Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICATING COMPOSITIONS AND METHODS OF OPERATING AN
INTERNAL COMBUSTION ENGINE
FIELD
[0001] The instant disclosure generally relates to lubricating
compositions having an oil
of lubricating viscosity having at least 50 weight percent of a Group IV base
oil, a mixture of
boron-containing and boron-free dispersants, an overbased magnesium-based
detergent, an
overbased calcium-based detergent, an ashless friction modifier, and,
optionally, other
performance additives. The instant lubricating compositions have a High
Temperature High
Shear (HTHS) viscosity according to ASTM D4683 less than 2.7 mPa.s. The
disclosed
lubricating compositions are suitable for performing one or more of improving
fuel economy,
reducing corrosion, reducing oxidation, improving cleanliness, improving TBN
retention,
mitigating low-speed preignition ("LSPI") and improving wear performance.
BACKGROUND
[0002] Modern engines are designed to provide ever-improving fuel
economy without
sacrificing cleanliness or durability. Current and proposed specifications for
crankcase
lubricants, such as API SN plus and ILSAC GF-6 for passenger car motor oils,
and API CK-
4 for heavy duty diesel engines specify increasingly stringent standards to
meet government
requirements for efficiency. Previous lubricating formulations may not perform
as acceptable
levels when addressing issues like cleanliness, fuel economy, TBN retention,
and/or low-
speed preignition. Thus, there is need for improved mid-saps lubricating
formulations that
demonstrate one or more of improved cleanliness, fuel economy, and oxidative
durability.
SUMMARY
[0003] The instant disclosure generally relates to lubricating
compositions having an oil
of lubricating viscosity having at least 50 weight percent of a Group IV base
oil, a mixture of
boron-containing additive, a boron-free dispersant, an overbased magnesium-
based detergent,
an overbased calcium-based detergent, an ashless friction modifier, and,
optionally, other
performance additives. The instant lubricating compositions have a High
Temperature High
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Shear (HTHS) viscosity according to ASTM D4683 less than 2.7 mPa.s. The
disclosed
lubricating compositions are suitable for performing one or more of improving
fuel economy,
reducing corrosion, reducing oxidation, improving cleanliness, improving TBN
retention,
mitigating low-speed preignition ("LSPI") and improving wear performance.
[0004] In another aspect of the disclosure relates to methods of
reducing low speed
preignition in a gasoline-fueled internal combustion engine operating at a
brake mean
effective pressure (BMEP) of greater than 12 bars and at a speed of less than
3,00 RPM' s by
supplying to said engine any one of the lubricating compositions disclosed
herein.
[0005] The instant disclosure further relates to methods of
improving TBN retention of a
lubricating composition in a gasoline-fueled internal combustion engine by
supplying to said
engine any one of the lubricating compositions disclosed herein.
[0006] The instant disclosure al so related to use of any one of
the lubricating compositions
disclosed herein to improve one or more of cleanliness, TBN retention, and
fuel economy in
a gasoline-fueled internal combustion engine.
DETAILED DESCRIPTION
[0007] The instant disclosure relates to lubricating compositions
for a gasoline-fueled
internal combustion engine. The lubricating compositions include an oil of
lubricating
viscosity where at least 50 wt % of the oil is a Group III base oil; a boron-
containing additive;
a boron-free polyisobutenyl succinimide dispersant; an overbased magnesium-
based
detergent in an amount to deliver at least 300 ppm magnesium to the
lubricating composition;
an overbased calcium-based detergent in an amount to deliver at least 400 ppm
calcium to the
lubricating composition; an ashless friction modifier; and, optionally, other
performance
additives as described herein.
Oils of Lubricating Viscosity
[0008] As used herein, an oil of lubricating viscosity may include
natural and synthetic
base oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined,
refined, re-refined base oils or mixtures thereof. A more detailed description
of unrefined,
refined and re-refined oils is provided in International Publication
W02008/147704,
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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]).
The cited portions of both references are incorporated herein. 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.
[0009] Suitable oils may be produced from biological, i.e.
natural, sources or by bio-
engineered processes. This includes both natural occurring oils, such as
vegetable oils and
triglyceride oils that may be further refined or purified by standard
processes, and those oils
that may be derived by biological conversion of a natural chemical into oil
directly or by bio-
formation of building block pre-cursor molecules capable of being further
converted into oil
by known processes.
100101 Oils of lubricating viscosity may also be defined as
specified in April 2008 version
of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car
Motor Oils
and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories".
The API
Guidelines are also summarised in US Patent US 7,285,516 (see column 11, line
64 to column
12, line 10), which are incorporated herein by reference.
100111 Group IV base oils (also known as polyalphaolefins or PAO)
are known in the art
and are prepared by oligomerization or polymerization of linear alpha olefins.
PAOs are
characteristically water white oils with superior low temperature viscosity
properties (as
measured, as well as high viscosity index. Typical PAOs suitable for use in
internal
combustion engines include PA0-4 and PA0-6, i.e. approximately 4 m2/s and 6
m2/s
respectively.
100121 In one embodiment the oil of lubricating viscosity may be a
base oil including API
Group I to IV oil, an ester or a synthetic oil, or mixtures thereof. In one
embodiment the oil
of lubricating viscosity may be an API Group II, Group III, Group IV oil, an
ester or a
synthetic oil, or mixtures thereof. In some embodiments, the oil of
lubricating viscosity
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comprises at least 50 wt %, or at least 60 wt %, or at least 70 wt %, or at
least 80 wt %, or at
least 90 wt %, or at least 95 wt %, or at least 100 wt % of a Group III or a
Group IV base oil.
100131 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 present in
the lubricating composition. In some embodiments, the oil of lubricating
viscosity is at least
80 weight percent of the lubricating composition. In other embodiments, the
oil of lubricating
viscosity is at least 80, or at least 81, or at least 85, or at least 87, or
at least 89, or at least 91,
or at least 93, or at least 95 weight percent of the lubrication composition.
In one embodiment,
the oil of lubricating viscosity is from 80 to 87, or from 82 to 86, or from
83 to 90 weigh
percent of the lubricating composition.
100141 The lubricating composition may be in the form of a
concentrate and/or a fully
formulated lubricant. If the lubricating composition of the instant disclosure
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 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.
100151 In the present disclosure, the lubricating composition can
include a base oil having
a kinematic viscosity measured at 100 C of 2.4 m2/s to 6.4 m2/s. In some
embodiments, the
kinematic viscosity is from 4.0 m2/s to 5.0 m2/s or from 5.2 m2/s to 5.8 m2/s
or from 6.0 m2/s
to 6.5 m2/s. In other embodiments, the kinematic viscosity is 6.2 m2/s or 5.6
m2/s or 4.6 m2/s.
Boron-Containing Additive
100161 The lubricating composition of the instant disclosure
includes a boron-containing
additive. The boron-containing additive may be in the form of any oil-soluble
boron additive,
such as a borated polyisobutenyl succinimide dispersant, a borate ester, or
any combination
thereof
100171 A borate ester (also known as a borated ester antiwear
agent), may be one or more
compounds represented by one or more of the formulas:
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RO RO OR 0
RO RO ¨ 0¨ OR
0
110
wherein each R may be independently an organic group and any two adjacent R
groups may
together form a cyclic group. Such materials may be the product of boric acid
with an alcohol.
Mixtures of two or more of the foregoing may be used. In one embodiment, each
R may be
independently a hydrocarbyl group. The total number of carbon atoms in the R
groups in each
formula may be sufficient to render the compound soluble in the base oil.
Generally, the total
number of carbon atoms in the R groups may be at least 8, and in one
embodiment at least 10,
and in one embodiment at least 12.
100181
In one embodiment, each R group may be independently a hydrocarbyl group
of 1
to 100 carbon atoms, and in one embodiment 1 to 50 carbon atoms, and in one
embodiment 1
to 30 carbon atoms, and in one embodiment 1 to 10 carbon atoms, with the
proviso that the
total number of carbons in the R group may be at least 8. Each R group may be
the same as
the other, although they may be different. Examples of useful R groups may
include isopropyl,
n-butyl, isobutyl, amyl, 1,3 dimethyl-butyl, 2-ethyl-1-hexyl (e.g., from 2-
ethylhexanol),
isooctyl, decyl, 2-propylheptyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl,
phenyl, naphthyl,
alkylphenyl, alkylnaphthyl, phenylalkyl,
naphthylalkyl, alkylphenyl alkyl, and
alkylnaphthylalkyl.
100191
In some embodiments, the boron-containing additive is present in an
amount to
deliver at least 75 ppm boron to the lubricating composition. In another
embodiment, the
boron-containing additive is present in an amount to deliver at least 100 ppm
boron to the
lubricating composition. In one embodiment, the boron-containing additive is
present in an
amount to deliver at least 125 ppm boron to the lubricating composition. In
some
embodiments, the boron-containing additive is present in an amount to deliver
at least 150
ppm boron to the lubricating composition. In one embodiment, the boron-
containing additive
is present in an amount to deliver at least 165 ppm boron to the lubricating
composition. In
one embodiment, the boron-containing additive is present in an amount to
deliver at least 200
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ppm boron to the lubricating composition. In one embodiment, the boron-
containing additive
is present in an amount to deliver from 85 to 250 ppm boron. In another
embodiment, the
boron-containing additive is present in an amount to deliver from 85 to 200
ppm boron to the
lubricating composition. In another embodiment, the boron-containing additive
is present in
an amount to deliver from 90 to 175 ppm boron to the lubricating composition.
In another
embodiment, the boron-containing additive is present in an amount to deliver
from 125 to 200
ppm boron to the lubricating composition. In another embodiment, the boron-
containing
additive is present in an amount to deliver from 75 to 175 ppm boron to the
lubricating
composition. In another embodiment, the boron-containing additive is present
in an amount
to deliver from 85 to 160 ppm boron to the lubricating composition.
100201 In some embodiment, the boron-containing additive may be a
boron-containing
polyisobutenyl succinimide dispersant, as described herein.
Polyisobutenyl Succinimide Di spersant(s):
100211 The lubricating composition of the instant disclosure
further includes a boron-free
polyisobutenyl succinimide dispersant and optionally a boron-containing
polyisobutenyl
succinimide dispersant. The reference herein to a polyisobutylene-based
dispersant refers to
both the boron-containing polyisobutenyl succinimide dispersant as well as the
boron-free
polyisobutenyl succinimide dispersant. The difference being that that boron-
containing
polyisobutenyl succinimide dispersant is post-treated with a boron compound,
as described
herein.
100221 The boron-containing polyisobutenyl succinimide and/or the
boron-free
polyisobutenyl succinimide dispersants can each be prepared from a
polyisobutylene ("PM")
succinimide dispersant that is either a "conventional" PM or a high vinylidene
PM. The
difference between a conventional polyolefin and a high vinylidene polyolefin
can be
illustrated by reference to the production of PIB. In a process for producing
conventional PIB,
isobutylene is polymerized in the presence of A1C13 to produce a mixture of
polymers
comprising predominantly tri sub stituted olefin (ITT) and tetra sub stituted
olefin (IV) end
groups, with only a very small amount (for instance, less than 20 percent) of
chains containing
a terminal vinylidene group (I). In an alternative process, isobutylene is
polymerized in the
presence of BF3 catalyst to produce a mixture of polymers comprising
predominantly (for
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instance, at least 70 percent) terminal vinylidene groups, with smaller
amounts of
tetrasubstituted end groups and other structures. The materials produced in
the alternative
method, sometimes referred to as "high vinylidene PM," are also described in
U.S. Patent
6,165,235, which is incorporated herein by reference in its entirety. In one
embodiment, the
polyisobutylene-based dispersant is a conventional polyisobutylene-based
dispersant. In
another embodiment, the polyisobutylene-based dispersant is a high or mid
vinylidene
succinimide dispersant. The polyisobutylene-based dispersant used herein is
generally known
in the art.
[0023] The polyisobutylene-based acylating agent may be
prepared/obtained/obtainable
from reaction with maleic anhydride by an "ene" or -thermal" reaction. The -
ene" reaction
mechanism and general reaction conditions are summarized in "Maleic
Anhydride", pages,
147-149, Edited by B. C. Trivedi and B. C. Culbertson and Published by Plenum
Press in
1982. The polyisobutylene-based dispersant prepared by a process that includes
an "ene"
reaction includes a dispersant having a carbocyclic ring present on less than
50 mole %, or 0
to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the
dispersant molecules.
The "ene" reaction may have a reaction temperature of 180 C. to less than 300
C., or 200
C. to 250 C., or 200 C. to 220 C.
100241 The polyisobutylene-based acylating agent may also be
obtained/obtainable from
a chlorine-assisted process, often involving Diels-Alder chemistry, leading to
formation of
carbocyclic linkages. The process is known to a person skilled in the art. The
chlorine-assisted
process may produce an acylating agent having a carbocyclic ring present on 50
mol % or
more, or 60 to 100 mol % of the molecules. Both the thermal and chlorine-
assisted processes
are described in greater detail in U.S. Pat. No. 7,615,521, columns 4-5 and
preparative
examples A and B.
[0025] The polyisobutylene-based acylating agent
may also be
prepared/obtained/obtainable from a free radical process, wherein the
acylating agent is
reacted with polyisobutylene in the presence of a free radical initiator. Free
radical processes
of this sort are well known in the art and may be carried out in the presence
of an additional
alpha-olefin.
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[0026] The polyisobutylene-based acylating agent can be obtained
from reacting
polyisobutylene with an acylating agent, i.e. an ethylenically unsaturated
carbonyl compound,
to form an acylated polyisobutylene which may be further functionalized with
an amine or
alcohol to form a suitable dispersant. Suitable acylating agents include
maleic anhydride or a
reactive equivalent thereof (such as an acid or ester), i.e., succinic acid,
and their reactive
equivalents. In one embodiment, polyisobutylene may be reacted with maleic
anhydride to
form acylated product with a conversion between 1 and 2. In one embodiment,
the
monosuccan is reacted with an amine so that the intended product comprises a
mixture
wherein all of the anhydride present in the acylating agent has been converted
to imide.
[0027] The polyisobutylene-based 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.
[0028] The polyisobutylene-based dispersant as described herein
can further be described
as having a TBN. In one embodiment, the polyisobutylene-based dispersant has a
TBN of
from 5 to 50. In another embodiment, the polyisobutylene-based dispersant has
a TBN of
from 10 to 40. In yet another embodiment, the polyisobutylene-based dispersant
has a TBN
of from 15 to 30.
100291 The lubricating composition of the instant disclosure
includes a polyisobutylene-
based dispersant that is a boron-free polyisobutylene succinimide dispersant
as described
herein. The boron-free polyisobutylene succinimide dispersant may be present
in the
lubricating composition in an amount ranging from 0.5 wt % to 6.5 wt %. In
some
embodiments, the boron-free polyisobutylene succinimide dispersant is present
in an amount
ranging from 0.7 to 6.5 wt %, or 1.5 to 4.1 wt %, or 2.0 to 3.1 wt %, or 2.5
to 2.8 wt %.
[0030] In one embodiment, the boron-free polyisobutylene
succinimide dispersant has a
number average molecular weight ranging from 750 to 2500. In some embodiments,
the
boron-free polyisobutylene succinimide dispersant has a number average
molecular weight
ranging from 750 to 1750, or 900 to 1450, or 1050 to 1250, or 1400 to 1600. In
other
embodiments, the boron-free polyisobutylene succinimide dispersant number
average
molecular weight can range from 1950 to 2500, or 2100 to 2400, or 2200 to
2350.
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[0031] In one embodiment, the boron-free polyisobutylene
succinimide dispersant
includes a first boron-free polyisobutylene succinimide dispersant having a
number average
molecular weight ranging from 750 to 1750 and a second boron-free
polyisobutylene
succinimide dispersant having a number average molecular weight ranging from
1950 to
2500. In another embodiment, the first boron-free polyisobutylene succinimide
dispersant has
a number average molecular weight ranging from 1150 to 1650 and a second boron-
free
polyisobutylene succinimide dispersant having a number average molecular
weight ranging
from 2100 to 2450. In one embodiment, the first boron-free polyisobutylene
succinimide
dispersant is present in the lubricating composition in an amount ranging from
0.5 to 4.5 wt.
% and the second boron-free polyisobutylene succinimide dispersant is present
in the
lubricating composition in an amount ranging from 0.2 to 2.0 wt. %. In another
embodiment,
the first boron-free polyisobutylene succinimide dispersant is present in the
lubricating
composition in an amount ranging from 1.8 to 2.5 wt % and the second boron-
free
polyisobutylene succinimide dispersant is present in the lubricating
composition in an amount
ranging from 0.5 to 0.8 wt %. In one embodiment, the first boron-free
polyisobutylene
succinimide dispersant has a number average molecular weight ranging from 750
to 1750 and
is present in the lubricating composition in an amount ranging from 0.5 to 4.5
wt. % and the
second boron-free polyisobutylene succinimide dispersant has a number average
molecular
weight ranging from 1950 to 2500 and is present in the lubricating composition
in an amount
ranging from 0.2 to 2.0 wt. %. In one embodiment, the first boron-free
polyisobutylene
succinimide dispersant comprises 60% to 90%, or 65% to 85%, or 70% to 80%, or
75% to
80% of the total combination of the first boron-free polyisobutylene
succinimide dispersant
and the second boron-free polyisobutylene succinimide dispersant.
[0032] Polyisobutylene succinimide dispersants of the invention
may be prepared by
reaction of the acylated PIB with a suitable amine compound. Suitable amines
include one or
more hydrocarbyl amines, aminoalcohols, polyetheramines, or combinations
thereof.
[0033] 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
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(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.
100341 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 aminodiphenyl amine (also N,N-
phenyldiamine), and (vii)
a ring-substituted benzylamine.
100351 In one embodiment, the polyetheramine compound may comprise
an amine-
terminated polyether compound. Amine terminated polyether compounds may
comprise units
derived from ethylene oxides, propylene oxides, butylene oxides, or some
combination
thereof. Suitable polyether compounds include Jeffamine line of polyether
amines available
from Huntsman.
100361 The lubricating composition of the instant disclosure
further includes a boron-
containing polyisobutylene succinimide dispersant. In preparing the boron-
containing
polyisobutylene succinimide dispersant, the polyisobutylene-based dispersant
as described
herein may be post-treated by conventional methods including a reaction with
boron
compounds to generate the boron-containing polyisobutylene succinimide
dispersant. Suitable
boron compounds that may be used to borate the polyisobutylene-based
dispersant include
one or more of a variety of agents selected from the group consisting of the
various forms of
boric acid (including metaboric acid, 1-I802, orthoboric acid, H3B03, and
tetraboric acid,
H2B407), boric oxide, boron trioxide, and alkyl borates. In one embodiment the
borating
agent is boric acid which may be used alone or in combination with other
borating agents.
Methods of preparing borated dispersants are known in the art. The borated
dispersant may
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be prepared in such a way that they contain 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.
100371
In one embodiment, the boron-containing polyisobutylene succinimide
dispersant
is derived from a polyisobutylene having a vinylidene content of greater than
70 mol %, or
greater than 80 mole %, or greater than 85 mol %, or greater than 90 mol %.
[0038]
In one embodiment, the boron-containing polyisobutylene succinimide
dispersant
has a number average molecular weight ranging from 1750 to 2200, or 1850 to
2150, or 1950
to 2250. The boron-containing polyisobutylene succinimide dispersant can be
present in the
lubricating composition in an amount ranging from 0.2 to 2.1 wt %, or 0.5 to
1.8 wt %, or 1
to 2.1 wt %, or 1.5 to 1.7 wt %. In some embodiments, the boron-containing
polyisobutylene
succinimide dispersant is present in an amount to deliver at least 75 ppm
boron to the
lubricating composition. In another embodiment, the boron-containing
polyisobutylene
succinimide dispersant is present in an amount to deliver at least 100 ppm
boron to the
lubricating composition.
In one embodiment, the boron-containing polyisobutylene
succinimide dispersant is present in an amount to deliver at least 125 ppm
boron to the
lubricating composition. In some embodiments, the boron-containing
polyisobutylene
succinimide dispersant is present in an amount to deliver at least 150 ppm
boron to the
lubricating composition.
In one embodiment, the boron-containing polyisobutylene
succinimide dispersant is present in an amount to deliver at least 165 ppm
boron to the
lubricating composition.
In one embodiment, the boron-containing polyisobutylene
succinimide dispersant is present in an amount to deliver at least 200 ppm
boron to the
lubricating composition.
In one embodiment, the boron-containing polyisobutylene
succinimide dispersant is present in an amount to deliver from 125 to 200 ppm
boron to the
lubricating composition.
Metal Overbased Detergents:
[0039]
The instant lubricating composition includes an overbased magnesium-
based
detergent and an overbased calcium-based detergent.
[0040]
Metal overbased detergents, otherwise referred to as overbased
detergents, metal-
containing overbased detergents or superbased salts, are characterized by a
metal content in
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excess of that which would be necessary for neutralization according to the
stoichiometry of
the metal and the particular acidic organic compound, i.e. the substrate,
reacted with the
metal. The overbased detergent may include one or more of non-sulfur
containing phenates,
sulfur containing phenates, sulfonates, salicylates, and mixtures thereof.
100411 The amount of excess metal is commonly expressed in terms
of substrate to metal
ratio. The terminology "metal ratio" is used in the prior art and herein to
define the ratio of
the total chemical equivalents of the metal in the overbased salt to the
chemical equivalents
of the metal in the salt which would be expected to result from the reaction
between the
hydrocarbyl substituted organic acid; the hydrocarbyl-substituted phenol or
mixtures thereof
to be overbased, and the basic metal compound according to the known chemical
reactivity
and the stoichiometry of the two reactants. Thus, in a normal or neutral salt
(i.e. soap) the
metal ratio is one and, in an overbased salt, the metal ratio is greater than
one, especially
greater than 1.3. The overbased detergent of the invention may have a metal
ratio of 5 to 30,
or a metal ratio of 7 to 22, or a metal ratio of at least 11.
100421 The metal-containing detergent may also include "hybrid"
detergents formed with
mixed surfactant systems including phenate and/or sulfonate components, e.g.
phenate/salicylates, sulfonate/phenates, sulfonate/salicylates,
sulfonates/phenates/salicylates,
as described, for example, in US Patents 6,429,178; 6,429,179; 6,153,565; and
6,281,179.
Where, for example, a hybrid sulfonate/phenate detergent is employed, the
hybrid detergent
would be considered equivalent to amounts of distinct phenate and sulfonate
detergents
introducing like amounts of phenate and sulfonate soaps, respectively.
Overbased phenates
and salicylates typically have a total base number of 180 to 600 TBN.
Overbased sulfonates
typically have a total base number of 250 to 600, or 500 to 850. Overbased
detergents are
known in the art.
100431 Alkylphenols are often used as constituents in and/or
building blocks for overbased
detergents. Alkylphenols may be used to prepare phenate, salicylate,
salixarate, or saligenin
detergents or mixtures thereof. Suitable alkylphenols may include para-
substitued
hydrocarbyl phenols. The hydrocarbyl group may be linear or branched aliphatic
groups of 1
to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20
carbon atoms, or
16 to 24 carbon atoms. In one embodiment, the alkylphenol overbased detergent
is prepared
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from an alkylphenol or mixture thereof that is free of or substantially free
of (i.e. contains less
than 0.1 weight percent) tetrapropenylphenol, i.e., p-dodecylphenol or PDDP.
In one
embodiment, the lubricating composition of the invention contains less than
0.3 weight
percent of alkylphenol, less than 0.1 weight percent of alkylphenol, or less
than 0.05 weight
percent of alkylphenol.
100441 The overbased magnesium-based detergent includes magnesium
salts, or mixtures
thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates
and salicylates. In
one embodiment, the overbased magnesium-based detergent is an overbased
alkylbenzene
sulfonate having a metal ratio of at least 8. In one embodiment, the overbased
magnesium-
based detergent is present in the lubricating composition to deliver at least
300 ppm or at least
330 ppm or at least 400 ppm of magnesium to the lubricating composition. In
one
embodiment, the overbased magnesium-based detergent is present in the
lubricating
composition to deliver at least 500 ppm of magnesium to the lubricating
composition. In
another embodiment, the overbased magnesium-based detergent is present in the
lubricating
composition to deliver at least 600 ppm of magnesium to the lubricating
composition. In
another embodiment, the overbased magnesium-based detergent is present in the
lubricating
composition to deliver from 300 to 1200 ppm or 400 to 1200 ppm of magnesium to
the
lubricating composition. In another embodiment, the overbased magnesium-based
detergent
is present in the lubricating composition to deliver from 300 or 700 or 330 or
700 or 400 to
700 or 400 to 800 of magnesium to the lubricating composition.
100451 The overbased magnesium-based detergent can be present in
the lubricating
composition in an amount of from 0.1 to 1.5 wt %, or 0.2 to 0.8 wt % or 0.2 to
0.4 wt %. In
some embodiments, the overbased magnesium-based detergent has a total base
number
("TBN") ranging from 200 to 600 KOH/g. In some embodiments, the TBN of the
overbased
magnesium-based detergent is from 300 to 500 KOH/g. In other embodiments, the
overbased
magnesium-based detergent has a TBN of 600 to 750 KOH/g.
100461 The overbased calcium-based detergent as used in the
instant lubricating
composition include calcium salts, or mixtures thereof of salixarates and
salicylates. In one
embodiment, the overbased calcium-based detergent has a metal ratio of at
least 5. In one
embodiment, the overbased calcium-based detergent is present in the
lubricating composition
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to deliver at least 400 ppm of calcium to the lubricating composition. In one
embodiment, the
overbased calcium-based detergent is present in the lubricating composition to
deliver at least
500 ppm of calcium to the lubricating composition. In another embodiment, the
overbased
calcium-based detergent is present in the lubricating composition to deliver
at least 600 ppm
of calcium to the lubricating composition. In another embodiment, the
overbased calcium-
based detergent is present in the lubricating composition to deliver from 400
to 1200 or 750
to 1200 or 800 to 1100 ppm of calcium to the lubricating composition. In
another
embodiment, the overbased calcium-based detergent is present in the
lubricating composition
to deliver from 400 to 700 of calcium to the lubricating composition.
100471 The overbased calcium-based detergent can be present in the
lubricating
composition in an amount of from 0.1 to 2.5 wt ()/0, or 0.3 to 1.5 wt % or 0.4
to 0.8 wt %, or
0.4 to 0.6 wt %. In some embodiments, the overbased calcium salicylate
detergent has a TBN
ranging from 300 to 600 KOH/g. In other embodiments, the overbased calcium
salicylate
detergent has a TBN ranging from 350 to 500, or 100 to 550, or 250 to 450
KOH/g.
100481 In one embodiment, the calcium-based detergent is an
overbased calcium
salicylate detergent. In another embodiment, the calcium-based detergent is an
overbased
calcium salixarate detergent. In another embodiment, the calcium-based
detergent is a
mixture of a calcium salicylate detergent and a calcium salixarate detergent.
Molybdenum -Containing Material
100491 In one embodiment, the lubricating composition may contain
a molybdenum-
containing material, which may also be referred to herein as a molybdenum
compound.
Molybdenum compounds as lubricant additives are known in the art and may serve
in various
functions, such as antiwear agents, friction modifiers and antioxidants. The
use of
molybdenum and sulfur containing compositions in lubricating oil compositions
as antiwear
agents and antioxidants is known. Such materials may be a molybdenum
hydrocarbyldithiocarbamate. U.S. Pat. No. 4,285,822, for instance, discloses
lubricating oil
compositions containing a molybdenum and sulfur containing composition
prepared by (1)
combining a polar solvent, an acidic molybdenum compound and an oil-soluble
basic nitrogen
compound to form a molybdenum-containing complex and (2) contacting the
complex with
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carbon disulfide to form the molybdenum and sulfur containing composition.
Other
molybdenum-containing materials include molybdenum dihydrocarbyldithio-
phosphates. Yet
other molybdenum-containing materials include molybdenum-amine compounds as
described
in U.S. Pat. No. 6,329,327; organomolybdenum compounds made from the reaction
of a
molybdenum source, fatty oil, and a diamine as described in U.S. Pat. No.
6,914,037; and
trinuclear molybdenum-sulfur complexes as described in U.S. Pat. No.
6,232,276. In one
embodiment, the molybdenum compound is a molybdenum dithiocarbamate complex, a
molybdenum dithiocarbamate dimer complex, or a tri-nuclear molybdenum
compound.
[0050] In certain embodiments, the lubricant formulation contains
a molbydenum-
containing material in an amount to provide 40 to 1200 parts per million by
weight
molybdenum to the lubricant, or alternatively 50 to 250, 50 to 500, 60 to 200,
300 to 1000, or
400 to 800 parts per million. The actual amount of the molybdenum-containing
material will
depend in part on the nature and formula weight of the anion or complexing
agent associated
with the molybdenum, in a way that may be readily calculated. In some
embodiments, the
molybdenum-containing compound is present in the lubricating composition in an
amount of
0 to 1.1 wt %, or 0.01 to 0.5 wt %, or 0.03 to 0.35 wt %, or 0.07 to 0.18 wt
%. In some
embodiments, the molybdenum-containing compound is present in the lubricating
composition in an amount of 0.02 to 0.2 wt %. In other embodiments, the
molybdenum-
containing compound is present in the lubricating composition in an amount of
0.04 to 0.18
wt %.
Ashless Friction Modifier:
[0051] The lubricating composition of the instant disclosure may
further include an
ashless friction modifier. Friction modifiers that may be useful in an
exemplary lubricating
composition include fatty acid derivatives such as amines, esters, epoxides,
fatty imidazolines,
condensation products of carboxylic acids and polyalkylene-polyamines and
amine salts of
alkylphosphoric acids. Ashless friction modifiers are those which typically do
not produce
any sulfated ash when subjected to the conditions of ASTM D 874. An additive
is referred to
as "non-metal containing" if it does not contribute metal content to the
lubricant composition.
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As used herein the term "fatty alkyl" or "fatty" in relation to friction
modifiers means a carbon
chain having 8 to 30 carbon atoms, typically a straight carbon chain.
100521
In one embodiment, the ash-free friction modifier may be represented by
the
formula:
/0 0
D __________________________________________
(E)q ___________________________________________________ D,_R22
where, D and D' are independently selected from -0-, >NH, >NR23, an imide
group formed
by taking together both D and D' groups and forming a R21-N< group between two
>C=0
groups; E is selected from
>CH2, >c11R26, >CR26R27, >C(OH)(CO2R22),
>C(CO2R22)2, and >CHOR28; where R24 and R25 are independently selected from
>CH2,
>cHR26, >CR26R27, >C(OH)(CO2R22), and >CHOR28; q is 0 to 10, with the proviso
that when
q=1, E is not >CH2, and when n=2, both Es are not >CH2; p is 0 or 1; R21 is
independently
hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms,
with the proviso
that when R21 is hydrogen, p is 0, and q is more than or equal to 1; R22 is a
hydrocarbyl group,
typically containing 1 to 150 carbon atoms; R23, R24, R25, R26 and
R27 are independently
hydrocarbyl groups; and R28 is hydrogen or a hydrocarbyl group, typically
containing 1 to 150
carbon atoms, or 4 to 32 carbon atoms, or 8 to 24 carbon atoms. In certain
embodiments, the
hydrocarbyl groups R23, R24, and R25, may be linear or predominantly linear
alkyl groups.
In certain embodiments, the ash-free friction modifier is a fatty ester,
amide, or imide of
various hydroxy-carboxylic acids, such as tartaric acid, malic acid lactic
acid, glycolic acid,
and mandelic acid. Examples of suitable materials include tartaric acid di(2-
ethylhexyl) ester
(i.e., di(2-ethylhexyl)tartrate), di(Cg-Cio)tartrate, di(C12-15)tartrate, di-
oleyltartrate,
oleyltartrimide, and oleyl maleimide.
[0053]
In certain embodiments, the ash-free friction modifier may be chosen
from 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;
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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
100541 Useful friction modifiers may also encompass materials such
as sulfurized fatty
compounds and olefins, sunflower oil or soybean oil monoester of a polyol and
an aliphatic
carboxylic acid.
100551 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 triglyceri de. In one
embodiment, the
ashless friction modifier is one or more of an ester, an amide, or an imide of
an alpha-hydroxy
carbonyl compound, and mixtures thereof
100561 In one embodiment, the ashless friction modifier is a fatty
amine, fatty amine
alkoxylate, alkoxylated fatty amides or imides, or combinations thereof In
another
embodiment, the ashless friction modifier is selected from ethoxylated tallow
amine and
ethoxylated oleyl amide.
100571 The ashless friction modifier may be present in the
lubricating composition in an
amount of from 0.01 to 1.1 wt %, or 0.1 to 0.5 wt %, or 0.2 to 0.4 wt %. In
some embodiments,
the ashless friction modifier is selected from one or more of an ethoxylated
tallow amine and
an ethoxylated oleyl amide and is present in the lubricating composition in an
amount of from
0.01 to 1.1 wt %, or 0.1 to 0.5 wt %, or 0.2 to 0.4 wt %.
Formulation Additives:
100581 Lubricating compositions as described herein may further
contain one or more
additives as described below:
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Anti--wear Agent:
100591 Anti-wear agents include phosphorus-containing compounds as
well as
phosphorus free compounds.
100601 Phosphorus-containing anti-wear agents are well known to
one skilled in the art
and include metal dialkyl(dithio)phosphate salts, hydrocarbyl phosphites,
hydrocarbyl
phosphines, hydrocarbyl phosphonates, alkylphosphate esters, amine or ammonium
(alkyl)phosphate salts, and combinations thereof.
100611 In one embodiment, the phosphorus-containing ant-wear agent
may be a metal
dialkyldithiophosphate, which may include a zinc dialkyldithiophosphate. Such
zinc salts are
often referred to as zinc dialkyldithiophosphates (ZDDP) or simply zinc
dithiophosphates
(ZDP). They are well known and readily available to those skilled in the art
of lubricant
formulation. Further zinc dialkyldithiophosphates may be described as primary
zinc
dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates,
depending on the
structure of the alcohol used in its preparation. In some embodiments the
instant compositions
may include primary zinc dialkyldithiophosphates. In some embodiments, the
compositions
include secondary zinc dialkyldithiophosphates. In some embodiments, the
compositions
include a mixture of primary and secondary zinc dialkyldithiophosphates. In
some
embodiments component (b) is a mixture of primary and secondary zinc
dialkyldithiophosphates where the ratio of primary zinc
dialkyldithiophosphates to secondary
zinc dialkyldithiophosphates (one a weight basis) is at least 1:1, or even at
least 1:1.2, or even
at least 1:1.5 or 1:2, or 1:10.
100621 Examples of suitable metal dialkyldithiophosphate include
metal salts of the
formula:
Rio 1,1
where RI- and R2 are independently hydrocarbyl groups containing 3 to 24
carbon atoms, or 3
to 12 carbon atoms, or 3 to 8 carbon atoms; M is a metal having a valence n
and generally
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incudes zinc, copper, iron, cobalt, antimony, manganese, and combinations
thereof. In one
embodiment le and le are secondary aliphatic hydrocarbyl groups containing 3
to 8 carbon
atoms, and M is zinc. Suitable hydrocarbyl groups may be selected from
isopropyl, n-butyl,
sec-butyl, amyl (also pentyl), methylamyl, 1,4-dimethyl butyl (derived from 4-
methylpentan-
2-ol), n-hexyl, iso-octyl, 2-ethylexyl, and combinations thereof.
100631 ZDDP may be present in the composition in an amount to
deliver 0.01 weight
percent to 0.12 weight percent phosphorus to the lubricating composition. ZDDP
may be
present in an amount to deliver at least 100 ppm, or at least 300 ppm, or at
least 500 ppm of
phosphorus to the composition up to no more than 1200 ppm, or no more than
1000 ppm, or
no more than 800 ppm phosphorus to the composition. Further, ZDDP may be
present in the
lubricating composition in an amount to deliver between 200 ppm un to 1000
ppm, or 450
ppm to 800 ppm, or 600 ppm to 800 ppm phosphorous to the lubricating
composition.
[0064] In one embodiment, the phosphorus-containing anti-wear
agent may be a zinc free
phosphorus compound. The zinc-free phosphorus anti-wear agent may contain
sulfur or may
be sulfur-free. Sulfur-free phosphorus-containing antiwear agents include
hydrocarbyl
phosphites, hydrocarbyl phosphines, hydrocarbyl phosphonates, alkylphosphate
esters, amine
or ammonium phosphate salts, or mixtures thereof.
100651 In one embodiment, the anti-wear agent may be a phosphorus-
free compound.
Examples of suitable phosphorus-free antiwear agents include titanium
compounds, hydroxy-
carboxylic acid derivatives such as esters, amides, imides or amine or
ammonium salt,
sulfurized olefins, (thio)carbamate-containing compounds, such as
(thio)carbamate esters,
(thio)carbamate amides, (thio)carbamic ethers, alkylene-coupled
(thio)carbamates, and bis(S-
alkyl(dithio)carbamyl) disulfides. Suitable hydroxy-carboxylic acid
derivatives include
tartaric acid derivatives, malic acid derivatives, citric acid derivatives,
glycolic acid
derivatives, lactic acid derivatives, and mandelic acid derivatives.
100661 The antiwear agent may in one embodiment include a tartrate
or tartrimide as
disclosed in International Publication WO 2006/044411 or Canadian Patent CA 1
183 125.
The tartrate or tartrimide may contain alkyl-ester groups, where the sum of
carbon atoms on
the alkyl groups is at least 8. The antiwear agent may in one embodiment
include a citrate as
is disclosed in US Patent Application 20050198894.
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[00671 The anti-wear agent may be represented by the formula:
/0) 0
y ___________________________________________
_______________________________________________________ Y-R2
wherein Y and Y' are independently -0-, >NH, >NR3, or an imide group formed by
taking
together both Y and Y' groups and forming a RI--N< group between two >C=0
groups; X is
independently -Z-0-Z'-, >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), >C(CO2R2)2, or
>CHOR6; Z and Z' are independently >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), or
>CHOR6;
n is 0 to 10, with the proviso that when n=1, X is not >CH2, and when n=2,
both X's are not
>CH2; m is 0 or 1; RI- is independently hydrogen or a hydrocarbyl group,
typically containing
1 to 150 carbon atoms, with the proviso that when RI- is hydrogen, m is 0, and
n is more than
or equal to 1; R2 is a hydrocarbyl group, typically containing 1 to 150 carbon
atoms; R3, R4
and R5 are independently hydrocarbyl groups; and R6 is hydrogen or a
hydrocarbyl group,
typically containing 1 to 150 carbon atoms.
100681 The phosphorus-free antiwear agent may be present at 0 wt %
to 3 wt %, or 0.1 wt
% to 1.5 wt %, or 0.5 wt % to 1.1 wt % of the lubricating composition.
100691 The antiwear agent, be it phosphorus-containing, phosphorus
free, or mixtures,
may be present at 0.15 weight % to 6 weight %, or 0.2 weight % to 3.0 weight
%, or 0.5 weight
% to 1.5 weight % of the lubricating composition.
[0070] Another class of additives includes oil-soluble titanium
compounds as disclosed in
U.S. Pat. No. 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) i sopropoxi de. 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.
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Ashless Antioxidant
100711
The instant compositions may include an ashless antioxidant. Ashless
antioxidants
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 includes an antioxidant, or mixtures thereof. The
antioxidant may
be present at least 0.9 wt %, or 0.9 to 2.5 wt %, or 1.1 to 2.0 wt %, or 1.2
weight % to 7 weight
%, or 1.2 weight % to 6 weight %, or 1.5 weight % to 5 weight %, of the
lubricating
composition.
[0072]
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.
[0073]
The diarylamine antioxidant may be present on a weight basis of this
lubrication
composition at 0.1% to 10%, 0.35% to 5%, or even 0.5% to 2%.
[0074]
The phenolic antioxidant may be a simple alkyl phenol, a hindered
phenol, or
coupled phenolic compounds.
[0075]
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-butyl¨phenol or 4-butyl-2,6-di-tert-butylphenol,
4-dodecy1-2,6-di-tert-
butyl¨phenol, or butyl 3-(3,5-ditert-buty1-4-hydroxyphenyl)propanoate. In one
embodiment,
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the hindered phenol antioxidant may be an ester and may include, e.g.,
IrganoxTM L-135 from
Ciba.
100761 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), 2,21-methylenebis(4-
methy1-6-t-
butylphenol), and 2,2'-methylene bis(4-ethy1-6-t-butylphenol).
100771 Phenols may 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
100781 In one embodiment, the phenolic antioxidant comprises a
hindered phenol. In
another embodiment the hindered phenol is derived from 2,6-ditertbutyl phenol.
100791 In one embodiment the lubricating composition comprises a
phenolic antioxidant
in a range of 0.01 wt % to 5 wt %, or 0.1 wt % to 4 wt %, or 0.2 wt % to 3 wt
%, or 0.5 wt %
to 2 wt % of the lubricating composition.
100801 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
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. Suitable sulfurized
olefins include
sulfurized alpha olefins containing 10 to 22 carbon atoms, sulfurized
isobutylene, sulfurized
di-isobutylene, 4-Carbobutoxy cyclohexene, and combinations thereof.
100811 Ashless antioxidants may be used separately or in
combination. In one
embodiment, 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 1.2 to 7 weight percent. In one
embodiment, there may
be at least 0.25 to 3 weight percent of each ashless antioxidant.
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Additional Metal-Based Detergent:
[0082] In addition to the magnesium-based and calcium-based
detergents described
above, lubricating compositions according to the instant disclosure may
further contain
additional metal-based detergent(s). The additional metal-based detergent will
be a detergent
that differs from either the magnesium-based and calcium-based detergents even
though they
may contain the same metal salt, i.e., a magnesium sulphonate detergent and a
magnesium
phenate will be considered different detergents. Metal based detergents are
generally
described above; however, the additional metal-based detergent may be alkali
metal or
alkaline earth metal salt including sodium salts, calcium salts, magnesium
salts, or mixtures
thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates
and salicylates.
The additional metal-based detergent may be either a neutral or overbased
detergent.
Additional metal-based detergents may be present in the lubricating
composition at 0.2 wt %
to 15 wt %, or 0.3 wt % to 10 wt %, or 0.3 wt % to 8 wt %, or 0.4 wt % to 3 wt
%.
Additional Friction Modifier
[0083] The lubricating composition may contain an additional
friction modifier(s)
different from those described in the foregoing compositions or combinations
thereof.
Examples of the additional friction modifier(s) include long chain fatty acid
derivatives of
amines, fatty esters, or epoxides; fatty imidazolines such as condensation
products of
carboxylic acids and polyalkylene-polyamines; and amine salts of
alkylphosphoric acids. The
term fatty, as used herein, can mean having a C8-22 linear alkyl group. In one
embodiment,
the friction modifier may be a glycerol mono-ester, such as glycerol mono-
oleate, or a
triglyceride, such as sunflower oil, soybean oil, or combinations thereof
[0084] Additional friction modifiers may be present in the
lubricating composition from
0.01 wt % up to 2 wt %, or 0.05 wt % up to 1 wt %, or 0.1 wt % up to 0.5 wt %.
Polymeric Viscosity Modifier:
[0085] The lubricating composition may contain a polymeric
viscosity modifier, a
dispersant viscosity modifier different from that of that invention, or
combinations thereof.
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The dispersant viscosity modifier may be generally understood to be a
functionalized, i.e.
derivatized, form of a polymer similar to that of the polymeric viscosity
modifier.
100861 The polymeric viscosity modifier may be an olefin
(co)polymer, a
poly(meth)acrylate (PMA), a vinyl aromatic-diene copolymer, or mixtures
thereof In one
embodiment, the polymeric viscosity modifier is an olefin (co)polymer.
100871 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.
100881 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 C 1 0 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-
hexadiene, 1,4-
cy cl ohexadi ene, di cy cl op entadi ene, 5-ethyldiene-2-norbornene, 5 -m
ethyl ene-2-norb omen e,
1,5-heptadiene, and 1,6-octadiene.
100891 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 `)/0
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.
[0090] 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.
[0091] Useful olefin polymers, in particular, ethylene-a-olefin
copolymers have a number
average molecular weight ranging from 4500 to 500,000, for example, 5000 to
100,000, or
7500 to 60,000, or 8000 to 45,000.
[0092] 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]).
[0093] In one embodiment, the lubricating composition comprises a
dispersant viscosity
modifier (DVM). The DVM may comprise an olefin polymer that has been modified
by the
addition of a polar moiety.
[0094] The olefin polymers are functionalized by modifying the
polymer by the addition
of a polar moiety. In one useful embodiment, the functionalized copolymer is
the reaction
product of an olefin polymer grafted with an acylating agent. In one
embodiment, the acylating
agent may be an ethylenically unsaturated acylating agent. Useful acylating
agents are
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typically a,p 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.
[0095] 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.
[0096] Amine functional groups may 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.
100971 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-phenyl-
phenylenediamine),
and (vii) a ring-substituted benzyl amine.
[0098] 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
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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
100991 In another one embodiment, the polar moiety added to the
functionalized ethylene-
cc-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, butyl ene 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.
101001 In one embodiment, lubricating composition may comprise a
poly(meth)acrylate
polymeric viscosity modifier. As used herein, the term "(meth)acrylate- and
its cognates
means either methacrylate or acrylate, as will be readily understood.
101011 In one embodiment, the poly(meth)acrylate polymer is
prepared from a monomer
mixture comprising (meth)acrylate monomers having alkyl groups of varying
length. The
(meth)acrylate monomers may contain alkyl groups that are straight chain or
branched chain
groups. The alkyl groups may contain 1 to 24 carbon atoms, for example 1 to 20
carbon atoms.
101021 The poly(meth)acrylate polymers described herein are formed
from monomers
derived from saturated alcohols, such as methyl (meth)acrylate, ethyl
(meth)acrylate, propyl
(meth)acrylate, butyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 2-
propylheptyl
(meth)acrylate, 2-butyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
octyl
(meth)acryl ate, nonyl (m eth)acryl ate, i sooctyl (m eth)acryl ate, i sononyl
(m eth)acryl ate, 2-tert-
butylheptyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl
(meth)acrylate, undecyl
(meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-
methyldodecyl
(meth)acrylate, tridecyl (m eth)acryl ate, 5-m ethy ltri decyl (m eth)acryl
ate, tetradecyl
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(meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-
methylhexadecyl
(meth)acrylate, heptadecyl (m eth)acryl ate, 5-i sopropylheptadecyl (m
eth)acryl ate, 4-tert-
butyl octadecyl (m eth)acryl ate, 5 -
ethyl octadecyl (m eth)acryl ate, 3-i sopropyl -
octadecyl -(meth)acryl ate, octadecyl (meth)acrylate, nonadecyl
(meth)acrylate, eicosyl
(meth)acrylate, (meth)acrylates derived from unsaturated alcohols, such as
oleyl
(meth)acrylate; and cycloalkyl (meth)acrylates, such as 3-viny1-2-
butylcyclohexyl
(meth)acrylate or bornyl (meth)acrylate.
101031
Other examples of monomers include alkyl (meth)acrylates with long-chain
alcohol-derived groups which may be obtained, for example, by reaction of a
(meth)acrylic
acid (by direct esterification) or methyl (meth)acrylate (by
transesterification) with long-chain
fatty alcohols, in which reaction a mixture of esters such as (meth)acrylate
with alcohol groups
of various chain lengths is generally obtained. These fatty alcohols include
Oxo Alcohol
7911, Oxo Alcohol 7900 and Oxo Alcohol 1100 of Monsanto; Alphanol 79 of
ICI;
Nafol 1620, Alfol 610 and Alfol 810 of Condea (now Sasol); Epal 610 and
Epal 810
of Ethyl Corporation; Linevol 79, Linevol 911 and Dobanol 25 L of Shell AG;
Lial
125 of Condea Augusta, Milan, Dehydad and Lorol of Henkel KGaA (now Cognis)
as
well as Linopol 7-11 and Acropol 91 of Ugine Kuhlmann.
101041
In one embodiment, the poly(meth)acrylate polymer comprises a dispersant
monomer; dispersant monomers include those monomers which may copolymerize
with
(meth)acrylate monomers and contain one or more heteroatom s in addition to
the carbonyl
group of the (meth)acrylate. The dispersant monomer may contain a nitrogen-
containing
group, an oxygen-containing group, or mixtures thereof.
101051
The oxygen-containing compound may include hydroxyalkyl(meth)acrylates
such
as 3 -hy droxypropyl (m eth)acryl ate,
,4- di hy droxybutyl (m eth)acryl ate, 2-
hy droxy ethyl (m eth)acryl ate, 2-hy droxypropyl (m eth)acryl ate, 2,5 -dim
ethyl -1,6-hexanedi ol
(meth)acrylate, 1, 10-dec anedi ol (m eth)acryl ate, carbonyl-containing
(meth)acrylates such as
2-carb oxyethyl (m eth)acryl ate,
carboxym ethyl (m eth)acryl ate,
oxazol i di nyl ethyl (m eth)acrylate, N-(m ethacryl oyl oxy)form ami de,
acetonyl(meth)acrylate,
N-methacryloylmorpholine, N-methacryloy1-2-pyrrolidinone, N-(2-methacryloyl-
oxyethyl)-
2-pyrrolidinone, N-(3-
methacryloyloxypropy1)-2-pyrrolidinone, N-(2-
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methacryloyloxypentadecy1)-2-pyrrolidinone,
N-(3 -m ethacryl oyloxy-heptadecy1)-2-
pyrrolidinone; glycol di (meth)acryl ates such as 1,4 -butan edi ol
(meth)acryl ate, 2-
butoxy ethyl(m eth)acryl ate, 2- ethoxy ethoxym ethyl (m eth)acryl
ate, 2-
ethoxyethyl(meth)acrylate, or mixtures thereof
[0106]
The nitrogen-containing compound may be a (meth)acrylamide or a nitrogen
containing (meth)acrylate monomer. Examples of a suitable nitrogen-containing
compound
include N,N-dimethylacrylamide, N-vinyl carbonamides such as N-vinyl-
formamide, vinyl
pyridine, N-vinylacetoamide, N-vinyl propionamides, N-vinyl hydroxy-
acetoamide, N-vinyl
imidazole, N-vinyl pyrrolidinone, N-vinyl caprolactam, dimethylaminoethyl
acrylate
(DMAEA), dimethylaminoethyl methacryl ate (DMAEMA), dimethylaminobutyl acryl
ami de,
dim ethyl aminop ropyl m ethacryl ate (DMAPMA), dim ethyl aminopropyl acryl
ami de,
dim ethyl -ami nopropyl methacryl ami de, dim ethyl ami noethyl acryl ami de
or mixtures thereof.
[0107]
Dispersant monomers may be present in an amount up to 5 mol percent of
the
monomer composition of the (meth)acrylate polymer. In one embodiment, the
poly(meth)acrylate is present in an amount 0 to 5 mol percent, 0.5 to 4 mol
percent, or 0.8 to
3 mol percent of the polymer composition. In one embodiment, the
poly(meth)acrylate is free
of or substantially free of dispersant monomers.
101081
In one embodiment, the poly(meth)acrylate comprises a block copolymer or
tapered block copolymer. Block copolymers are formed from a monomer mixture
comprising
one or more (m eth)acryl ate monomers, wherein, for example, a first (m
eth)acryl ate monomer
forms a discrete block of the polymer joined to a second discrete block of the
polymer formed
from a second (meth)acrylate monomer. While block copolymers have
substantially discrete
blocks formed from the monomers in the monomer mixture, a tapered block
copolymer may
be composed of, at one end, a relatively pure first monomer and, at the other
end, a relatively
pure second monomer. The middle of the tapered block copolymer is more of a
gradient
composition of the two monomers.
[0109]
In one embodiment, the poly(meth)acrylate polymer (P) is a block or
tapered block
copolymer that comprises at least one polymer block (BO that is insoluble or
substantially
insoluble in the base oil and a second polymer block (132) that is soluble or
substantially
soluble in the base oil.
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[0110] In one embodiment, the poly(meth)acrylate polymers may have
an architecture
selected from linear, branched, hyper-branched, cross-linked, star (also
referred to as
"radial"), or combinations thereof. Star or radial refers to multi-armed
polymers. Such
polymers include (meth)acrylate-containing polymers comprising 3 or more arms
or branches,
which, in some embodiments, contain at least about 20, or at least 50 or 100
or 200 or 350 or
500 or 1000 carbon atoms. The arms are generally attached to a multivalent
organic moiety
which acts as a "core" or "coupling agent." The multi-armed polymer may be
referred to as a
radial or star polymer, or even a "comb" polymer, or a polymer otherwise
having multiple
arms or branches as described herein.
101111 Linear poly(meth)acrylates, random, block or otherwise, may
have weight average
molecular weight (M,) of 1000 to 400,000 Daltons, 1000 to 150,000 Daltons, or
15,000 to
100,000 Daltons. In one embodiment, the poly(meth)acryl ate may be a linear
block copolymer
with a Mw of 5,000 to 40,000 Daltons, or 10,000 to 30,000 Daltons.
101121 Radial, cross-linked or star copolymers may be derived from
linear random or di-
block copolymers with molecular weights as described above. A star polymer may
have a
weight average molecular weight of 10,000 to 1,500,000 Daltons, or 40,000 to
1,000,000
Daltons, or 300,000 to 850,000 Daltons.
101131 In one embodiment, the lubricating composition may comprise
a vinylaromatic-
diene copolymer. The vinylaromatic-diene copolymer may be a linear or radial
block
copolymer. In one embodiment the vinylaromatic-diene copolymer may be a
hydrogenated
styrene-(conjugated diene) block copolymer.
101141 The block copolymer in different embodiments may be a
hydrogenated styrene-
butadiene copolymer or a hydrogenated styrene-isoprene copolymer. Both block
copolymers
are known in the art and are disclosed for example in EP 2 001 983 A (Price et
al.) for
hydrogenated styrene-butadiene and U.S. Pat. No. 5,490,945 (Smith et al.) for
hydrogenated
styrene-isoprene.
101151 The butadiene block of the hydrogenated styrene-butadiene
copolymer may be
prepared with by either 1,2-addition or 1,4-addition, with 1,2-addition
preferred as is disclosed
in EP 2 001 983 A. Using 1,2-addition results in a butadiene block having 20
mol % to 80 mol
%, or 25 mol % to 75 mol %, or 30 mol % to 70 mol %, or 40 mol % to 65 mol %
of repeat
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units of branched alkyl groups due to initially-formed pendant unsaturated or
vinyl groups,
upon hydrogenation, become alkyl branches.
101161 The lubricating compositions may comprise 0.05 weight % to
2 weight %, or 0.08
weight % to 1.8 weight %, or 0.1 to 1.2 weight % of the one or more polymeric
viscosity
modifiers and/or dispersant viscosity modifiers as described herein.
Oxyalkkylated hydrocarbyl phenol:
101171 The lubricating compositions described herein may further
include an
oxyalkylated hydrocarbyl phenol. The oxyalkylated hydrocarbyl phenol may be
represented
by the following formula:
/-
(R2 \
0 ______________________________________________________________ R3
____________________________________________ 0 ________
2
wherein
each R' is independently hydrogen or a hydrocarbyl group of 1 to 6 carbon
atoms;
IV 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 le is independently a hydrocarbyl group of 1 to 220 carbon atoms, wherein
at least one
R4 contains 35 to 140, or 40 to 96 carbon atoms;
n = 1 to 10; and
m = 1 to 3.
101181 In another embodiment, the oxyalkylated hydrocarbyl phenol
may be represented
by the following formula:
R3
R4
0 _______________________________________________________________
0
2 1n
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wherein each le 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)R5;
R5 is a hydrocarbyl group of 1 to 24 carbon atoms;
R4 is a polyisobutenyl group having a number average molecular weight of 550
to 2300; and
n = 1 to 10.
101191 In some embodiments, the oxyalkylated hydrocarbyl phenol
may be present in an
amount ranging from 0.01 wt % to 5 wt %, or 0.05 to 3 wt %, or 0.1 to 1.5 wt %
of the
lubricating composition. In other embodiments, the oxyalkylated hydrocarbyl
phenol is
present in an amount from 0.1 to 1.5 wt % of the lubricating composition.
Other Performance Additives:
101201 Various embodiments of the compositions disclosed herein
may optionally
comprise one or more additional performance additives. These additional
performance
additives may include one or more metal deactivators, corrosion inhibitors,
extreme pressure
agents, 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. However, such performance additives are included based on the
application of the
lubricating composition, and the specific performance additive and treat rate
thereof would be
apparent to one of ordinary skill in the art in view of this disclosure.
101211 In one embodiment, a lubricating composition may further
comprise 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
101221 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
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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 ANIS, published by The Dow Chemical Company. The product
brochure is
entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding
Applications."
101231 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 acryl ate and 2-ethyl h exyl acryl ate 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.
101241 Pour point depressants that may be useful in the
lubricating compositions disclosed
herein further include polyalphaolefins, esters of maleic anhydride-styrene,
poly(meth)acrylates, polyacrylates or polyacrylamides.
101251 In different embodiments, the lubricating composition may
have a composition as
described in the following table.
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Additive Embodiments (weight %)
A
Boron-free PIB succinimide
0.5 to 5 0.9 to 4.1 1.5 to 3.2
1.9 to 2.4
dispersant (MN 750-1750)
Boron-free PIB succinimide
0.1 to 4 0.2 to 2 0.4 to 1.4
0.5 to 0.8
dispersant (MN 1950-2500)
Boron-containing PIB
succinimide dispersant (Mn 0 to 2.1 0.5 to 1.8 1 to 2.1
1.5 to 1.7
1750-2200)
Overbased calcium-based
0 to 2 0 to 1,4 0.1 to 1.2
0 to 0.9
detergent
Overbased Magnesium-based
0.1 to 2.8 0.15 to 1.6 0.2 to 0.9
0.25 to 0.65
detergent
Other Boron Additives 0 to 3 0 to 2.1 0.3 to 1.4
0.4 to 1.3
Ashless friction modifier 0 to 0.5 0.1 to 1.6 0.3 to 1.1
0.3 to 0.8
Ashless Antioxidants 0 to 5 0.5 to 4.2 0.8 to 2.7
1.2 to 2.2
Antiwear agent 0 to 5 0.1 to 2.3 0.3 to 1.3
0.4 to 1.0
Any Other Performance Additive 0 to 2.5 0.01 to 1.7
0.15 to 1.2 0.2 to 0.85
Oil of Lubricating Viscosity Balance to 100 %
101261 In one embodiment the lubricating composition may have (i)
a sulfur content of
0.3 wt % or less, (ii) a phosphorus content of 0.15 wt % or less, and (iii) a
sulfated ash content
of 0.5 wt % to 1.5 wt % or less. In one embodiment the lubricating composition
may have (i)
a sulfur content of 0.3 wt % or less, (ii) a phosphorus content of 0.09 wt %
or less, and (iii) a
sulfated ash content of 0.5 wt % to 0.9 wt % or less. In another embodiment,
the lubricating
composition may have at least one of (i) a sulfur content of 0.2 wt % to 0.4
wt % or less, (ii)
a phosphorus content of 0.05 wt % to 0.15 wt %, and (iii) a sulfated ash
content of 0.5 wt %
to 1.5 wt % or less.
101271 The lubricating compositions disclosed herein can have a
kinematic viscosity at
100 C of from 5 to 12 cSt (mm2/s) and a kinematic viscosity at 40 C of from 40
to 50 cSt
(mm2/s). In another embodiment, the lubricating composition has a kinematic
viscosity at
100 C of from 6 to 10 cSt (mm2/s) and a kinematic viscosity at 40 C of from 40
to 47 cSt
(mm2/s).
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[0128] Lubricating compositions as described herein have a high
temperature, high shear
viscosity (HTHS) of less than 2.7 mPa-s measured at 150 C per ASTM D4683. In
one
embodiment, the HTHS viscosity is less than 2.65 mPa-s. In another embodiment,
the HTHS
of the lubricating composition is less than 2.5 mPa-s. In another embodiment,
the HTHS of
the lubricating composition is less than 2.3 mPa-s.
101291 In another embodiment, the HTHS of the lubricating
composition is from 1.5 to
2.7 mPa-s. In another embodiment, the HTHS of the lubricating composition is
from 1.5 to
2.5 mPa-s. In another embodiment, the HTHS of the lubricating composition is
from 1.5 to
2.2 mPa-s. In another embodiment, the HTHS of the lubricating composition is
from 1.8 to
2.5 mPa-s. In another embodiment, the HTHS of the lubricating composition is
from 1.8 to
2.2 mPa-s. In another embodiment, the HTHS of the lubricating composition is
from 1.9 to
2.3 mPa-s. In another embodiment, the HTHS of the lubricating composition is
from 1.9 to
2.1 mPa-s.
101301 The lubricating compositions described herein may have an
evaporative loss (also
called Noack volatility) of less than 20 wt %, as measured by ASTM D5800 and
CEC L-40-
93. In one embodiment the evaporative loss of the lubricating composition is
less from 10 wt
% to 20 wt %, or from 11 wt% to 19 wt %.
101311 In one embodiment, the lubricating compositions described
herein have an HTHS
of from 1.5 to 2.2 and a Noack volatility of 9 wt % to 13 wt %, as measured by
ASTM D5800
and CEC L-40-93. In another embodiment, the lubricating compositions described
herein
have an HTHS of from 1.5 to 2.2 and a Noack volatility of 10 wt % to 12 wt %,
as measured
by ASTM D5800 and CEC L-40-93. In another embodiment, the lubricating
compositions
described herein have an HTHS of from 1.9 to 2.1 and a Noack volatility of 9
wt % to 13 wt
%, as measured by ASTM D5800 and CEC L-40-93. In another embodiment, the
lubricating
compositions described herein have an HTHS of from 1.9 to 2.1 and a Noack
volatility of 10
wt % to 12 wt %, as measured by ASTM D5800 and CEC L-40-93.
101321 In one embodiment, the lubricating compositions described
herein have an HTHS
of from 1.8 to 2.2 and a Noack volatility of 13 wt % to 20 wt %, as measured
by ASTM D5800
and CEC L-40-93. In one embodiment, the lubricating compositions described
herein have
an HTHS of from 1.8 to 2.2 and a Noack volatility of 14 wt % to 19 wt %, as
measured by
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ASTM D5800 and CEC L-40-93. In one embodiment, the lubricating compositions
described
herein have an HTHS of from 1.9 to 2.1 and a Noack volatility of 13 wt % to 20
wt %, as
measured by ASTM D5800 and CEC L-40-93. In one embodiment, the lubricating
compositions described herein have an HTHS of from 1.9 to 2.1 and a Noack
volatility of 14
wt % to 19 wt %, as measured by ASTM D5800 and CEC L-40-93.
[0133] The lubricating composition including the dispersant
additive package has a TBN
of from 4 to 14 mg KOH/g. In another embodiment, the lubricating TBN is from 5
to 10 or 6
to 8 mg KOH/g.
[0134] The instant disclosure further provides for methods of
lubricating an internal
combustion engine by supplying the engine a lubricating composition as
disclosed herein. In
one embodiment, the internal combustion engine is a gasoline-fueled engine. In
another
embodiment, the internal combustion engine is a diesel engine. 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.
[0135] The lubricating compositions described above may be
utilized in an internal
combustion engine having a surface of steel or aluminum (typically a surface
of steel) and
may also be coated for example with a diamondlike carbon (DLC) coating.
[0136] 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), gasoline particulate filters (GPF), systems employing selective
catalytic reduction
(SCR), and combinations thereof
[0137] The internal combustion engines may be port fuel injected
(PFI) or direct injected.
In one embodiment, the internal combustion engine is a gasoline direct
injection engine (GDI).
Direct injection engines are characterized by injection of the fuel, e.g.,
gasoline, directly into
the cylinder. This is distinct from port fuel injection (PFI) and can result
in higher efficiency,
higher compression, and/or higher brake mean effective pressure than analogous
PFI engines.
[0138] In one embodiment, the internal combustion engine is
equipped with a
turbocharger, a supercharger, or combinations thereof. Turbochargers and
superchargers both
work to increase the volumetric efficiency of engines, i.e. the volume of air
that fills a cylinder
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relative to the volume of the cylinder. Turbochargers and superchargers work
by forcing more
air into the cylinder, resulting in higher torque for a given displacement,
and hence higher
BMEP. In addition to improving the efficiency of an engine, turbochargers and
superchargers
can increase the likelihood of stochastic pre-ignition, especially at lower
speeds.
101391 The lubricating compositions as disclosed herein may be
used to lubricate an
internal combustion engine operating with a brake mean effective pressure
(BMEP) of greater
than 12 bars and at a speed of less than 3,000 rpm by supplying to said engine
the lubricating
composition. In some embodiments, the internal combustion engine is a turbo-
charged direct-
injection (TDi) engine.
101401 The method embodiments of the instant disclosure may
include supplying to an
internal combustion engine a lubricating composition including an oil of
lubricating viscosity
comprising at least 50 wt % of a Group IV base oil; a one boron-containing
polyisobutenyl
succinimide dispersant; a boron-free polyisobutenyl succinimide dispersant; an
overbased
magnesium-based detergent in an amount to deliver at least 300 ppm or at least
400 ppm of
magnesium to the lubricating composition; an overbased calcium-based detergent
in an
amount to deliver at least 400 ppm calcium to the lubricating composition; an
ashless friction
modifier; and, optionally, other additives, wherein the lubricating
composition has a High
Temperature High Shear (HTHS) viscosity according to ASTM D4683 less than 3.0
mPa- s.
101411 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 including one or more double bonds.
Examples of
hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic
(e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-,
aliphatic-, and alicyclic-
substituted aromatic substituents, as well as cyclic substituents wherein the
ring is completed
through another portion of the molecule (e.g., two substituents together form
a ring); [0081]
substituted hydrocarbon substituents, that is, substituents containing non-
hydrocarbon groups
which, in the context of this invention, do not alter the predominantly
hydrocarbon nature of
the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,
mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is,
substituents which,
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while having a predominantly hydrocarbon character, in the context of this
invention, contain
other than carbon in a ring or chain otherwise composed of carbon atoms and
encompass
substituents as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include
sulfur, oxygen, and
nitrogen. In general, no more than two, or no more than one, non- hydrocarbon
substituent
will be present for every ten carbon atoms in the hydrocarbyl group;
alternatively, there may
be no non-hydrocarbon substituents in the hydrocarbyl group.
101421 The present disclosure is not to be limited in terms of the
particular embodiments
described in this application, which are intended as illustrations of various
aspects. Many
modifications and variations can be made without departing from its spirit and
scope, as will
be apparent to those skilled in the art. Functionally equivalent methods and
components within
the scope of the disclosure, in addition to those enumerated herein, will be
apparent to those
skilled in the art from the foregoing descriptions. Such modifications and
variations are
intended to fall within the scope of the appended claims. The present
disclosure is to be limited
only by the terms of the appended claims, along with the full scope of
equivalents to which
such claims are entitled. It is to be understood that this disclosure is not
limited to particular
methods, reagents, compounds, or compositions, which can, of course, vary. It
is also to be
understood that the terminology used herein is for the purpose of describing
particular
embodiments only and is not intended to be limiting.
101431 As used in this document, the singular forms "a," "an," and
"the" include plural
references unless the context clearly dictates otherwise. Unless defined
otherwise, all
technical and scientific terms used herein have the same meanings as commonly
understood
by one of ordinary skill in the art. Nothing in this disclosure is to be
construed as an admission
that the embodiments described in this disclosure are not entitled to antedate
such disclosure
by virtue of prior invention. As used in this document, the term "comprising"
means
"including, but not limited to."
101441 While various compositions, methods, and devices are
described in terms of
"comprising" various components or steps (interpreted as meaning "including,
but not limited
to"), the compositions, methods, and devices can also "consist essentially of'
or "consist of'
the various components and steps, and such terminology should be interpreted
as defining
essentially closed-member groups.
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101451 With respect to the use of substantially any plural and/or
singular terms herein,
those having skill in the art can translate from the plural to the singular
and/or from the
singular to the plural as is appropriate to the context and/or application.
The various
singular/plural permutations may be expressly set forth herein for sake of
clarity.
101461 It will be understood by those within the art that, in
general, terms used herein, and
especially in the appended claims (e.g., bodies of the appended claims) are
generally intended
as "open" terms (e.g., the term "including" should be interpreted as
"including but not limited
to," the term "having" should be interpreted as "having at least," the term
"includes" should
be interpreted as "includes but is not limited to," etc.). It will be further
understood by those
within the art that if a specific number of an introduced claim recitation is
intended, such an
intent will be explicitly recited in the claim, and in the absence of such
recitation, no such
intent is present. For example, as an aid to understanding, the following
appended claims may
contain usage of the introductory phrases "at least one" and "one or more" to
introduce claim
recitations. However, the use of such phrases should not be construed to imply
that the
introduction of a claim recitation by the indefinite articles "a" or "an"
limits any particular
claim containing such introduced claim recitation to embodiments containing
only one such
recitation, even when the same claim includes the introductory phrases "one or
more" or "at
least one" and indefinite articles such as "a" or "an" (e.g., "a" and/or "an"
should be interpreted
to mean "at least one" or "one or more"); the same holds true for the use of
definite articles
used to introduce claim recitations. In addition, even if a specific number of
an introduced
claim recitation is explicitly recited, those skilled in the art will
recognize that such recitation
should be interpreted to mean at least the recited number (e.g., the bare
recitation of "two
recitations," without other modifiers, means at least two recitations, or two
or more
recitations). Furthermore, in those instances where a convention analogous to
"at least one of
A, B, and C, etc." is used, in general, such a construction is intended in the
sense one having
skill in the art would understand the convention (e.g., "a system having at
least one of A, B,
and C" would include but not be limited to systems that have A alone, B alone,
C alone, A
and B together, A and C together, B and C together, and/or A, B, and C
together, etc.). In
those instances where a convention analogous to "at least one of A, B, or C,
etc." is used, in
general, such a construction is intended in the sense one having skill in the
art would
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understand the convention (e.g., "a system having at least one of A, B, or C"
would include
but not be limited to systems that have A alone, B alone, C alone, A and B
together, A and C
together, B and C together, and/or A, B, and C together, etc.). It will be
further understood by
those within the art that virtually any disjunctive word and/or phrase
presenting two or more
alternative terms, whether in the description, claims, or drawings, should be
understood to
contemplate the possibilities of including one of the terms, either of the
terms, or both terms.
For example, the phrase "A or B" will be understood to include the
possibilities of "A" or "B"
or "A and B."
[0147] In addition, where features or aspects of the disclosure
may be described in terms
of Markush groups, those skilled in the art will recognize that the disclosure
is also thereby
described in terms of any individual member or subgroup of members of the
Markush group.
[0148] As will be understood by one skilled in the art, for any
and all purposes, such as in
terms of providing a written description, all ranges disclosed herein also
encompass any and
all possible subranges and combinations of subranges thereof. Any listed range
can be easily
recognized as sufficiently describing and enabling the same range being broken
down into at
least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting
example, each range
discussed herein can be readily broken down into a lower third, middle third
and upper third,
etc. As will also be understood by one skilled in the art all language such as
"up to," "at least,"
and the like include the number recited and refer to ranges which can be
subsequently broken
down into subranges as discussed above. Finally, as will be understood by one
skilled in the
art, a range includes each individual member. Thus, for example, a group
having 1-3 wt. %
refers to groups having 1, 2, or 3 wt.%. Similarly, a group having 1-5 wt. %
refers to groups
having 1, 2, 3, 4, or 5 wt. %, and so forth, including all points
therebetween.
[0149] As used herein, the term "about" means that a value of a
given quantity is within
20% of the stated value. In other embodiments, the value is within 15% of the
stated
value. In other embodiments, the value is within 10% of the stated value. In
other
embodiments, the value is within +5% of the stated value. In other
embodiments, the value is
within +2.5% of the stated value. In other embodiments, the value is within
+I% of the stated
value.
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[0150] Unless otherwise stated, "wt %" as used herein shall refer
to the weight percent
based on the total weight of the composition.
101511 The instant disclosure is suitable for lubricant
formulations exhibiting one or more
of improved cleanliness ratings, improved fuel economy, reduced low speed
preignition
("LSPI") and improved TBN retention over lubricant formulations not including
the additives
of the instant lubricating formulations. It is contemplated that cleanliness
ratings, improved
fuel economy, reduced low speed preignition ("LSPI") and improved TBN
retention can be
measured and compared under industry standard test, which are apparent to one
of ordinary
skill in the art in view of this disclosure. The forgoing may be better
understood with reference
to the following examples:
Examples
101521 Embodiments will be further illustrated by the following
examples, which set forth
particularly advantageous embodiments. While the examples are provided to
illustrate certain
embodiments, they are not intended to be limiting.
Lubricating Compositions
101531 A series of OW-12 engine additive formulations are prepared
containing the
dispersant and detergent additives described above as well as conventional
additives including
friction modifiers, anti-wear agents, polymeric viscosity modifier,
antioxidants (combination
of phenolic ester and diarylamine), as well as other performance additives as
follows (Table
1). The calcium, magnesium, phosphorus, sulfur 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
examples
according to embodiments described herein. Also included are the high
temperature high shear
(HTHS) viscosity (CEC L-36-90) and the Noack evaporative loss (CEC L-40-93) to
further
illustrate the impact of base oil and additives.
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Table 1 - Lubricating Compositions'
EX1 EX6
EX2 EX3 EX4 EX5 EX7
<C> <C> EX8
4 cSt Group IV Base Oil 81.2 80.2 80.7 81.1 80
60 60.1 59.8
6 cSt Group IV Base Oil 5 5 5
2 cSt Group IV Base Oil 4 4
3 cSt Group III Base Oil 24 24
24
Boron-free P1B
succinimide dispersant
1.8 1.8 1.8 1.8 1.8 2.8 2.8 2.8
(MN 750-1750)
Boron-containing PTB
succinimide dispersant 1.1 0.93 0.93 1.1 0.93 0.93
0.93 0.93
(Mn 1750-2200)
Calcium Salicylate
0.52 0.52 0.52 0.52 0.52 0.58 0.58 0.58
Detergent2
Magnesium Sulfonate
0.35 0.32 0.32 0.32 0.32 0.28 0.28 0.28
Detergent3
High TBN low Mn
0.4 0.14 0.14 0.4 0.14 0.14 0.14 0.14
Dispersant4
C3/C6 Secondary ZDDP 0.7 0.7 0.7 0.18 0.18 0
0.7 0
C6 Secondary ZDDP 0 0 0 0.62 0.62 0.83
0 0
C8 Primary ZDDP 0 0 0 0 0 0 0
1.0
Borated Friction 0 1.3 1.3 0 1.3 1.3
1.3 1.3
Modifiers
Ethoxylated Tallow 0 0 0 0.5 0.5 0 0
0
Amine
Diarylamine
1.0 1.0 1.5 1.5 1.5 1.5 1.5 1.5
Antioxidant6
Sulfurized Olefin 0.5 0.5 0.5 0.5 0.5 0.5
0.5 0.5
Propoxylated PIBphcnol 1.5 1.5 1.5 1.5 1.5 0 0
0
Hindered Phenol 0 0 0 0 0 1.0
1.0 1.0
Antioxidant
Dispersant Viscosity
0.26 0.26 0.14 0 0 0 0 0
Modifier
Comb PMA 0 0 0 0.6 0.6 0.5
0.5 0.5
Additional Additives7 0.25 0.25 0.25 0.25 0.25
0.25 0.25 0.25
Boron (ppm) 80 150 150 90 150 150
150 156
Calcium (ppm) 1060 1040 1090 1030 1050
1160 1130 1129
Magnesium (ppm) 620 520 530 540 510 460
470 473
Zinc (ppm) 860 850 860 850 860 840
870 855
Phosphorus (ppm) 780 770 780 770 770 750
780 768
Sulfur (ppm) 2370 2440 2450 2400 2360
2320 2400 2355
HTHS (mPa.$) 2.13 2.06 1.99 1.97 2.02
2.04 2.06 2.06
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EX1 EX6
EX2 EX3 EX4 EX5
EX7
<C> <C>
EX8
(CEC L-36-90)
Evaporative Loss (% wt)
(CEC L-40-93) 10.5 11.0 11.2 14.1 14.2 18.8
18.6 18.7
All amounts shown above are in weight percent and are on an oil-free basis
unless otherwise noted.
2 - Overbased calcium salicylate (TBN = 485 mg KOH/g; metal ratio 5.5)
3- Overbased magnesium alkylbenzene sulfonate (TBN 690 mg KOH/g: metal ratio
14)
4- Polyisobutenyl succinimide dispersant prepared by chlorine process derived
from 98011n PIB (TBN 115 mg KOH/g)
5- Combination of oleyl tartrimide, trialkyl borate ester, and succinimide
dispersant (0.469'6 boron)
6- Nonylated &phenyl amine
- The Additional Additives used in the examples include anti-foam agents,
pourpoint depressant, and includes sonic
amount of diluent oil
101541
Lubricating compositions are evaluated for their ability to improve
engine
cleanliness (deposits), improve fuel economy, and improve corrosion control.
Cleanliness is
evaluated in the Volkswagen TDI deposit cleanliness engine test (CEC L-78-99)
and the
Volkswagen FSI Valve deposit test (PV1481). The Volkswagen TDI engine test
rates
lubricants on piston cleanliness (merit) and ring sticking. Fuel economy is
evaluated in the
Audi EA888 Fuel Economy test (PV1496). Corrosion control is evaluated in the
PV1401
Humidity Cabinet Test.
Table 2 - Deposit and Fuel Economy Performance Testing
EX1 EX2 EX3 EX4 EX5 EX6 EX8
VW TDT
Piston Cleanliness Average Rating 66 64
Ring Sticking 0 0
VW FSI
Inlet Valve Total deposit
(<542.3mg required for OEM
464,5mg
"pass")
Audi EA888
Fuel Consumption - Pre Reference-
579.33 583.16 583.81 581.12 582.58 576.96
Test (g)
Fuel Consumption - Candidate
567.86 569.57 569.31 563.65 566.38 561.95
Test (g)
Fuel Consumption - Post
579.64 583.26 583.8 580.72 582.19 578.64
Reference Test (g)
Difference Pre Reference -
11.47 13.59 14.5 17.47 16.2 15.01
Candidate (g)
Fuel Economy Improvement (%) 1.98 2.33 2.48 3.01 2.78
2.6
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EX1 EX2 EX3 EX4 EX5 EX6 EX8
Basis Drift (%) 0.05 0.02 0 0.07 -
0.07 0.29
PV1401 Humidity Cabinet
Cycle 1 1 1 1
1
Cycle 2 4 1 1
1
Test Panel A
Cycle 3 4 2 1
1
Cycle 4 5 3 1
1
Cycle 1 1 1 1
1
Cycle 2 4 1 1
1
Test Panel B
Cycle 3 4 2 1
1
Cycle 4 5 3 1
1
101551 Oxidation and corrosion control are also evaluated in the
Bio-Diesel Oxidation
Bench Test (CEC L-109) as well as the High Temperature Corrosion Bench Test
(HTCBT)
according to ASTM D6594. In the Bio-Diesel Oxidation Test, kinematic viscosity
at 100 C
is measured at start of test and at various intervals during the test to
evaluate the lubricant
composition resistance to oxidation when contaminated with biodiesel fuel
fractions (B10).
Table 3 - Lubricating Compositions'
EX9 EX10 EX11 EX12 EX13 EX14
Viscosity Grade OW-12 OW-20 OW-12 OW-20 OW-
12 OW-20
4 cSt Group IV Base Oil 60 61 55
6 cSt Group IV Base Oil 15 15
15
2.5 cSt Group IV Base Oil 21 22
3 cSt Group III Base Oil 25.5
4 cSt Group III+ Base Oil 56 59
57
6 cSt Group III Base Oil 7 5.5
4.5
Boron-free PIB succinimide
2.6 2.6 0 0 4.5 3.7
dispersant (Mn 750-1750)
Boron-free PIB succinimide
0 0 3.3 3.3 0
0
dispersant (Mn 1750-2200)
Boron-containing PI B
succinimide dispersant (Mn 3.1 3.1 2.0 2.0 1.1
1.8
1750-2200)
Calcium Salicylate Detergent2 0.5 0.5 0.5 0.5 0.51
0.51
Calcium Salicylate Detergent3 0.36 0.36 0.36 0.36 0.39
0.39
Magnesium Sulfonate
0.21 0.21 0.23 0.23 0.21 0.21
Detergent'
High TBN low Mn Dispersant' 0.43 0.43 0.27 0.27 0
0.43
C3/C6 Secondary ZDDP 0.2 0.2 0.2 0.2 0.2
0.2
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EX9 EX10 EX11 EX12 EX13 EX14
C8 Primary ZDDP 0.74 0.74 0.74 0.74 0.74
0.74
Borated Friction Modifier6 0 0 1 1 1.8
0
Oleamide Friction Modifier 0.05 0.05 0.05 0.05 0.05
0.05
Diarylamine Antioxidant' 1 1 1.5 1.5 1.5
1.5
Sulfurized Olefin 0.2 0.2 0.2 0.2 0.2
0.2
Hindered Phenol Antioxidant 1.5 1.5 1 1 1
1
Styrene-cliene block copolymer 0 0.36 0 0.25 0
0.5
Comb PMA 0.5 0 0.1 0 0.3
0
Additional Additives8 0.38 0.38 0.38 0.38 0.38
0.38
Boron (ppm) 260 260 205 210 170
140
Calcium (ppm) 1230 1270 1200 1260 1270
1270
Magnesium (ppm) 350 355 380 390 340
340
Zinc (ppm) 940 885 890 870 875
860
Phosphorus (ppm) 770 790 770 770 780
750
Sulfur (ppm) 1990 1970 1960 1925 2060
2025
HTHS (mPa-s) (CEC L-36-90) 2.09 2.64 2.03 2.67 2.04
2.63
Evaporative Loss (% wt)
20 11 20 11 18
11
(CEC L-40-93)
1- All amounts shown above are in weight percent and are on an oil-free basis
unless otherwise noted.
2 - Overbased calcium salicylate (TBN = 485 mg KOH/g; metal ratio 5.5)
3 - Overbased calcium salicvlate (TBN 300 mg KOH/g: metal ratio 2.9)
4- Overbased magnesium alkylbenzene sulfonate (TBN 690 mg KOH/g: metal ratio
14)
- Polyisobutenyl succinimide dispersant prepared by chlorine process derived
from 980 Mn FIB (TBN 115 mg KOH/g)
6- Combination of ley' tartrimide, trialkyl borate ester, and succinimide
dispersant (0.46% boron)
7- Nonylaled diphenyl amine.
8 - The Additional Additives used in the examples include anti -foam agents,
pourpoint depressant, corrosion inhibitors,
and includes some amount of diluent oil.
Table 4 - Oxidation and Corrosion Testing
EX1 EX2 EX6 EX7 EX8
Bio-Diesel Oxidation (CEC L-109)
KV100 - Start of Test (mYs) 5.68 5.66 5.39 5.29
5.31
KV100 @72 hours 6.66 6.97 6.08 6.13
6.02
% Increase in KV @72 hours 17.1 23.1 14.9 16.08
13.4
KV100 (# 144 hours 7.57 8.79 6.8 6.91
6.81
% Increase in KV (# 144 hours 33.1 55.1 28.5 30.65
28.2
KV100 # 168 hours 8.06 10.03 7.08 7.27
7.23
% Increase in KV A 168 hours 41.9 77.2 33.8 37.5
36.0
KV100 @216 hours 9.59 15.73 7.83 8.19
8.49
% Increase in KV # 216 hours 68.6 177.8 48.0 54.9
59.9
HTCBT (ASTM D6594)
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EX1 EX2 EX6 EX7
EX8
Copper Change (ppm) 7.8 13 55 10
12
Lead Change (ppm) 15.9 14.6 31 19
7
Copper Strip Rating lA lA 4A lA
1B
Table 5 - Deposit, Oxidation, and Fuel Economy Performance Testing
EX9 EX10 EX11 EX12 EX13 EX14
VW TDI
Piston Cleanliness Average Rating 57 61 55 53 54
59
Ring Sticking 0 0 0 0 0
0
Audi EA888
Fuel Consumption - Pre Reference-Test (g) 575.9 580.5 582.2 580.0
577.9 578.6
Fuel Consumption - Candidate Test (g) 562.5 572.5 567.1 572.7
563.2 569.6
Fuel Consumption - Post Reference Test (g) 575.4 580.9 581.6 580.5
578.8 577.9
Difference Pre Reference - Candidate (g) 13.39 7.96 15.1 7.35
14.73 8.98
Fuel Economy improvement (%) 2.32 1.37 2.59 1.27
2.55 1.55
Basis Drift (%) 0.10 0.08 0.10 0.07
0.15 0.12
Bio-Diesel Oxidation (CEC L-109) 575.92 580.48 582.18
580.05 577.9
KV100 - Start of Test (m7s) 5.42 7.10 5.29 7.16
7.18
KV100 (a), 72 hours 6.24 8.22 6.08 8.24
8.11
% Increase in KV Ed, 72 hours 15.1 15.9 14.9 15.1
12.9
KV100 @ 144 hours 9.66 6.77 9.16
9.35
%increase in KV @144 hours 36.1 28.0 27.9
30.2
KV100 (d, 168 hours 10.4 7.06 9.65
10.0
% Increase in KV (ct, 168 hours 46.1 33.4 34.8
39.3
KV100 @216 hours 12.3 7.80 10.8
12.3
% Increase in KV @ 216 hours 73.0 47.4 50.2
71.7
101561 Lubricating compositions are evaluated for their ability to
improve engine
cleanliness (deposits), improve fuel economy, and improve corrosion control.
Cleanliness is
evaluated in the Volkswagen TDI deposit cleanliness engine test (CEC L-78-99)
and the
Volkswagen FSI Valve deposit test (PV1481). The Volkswagen TDI engine test
rates
lubricants on piston cleanliness (merit) and ring sticking. Fuel economy is
evaluated in the
Audi EA888 Fuel Economy test (PV1496). Corrosion control is evaluated in the
PV1401
Humidity Cabinet Test.
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101571 Oxidation and corrosion control are also evaluated in the
Bio-Diesel Oxidation
Bench Test (CEC L-109) as well as the High Temperature Corrosion Bench Test
(HTCBT)
according to ASTM D6594. In the Bio-Diesel Oxidation Test, kinematic viscosity
at 100 C
is measured at start of test and at various intervals during the test to
evaluate the lubricant
composition resistance to oxidation when contaminated with biodiesel fuel
fractions (B10).
101581 The results indicate that compositions with lower HTHS
viscosity deliver
improved fuel economy without sacrificing oxidative durability, cleanliness,
or corrosion
control.
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