer and a polyamine compound, wherein the olefin
copolymer dispersant viscosity index improver is present in an amount
effective
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to inhibit coolant-induced filter plugging, as measured by the Cummins ISM
EGR Test, upon the lubricating oil composition being contaminated by about 2
percent engine coolant composed of an approximately 50:50 mixture of water
and pure (poly)ethylene glycol (total), relative to a modified form of the
lubricating oil composition which instead contains a non-amine functionalized,
non-acylated form of the olefin copolymer dispersant but otherwise is the
same.
[0021] US
2006/025316 (Covitch et al., published 2 February 2006) discloses
a method for lubricating a heavy-duty diesel engine equipped with exhaust gas
recirculation, comprising supplying thereto a composition comprising an oil of
lubricating viscosity and the reaction product of: (a) a polymer comprising
carboxylic acid functionality or a reactive equivalent thereof, said polymer
having a number average molecular weight of greater than 5,000; and (b) an
amine component comprising at least one aromatic amine containing at least one
amino group capable of condensing with said carboxylic acid functionality 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 (such as 3-
nitroaniline), (ii)
amines 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, and (vi) a ring-substituted benzylamine.
[0022] US
2004/038836 (Devlin et al., published 26 February 2004) discloses
a lubricant suitable for use in a diesel engine comprising: a lubricating oil
having
a viscosity suitable for use in a diesel engine; at least one functionalized
olefin
polymer; and a zinc dialkyl dithiophosphate (ZDDP) wherein the ZDDP is made
from a mixture of primary alcohols or a mixture of primary and secondary
alcohols, wherein the lubricant has high boundary film friction value as
measured by using a High Frequency Reciprocating Rig (HFRR) of greater than
or equal to 15.
[0023] US
2003/134754 (Kelley, published 17 July 2003) discloses a
composition comprising: (a) a major amount of an API Group I mineral oil base
stock containing at least 300 ppm sulfur by weight; (b) a molybdenum
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dithiocarbamate in an amount suitable to provide about 25 to about 600 ppm
molybdenum to the composition; (c) a succinimide dispersant based on a
polyolefin-substituted succinic structure, where the polyolefin has a number
average molecular weight of at least about 1300; (d) a zinc
dialkyldithiophosphate derived from at least one secondary alcohol; and (e) at
least one oxidation inhibitor selected from the group consisting of hindered
phenols, alkylated aromatic amines, and sulfurized olefins. The composition is
noted as useful for lubricating engine oils formulated the meet the new
specifications of ILSAC GF-3 using conventional high sulfur base stocks and
tested in Sequence ITIF gasoline engine.
[0024] For a
passenger car diesel engine designed having an end-pivot finger
follower valve train with a lash adjuster, fewer studies have been reported
attempting to improve lubricant performance by reducing wear. As a result,
Peugeot have introduced a test method entitled DW10 Lash Adjuster Test, run at
APL testing laboratory (Automobil-Priiftechnik Landau GmbH) for engine
having this design. A lubricant must obtain a wear rating of 7 or higher to
pass
the wear requirements of this test. The objective of the present invention is
to
reduce wear in passenger car diesel engine having an end-pivot finger follower
valve train with a lash adjuster and in a specific embodiment have a wear
rating
of greater than 7 as measured in the DW10 Lash Adjuster Test.
SUMMARY OF THE INVENTION
[0025] As
used herein reference to the amounts of additives present in the
lubricating composition disclosed herein are quoted on an oil free basis,
i.e.,
amount of actives, unless otherwise indicated.
[0026] As used herein,
the transitional term "comprising," which is
synonymous with "including," "containing," or "characterized by," is inclusive
or open-ended and does not exclude additional, un-recited elements or method
steps. However, in each recitation of "comprising" herein, it is intended that
the
term also encompass, as alternative embodiments, the phrases -consisting
essentially of" and "consisting of," where "consisting of" excludes any
element or
step not specified and "consisting essentially of" permits the inclusion of
additional un-recited elements or steps that do not materially affect the
basic and
novel characteristics of the composition or method under consideration.
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[0027] The
invention relates to a method of lubricating an end-pivot finger
follower valve train lash adjuster of a passenger car compression ignition
internal combustion engine having a reference mass not exceeding 2610 kg
comprising supplying to the internal combustion engine a lubricating
composition comprising an oil of lubricating viscosity 0.01 wt % to 3 wt % of
a
dispersant viscosity modifier, and 0.01 wt % to 3 wt % of a zinc free sulphur-
containing antiwear agent, wherein the lubricating composition has a sulphur-
content of less than 5000 ppm, a phosphorus content of 1000 ppm or less, and a
sulphated ash content of (typically 3000 to 12,000 ppm), or 10,000 ppm or
less.
[0028] The passenger
car reference mass not exceeding 2610 kg is a technical
feature defined by the European Union as specified in Euro 5 and 6 emission
requirements. The same standard is applied by the professional industry
association ACEA (European Automobile Manufacturers Association) such that
it defines a light passenger car in Section C of the ACEA European Oil
Sequences for 2010. As such the method of the present invention relates to
lubricating a light passenger car compression ignition internal combustion
engine
(a diesel engine) comprising an end-pivot finger follower valve train lash
adjuster.
[0029] The
lubricating composition may have a sulphur-content of 500 to
4000 ppm, or 1000 to 3000 ppm, a phosphorus content of 300 to 900 ppm, or 400
to 750 ppm, and a sulphated ash content of 3000 to 7000 ppm.
[0030] The
lubricating composition may comprise a zinc free sulphur-
containing antiwear agent comprising 0.1 to 0.5 wt % sulphurised olefin, and
0.1
to 0.5 wt % of an olefin copolymer further functionalised with a dispersant
amine group, wherein the olefin copolymer is an ethylene-propylene copolymer.
[0031] The
lubricating composition may comprise 0.1 wt % to 0.4 wt % of
molybdenum dithiocarbamate a zinc free sulphur-containing antiwear agent, and
0.1 to 0.5 wt %, an olefin copolymer further functionalised with a dispersant
amine group, wherein the olefin copolymer is an ethylene-propylene copolymer.
[0032] The lubricating
composition disclosed herein may further comprise
calcium sulphonate overbased detergent present at 0.01 to 0.5 wt %, or 0.05 to
0.3 wt % of the lubricating composition (typically wherein the calcium
sulphonate overbased detergent has a TBN of 300 to 500 mg KOH/g).
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[0033] The lash adjuster typically comprises a ball and socket joint.
[0034] The lash adjuster typically is a hydraulic lash adjuster.
[0035] The
lash adjuster is typically a hydraulic lash adjuster comprising a
ball and socket joint. In one embodiment the lash adjuster does not have a
chrome coating, a tin coating, a nitride coating, or a boride coating.
[0036] The
invention further provides for the method or use of a lubricating
composition comprising:
an oil of lubricating viscosity,
0.01 wt % to 3 wt % of a dispersant viscosity modifier, and
0.01 wt % to 3 wt % of a zinc free sulphur-containing antiwear agent,
wherein the lubricating composition has a sulphur-content of less than 5000
ppm,
a phosphorus content of 1000 ppm or less, and a sulphated ash content of
typically 3000 to 12,000 ppm, or 10,000 ppm or less,
to reduce wear in an internal combustion engine comprising an end-pivot finger
follower valve train lash adjuster.
[0037] The
reduction in wear may be measured by Peugeot DW10 Lash
Adjuster Test with a pass rating of 7 or higher.
DETAILED DESCRIPTION OF THE INVENTION
[0038] The
present invention provides a method for lubricating an internal
combustion engine and a use as disclosed above.
Oils of Lubricating Viscosity
[0039] The
lubricating composition comprises 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 hydroisomerised Fischer-
Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a
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Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-
liquid
oils.
[0040] 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 summarised in US Patent
US 7,285,516 (see column 11, line 64 to column 12, line 10).
[0041] In one
embodiment the oil of lubricating viscosity may be an API
Group I to IV mineral 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 mineral oil, an ester or a synthetic oil, or mixtures thereof.
[0042] 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 invention and the other performance additives.
[0043] The lubricating
composition may be in the form of a concentrate
and/or a fully formulated lubricant. If the lubricating composition of the
invention (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 of
the invention comprises 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.
Dispersant Viscosity Modifier
[0044] The lubricating
composition of the invention contains a dispersant
viscosity modifier. The dispersant viscosity modifier may be present at 0.05
wt
% to 1.5 wt %, or 0.1 wt % to 1 wt %, or 0.1 to 0.5 wt %.
[0045] The dispersant viscosity modifier may include functionalised
polyolefins, for example, ethylene-propylene copolymers that have been
functionalised with an acylating agent such as maleic anhydride and an amine;
polymethacrylates functionalised with an amine, or styrene-maleic anhydride
copolymers reacted with an amine. More detailed description of dispersant
viscosity modifiers are disclosed in International Publication W02006/015130
or
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U.S. Patents 4,863,623; 6,107,257; 6,107,258; 6,117,825; and US 7,790,661. In
one embodiment the dispersant viscosity modifier 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]).
[0046] In one
particular embodiment the dispersant viscosity modifier
comprises an olefin copolymer further functionalised with a dispersant amine
group. Typically, the olefin copolymer is an ethylene-propylene copolymer.
[0047] The
olefin copolymer has a number average molecular weight of 5000
to 100,000, or 7500 to 60,000, or 8000 to 45,000.
[0048] The
dispersant amine group may be prepared/derived from reacting
the olefin copolymer (typically, a ethylene-propylene copolymer) with an
acylating agent (typically maleic anhydride) and an aromatic amine having a
primary or secondary amino group. Typically, the dispersant viscosity modifier
may be an ethylene-propylene copolymer acylated with maleic anhydride and
reacted with an aromatic amine.
[0049] The
formation of a dispersant viscosity modifier is well known in the
art. The dispersant viscosity modifier may include for instance those
described
in U.S. Patent US 7,790,661 column 2, line 48 to column 10, line 38.
[0050] In one
embodiment the dispersant viscosity modifier may be prepared by
grafting of an olefinic carboxylic acid acylating agent onto a polymer of 15
to 80
mole percent of ethylene, from 20 to 85 mole percent of C1_10 ct-monoolefin,
and from
0 to 15 mole percent of non-conjugated diene or triene, said polymer having an
average molecular weight ranging from 5000 to 500,000, and further reacting
said
grafted polymer with an amine (typically an aromatic amine).
[0051] In
another embodiment the dispersant viscosity modifier may be a
reaction product of: (a) a polymer comprising carboxylic acid functionality or
a
reactive equivalent thereof, said polymer having a number average molecular
weight of greater than 5,000; and (b) an amine component comprising at least
one aromatic amine containing at least one amino group capable of condensing
with said carboxylic acid functionality 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-
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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 -SO2-
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.
[0052] The
aromatic amine of the dispersant viscosity modifier may also
include those which can be represented by the general structure NH,-Ar or T-
NH-Ar, where T may be alkyl or aromatic, Ar is an aromatic group, including
nitrogen-containing or amino-substituted aromatic groups and Ar groups
including any of the following structures:
vR
/(¨)
Rv Rv
KRvI KR ______ RV
Rvn
as well as multiple non-condensed or linked aromatic rings. In these and
related
structures, Rv, Rvi, and Rvi1 can be independently, among other groups
disclosed
herein, -H, -C1_18 alkyl groups, nitro groups, -NH-Ar, -N=N-Ar, -NH-CO-Ar,
-00C-Ar, -00C-Ci_18 alkyl, -COO-C118 alkyl, -OH, -0-(CH2CH2-0)11C1 is alkyl
groups, and -0-(CH2CH20)õAr (where n is 0 to 10).
[0053]
Aromatic amines include those amines wherein a carbon atom of the
aromatic ring structure is attached directly to the amino nitrogen. The amines
may be monoamines or polyamines. The aromatic ring will typically be a
mononuclear aromatic ring (i.e., one derived from benzene) but can include
fused aromatic rings, especially those derived from naphthalene. Examples of
aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-
butylaniline, di-(para-methylphenyl)amine, 4-aminodiphenylamine, N,N-
dimethylphenylenediamine, naphthylamine, 4-(4 -
nitrophenylazo)aniline
(disperse orange 3), sulphamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-
aminoacetanili de (N-(4-aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic
acid phenyl ester (phenyl amino salicylate), N-(4-amino-phenyl)-benzamide,
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various benzylamines such as 2,5-dimethoxybenzylamine, 4-phenylazoaniline,
and substituted versions of these. Other examples include para-ethoxyaniline,
para-dodecylaniline, cyclohexyl-substituted naphthylamine, and thienyl-
substituted aniline. Examples of other suitable aromatic amines include amino-
substituted aromatic compounds and amines in which the amine nitrogen is a
part
of an aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-
aminoquinoline. Also
included are aromatic amines such as 2-
aminobenzimidazole, which contains one secondary amino group attached
directly to the aromatic ring and a primary amino group attached to the
imidazole
ring. Other amines include N-(4-anilinopheny1)-3-aminobutanamide or 3-amino
propyl imidazole. Yet other amines include 2,5-dimethoxybenzylamine.
[0054]
Additional aromatic amines and related compounds are disclosed in
U.S. Patent 6,107,257 and 6,107,258; some of these include aminocarbazoles,
benzoimidazoles, aminoindoles, aminopyrroles, amino-indazolinones, amino-
perimidines, mercaptotriazoles, aminophenothiazines, aminopyridines, amino-
pyrazines, aminopyrimidines, pyridines, pyrazines, pyrimidines, amino-
thiadiazoles, aminothiothiadiazoles, and aminobenzotriaozles. Other suitable
amines include 3-amino-N-(4-anilinopheny1)-N-isopropyl butanamide, and N-(4-
ani 1 inoph eny1)-3- 1(3 -aminopropy1)-(cocoal kyl)ami no 1 butan
am i de . Other
aromatic amines which can be used include various aromatic amine dye
intermediates containing multiple aromatic rings linked by, for example, amide
structures. Examples include materials of the general structure:
Rix
4 H =
C-N NH2
and isomeric variations thereof, where Rviii and Rix are independently alkyl
or
alkoxy groups such as methyl, methoxy, or ethoxy. In one instance, Rvili and
R.
are both ¨OCH3 and the material is known as Fast Blue RR [CAS# 6268-05-9].
i [0055] In
another instance, Rix is ¨OCH3 and Ry s ¨CH3, and the material is
known as Fast Violet B [99-21-8]. When both Rviii and Rix are ethoxy, the
material is Fast Blue BB [120-00-3]. U.S. Patent 5,744,429 discloses other
aromatic amine compounds, particularly aminoalkylphenothiazines. N-aromatic
substituted acid amide compounds, such as those disclosed in U.S. Patent
Application 2003/0030033 Al, may also be used for the purposes of this
invention. Suitable aromatic amines include those in which the amine nitrogen
is
a substituent on an aromatic carboxyclic compound, that is, the nitrogen is
not
sp2 hybridized within an aromatic ring.
[0056] The aromatic amine may also comprise an amine formed by
reacting
an aldehyde with 4-aminodiphenylamine. The resultant amine may be described
as an alkylene coupled amine having at least 4 aromatic groups, at least one -
NH2
functional group, and at least 2 secondary or tertiary amino groups. The
aldehyde
may be aliphatic, alicyclic or aromatic. The aliphatic aldehyde may be linear
or
branched. Examples of a suitable aromatic aldehyde include benzaldehyde or o-
vanillin. Examples of an aliphatic aldehyde include formaldehyde (or a
reactive
equivalent thereof such as formalin or paraformaldehyde), ethanal or propanal.
Typically the aldehyde may be formaldehyde or benzaldehyde. Alternatively,
this aromatic amine may also be prepared by the methodology described in
Reports of the German Chemical Society (1910), 43, 728-39.
[0057] The aromatic amine formed by coupling an aldehyde and
4-aminodiphenylamine is described European Patent application EP 2 401 348 A
in and may also be represented by the formula:
N
H,Nt
NH,
I=J
wherein each variable
may be hydrogen or a Ch5 alkyl group (typically hydrogen);
R2 may be hydrogen or a Ch5 alkyl group (typically hydrogen);
U may be an aliphatic, alicyclic or aromatic group, with the proviso that when
U
is aliphatic, the aliphatic group may be linear or branched alkylene group
containing 1 to 5, or 1 to 2 carbon atoms; and
w may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).
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[0058] In one embodiment the aromatic amine includes
4 -aminodiphenylamine, aldehyde (typically formaldehyde)
coupled
4-aminodiphenylamine, nitro-aniline (3- nitro-aniline), disperse orange-3
(D03),
or mixtures thereof.
Zinc Free Sulphur-Containing Antiwear Agent
[0059] The
lubricating composition of the invention contains a zinc free
sulphur-containing antiwear agent. The zinc free sulphur-containing antiwear
agent may be present at 0.01 wt % to 1.5 wt %, 0.05 wt % to 1 wt %, or 0.1 to
0.5 wt % of the lubricating composition.
[0060] The zinc free
sulphur-containing antiwear agent may be selected from
the group consisting of a sulphurised olefin, a molybdenum compound, an amine
salt of a (thio)phosphorus-containing compound, a thiadiazole, and mixtures
thereof.
[0061] In one
embodiment the zinc free sulphur-containing antiwear agent
may be a molybdenum compound. The molybdenum compound may be an
antiwear agent or an antioxidant. The molybdenum compound may be selected
from the group consisting of molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof.
Typically the molybdenum compound may be molybdenum dithiocarbamate, or
molybdenum dithiophosphate.
[0062] The
molybdenum compound may provide the lubricating composition
with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 400 ppm, or 20
ppm to 350 ppm of molybdenum. Examples of molybdenum dithiocarbamates,
which may be used as an antioxidant, include commercial materials sold under
the trade names such as Vanlube 822TM and MolyvanTM A from R. T. Vanderbilt
Co., Ltd., and Adeka SakuraLubeTM S-100, S-165, S-600 and 525, or mixtures
thereof.
[0063] In
another embodiment the zinc free sulphur-containing antiwear
agent may be a sulphurised-olefin. The
sulphurised olefin may be a
polysulphide.
[0064] In an
embodiment the sulphurised-olefin includes dihydrocarbyl
polysulphides; sulphurised olefins; sulphurised fatty acid esters of both
natural
and synthetic origins; trithiones; sulphurised thienyl derivatives;
sulphurised
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terpenes; sulphurised oligomers of C2-C8 monoolefins; and sulphurised Diets-
Alder adducts such as those disclosed in U.S. Patent Number Re 27,331.
Specific
examples include sulphurised polyisobutene, sulphurised isobutylene,
sulphurised diisobutylene, sulphurised triisobutylene, dicyclohexyl
polysulphide,
diphenyl polysulphide, dibenzyl polysulphide, dinonyl polysulphide, and
mixtures of di-tert-butyl polysulphide such as mixtures of di-tert-butyl
trisulphide, di-tert-butyl tetrasulphide and di-tert-butyl pentasulphide,
among
others. Combinations of such categories of sulphur-containing antiwear and/or
extreme pressure agents may also be used, such as a combination of sulphurised
isobutylene and di-tert-butyl trisulphide, a combination of sulphurised
isobutylene and dinonyl trisulphide, a combination of sulphurised tall oil and
dibenzyl polysulphide.
[0065] In a
further embodiment at least 50 wt % of the polysulphide
molecules are a mixture of tri- or tetra- sulphides. In other embodiments at
least
55 wt %, or at least 60 wt % of the polysulphide molecules are a mixture of
tri-
or tetra- sulphides.
[0066] The
polysulphide includes a sulphurised organic polysulphide from oils,
fatty acids or ester (such as ester-containing sulphurised olefin), olefins or
polyolefins.
[0067] Oils which may
be sulfurized include natural or synthetic oils such as
mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols and
fatty
acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate),
and
synthetic unsaturated esters or glycerides.
[0068] Fatty
acids include those that contain 8 to 30, or 12 to 24 carbon
atoms. Examples of fatty acids include oleic, linoleic, linolenic, and tall
oil.
Sulphurised fatty acid esters prepared from mixed unsaturated fatty acid
esters
such as are obtained from animal fats and vegetable oils, including tall oil,
linseed oil, soybean oil, rapeseed oil, and fish oil.
[0069] The
polysulphide includes olefins derived from a wide range of
alkenes. The alkenes typically have one or more double bonds. The olefins in
one embodiment contain 3 to 30 carbon atoms. In other embodiments, olefins
contain 3 to 16, or 3 to 9 carbon atoms. In one embodiment the sulphurised
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olefin includes an olefin derived from propylene, isobutylene, pentene or
mixtures thereof.
[0070] In
another embodiment the polysulphide comprises a polyolefin
derived from polymerising by known techniques, an olefin as described above.
[0071] In still
another embodiment the polysulphide includes dibutyl
tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised
alkylphenol,
sulphurised dipentene, sulphurised dicyclopentadiene, sulphurised terpene, and
sulphurised Diels-Alder adducts.
[0072] In a
further embodiment the sulphurised olefin may be an ester-
containing sulphurised olefin. The ester-containing sulphurised olefin may
include a sulphurised 4-carbobutoxy cyclohexene.
[0073] In a
still further embodiment the zinc free sulphur-containing antiwear
agent may be a thiadiazole compound. Examples of a thiadiazole include 2,5-
dimercapto-1,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole, a hydrocarbylthio-substituted 2,5-dimercapto-
1,3,4-thiadiazole, or oligomers thereof. The
oligomers of hydrocarbyl-
substituted 2,5-dimercapto-1,3,4-thiadiazolc typically form by forming a
sulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazolc units to form
oligomers of two or more of said thiadiazole units. These
thiadiazole
compounds may also be used in the post treatment of dispersants as mentioned
below in the formation of a dimercaptothiadiazole derivative of a
poly isob utylene succinimide.
[0074]
Examples of a suitable thiadiazole compound include at least one of a
dimercaptothiadiazole, 2,5-dimercapto-[1,3,41-thiadiazole, 3,5 -
dimerc apto-
[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole, or 4-5-dimercapto-
[1,2,3]-thiadiazole.
Typically readily available materials such as
2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-
1,3 ,4-thiadiazole or a hydrocarbylthio -substituted 2,5 -dimercapto -1,3 ,4 -
thiadiazole arc commonly utilised.
[0075] In one
embodiment the zinc free sulphur-containing antiwear agent
may be an amine salt of a (thio)phosphorus-containing compound. The an amine
salt of a (thio)phosphorus-containing compound may be an amine salt of a
phosphate hydrocarbon ester (i.e., an amine salt of a hydrocarbon ester of
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phosphoric acid). The amine salt of a phosphate hydrocarbon ester may be
derived from an amine salt of a phosphate. The amine salt of the phosphate
hydrocarbon ester may be represented by the formula:
0 R5
R¨O
0-
+R6
P-
R4-0/ \R7
R5
wherein
R3 and R4 may be independently hydrogen or hydrocarbon typically containing 4
to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms, with the proviso that
at
least one is a hydrocarbon group; and
R5, R6, R7 and R8 may be independently hydrogen or a hydrocarbyl group, with
the proviso that at least one is a hydrocarbyl group.
[0076] The hydrocarbon groups of R3 and/or R4 may be linear, branched,
or
cyclic.
[0077] The amine salt of a phosphate hydrocarbon ester may be prepared
as is
described in US Patent 6,468,946. Column 10, lines 15 to 63 describes
phosphoric acid esters formed by reaction of phosphorus compounds, followed
by reaction with an amine to form an amine salt of a phosphate hydrocarbon
ester. Column 10, line 64, to column 12, line 23, describes preparative
examples
of reactions between phosphorus pentoxide with an alcohol (having 4 to 13
carbon atoms), followed by a reaction with an amine (typically Primene081-R)
to form an amine salt of a phosphate hydrocarbon ester.
[0078] The amine salt of a (thio)phosphorus-containing compound may
also
be a compound described in European patent applications EP 2 318 493 A, and 2
113 023 A. Disclosed in both EP applications is a sulphur-free amine salt of a
phosphorus compound obtained/obtainable by a process comprising: reacting an
amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or
(ii) a
phosphorylated hydroxy-substituted di- or tri- ester of phosphoric acid, and
represented by Formula (1) and (la) in both publications.
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[0079] The
lubricating composition may comprise 0.01 wt % to 1.5 wt %
sulphurised olefin, 0.05 wt % to 1.5 wt %, an olefin copolymer further
functionalised with a dispersant amine group.
[0080] The
lubricating composition may further comprise a mobybdenum-
containing compound selected from the group consisting essentially of
molybdenum dithiocarbamate, and molybdenum dithiophosphate (typically
molybdenum dithiocarbamate) present in an amount ranging from 0.01 to 0.75
wt %, or 0.05 wt % to 0.5 wt %, or 0.1 wt % to 0.4 wt %.
[0081] The
lubricating composition may comprise 0.01 wt %to 0.75 wt %
molybdenum dithiocarbamate, 0.05 wt % to 1.5 wt %, an olefin copolymer
further functionalised with a dispersant amine group, wherein the olefin
copolymer is an ethylene-propylene copolymer.
[0082] The
lubricating composition may comprise 0.01 wt % to 1.5 wt %
sulphurised olefin, 0.01 wt % to 0.75 wt % molybdenum dithiocarbamate, 0.05
wt % to 1.5 wt %, an olefin copolymer further functionalised with a dispersant
amine group, wherein the olefin copolymer is an ethylene-propylene copolymer.
Other Performance Additives
[0083] A
lubricating composition may be prepared by adding the product of the
process described herein to an oil of lubricating viscosity, optionally in the
presence
of other performance additives (as described herein below).
[0084] The
lubricating composition of the invention optionally comprises other
performance additives. The other performance additives include at least one of
metal deactivators, viscosity modifiers, detergents, friction modifiers,
antiwear
agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers,
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.
[0085] In one
embodiment the invention provides a lubricating composition
further comprising an overbased metal-containing detergent. The metal of the
metal-containing detergent may be zinc, sodium, calcium, barium, or
magnesium. Typically the metal of the metal-containing detergent may be
sodium, calcium, or magnesium.
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[0086] The
overbased metal-containing detergent may be selected from the
group consisting of non-sulphur containing phenates, sulphur containing
phenates, sulphonates, salixarates, salicylates, and mixtures thereof, or
borated
equivalents thereof. The overbased detergent may be borated with a borating
agent such as boric acid.
[0087] The
overbased metal-containing detergent may also include "hybrid"
detergents formed with mixed surfactant systems including phenate and/or
sulphonate components, e.g. phenate/salicylates, sulphonate/phenates,
sulph onate/salicyl ates, sulphonates/ph en ates/sal i cylates, 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 sulphonate/phenate detergent is employed, the hybrid
detergent would be considered equivalent to amounts of distinct phenate and
sulphonate detergents introducing like amounts of phenate and sulphonate
soaps,
respectively.
[0088] Typically, an
overbased metal-containing detergent may be a zinc,
sodium, calcium or magnesium salt of a phenate, sulphur containing phenate,
sulphonate, salixarate or salicylatc.
Overbascd salixarates, phenates and
salicylates typically have a total base number of 180 to 450 TBN. Overbased
sulphonates typically have a total base number of 250 to 600, or 300 to 500.
Overbased detergents are known in the art. In one embodiment the sulphonate
detergent may be a predominantly linear alkylbenzene sulphonate detergent
having a
metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US
Patent
Application 2005065045 (and granted as US 7,407,919). The predominantly linear
alkylbenzene sulphonate detergent may be particularly useful for assisting in
improving fuel economy.
[0089]
Typically, the overbased metal-containing detergent may be a calcium
or magnesium an overbased detergent.
[0090]
Overbased detergents are known in the art. Overbased materials,
otherwise referred to as overbased or superbascd salts, are generally single
phase, homogeneous Newtonian systems characterized by a metal content in of
that which would be present for neutralization according to the stoichiometry
of
the metal and the particular acidic organic compound reacted with the metal.
The overbased materials are prepared by reacting an acidic material (typically
an
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inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a
mixture comprising an acidic organic compound, a reaction medium comprising
at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene,
etc.) for
said acidic organic material, a stoichiometric excess of a metal base, and a
promoter such as a calcium chloride, acetic acid, phenol or alcohol. The
acidic
organic material will normally have a sufficient number of carbon atoms to
provide a degree of solubility in oil. The amount of "excess" metal
(stoichiometrically) is commonly expressed in terms of metal ratio. The term
"metal ratio" is the ratio of the total equivalents of the metal to the
equivalents of
the acidic organic compound. A neutral metal salt has a metal ratio of one. A
salt having 3.5 times as much metal as present in a normal salt will have
metal
excess of 3.5 equivalents, or a ratio of 4.5. The term "metal ratio is also
explained in standard textbook entitled "Chemistry and Technology of
Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik,
Copyright 2010, page 219, sub-heading 7.25.
[0091] In
another embodiment the lubricating composition further comprises
a calcium sulphonatc overbased detergent and a calcium phenate overbased
detergent in an amount such that the sulphated ash content is 1000 ppm or less
(such as 100 ppm to 1000 ppm, or 300 ppm to 900 ppm).
[0092] 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
antioxidant is 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.
[0093] 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
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diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine. The
alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or
di-decyl
phenylnapthylamines.
[0094] The
hindered phenol antioxidant often contains a secondary butyl
and/or a tertiary butyl group as a sterically hindering group. The phenol
group
may be further substituted with a hydrocarbyl group (typically linear or
branched
alkyl) and/or a bridging group linking to a second aromatic group. Examples of
suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-
methyl-
2,6-di -tert-butylphenol , 4-ethyl-2,6-di -tert-butylphenol , 4-
propy1-2, 6-di -tert-
butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecy1-2,6-di-tert-butyl-
phenol. In one embodiment the hindered phenol antioxidant may be an ester and
may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of
suitable ester-containing hindered phenol antioxidant chemistry is found in US
Patent 6,559,105.
[0095] The lubricating
composition may in a further embodiment include a
dispersant, or mixtures thereof. The dispersant may be a succinimide
dispersant,
a Mannich dispersant, a succinamidc dispersant, a polyolefin succinic acid
ester,
amide, or ester-amide, or mixtures thereof. In one embodiment the dispersant
may be present as a single dispersant. In one embodiment the dispersant may be
present as a mixture of two or three different dispersants, wherein at least
one
may be a succinimide dispersant.
[0096] The
succinimide dispersant may be derived from an aliphatic polyamine,
or mixtures thereof. The aliphatic polyamine may be aliphatic polyamine such
as an
ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures
thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine.
In one embodiment the aliphatic polyamine may be selected from the group
consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetra-
ethylenepentamine, pentacthylenchexamine, polyamine still bottoms, and
mixtures thereof.
[0097] In one
embodiment the dispersant may be a polyolefin succinic acid
ester, amide, or ester-amide. For instance, a polyolefin succinic acid ester
may
be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures
thereof.
A polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid
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reacted with an alcohol (such as pentaerythritol) and a polyamine as described
above.
[0098] The dispersant may be an N-substituted long chain alkenyl
succinimide. An example of an N-substituted long chain alkenyl succinimide is
polyisobutylene succinimide. Typically the
polyisobutylene from which
polyisobutylene succinic anhydride is derived has a number average molecular
weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants
and their preparation are disclosed, for instance in US Patents 3,172,892,
3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170,
3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433,
and
6,165,235, 7,238,650 and EP Patent Application 0 355 895 A.
[0099] The
dispersants may also be post-treated by conventional methods by
a reaction with any of a variety of agents. Among these are boron compounds
(such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon
disulphide,
aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-
substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and
phosphorus compounds. In one embodiment the post-treated dispersant is
boratcd. In one
embodiment the post-treated dispersant is reacted with
dimercaptothiadiazoles. In one
embodiment the post-treated dispersant is
reacted with phosphoric or phosphorous acid. In one embodiment the post-
treated dispersant is reacted with terephthalic acid and boric acid (as
described in
US Patent Application US2009/0054278.
[00100]
[0100] When
present, the dispersant may be present at 0.01 wt % to 20 wt %,
or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1 to 3
wt % of the lubricating composition.
[0101] In one
embodiment the friction modifier may be selected from the
group consisting of long chain fatty acid derivatives of amines, long chain
fatty
esters, or derivatives of long chain fatty epoxides; fatty imidazolincs; amine
salts
of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides;
fatty alkyl
tartramides; fatty glycolates; and fatty glycolamides. The friction modifier
may
be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt
%,
or 0.1 wt % to 2 wt % of the lubricating composition.
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[0102] As
used herein the term "fatty alkyl" or "fatty" in relation to friction
modifiers means a carbon chain having 10 to 22 carbon atoms, typically a
straight carbon chain.
[0103]
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-polyamines; 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.
[0104]
Friction modifiers may also encompass materials such as sulphurised
fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates, sunflower oil or soybean oil monoester of a polyol and an
aliphatic carboxylic acid.
[0105] 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.
[0106] The
lubricating composition optionally further includes at least one
antiwear agent. Examples of
suitable antiwear agents include titanium
compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus
compounds, sulphurised olefins, metal dihydrocarbyldithiophosphates (such as
zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite),
phosphonates, thiocarbamate-containing compounds, such as thiocarbamate
esters, thiocarbamate amides, thiocarbamic ethers, alkyl ene-coupl ed thio-
carbamates, 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.
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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.
[0107] 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.
[0108] In one
embodiment, the oil soluble titanium compound is a titanium
carboxylate. In a further embodiment the titanium (IV) carboxylate is titanium
neodecanoate.
[0109] The lubricating
composition may in one embodiment further include a
phosphorus-containing antiwear agent. Typically the phosphorus-containing
antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate,
phosphonate, and ammonium phosphate salts, or mixtures thereof. Zinc
dialkyldithiophosphates are known in the art. The antiwear agent may be
present
at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the
lubricating composition.
[0110]
Extreme Pressure (EP) agents that are soluble in the oil include
sulphur- and chlorosulphur-containing EP agents, dimercaptothiadiazole or CS2
derivatives of dispersants (typically succinimide dispersants), derivative of
chlorinated hydrocarbon EP agents and phosphorus EP agents. Examples of such
EP agents include chlorinated wax; sulphurised olefins (such as sulphurised
isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or
oligomers thereof, organic sulphides and polysulphides such as dibenzyl-
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disulphide, bis¨(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised
methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene,
sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised
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,
dicyclo-
hexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl
phosphite, di stearyl phosphite and polypropylene substituted phenol
phosphite;
metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptyl-
phenol 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).
[0111] Foam
inhibitors that may be useful in the compositions of the invention
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.
[0112] Pour
point depressants that may be useful in the compositions of the
invention include polyalphaolefins, esters of maleic anhydride-styrene
copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
[0113]
Demulsifiers include trialkyl phosphates, and various polymers and
copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof.
[0114] 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.
[0115] Seal
swell agents include sulfolene derivatives Exxon Necton-37'm
(FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
Industrial Application
[0116] The
internal combustion engine may be a 4-stroke engine. The
internal combustion engine may or may not have an Exhaust Gas Recirculation
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system. The internal combustion engine may be fitted with an emission control
system or a turbocharger. Examples of the emission control system include
diesel
particulate filters (DPF), or systems employing selective catalytic reduction
(SCR).
[0117] The
sulphur 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 sulphur 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 A) 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 sulphated ash content may be 0.3 wt % to 1.2 wt %, or
0.5
wt % to 1.1 wt % of the lubricating composition. In one embodiment the
sulphated ash content may be 0.5 wt % to 1.1 wt % of the lubricating
composition.
[0118] In one
embodiment the lubricating composition may be characterised
as having at least one of (i) a sulphur content of 0.5 wt % or less, (ii) a
phosphorus content of 0.12 wt % or less, and (iii) a sulphated ash content of
0.5
wt % to 1.1 wt % of the lubricating composition.
[0119] The lubricating
composition may have a SAE viscosity grade of
XW-Y, wherein X may be 0, 5, 10, or 15; and Y may be 20, 30, or 40.
[0120] The
following examples provide illustrations of the invention. These
examples are non-exhaustive and are not intended to limit the scope of the
invention.
EXAMPLES
[0121]
Example 1 (EX1): is OW-30 lubricating composition comprising at
least 74 wt % of an API Group III/Group IV base oil mixture, molybdenum
dithiocarbamate present in an amount to deliver about 300 ppm of molybdenum,
0.33 wt % of a dispersant viscosity modifier prepared by reacting ethylene-
propylene copolymer with maleic anhydride and reacting it with 3-nitroaniline
and dimethylaminopropylamine (DMAPA). The lubricating composition further
contains a polyisobutylene succinimide, 2.1 wt % of a mixture of aminic and
phenolic antioxidants, 0.65 wt % of zinc dialkyldithiophosphate, 0.1 wt % of
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calcium overbased sulphonate, 1 wt % calcium overbased phenate, and 0.6 wt %
of a viscosity modifier. The lubricating composition has sulphur-content of
less
than 0.3 wt %, a phosphorus content of about 600 ppm, and a sulphated ash
content of 0.55 wt %.
[0122] Example 2 (EX2): is a OW-30 lubricating composition comprising at
least 74 wt % of an API Group III/Group IV base oil mixture, 0.3 wt % of a
sulphurised olefin, 0.33 wt % of a dispersant viscosity modifier prepared by
reacting ethylene-propylene copolymer with maleic anhydride and reacting it
with 3-nitroaniline and dimethylaminopropylamine (DMAPA). The lubricating
composition further contains a polyisobutylene succinimide, 2.1 wt % of a
mixture of aminic and phenolic antioxidants, 0.65 wt % of zinc
dialkyldithiophosphate, 0.1 wt % of calcium overbased sulphonate, 1 wt %
calcium overbased phenate, and 0.6 wt % of a viscosity modifier. The
lubricating composition has sulphur-content of less than 0.3 wt %, a
phosphorus
content of about 600 ppm, and a sulphated ash content of 0.55 wt %.
[0123] Comparative Example 1 (CE1): is similar to EX1 except the
lubricant
does not contain a molybdenum dithiocarbamate, a dispersant viscosity
modifier,
or a sulphurised-olefin. The lubricating composition has sulphur-content of
less
than 0.3 wt %, a phosphorus content of about 600 ppm, and a sulphated ash
content of 0.55 wt %..
[0124] Comparative Example 2 (CE2): is similar to EX1 except it
contains a
molybdenum dithiocarbamate present in an amount to deliver 500 ppm of
molybdenum, and no dispersant viscosity modifier, or sulphurised-olefin. The
lubricating composition has sulphur-content of less than 0.3 wt %, a
phosphorus
content of about 600 ppm, and a sulphated ash content of 0.55 wt %.
[0125] Comparative Example 3 (CE3): is similar to EX2 except it
contains
0.2 wt % of sulphurised olefin and does not contain a molybdenum
dithiocarbamate, or a dispersant viscosity modifier. The lubricating
composition
has sulphur-content of less than 0.3 wt %, a phosphorus content of about 600
ppm, and a sulphated ash content of 0.55 wt %.
[0126] Comparative Example 4 (CE4): is similar to EX1 except it does
not
contain molybdenum dithiocarbamate. The lubricating composition has sulphur-
content of less than 0.3 wt %, a phosphorus content of about 600 ppm, and a
sulphated ash content of 0.55 wt %.
[0127] Lubricating Examples EX1, EX2, and CE1 to CE4 are evaluated by
DW10 engine test protocol run by APL in 2011-2013. The results obtained for
the testing are presented in the following table. Typically better results are
obtained for samples with a rating of 7 or more, and the test specifies a
minimum
pass rating of 7.
Lubricant Example Rating
CE1 5.75
CE2 6.43
CE3 5.89
CE4 6.41
EX1 8.52
EX2 7.46
[0128] The results obtained from the DW10 lash adjuster test indicate that
a
lubricating composition defined by the present invention passes the test, and
lubricating compositions outside the scope of the claimed invention fail the
test.
[0129] It is known that some of the materials described above may
interact in
the final formulation, so that the components of the final formulation may be
different from those that are initially added. The products formed thereby,
including the products formed upon employing lubricant composition of the
present invention in its intended use, may not be susceptible of easy
description.
Nevertheless, all such modifications and reaction products are included within
the scope of the present invention; the present invention encompasses
lubricant
composition prepared by admixing the components described above.
[0130]
Except in the Examples, or where otherwise explicitly indicated, all
numerical quantities in this description specifying amounts of materials,
reaction
conditions, molecular weights, number of carbon atoms, and the like, are to be
understood as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as being a
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commercial grade material which may contain the isomers, by-products,
derivatives, and other such materials which are normally understood to be
present in the commercial grade. However, the amount of each chemical
component is presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise indicated. It
is
to be understood that the upper and lower amount, range, and ratio limits set
forth herein may be independently combined. Similarly, the ranges and amounts
for each element of the invention may be used together with ranges or amounts
for any of the other elements.
[0131] As used herein,
the term "hydrocarbyl substituent" or "hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the
art. Specifically, it refers to a group having a carbon atom directly attached
to
the remainder of the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents, including
aliphatic, alicyclic, and aromatic substituents; 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; and hetero substituents, that is, substituents which
similarly
have a predominantly hydrocarbon character but contain other than carbon in a
ring or chain. A more detailed definition of the term "hydrocarbyl
substituent"
or "hydrocarbyl group" is described in paragraphs [0118] to [0119] of
International Publication W02008147704, or a similar definition in paragraphs
[0137] to [0141] of published application US 2010-0197536.
[0132] As
used herein the detergent total base number (TBN) may be measure
by ASTM D2896.
[0133] 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.
32
