Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Low Dispersant Lubricant Composition
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to lubricants for compression
ignition internal
combustion engines, particularly those demonstrating at least one of improved
seals
performance, reduced deposit formation, and excellent durability.
[0002] Lubrication of internal combustion engines has been a practice for
many
decades, yet continual improvement in lubricant technology is ongoing as new
engines and
new standards have been developed. Formulations directed to spark ignition
engines and
compression ignition engines, for instance, must address limits placed on
sulfated ash,
phosphorus, and sulfur content ("SAPS"), and restrictions in these components
often lead to
upper limits on the amount of metal-containing additives that can be included
in the lubricant.
Reduction in metal containing additives is necessary to reduce the impact of
metal ash on
exhaust aftertreatment devices and to reduce the emission of particulate
matter.
[0003] Chief among these metal-containing additives are zinc
dialkyldithiophosphates
(ZDDP) for wear and oxidation protection and overbased metal detergents for
cleanliness and
acid control. ZDDP has been the industry standard for reducing valve train
wear, protecting
against liner wear, and reducing oxidation leading to corrosive wear. However
the zinc
contributes to an increase in sulfated ash in the lubricating oil and the
phosphorus causes
inactivation of oxidation catalysts used in exhaust after-treatment devices.
[0004] Ashless dispersants are often utilized to provide cleanliness,
including sludge
and soot control. Polyisobutylene succinimide dispersants have been widely
used to
supplement detergents in providing deposit control. These succinimide
dispersants often
contribute to seals degradation and can have a negative impact on low
temperature
viscometrics, especially in modern fuel economy lubricants.
[0005] WO/PCT Patent Publication 2014-193543 discloses lubricant
compositions for
heavy duty diesel engines comprising oxyalkylated hydrocarbyl phenol
compounds.
[0006] The disclosed technology provides a lubricant composition with a
reduced
level of ashless dispersant, i.e. a low dispersant lubricating composition;
such compositions
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are suitable for reducing deposit formation in compression ignition internal
combustion
engines, while maintaining cleanliness. The disclosed technology further
provides a lubricant
composition with a reduced concentration of zinc-containing additives.
SUMMARY OF THE INVENTION
[0007] The present invention provides a low dispersant lubricating
composition
comprising (a) an oil of lubricating viscosity, (b) about 0.5 weight percent
to 3.0 weight
percent of an oxyalkylated hydrocarbyl-substituted phenol compound, (c) about
0.01 weight
percent to 2.6 weight percent of a polyalkenylsuccinimide dispersant, and (d)
about 0.05
weight percent to 2.0 weight percent of a polyolefin dispersant viscosity
modifier, and wherein
the lubricating composition contains zinc in an amount less than about 700 ppm
by weight of
the composition.
[0008] The present invention provides a low dispersant lubricating
composition
comprising (a) an oil of lubricating viscosity, (b) 0.5 weight percent to 3.0
weight percent of
an oxyalkylated hydrocarbyl phenol compound according to the formula:
R2
0 R3
\\ 0
(R44. in
R2
wherein each R2 is independently hydrogen or a hydrocarbyl group of 1 to 6
carbon atoms; R3
is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, an acyl group
represented by ¨
C(=0)R5, where R5 is a hydrocarbyl group of 1 to 24 carbon atoms, or mixtures
thereof; each
R4 is independently a hydrocarbyl group of 1 to 225 carbon atoms, wherein at
least one R4
contains 20 to 225 carbon atoms; n = 1 to 20; and m = 1 to 3; (c) 0.01 weight
percent to 2.6
weight percent of a polyalkenylsuccinimide dispersant, and (d) 0.05 weight
percent to 2.0
weight percent of a polyolefin dispersant viscosity modifier , and wherein the
lubricating
composition contains zinc in an amount less than 700 ppm by weight of the
composition.
[0009] The invention further provides a method of lubricating a light-
duty vehicle
equipped with a compression-ignition internal combustion engine with a low
dispersant
lubricating composition comprising (a) an oil of lubricating viscosity, (b)
about 0.5 weight
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percent to 3.0 weight percent of an oxyalkylated hydrocarbyl-substituted
phenol compound,
(c) about 0.01 weight percent to 2.6 weight percent of a
polyalkenylsuccinimide dispersant,
and (d) about 0.05 weight percent to 2.0 weight percent of a polyolefin
dispersant viscosity
modifier, and wherein the lubricating composition contains zinc in an amount
less than about
700 ppm by weight of the composition. A light duty vehicle, especially a light-
duty diesel
vehicle, is understood to be any vehicle with a gross weight of less than
about 8,500 pounds
(or approximately 3900 kg).
[0010] The invention further provides a method of reducing deposit
formation in a
light-duty compression ignition internal combustion engine by operating the
engine with a
lubricant composition comprising (a) an oil of lubricating viscosity, (b) an
0.5 weight percent
to 3.0 weight percent of an oxyalkylated hydrocarbyl-substituted phenol
compound, (c) 0.01
weight percent to 2.6 weight percent of a polyalkenylsuccinimide dispersant,
and (d) 0.05
weight percent to 2.0 weight percent of a polyolefin dispersant viscosity
modifier , and
wherein the lubricating composition contains zinc in an amount less than 700
ppm by weight
of the composition.
[0011] The invention further provides a method of improving the retention
of base
number, i.e., total base number (TBN), further into an engine oil drain
interval. TBN retention
may assist in mitigating the effects of acid build-up in an engine oil
lubricant composition.
DETAILED DESCRIPTION
[0012] Various preferred features and embodiments will be described below
by way
of non-limiting illustration.
[0013] The disclosed technology provides a low zinc lubricating
composition, a
method for lubricating an internal combustion engine with a low zinc
lubricating composition,
and the use as disclosed above.
Oil of Lubricating Viscosity
[0014] 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
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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 Fischer-Tropsch gas-to-liquid synthetic
procedure as
well as other gas-to-liquid oils.
[0015] Oils of lubricating viscosity may also be defined as specified in
the 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). In one embodiment, the oil of lubricating viscosity may be an
API Group II,
Group III, or Group IV oil, or mixtures thereof The five base oil groups are
as follows:
Base Oil Category Sulfur (%) Saturates (%) Viscosity Index
Group I >0.03 and/or <90 80 to 120
Group II <0.03 and >90 80 to 120
Group III <0.03 and >90 >120
Group IV All polyalphaolefins (PAO)
Group V All others not included in Groups I, II, III, or IV
[0016] The amount of the oil of lubricating viscosity present is
typically the balance
remaining after subtracting from 100 weight % (weight %) the sum of the amount
of the
compound of the invention and the other performance additives.
[0017] 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.
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[0018] In one embodiment, the base oil has a kinematic viscosity at 100 C
from 2
mm2/s (centi Stokes - cSt) to 16 mm2/s, from 3 mm2/s to 10 mm2/s, or even from
4 mm2/s to 8
mm2/s.
[0019] In one embodiment, the base oil comprises at least 30 weight % of
Group II or
Group III base oil. In another embodiment, the base oil comprises at least 60
weight % of
Group II or Group III base oil, or at least 80 weight % of Group II or Group
III base oil. In
one embodiment, the lubricant composition comprises less than 20 weight % of
Group IV
(i.e., polyalphaolefin) base oil. In another embodiment, the base oil
comprises less than 10
weight % of Group IV base oil. In one embodiment, the lubricating composition
is
substantially free of (i.e., contains less than 0.5 weight %) of Group IV base
oil.
[0020] Ester base fluids, which are characterized as Group V oils, have
high levels of
solvency as a result of their polar nature. Addition of low levels (typically
less than 10 weight
%) of ester to a lubricating composition may significantly increase the
resulting solvency of
the base oil mixture. Esters may be broadly grouped into two categories:
synthetic and natural.
An ester base fluid would have a kinematic viscosity at 100 C suitable for use
in an engine oil
lubricant, such as between 2 cSt and 30 cSt, or from 3 cSt to 20 cSt, or even
from 4 cSt to 12
cSt.
[0021] 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,
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and tripentaerythritol. Esters can also be monoesters of mono-carboxylic acids
and
monohydric alcohols.
[0022] 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 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 is described
in, e.g., United
States patent application 2011/0009300A1.
[0023] In one embodiment, the lubricating composition comprises at least 2
weight %
of an ester base fluid. In one embodiment, the lubricating composition of the
invention
comprises at least 4 weight %of an ester base fluid, or at least 7 weight % of
an ester base
fluid, or even at least 10 weight % of an ester base fluid.
Oxyalkylated Hydrocarbyl Phenol
[0024] In some embodiments, the lubricating composition may comprise an
oxyalkylated hydrocarbyl phenol represented by Formula 1:
R2
0): (R4\ R3
R2
FORMULA 1
wherein
each R2 is independently hydrogen or a hydrocarbyl group of 1 to 6 carbon
atoms;
R3 is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl group
represented
by -C(=0)1e,
R5 is a hydrocarbyl group of 1 to 24 carbon atoms;
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each R4 is independently a hydrocarbyl group of 1 to 220, or 20 to 220,
wherein at least one
R4 contains 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96
carbon atoms;
n = 1 to 10; and
m = 1 to 3.
[0025] The oxyalkylated hydrocarbyl phenol of Formula 1 is selected such
that one
R2 group is methyl, and the second R2 group is hydrogen; R3 is hydrogen, a
hydrocarbyl group
of 1 to 24 carbon atoms, or an acyl group represented by -C(=0)R5; R5 is a
hydrocarbyl group
of 1 to 24 carbon atoms; each R4 is a hydrocarbyl group of 25 to 200, or 35 to
180 or 40 to
180 to 60 to 180 or 40 to 96 carbon atoms; n = 1 to 10; and m = 1.
[0026] The oxyalkylated hydrocarbyl phenol of Formula 1 is selected such
that one
R2 is methyl, and the second R2 is hydrogen; R3 is hydrogen, a hydrocarbyl
group of 1 to 24
carbon atoms, or an acyl group represented by -C(=0)R5, R5 is a hydrocarbyl
group of 1 to 24
carbon atoms; R4 is a hydrocarbyl group of 1 to 220 or 20 to 220 carbon atoms,
wherein at
least one R4 comprises a polyalk(en)yl group containing 25 to 200, or 35 to
180 or 40 to 180
to 60 to 180 or 40 to 96 carbon atoms; n = 2 to 8; and m = 1.
[0027] The oxyalkylated hydrocarbyl phenol of Formula 1 is selected such
that one
R2 is methyl, and the second R2 is hydrogen; R3 is hydrogen, a hydrocarbyl
group of 1 to 24
carbon atoms, or an acyl group represented by -C(=0)R5, R5 is a hydrocarbyl
group of 1 to 24
carbon atoms; each a hydrocarbyl group of 1 to 220 or 20 to 220 carbon atoms
comprises a
polyisobutenyl group containing 25 to 200, or 35 to 180 or 40 to 180 to 60 to
180 or 40 to 96
carbon atoms; n = 2 to 8 (or 3 to 5); and m = 1.
[0028] The R4 group of each of the formulae above may be located in the
para-
position relative to the oxyalkylated group, and the resultant formula is
represented by the
structure:
R2
0 R3
n
R2
R4
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FORMULA 1(a)
wherein variables R2 to R5, and n, are defined previously.
[0029] In one embodiment, the oxyalkylated hydrocarbyl phenol of the
present
invention is represented by Formula 1(a), wherein R4 is a polyolefinic group
such as a
polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and
variables R2,
R3, R5, and n are defined previously. The polyisobutenyl group has a number
average
molecular weight of 350 to 2500, or 550 to 2300, or 750 to 1150. In one
embodiment, the
polyisobutenyl group has a number average molecular weight of 950-1000. The
polypropenyl
group may have a number average molecular weight of 740 to 1200, or 800-850.
In one
embodiment, the polypropenyl group has a number average molecular weight of
825.
[0030] In one embodiment, the oxyalkylated hydrocarbyl phenol of the
present
invention is represented by Formula 1(b):
R2
0< \R2 ),R3
R4 401 0
FORMULA 1(b)
wherein R4 is a polyolefinic group such as a polypropenyl or a polyisobutenyl
group (typically
a polyisobutenyl group), and variables R2, R3, R5, and n, are defined
previously. The
polyisobutenyl group may have a number average molecular weight of 350 to
2500, or 550 to
2300, or 750 to 1150. In one embodiment, the polyisobutenyl group has a number
average
molecular weight of 950-1000.
[0031] The oxyalkylated group of the oxyalkylated hydrocarbyl phenol has
the
formula ¨(R10),¨, wherein le is an ethylene, propylene, butylene group, or
mixtures
thereof; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2
to 5.
[0032] The oxyalkylated group of the oxyalkylated hydrocarbyl phenol may
be either
a homopolymer or copolymer or oligomers thereof If the oxyalkylated group is
in the form
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of a copolymer, or oligomer thereof, the oxyalkylated group may have either
random or block
architecture.
[0033] In one embodiment, the oxyalkylated group (or Rl is a propylene,
or butylene
group i.e., the oxyalkylated group does not require an ethylene group. If an
ethylene group is
present the oxyalkylate group may be a copolymer, or oligomer thereof with
either propylene
or butylene oxide i.e., blocks of (i) -CH2 CH20- with (ii) -CH2CH2CH2CH20-
or -CH2CH(CH3)CH20- or -CH2CH(CH3)0-.
[0034] In one embodiment, the oxyalkylated group is based upon propylene
oxide.
[0035] The oxyalkylated hydrocarbyl phenol is prepared by reacting a
hydrocarbyl
substituted phenol with an alkylene oxide (typically ethylene oxide, propylene
oxide or
butylene oxide), optionally in the presence of a base catalyst. Typically the
reaction occurs
in the presence of a base catalyst.
[0036] The base catalyst may include, but is not limited to, sodium
chloroacetate,
sodium hydride or potassium hydroxide
[0037] The aliphatic hydrocarbyl group (also represented by R4) is linear
or branched,
typically with at least one branching point. The aliphatic hydrocarbyl group
typically has one,
although it may in some embodiments be desirable to have to R4 groups, with
the second
group being methyl. If a second R4 group is present and is methyl, then the
oxyalkylated
hydrocarbyl phenol is a cresol.
[0038] In different embodiments, the oxyalkylated hydrocarbyl phenol of
the present
invention is present in an amount ranging from 0.01 weight % to 5 weight %, or
0.05 to 3.5
weight %, or 0.1 to 2.5 weight % of the lubricating composition. Typically the
oxyalkylated
hydrocarbyl phenol is present in an amount from 0.25 to 2 weight % of the
lubricating
composition.
Polyalkenylsuccinimide Dispersant
[0039] The lubricating compositions of the present invention comprises a
polyalkenylsuccinimide dispersant. The dispersant may be borated using 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, H3B03, and tetraboric acid,
H2B407), boric
oxide, boron trioxide, and alkyl borates. In one embodiment the borating agent
is boric acid
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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 the borated dispersant contains 0.1weight % 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.
[0040] The succinimide dispersant may be a derivative of 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, tetraethylenepentamine,
pentaethylenehexamine,
polyamine still bottoms, and mixtures thereof.
[0041] The succinimide dispersant may be a derivative of an aromatic
amine, an
aromatic polyamine, or mixtures thereof The aromatic amine may be 4-
aminodiphenylamine
(ADPA) (also known as N-phenylphenylenediamine), derivatives of ADPA (as
described in
United States Patent Publications 2011/0306528 and 2010/0298185), a
nitroaniline, an
aminocarbazole, an amino-indazolinone, an aminopyrimidine, 4-(4-
nitrophenylazo)aniline, or
combinations thereof In one embodiment, the dispersant is derivative of an
aromatic amine
wherein the aromatic amine has at least three non-continuous aromatic rings.
[0042] The succinimide dispersant may be a derivative of a polyether
amine or
polyether polyamine. Typical polyether amine compounds contain at least one
ether unit and
will be chain terminated with at least one amine moiety. The polyether
polyamines can be
based on polymers derived from C2-C6 epoxides such as ethylene oxide,
propylene oxide, and
butylene oxide. Examples of polyether polyamines are sold under the Jeffamine
brand and
are commercially available from Hunstman Corporation located in Houston,
Texas.
[0043] The dispersant is based upon a polyisobutylene succinimide
dispersant,
wherein the polyisobutylene of the borated polyisobutylene succinimide has a
number average
molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500 or 350 to 2200,
or 350 to
1350, or 350 to 1150 or 350 to 750 or 550 to 2200 or 550 to 1350 or 750 to
2200.
[0044] Suitable polyisobutylenes for use in the succinimide
dispersant,may include
those formed from polyisobutylene or highly reactive polyisobutylene having at
least about
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50 mol %, such as about 60 mol %, and particularly from about 70 mol % to
about 90 mol %
or greater than 90 mol%, terminal vinylidene content. Suitable polyisobutenes
may include
those prepared using BF3 catalysts. In one embodiment, the borated dispersant
is derived from
a polyolefin having number average molecular weight of 350 to 3000 Daltons and
a vinylidene
content of at least 50 mol %, or at least 70 mol %, or at least 90 mol %.
[0045] The dispersant is obtained from reaction of succinic anhydride by
an "ene" or
"thermal" reaction, by what is referred to as a "direct alkylation process."
The "ene" reaction
mechanism and general reaction conditions are summarised in "Maleic
Anhydride", pages,
147-149, Edited by B.C. Trivedi and B.C. Culbertson and Published by Plenum
Press in 1982.
The dispersant prepared by a process that includes an "ene" reaction may be a
polyisobutylene
succinimide 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.
[0046] The dispersant may also be obtained 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 a dispersant
that is a polyisobutylene succinimide having a carbocyclic ring present on 50
mole % or more,
or 60 to 100 mole % of the dispersant molecules. Both the thermal and chlorine-
assisted
processes are described in greater detail in U.S. Patent 7,615,521, columns 4-
5 and preparative
examples A and B.
[0047] In one embodiment, the dispersant may further comprise 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 reacted with
an alcohol
(such as pentaerythritol) and an amine (such as a diamine, typically
diethyleneamine).
[0048] The dispersant is used alone or as part of a mixture of non-
borated and borated
dispersants. If a mixture of dispersants is used, there may be two to five, or
two to three or
two dispersants.
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[0049] The dispersant is typically present at 0.1 weight % to 10 weight
%, or 0.5
weight % to 7 weight %, or 0.8 weight % to 4.5 weight %, or 1.0 weight % to
4.5 weight %
or 2.0 weight % to 4.0 weight % or 1.5 weight % to 3 weight % of the
lubricating oil
composition.
[0050] The lubricating composition may further comprise a
polyalphaolefins (PAO)
containing dispersant selected from the group consisting of a polyalphaolefin
succinimide, a
polyalphaolefin succinarnicle, a polyalphai.plefin acid ester, a
pi.plyalphaolefin oxazoline, a
polyalpha.olefin itnidazoline, a polyal.phaolefin succinamide imida.zoline,
and combinations
thereof
[005 /I Polyalphaolefins (PAO) useful as feedstock in fonning the PAO
containing
dispersants are those derived from oligomerization or polymerization of
ethylene, propylene,
and a-olefins. Suitable a-olefins include 1-butene, 1-pentene, 1-hexene, 1-
heptene, 1-octene,
1-nonene, 1-decen.e, 1-undecene, 1-dodecene, 1-tetradecen.e, and 1-octadecene.
Feedstocks
containing a mixture of two or more of the foregoing monomers as well as other
hydrocarbons
are typically employed when manufacturing PAOs commercially. The PAO may take
the form
of dirners, trim ers, tetramers, polymers, and the like.
[0052] The PAO may be reacted with maleic anhydride (MA) to form the
polyalphaolefin succinic anhydride (PAO-SA) and subsequently the anhydride may
reacted
with one or more of polyamines, arninoalcohols, and alcohols/polyols to form
polyalphaolefin
succinimide, polyalphaolefi n succinatni de, pol yalphaolefi n succinic acid
ester,
polyalplaaol efin oxazoline, polyalphaolefin imidazoline, polyalphaolefin-
succinamide-
imidazoline, and mixtures thereof.
[0053] The polyalkenyl succinimide dispersant may be present at 0.1
weight % to 10
weight %, or 0.5 weight % to 7 weight %, or 1 weight % to 5 weight %, or 1.5
weight % to 4
weight % of the lubricating oil composition.
[0054] Any or all borated and non-borated 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, or 0.9:1 to 1.6:1, or 0.95:1 to 1.5:1, or 1:1 to 1:4.
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Polyolefin Dispersant Viscosity Modifier
[0055] The lubricating composition of the invention comprises a
polyolefin dispersant
viscosity modifier. In one embodiment, the dispersant viscosity modifier may
be a
functionalized ethylene-a-olefin copolymer. As used herein, the term
"functionalized" means
that the olefin polymer has been modified by the addition of a polar moiety.
[0056] 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.
[0057] In one embodiment, the olefin polymer may be a polymer of 15 to 80
mole
percent of ethylene, for example, 30 mol percent to 70 mol percent ethylene
and from and
from 20 to 85 mole percent of C3 to C10 mono-olefins, such as propylene, for
example, 30 to
70 mol percent propylene or higher mono-olefins. Terpolymer variations of the
olefin
copolymer may also be used and may contain up to 15 mol percent of a non-
conjugated diene
or triene. Non-conjugated dienes or trienes may have 5 to about 14 carbon
atoms. The non-
conjugated diene or triene monomers may be characterized by the presence of a
vinyl group
in the structure and can include cyclic and bicycle compounds. Representative
dienes include
1,4-hex adiene, 1,4- cycl ohex adi ene, di cycl op entadi ene, 5-ethyl di ene-
2-norbornene, 5-
methylene-2-norbornene, 1,5-heptadiene, and 1,6-octadiene.
[0058] In one embodiment, the olefin copolymer may be a copolymer of
ethylene,
propylene, and butylene. The polymer may be prepared by polymerizing a mixture
of
monomers comprising ethylene, propylene and butylene. These polymers may be
referred to
as copolymers or terpolymers. The terpolymer may comprise from about 5 mol %
to about 20
mol %, or from about 5 mol % to about 10 mol % structural units derived from
ethylene; from
about 60 mol % to about 90 mol %, or from about 60 mol % to about 75 mol
structural units
derived from propylene; and from about 5 mol % to about 30 mol %, or from
about 15 mol %
to about 30 mol % structural units derived from butylene. The butylene may
comprise any
isomers or mixtures thereof, such as n-butylene, iso-butylene, or a mixture
thereof The
butylene may comprise butene-1. Commercial sources of butylene may comprise
butene-1 as
well as butene-2 and butadiene. The butylene may comprise a mixture of butene-
1 and
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isobutylene wherein the weight ratio of butene-1 to isobutylene is about 1:0.1
or less. The
butylene may comprise butene-1 and be free of or essentially free of
isobutylene.
[0059] In one embodiment, the olefin copolymer may be a copolymer of
ethylene and
butylene. The polymer may be prepared by polymerizing a mixture of monomers
comprising
ethylene and butylene wherein, the monomer composition is free of or
substantially free of
propylene monomers (i.e., contains less than 1 weight percent of intentionally
added
monomer). The copolymer may comprise 30 to 50 mol percent structural units
derived from
butylene; and from about 50 mol percent to 70 mol percent structural units
derived from
ethylene. The butylene may comprise a mixture of butene-1 and isobutylene
wherein the
weight ratio of butene-1 to isobutylene is about 1:0.1 or less. The butylene
may comprise
butene-1 and be free of or essentially free of isobutylene.
[0060] The olefin polymers useful in the present invention, in
particular, the 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.
[0061] The olefin polymers are functionalized by modifying the polymer by
the
addition of a polar moiety. In one 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,f3 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.
[0062] In one embodiment, the functionalized ethylene-a-olefin copolymer
comprises
an olefin copolymer grafted with the acyl group which is further
functionalized with a
hydrocarbyl amine, a hydrocarbyl alcohol group, amino- or hydroxy- terminated
polyether
compounds, and mixtures thereof.
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[0063] Amine functional groups are be added to the olefin polymer by
reacting the
olefin copolymer (typically, an ethylene-a-olefin copolymer, such as an
ethylene-propylene
copolymer) with an acylating agent (typically maleic anhydride) and a
hydrocarbyl amine
having a primary or secondary amino group. In one embodiment, the hydrocarbyl
amine may
be selected from aromatic amines, aliphatic amines, and mixtures thereof
[0064] 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.
[0065] Aromatic amines useful for providing the polar moiety of the
functionalized
ethylene-a-olefin copolymer also include those which can be represented by the
general
structure NH2-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:
Rvi
-R"
Rv
K __________
IR"
( _______________________________________________________________ Rvil
as well as multiple non-condensed or linked aromatic rings. In these and
related structures,
Rvi, and Wu 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-C1-18 alkyl, -
COO-
C-1-18 alkyl, -OH, 0-(CH2CH2 0)nC1-18 alkyl groups, and 0 (CH2CH20)nAr (where
n
is 0 to 10).
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[0066]
Aromatic amines may also 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-nitrophenyl¨azo)aniline
(disperse
orange 3), sulphamethazine, 4-phenoxyaniline, 3-nitro¨aniline, 4-
aminoacetanilide (N-(4-
aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl
amino
salicylate), N-(4-amino-phenyl)-benzamide, various benzyl¨amines such as 2,5-
dimethoxybenzylamine, 4-phenylazoaniline, and substituted versions of these.
Other
examples include para-ethoxyaniline, para-dodecyl¨aniline, 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.
[0067]
Additional aromatic amines and related compounds that make up the functional
group 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-anilinopheny1)-3-{(3-
aminopropy1)-
(coco¨alkyl)¨amino} butanamide. 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:
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Rix
41 0
H
C¨N = NH2
Rviii
and isomeric variations thereof, where Rviii and Rix are independently alkyl
or alkoxy groups
such as methyl, methoxy, or ethoxy. In one instance, Rviii and Rix are both
¨OCH3 and the
material is known as Fast Blue RR [CAS# 6268-05-9].
[0068] In another instance, Rix is ¨OCH3 and Rviii is ¨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.
[0069] In another embodiment, a useful 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 Berichte der Deutschen Chemischen Gesellschaft (1910), 43, 728-
39.
[0070] 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:
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NH
HN 2
N
wherein each variable le may be hydrogen or a C1-5 alkyl group (typically
hydrogen); R2
may be hydrogen or a C1-5 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 may
be 0 to 9 or 0
to 3 or 0 to 1 (typically 0).
[0071] 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.
[0072] 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.
[0073] In another one embodiment, the polar moiety added to the
functionalized
ethylene-a-olefin copolymer may be derived from a hydrocarbyl alcohol group,
containing at
least one hydroxy 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. The alcohol functional groups may be added to the olefin polymer by
reacting the olefin
copolymer with an acylating agent (typically maleic anhydride) and a
hydrocarbyl alcohol.
The hydrocarbyl alcohol may be a polyol compound. Suitable hydrocarbyl polyols
include
ethylene glycol and propylene glycol, trimethylol propane (TMP),
pentaerythritol, and
mixtures thereof
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[0074] In another one embodiment, the polar moiety added to the
functionalized
ethylene-a-olefin copolymer may be amine-terminated polyether compounds,
hydroxy-
terminated polyether compounds, and mixtures thereof The hydroxy terminated or
amine
terminated polyether may be selected from the group comprising polyethylene
glycols,
polypropylene glycols, mixtures of one or more amine terminated polyether
compounds
containing units derived from ethylene oxides, propylene oxides, butylene
oxides or some
combination thereof, or some combination thereof Suitable polyether compounds
include
Synalox line of polyalkylene glycol compounds, the UCONTM OSP line of
polyether
compounds available from Dow Chemical, Jeffamine line of polyether amines
available
from Huntsman.
[0075] 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]).
[0076] The lubricating compositions of the present invention comprise
0.05 weight %
to 2 weight %, or 0.08 weight % to 1.8 weight %, or 0.1 to 1.2 weight % of the
functionalized
ethylene-a-olefin copolymer as described herein.
Overbased Detergent
[0077] In one embodiment, the invention provides a lubricating
composition further
comprising a metal containing detergent. The metal-containing detergent may be
an overbased
detergent. Overbased detergents, otherwise referred to as overbased 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 reacted
with the metal.
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[0078] The overbased metal-containing detergent is selected from the
group
consisting of non-sulfur containing phenates, sulfur containing phenates,
sulfonates,
salixarates, salicylates, and mixtures thereof, or borated equivalents
thereof. The overbased
detergent may be borated with a borating agent such as boric acid.
[0079] The metal-containing detergent includes calcium salts, magnesium
salts,
sodium salts, or mixtures thereof of one or more sulfonates. Other useful
metals may include
titanium and zirconium. Overbased sulfonates 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
sulfonate detergent may be predominantly a linear alkylbenzene sulfonate
detergent having a
metal ratio of at least about 8 as is described in paragraphs [0026] to [0037]
of US Patent
Publication 2005065045 (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.
Overbased sulfonate
detergents are known in the art.
[0080] In one embodiment, the overbased calcium sulfonate detergent may
be present
in an amount to deliver at least 500 ppm calcium by weight and no more than
3000 ppm
calcium by weight, or at least 1000 ppm calcium by weight, or at least 2000
ppm calcium by
weight, or no more than 2500 ppm calcium by weight to the lubricating
composition. In one
embodiment, the overbased magnesium sulfonate detergent may be present in an
amount to
deliver no more than 500 ppm by weight of magnesium to the lubricating
composition, or no
more than 330 ppm by weight, or no more than 125 ppm by weight, or no more
than 45 ppm
by weight. In one embodiment, the overbased a magnesium sulfonate detergent
may be
present in an amount to deliver at least 200 ppm by weight of magnesium, or at
least 450 ppm
by weight magnesium, or at least 700 ppm by weight magnesium to the
lubricating
composition. In one embodiment, both calcium and magnesium containing
sulfonate
detergents may be present in the lubricating composition. Calcium and
magnesium sulfonate
detergents may be present such that the weight ratio of calcium to magnesium
is 10:1 to 1:10,
or 8:3 to 4:5, or 1:1 to 1:3.
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[0081] In one embodiment, the detergent may comprise a mixture of calcium
and
magnesium containing detergents. The detergent may provide, in one embodiment,
800 to
1300 ppm calcium and 450 to 800 ppm magnesium and in another embodiment 900 to
1200
ppm calcium and 500 to 750 ppm magnesium.
[0082] The overbased detergent may be present at 0.1 weight % to 15
weight %, or
0.1 weight % to 10 weight %, or 0.2 weight % to 8 weight %, or 0.2 weight % to
3 weight %
of the composition.
[0083] In one embodiment, the lubricating composition may further
comprise an alkali
or alkaline earth metal salicylate detergent or salixarate detergent or
mixture thereof The
metal containing salicylate or salixarate detergent may be an overbased
detergent. Useful
salicylate and salixarate detergents may include calcium salts, magnesium
salts, sodium salts
or mixtures thereof Other useful metals may include titanium and zirconium.
The overbased
metal salicylate detergent may be present at 0.1 weight % to 15 weight %, or
0.1 weight % to
weight %, or 0.2 weight % to 8 weight %, or 0.2 weight % to 3 weight %. The
overbased
metal salixarate detergent may be present at 0.1 weight % to 15 weight %, or
0.1 weight % to
10 weight %, or 0.2 weight % to 8 weight %, or 0.2 weight % to 3 weight %. In
one
embodiments, the lubricating composition may free or substantially free of a
metal containing
salicylate detergent or metal containing salixarate detergent or both. In one
embodiment, the
lubricating composition comprises less than 0.2 weight. % or 0.1 weight. % or
0.05 weight. %
or 0.01 weight. % of a metal containing salicylate detergent, metal containing
salixarate
detergent or both.
[0084] In one embodiment, the lubricating composition is free or
substantially free of
a metal containing sulfur coupled alkyl phenol compound. Such compounds may be
exemplified by alkali and alkaline earth metal containing phenate detergents,
such as
magnesium phenate detergents, calcium phenate detergents and sodium phenate
detergents
and further including overbased metal containing phenate detergents, all of
which are known
in the art. In one embodiment, the lubricating composition comprises less than
0.2 weight. %
or 0.1 weight. % or 0.05 weight. % or 0.01 weight. % or 0.005 weight % of a
metal containing
sulfur coupled alkyl phenol compound.
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[0085] In one embodiment, the lubricating composition is free of or
substantially free
of a metal containing saligenin detergent, such as magnesium saligenin
detergent, calcium
saligenin detergents and sodium saligenin detergents and further including
overbased metal
containing saligenin detergents, all of which are known in the art. In one
embodiment, the
lubricating composition comprises less than 0.2 weight. % or 0.1 weight. % or
0.05 weight. %
or 0.01 weight. % or 0.005 weight % of a metal containing saligenin detergent.
[0086] The total amount of soap contributed by the detergent may be from
about 0.08
or 1 0 to less than 0.9 or 0.7 or 0.5 or 0.4 or 0.3 or 0.25 weight. % with
respect to the lubricating
composition. The lubricating composition may be free or substantially free of
phenate soap.
The soap may substantially consist of sullonate soap. As used herein the term
"soap" means
the surfactant portion of a detergent and does not include a metal base, such
as calcium
carbonate. The soap term may also be referred to as a detergent substrate. For
example, the
sulfonate detergents described herein, the soap or substrate may be a neutral
salt of an
alkylbenzenesulfonic acid.
[0087] Metal-containing detergents also contribute sulfated ash to a
lubricating
composition. Sulfated ash may be determined by ASTM D874. In one embodiment,
the
lubricating composition of the invention comprises a metal-containing
detergent in an amount
to deliver at least 0.4 weight. % sulfated ash to the total composition. In
another embodiment,
the metal-containing detergent is present in an amount to deliver at least 0.6
weight. % sulfated
ash, or at least 0.75 weight. % sulfated ash, or even at least 0.9 weight. %
sulfated ash to the
lubricating composition.
Ashless Antioxidant
[0088] Antioxidants provide and/or improve the anti-oxidation performance
of
organic compositions, including lubricant compositions that contain organic
components, by
preventing or retarding oxidative and thermal decomposition. Suitable
antioxidants may be
catalytic or stoichiometric in activity and include any compound capable of
inhibiting or
decomposing free radicals, including peroxide.
[0089] Ashless antioxidants of the invention may comprise one or more of
arylamines,
diarylamines, alkylated arylamines, alkylated diaryl amines, phenols, hindered
phenols,
sulfurized olefins, or mixtures thereof. In one embodiment the lubricating
composition
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includes an antioxidant, or mixtures thereof The antioxidant may be present at
0.05 weight
% to 15 weight %, or 0.1 weight % to 10 weight %, or 0.5 weight % to 5 weight
%, or 0.5
weight % to 3 weight %, or 0.3 weight % to 1.5 weight % of the lubricating
composition.
[0090] 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 one 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.
[0091] Diarylamines of the invention may also be represented by Formula
2:
R5
R7 6
R
- - 4
R2
R3
FORMULA 2
wherein Ri and R2 are moieties which, together with the carbon atoms to which
they are
bonded, are joined together to form a 5-, 6-, or 7-membered ring (such as a
carbocyclic ring
or cyclic hydrocarbylene ring); R3 and R4 are independently hydrogen,
hydrocarbyl groups,
or are moieties which, taken together with the carbon atoms to which they are
bonded, form a
5-, 6-, or 7-membered ring (such as a carbocyclic ring or cyclic
hydrocarbylene ring); R5 and
R6 are independently hydrogen, hydrocarbyl groups, or are moieties (typically
hydrocarbyl
moieties) which, taken together with the carbon atoms to which they are
attached, form a ring,
or represent a zero-carbon or direct linkage between the rings; and R7 is
hydrogen or a
hydrocarbyl group
[0092] In one embodiment, the diarylamine is a N-phenyl-naphthylamine
(PNA).
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[0093] In another embodiment, the diarylamine may be represented by
Formula (2a):
R3
R
N 4
FORMULA (2a)
wherein R3 and R4 are defined as above.
[0094] In another embodiment, the diarylamine compounds include those
having the
general Formula (2b):
R5 R6
Z =
N
F17
FORMULA (2b)
wherein R7 is defined as above; R5 and R6 are independently hydrogen,
hydrocarbyl groups
or taken together may form a ring, such as a dihydroacridan; n = 1 or 2; and Y
and Z
independently represent carbon or heteroatoms such as N, 0 and S.
[0095] In a particular embodiment, compounds of Formula (2) further
comprise an N-
ally1 group, for example the compound of Formula (2c):
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FORMULA (2c)
[0096] In one embodiment, the diarylamine is a dihydroacridan derivative
of Formula
(2d):
R9 R9
R4
Ri
p
-.
R2 N
FORMULA (2d)
wherein R1, R2, R3, and R4 are defined above; R8 and R9 are independently
hydrogen or a
hydrocarbyl group of 1 to 20 carbon atoms.
[0097] In one embodiment, the diarylamine of Formula (2) is chosen such
that R5 and
R6 represent a direct (or zero-carbon) link between the aryl rings. The result
is a carbazole of
Formula (2g):
Ri
R2
R4
R3
FORMULA (2g)
wherein Ri, R2, R3, and R4 are defined as above.
[0098] The diarylamine antioxidant of the invention may be present on a
weight basis
of the lubrication composition at 0.1% to 10%, 0.35% to 5%, or even 0.5% to
2%.
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[0099] The phenolic antioxidant may be a simple alkyl phenol, a hindered
phenol, or
coupled phenolic compounds.
[00100] 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-ethy1-2,6-
di-tert-
butylphenol, 4-propy1-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-
butylphenol, 4-dodecy1-
2,6-di-tert-butylphenol, or butyl 3-(3,5-ditert-buty1-4-
hydroxyphenyl)propanoate. In one
embodiment, the hindered phenol antioxidant may be an ester and may include,
e.g.,
IrganoxTM L-135 from Cib a.
[00101] Coupled phenols often contain two alkylphenols coupled with
alkylene groups
to form bisphenol compounds. Examples of suitable coupled phenol compounds
include 4,4'-
methylene bis-(2,6-di-tert-butyl phenol), 4-methyl-2,6-di-tert-butylphenol,
2,2'-bis-(6-t-
buty1-4-heptylphenol); 4,4'-bis(2,6-di-t-butyl phenol), 2,2'-m ethyl eneb i
s(4 -m ethyl -6-t-
butylphenol), and 2,2'-methylene bis(4-ethy1-6-t-butylphenol).
[00102] Phenols of the invention also include polyhydric aromatic
compounds and their
derivatives. Examples of suitable polyhydric aromatic compounds include esters
and amides
of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 1,4-
dihydroxy-2-
naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7-dihydroxy naphthoic acid, and
mixtures
thereof
[00103] In one embodiment, the phenolic antioxidant comprises a hindered
phenol. In
another embodiment the hindered phenol is derived from 2,6-ditertbutyl phenol.
[00104] In one embodiment, the lubricating composition of the invention
comprises a
phenolic antioxidant in a range of 0.01 weight % to 5 weight %, or 0.1 weight
% to 4 weight
%, or 0.2 weight % to 3 weight %, or 0.5 weight % to 2 weight % of the
lubricating
composition.
[00105] Sulfurized olefins are well known commercial materials, and those
which are
substantially nitrogen-free, that is, not containing nitrogen functionality,
are readily available.
The olefinic compounds which may be sulfurized are diverse in nature. They
contain at least
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one olefinic double bond, which is defined as a non-aromatic double bond; that
is, one
connecting two aliphatic carbon atoms. These materials generally have sulfide
linkages having
1 to 10 sulfur atoms, for instance, 1 to 4, or 1 or 2. In one embodiment, the
lubricating
composition of the invention comprises a sulfurized olefin in a range 0.2
weight percent to
2.5 weight percent, or 0.5 weight percent to 2.0 weight percent, or 0.7 weight
percent to 1.5
weight percent.
[00106] The ashless antioxidants of the invention may be used separately
or in
combination. In one embodiment of the invention, two or more different
antioxidants are used
in combination, such that there is at least 0.1 weight percent of each of the
at least two
antioxidants and wherein the combined amount of the ashless antioxidants is
0.5 to 5 weight
percent. In one embodiment, there may be at least 0.25 to 3 weight percent of
each ashless
antioxidant. In one embodiment, there may be 1.0 to 5.0 weight percent of one
or more ashless
antioxidants, or 1.4 to 3.0 weight percent of one or more antioxidants.
[00107] In one embodiment, the invention provides a lubricating
composition further
comprising a molybdenum compound. The molybdenum compound may be selected from
the group consisting of molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates,
amine salts of molybdenum compounds, and mixtures thereof. The molybdenum
compound
may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm,
or 10 to 750
ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
[00108] In one embodiment, the invention provides a lubricating
composition further
comprising a friction modifier. Examples of friction modifiers include long
chain fatty acid
derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as
condensation
products of carboxylic acids and polyalkylene-polyamines; amine salts of
alkylphosphoric
acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl
tartramides. The term fatty, as
used herein, can mean having a C8-22 linear alkyl group.
Anti-Wear Additive
[00109] In one embodiment, the lubricating composition of the invention
further
includes an anti-wear agent, typically a phosphorus-containing anti-wear
agent. Examples of
suitable phosphorus-containing anti-wear agents include metal dialkyl
dithiophosphates,
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organo-phosphates, phosphites, phosphonates, amine salted alkylphosphoric acid
compounds,
and mixtures thereof
[00110] In one embodiment, the invention provides a lubricating
composition which
further includes a metal dialkyldithiophosphate. Typically, the metal
dialkyldithiophosphate
may be a zinc dialkyldithiophosphate (ZDDP), or mixtures thereof Zinc
dialkyldithiophosphates are known in the art. The zinc dialkyldithiophosphate
may be present
at 0 weight % to 3 weight %, or 0.1 weight % to 1.5 weight %, or 0.5 weight %
to 0.9 weight
% of the lubricating composition, such that the total zinc contributed to the
lubricant
composition does not exceed 0.06 weight percent of the composition. In another
embodiment,
the ZDDP may be present in an amount to provide 0.05 weight % or 0.03 weight %
zinc to
the lubricating composition.
[00111] The zinc dialkyldithiophosphate may be derived from primary
alcohols,
secondary alcohols, or combinations thereof. Typically they are derived from
primary and
secondary alcohols containing 3 to 12 carbon atoms and combinations thereof.
In one
embodiment the zinc alkyldithiophosphate comprises at least 25 mol % secondary
alkyl
groups, or at least 40 mol % secondary alkyl groups, or at least 75 mol %
secondary alkyl
groups, or at least 90 mol % secondary alkyl groups
[00112] The phosphorus-containing anti-wear agent may be a metal free
organo-
phosphorus anti-wear agent. The organo-phosphorus agent may contain sulfur or
may be
sulfur-free. Sulfur-free phosphorus-containing antiwear agents may be
phosphites,
phosphonates, alkylphosphate esters, amine or ammonium phosphate salts, or
mixtures
thereof
[00113] 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
dialkyldithiophosphoric acid
with propylene oxide and subsequently followed by a further reaction with
P205; and mixtures
thereof (as described in US 3,197,405).
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[00114] Amine phosphates may be amine salts of (i)
monohydrocarbylphosphoric acid,
(ii) dihydrocarbylphosphoric acid, (iii) hydroxy-substituted di-ester of
phosphoric acid, or (iv)
phosphorylated hydroxy-substituted di- or tri-ester of phosphoric acid. The
amine salt of a
sulfur-free phosphorus-containing compound may be salts of primary amines,
secondary
amines, tertiary amines, or mixtures thereof
[00115] Amine phosphate salts may be derived from mono- or di- hydrocarbyl
phosphoric acid (typically alkyl phosphoric acid), or mixtures thereof. The
alkyl of the mono-
or di- hydrocarbyl phosphoric acid may comprise linear or branched alkyl
groups of 3 to 36
carbon atoms. The hydrocarbyl group of the linear or branched
hydrocarbylphosphoric acid
may contain 4 to 30, or 8 to 20 carbon atoms. Examples of a suitable
hydrocarbyl group of
the hydrocarbyl phosphoric acid may include isopropyl, n-butyl, sec-butyl,
amyl, 4-methy1-2-
pentyl (i.e. methylamyl), n-hexyl, n-heptyl, n-octyl, iso-octyl, 2-ethylhexyl,
nonyl, 2-
propylheptyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, oleyl, or
combinations thereof.
In one embodiment, the phosphate is a mixture of mono- and di- (2-
ethyl)hexylphosphate.
[00116] Examples of suitable primary amines include ethylamine,
propylamine,
butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, as well as such
fatty amines
as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-
hexadecylamine, n-
octadecylamine and oleyamine. Other useful fatty amines include commercially
available
fatty amines such as "Armeen®" amines (products available from Akzo
Chemicals,
Chicago, Ill.), such as Armeen C, Armeen 0, Armeen 0 L, Armeen T, Armeen H T,
Armeen
S and Armeen S D, wherein the letter designation relates to the fatty group,
such as coco,
oleyl, tallow, or stearyl groups.
[00117] In one embodiment, the phosphorus anti-wear agent may be present
in the
lubricant composition in amount of 0.01 to 5 weight %, or 0.1 to 3.2 weight %,
or 0.35 to
1.8 weight %, or 0.5 to 1.5 weight %, or 0.5 to 0.9 weight %. In one
embodiment, the
phosphorus anti-wear agent may be present in an amount to provide 0.01 weight
% to
0.15 weight % phosphorus, or 0.01 to 0.08 weight % phosphorus, or 0.025 to
0.065 weight %
phosphorus to the composition.
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Other Performance Additives
[00118] The compositions of the invention may optionally comprise one or
more
additional additives. These additional additives may include one or more metal
deactivators,
viscosity modifiers, detergents, friction modifiers, antiwear agents,
corrosion inhibitors,
dispersants different from the borated dispersant of the invention, dispersant
viscosity
modifiers, extreme pressure agents, antioxidants, foam inhibitors,
demulsifiers, pour point
depressants, seal swelling agents, and any combination or mixture thereof.
Typically, fully-
formulated lubricating oil will contain one or more of these performance
additives, and often
a package of multiple performance additives.
[00119] The lubricating composition further comprises an anti-wear agent
(different
from the phosphorus-containing anti-wear agent above), a friction modifier, a
viscosity
modifier, a corrosion inhibitor or a combination thereof, where each of the
additives listed
may be a mixture of two or more of that type of additive. In one embodiment,
the invention
provides a lubricating composition further comprising an ashless antiwear
agent, a friction
modifier, a viscosity modifier (typically an olefin copolymer such as an
ethylene-propylene
copolymer), or a combination thereof, where each of the additives listed may
be a mixture of
two or more of that type of additive.
[00120] The lubricating composition further comprises an ashless antiwear
agent
different from the phosphorus antiwear agent described above. Examples of
suitable antiwear
agents include hydroxy-carboxylic acid derivatives such as esters, amides,
imides or amine or
ammonium salt, sulfurized olefins, thiocarbamate-containing compounds, such as
thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-
coupled thio-
carbamates, and bis(S-alkyldithiocarbamyl) disulphides.
[00121] In one embodiment, the ashless antiwear agent comprises a compound
derived
from a hydroxycarboxylic acid. In one embodiment the ashless antiwear agent is
derived from
at least one of hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic
acid di-amide,
a hydroxy-polycarboxylic acid imide, and a hydroxy-polycarboxylic acid ester
amide. In one
embodiment the ashless antiwear agent is derived from a hydroxy-polycarboxylic
acid imide.
[00122] Examples of a suitable a hydroxycarboxylic acid include citric
acid, tartaric
acid, lactic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric
acid, or mixtures
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thereof. In one embodiment, ashless antiwear agent is derived from tartaric
acid, citric acid,
hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures
thereof In
one embodiment, the ashless antiwear agent includes a compound derived from
tartaric acid
or citric acid. In one embodiment, the ashless antiwear agent includes a
compound derived
from tartaric acid.
[00123] US Patent Application 2005/198894 discloses suitable
hydroxycarboxylic acid
compounds, and methods of preparing the same.
[00124] Canadian Patent 1 183 125; US Patent Publication numbers
2006/0183647 and
US-2006-0079413: U.S. Patent Application No. 60/867,402; and British Patent 2
105743 A.
all disclose examples of suitable tartaric acid derivatives. 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.
[00125] The ashless phosphorus-free antiwear agent is present at 0.1 to 5
weight %, 0.1
weight % to 3 weight %, or 0.2 to 3 or 0.1 weight % to 1.5 weight %, or 0.5
weight % to 1.1
weight % of the lubricating composition.
[00126] Friction modifiers may also encompass materials such as sulfurized
fatty
compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic
carboxylic acid.
[00127] In one embodiment, the friction modifier is selected from the
group consisting
of long chain fatty acid derivatives of amines, long chain fatty esters, or
long chain fatty
epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty
alkyl tartrates; fatty
alkyl tartrimides; and fatty alkyl tartramides. The friction modifier may be
present at 0.05
weight % to 6 weight %, or 0.05 weight % to 4 weight %, or 0.1 weight % to 2
weight % of
the lubricating composition.
[00128] In one 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 or a
diester or a
mixture thereof, and in another embodiment the long chain fatty acid ester may
be a
triglyceride.
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[00129] Other performance additives such as corrosion inhibitors include
those
described in paragraphs 5 to 8 of US Application US05/038319, published as
W02006/047486, octyl octanamide, condensation products of dodecenyl succinic
acid or
anhydride and a fatty acid such as oleic acid with a polyamine. In one
embodiment, the
corrosion inhibitors include the Synalox (a registered trademark of The Dow
Chemical
Company) corrosion inhibitor. The Synalox corrosion inhibitor may be a
homopolymer or
copolymer of propylene oxide. The Synalox corrosion inhibitor is described in
more detail
in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow
Chemical
Company. The product brochure is entitled "SYNALOX Lubricants, High-
Performance
Polyglycols for Demanding Applications."
[00130] The lubricating composition may further include metal
deactivators, including
derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole
derivatives,
1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-
alkyldithiobenzothiazoles;
foam inhibitors, including copolymers of ethyl acrylate and 2-
ethylhexylacrylate and
copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate;
demulsifiers
including trialkyl phosphates, polyethylene glycols, polyethylene oxides,
polypropylene
oxides and (ethylene oxide-propylene oxide) polymers; and pour point
depressants, including
esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or
polyacrylamides.
[00131] Pour point depressants that may be useful in the compositions of
the invention
further include polyalphaolefins, esters of maleic anhydride-styrene,
poly(meth)acrylates,
polyacrylates or polyacrylamides.
[00132] In different embodiments the lubricating composition may have a
composition
as described in the following table:
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Additive Embodiments (weight %)
A
Oxyalkylated phenol
Polyalkenylsuccinimide Dispersant 0.01 to 2.6 0.5 to 2.0 0.75 to 1.75
Dispersant Viscosity Modifier 0.05 to 3 0.1 to 2 0.2 to 1.6
Overbased Sulfonate Detergent 0 to 12 0.1 to 10 0.5 to 5
Antioxidant 0 to 15 0.1 to 8 0.5 to 3
Metal dialkyldithiophosphate 0 to 1 0.01 to 0.8 0.1 to 0.6
Other Anti-Wear Agent 0 to 2.5 0.01 to 1.4 0.1 to 1.2
Other Detergent 0 to 8 0.1 to 4 0.2 to 2
Other Dispersant 0 to 2.1 0.1 to 1.8 0.5 to 1.4
Friction Modifier 0 to 6 0.1 to 2.4 0.2 to 1.5
Viscosity Modifier 0 to 10 0.5 to 8 1 to 6
Any Other Performance Additive 0 to 10 0 to 6 0 to 2
Oil of Lubricating Viscosity Balance to 100 %
[00133] The present invention provides a surprising ability to control
damage to an
engine in operation due to wear and deposit formation. This is accomplished
while
maintaining fuel economy performance, low sulfated ash levels, seals
compatibility, corrosion
control, and other limitations, required by increasingly stringent government
regulations.
Industrial Application
[00134] As described above, the invention provides for a method of
lubricating an
internal combustion engine comprising supplying to the internal combustion
engine a
lubricating composition as disclosed herein. Generally, the lubricant is added
to the
lubricating system of the internal combustion engine, which then delivers the
lubricating
composition to the critical parts of the engine, during its operation, that
require lubrication
[00135] The lubricating compositions described above may be utilized in an
internal
combustion engine. The engine components may have a surface of steel or
aluminum
(typically a surface of steel), and may also be coated for example with a
diamond-like carbon
(DLC) coating.
[00136] An aluminum surface may be comprised of an aluminum alloy that may
be a
eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum
silicates,
aluminum oxides, or other ceramic materials). The aluminum surface may be
present on a
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cylinder bore, cylinder block, or piston ring having an aluminum alloy, or
aluminum
composite.
[00137] 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).
[00138] The internal combustion engine of the present invention is
distinct from a gas
turbine. In an internal combustion engine, individual combustion events
translate from a
linear reciprocating force into a rotational torque through the rod and
crankshaft. In contrast,
in a gas turbine (which may also be referred to as a jet engine) a continuous
combustion
process generates a rotational torque continuously without translation, and
can also develop
thrust at the exhaust outlet. These differences in operation conditions of a
gas turbine and
internal combustion engine result in different operating environments and
stresses.
[00139] The lubricant composition for an internal combustion engine may be
suitable
for any engine lubricant irrespective of the sulfur, phosphorus or sulfated
ash (ASTM D-874)
content. The sulfur content of the engine oil lubricant may be 1 weight % or
less, or 0.8 weight
% or less, or 0.5 weight % or less, or 0.3 weight % or less. In one
embodiment, the sulfur
content may be in the range of 0.001 weight % to 0.5 weight %, or 0.01 weight
% to 0.3 weight
%. The phosphorus content may be 0.2 weight % or less, or 0.12 weight % or
less, or 0.1
weight % or less, or 0.085 weight % or less, or 0.08 weight % or less, or even
0.06 weight %
or less, 0.055 weight % or less, or 0.05 weight % or less. 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 2 weight % or less, or 1.5 weight % or less, or 1.1 weight % or less,
or 1 weight % or
less, or 0.8 weight % or less, or 0.5 weight % or less, or 0.4 weight % or
less. In one
embodiment, the sulfated ash content may be 0.05 weight % to 0.9 weight %, or
0.1 weight
% to 0.2 weight % or to 0.45 weight %.
[00140] In one embodiment, the lubricating composition may be an engine
oil, wherein
the lubricating composition may be characterized as having at least one of (i)
a sulfur content
of 0.5 weight % or less, (ii) a phosphorus content of 0.1 weight % or less,
(iii) a sulfated ash
content of 1.5 weight % or less, or combinations thereof
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EXAMPLES
[00141] The invention will be further illustrated by the following
examples, which set
forth particularly advantageous embodiments. While the examples are provided
to illustrate
the invention, they are not intended to limit it.
Lubricating Compositions
[00142] A series of OW-30 diesel engine lubricants in Group III and Group
IV base oils
of lubricating viscosity are prepared containing the additives described above
as well as
conventional additives including polymeric viscosity modifier, overbased
detergents,
antioxidants (combination of phenolic ester and diarylamine), zinc
dialkyldithiophosphate
(ZDDP), as well as other performance additives as follows (Table 1). The
phosphorus, zinc
and ash contents of each of the examples are also presented in the table in
part to show that
each example has a similar amount of these materials and so provide a proper
comparison
between the comparative and invention examples.
Table 1 - Lubricating Oil Composition Formulations'
EX1 EX2 EX3 EX4
Polyalphaolefin 7 (PAO) 16 13.4 0 0
PAO 4 37.8 20 0 0
Group III Base Oil Balance to 100%
Oxyalkylated phenol' 0 2 0 1
Succinimide Dispersant3 5.4 1.4 5.6 3.5
EP DVI\44 0.32 0.32 0 0
Overbased Ca sulfonate5 0.09 0.09 0.1 0.1
Neutral Calcium phenate6 1.33 1.38 0.23 0.23
Secondary ZDDP7 0.57 0.58 0.63 0.63
Overbased Ca Phenate8 0.06 0.06 0.23 0.23
Ashless AW agent9 0.05 0.05 0 0
Hindered phenol' 0.96 1.00 1 1
Diarylaminell 1.15 1.20 2 2
Sulfurized olefin 0.24 0.25 0 0
VI Improver' 0.5 1.0 1.1 1.1
Additional Additives13 0.3 0.3 0.3 0.3
%Phosphorus 0.06 0.06 0.07 0.07
%Zinc 0.065 0.067 0.078 0.075
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EX1 EX2 EX3 EX4
%Calcium 0.12 0.13 0.083 0.085
Kin. Viscosity (100 C) mm2/s 9.53 9.96 11.9 11.0
TBN (ASTM D2896) 6.2 5.6 6.1 5.6
%Phenate soap 1.2 1.25 0.38 0.38
%Sulfonate soap 0.03 0.03 0.03 0.03
%Total soap 1.23 1.28 0.41 0.41
%Ash 0.55 0.55 0.4 0.4
I ¨All amounts shown above are in weight percent and are on an oil-free basis
unless otherwise noted.
2 ¨ Propoxylated p-alkylphenol; alkyl group is derived from ¨1000 Mn
polyisobutylene
3 ¨ Polyisobutylene succinimide dispersant derived from 950 Mn PIB having ¨85%
terminal vinylidene; TBN
17 mg KOH/g; N:CO ratio 1:1.45
4 ¨ Acylated ethylene-propylene copolymer (41 weight % ethylene; Mn = ¨50k
Da), aminated with a mixture
of nitroaniline and N,N-(dimethylamino)
¨ Overbased calcium alkylbenzene sulfonic acid with TBN at least 300 and metal
ratio at least 10
6 ¨ Neufral Ca Phenate is 200 TBN sulfur-coupled calcium phenate
7 ¨ Mixture of C3 and C6 secondary alkyl groups
8 ¨ Ca Phenate is 440 TBN sulfur-coupled calcium phenate
9 ¨ Oleyl amide
10¨ Hindered phenol ¨ Octyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate
11 ¨ Diaryl amine ¨ mixture of nonylated and dinonylated diphenylamine
12 ¨ Styrene-butadiene block copolymer
13 ¨ The Additional Additives used in the examples include pourpoint
depressants, anti-foam agents, corrosion
inhibitors, and includes some amount of diluent oil
Evaluation of Lubricant Formulations
[001431 Engine Cleanliness Test: The lubricant formulations of Table 1
were subjected
to a series of performance evaluations including engine test VW TIN CEC-1,78-T-
99 test,
also known as the PV1452 test. This test is regarded as an industry standard
and is a severe
assessment of a lubricant's performance capabilities. The test employs a 4-
cylinder, 1,9 liter,
81 kW passenger car diesel engine, which is a direct injection compression-
ignition engine in
which a turbocharger system is used to increase the power output of the unit.
The industry test
procedure consists of a repeating cycle of hot and cold running conditions.
This involves a 30
minute idle period at zero load followed by 180 minutes at full load and 4150
rpm. In the
standard test, the entire cycle is then repeated for a total of 54 hours, In
this 54 hour period
the initial oil fill of 4.5 liters of test lubricant is not topped up. At the
end of the 54 hour test,
the engine is drained, the engine disassembled and the pistons rated for
piston deposits and
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piston ring sticking. This affords a result which is assessed relative to an
industry reference
oil (R1206) to define passing or failing performance.
[00144] The pistons are rated against what is known as the DIN rating
system. The
m271three piston-ring grooves and the two piston lands that lie between the
grooves are rated
on a merit scale for deposits and given a score out of 100 by a method known
to those skilled
in the art. In summary, the higher the number the better the performance: 100
indicates totally
clean and 0 indicates totally covered with deposit. The five scores are then
averaged to give
the overall piston cleanliness merit rating. The scores for each of the four
pistons are then
averaged to afford the overall piston cleanliness for the test.
[00145] In addition, the lubricating compositions were subjected to panel
coker tests.
In the panel coker, the oil sample is splashed onto a metal panel held at 325
C in a cycle of
splashing and baking for 3.5 hours. The panel is weighed to determine amount
of deposit
formation and a visible rating is carried out, where 100% indicates no
deposits and 0 indicates
heavy black varnish.
[00146] Sludge Test: The lubricant fonnulation.s were evaluated in the MB
M271 SI,
Sludge Engine Test. This test is an industry standard for evaluating a
lubricating composition
to mitigate sludge in internal combustion engines.
[00147] Nitration/Oxidation test: The lubricant formulations were
evaluated in
a nitration/oxidation bench test which assesses the oxidation and nitration
resistance of
crankcase engine oil formulations. The formulation is treated with nitric acid
and iron
naphthanoate prior to administering 50 cc/min of NOx gas whilst heating to 145
C. for 22
hours. An IR spectroscopic method is used to determine degree of sample
nitration and
oxidation. Additionally, TBN (AS TM D2896 and D4739) and TAN (ASTM 1)664) are
measured SOT and EOT to determine TBN retention and TAN escalation profiles.
[00148] Friction and Wear test: The lubricant formulations were evaluated
under TE-
77 friction and wear testing. Tests were run at each of a higher temperature
and load (147 C
and 616N) and at a lower temperature and load (100 C and 100N).
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TE-77¨High T, high load
Temp. Ramp ( C) To 147 in 15 mins and hold for 2 hours
Ramp Load (N) Ramp to 616 in 5 mins and hold for 2 hours 10 mins
Stroke Length (mm) 10
Frequency (Hz) 10
Upper Test Piece Nitrided Steel Standard Phoenix 6mm dia. Cylinder
Lower Test Piece 8620 Steel
TE-77 ¨ Low T, low load
Temp. Ramp ( C) To 100 in 15 mins and hold for 1 hours
Ramp Load (N) Ramp to 100 in 5 mins and hold for 70 minutes
Stroke Length (mm) 10
Frequency (Hz) 10
Amplifier (N/V) 5
Upper Test Piece Nitrided Steel Standard Phoenix 6mm dia. Cylinder
Lower Test Piece 8620 Steel
[00149] PV3344 VW seals test: This is an industry standard test designed
to quantify
the adverse effect of a lubricating oil has on fluorelastomeric seal
materials. These materials
are commonly used as seals in internal combustion engines. These must be
passed in order to
receive a VW engine oil approval. The particular seals tests below use the AK6
elastomer
which is known to be challenging due to oil changes employed and the
particular sensitivity
to commonly used engine oil components.
Evaluation of Lubricant Formulations
1001501 Engine Cleanliness Test: The lubricant formulations of Table 3
were subjected
to a series of performance evaluations including the Volswagen l'Di engine
test (as above).
in addition to average piston deposit rating, end of test TBN is measured as
part of the test
procedure (Table 2 below).
Table 2 ¨ Engine Cleanliness Data for Engine Oil Lubricants
EX1 EX2 EX3 EX4
VW TDI
Piston cleanliness 64
Panel Coker
Deposits 82.9 28
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EX1 EX2 EX3 EX4
Universal Rating 11 28
MB M271 Sludge Test
Average Sludge 9.4 9.1
[00151] The results obtained from the deposit tests show that equal or
better cleanliness
can be achieved in formulations with significantly reduced levels of
conventional dispersant.
[00152] 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.
[00153] Each of the documents referred to above is incorporated herein by
reference,
as is the priority document and all related applications, if any, which this
application claims
the benefit of 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 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.
[00154] 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
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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:
(i) 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);
(ii) 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
sulphoxy);
(iii) 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.
[00155] Heteroatoms include sulfur, oxygen, nitrogen, and encompass
substituents as
pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,
preferably no more than
one, non-hydrocarbon substituent will be present for every ten carbon atoms in
the
hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in
the hydrocarbyl
group.
[00156] 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.
