Note: Descriptions are shown in the official language in which they were submitted.
CA 02549095 2012-10-22
TITLE
LUBRICATING COMPOSITION CONTAINING METAL
SALIXARATE AS DETERGENT
FIELD OF INVENTION
[0001] The present invention relates to a lubricating oil composition
containing
a dispersant package, a detergent package and antioxidant package. The
composition has improved engine cleanliness, improved detergency, decreased
sludge formation and decreased wear.
BACKGROUND OF THE INVENTION
[0002] It is well known for lubricating oils to contain a number of
additives used
to protect the engine from wear, the accumulation of sludge and filter
plugging.
Common additives for engine lubricating oils are zinc dialkyldithiophosphate
(ZDDP) as an antiwear additive, and overbased calcium sulphonate detergents.
It is
believed that ZDDP antiwear additives protect the engine by forming a
protective
film on metal surfaces. Typical treatment quantities of ZDDP range from 1 to 2
weight percent based on the total weight of the lubricant. Detergents such as
overbased calcium sulphonate help keep the engine parts clean of soot and
other
deposits, and offer an alkalinity reserve. Typical treatment quantities of
detergents
range from 0.05 to 10 weight percent based on the total weight of the
lubricant.
[0003] In recent years phosphates and sulphonates derived from engine
lubricants have been shown to contribute in part to particulate emissions.
Further,
sulphur and phosphorus tend to poison the NO catalysts used in catalytic
converters, resulting in a reduction in performance of said catalysts. Any
reduction
in the performance of catalytic converters tends to result in increased
amounts of
pollutants such as nitric oxide and/or sulphur oxides. However, reducing the
amount of ZDDP will increase the amount of wear in an engine. Also reducing
the
amount of detergent will decrease engine cleanliness and result in increased
soot
deposits.
[0004] International Publication W003/18728 (Cressey et al.) discloses
additives for lubricants containing linear compounds containing phenolic and
salicylic units in the form of oligomers or polymers. The linear compounds may
be
salted with calcium and optionally cosalted with boric acid. The additives
have
detergency and/or antiwear properties. Lubricant examples contain an ashless
dispersant and a zinc dithiophosphate.
[0005] US Patent Number 6,200,936 (Moreton) discloses compounds containing
phenolic units and salicylic units in a lubricating composition. The compounds
may
be salted with calcium. The examples of lubricating
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compositions contain phenolic units with a dodecyl alkyl group. The compounds
of the invention may be used as a detergent in gasoline or diesel fuel. They
also
stabilise gasoline or diesel compositions against thermal decomposition.
[0006] International Publication W099/25793 (Taylor) discloses a fuel
composition containing kerosene and compounds containing phenolic units and
salicylic units. The compounds may be salted with calcium. The examples of
lubricating compositions contain phenolic units with a dodecyl alkyl group.
[0007] International Publication W001/56968 (Taylor et al.) discloses a
cyclic compound containing phenolic units and salicylic units. The salicylic
units may be salted with a metal or an ammonium cation.
[0008] U.S. Patent Number 6,310,009 (Kocsis et al.) relates to the use of
saligenin derivatives in lubricating compositions. The formulations contain
borated or non-borated magnesium saligenin derivatives. These compositions
exhibit improved seal compatibility and reduced copper and lead corrosion.
[0009] It has now been found that the composition of the present invention
provides engine cleanliness, detergency and antioxidant performance to an oil
of
lubricating viscosity often used in engine oil.
SUMMARY OF THE INVENTION
[0010] The present invention provides a composition comprising:
(a) a detergent package comprising:
(i) a metal salixarate; and
(ii) optionally a detergent other than component (a)(i);
(b) a dispersant package comprising:
(i) a dispersant with a carbonyl to nitrogen ratio of 1 or higher;
and
(ii) a dispersant with a carbonyl to nitrogen ratio of less than 1;
(c) an antioxidant package comprising:
(i) a hindered phenol; and
(d) an oil of lubricating viscosity,
wherein the composition has a phosphorus content of less than or equal to 800
ppm; and wherein the sulphated ash content is less than or equal to 1.1 weight
percent of the composition.
[0011] The invention further provides a process for the preparation of a
composition comprising mixing:
(a) a detergent package comprising:
(i) a metal salixarate; and
(ii) optionally a detergent other than component (a)(i);
(b) a dispersant package comprising:
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(i) a dispersant with a carbonyl to nitrogen ratio of 1 or higher; and
(ii) a dispersant with a carbonyl to nitrogen ratio of less than 1;
(c) an antioxidant package comprising:
(i) a hindered phenol; and
(d) an oil of lubricating viscosity,
wherein the composition has a phosphorus content of less than or equal to 800
ppm; and wherein the sulphated ash content is less than or equal to 1.1 weight
percent of the composition.
[0012] The use of the composition of the invention is capable of imparting at
least one or more of improved engine cleanliness, improved detergency,
decreased sludge formation, decreased wear, decreased bore polishing and
decreased oil consumption.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention provides a composition as described above.
Often the composition has a total sulphur content in one aspect below 0.5 wt
%,
in another aspect below 0.3 wt %, in yet another aspect 0.2 wt % or less and
in
yet another aspect 0.1 wt % or less. Often the major source of sulphur in the
composition of the invention is derived from diluent oil.
[0014] Often the composition has a total phosphorus content of less than or
equal to 800 ppm, in another aspect equal to or less than 700 ppm, in yet
another
aspect equal to or less than 600 ppm, in yet another aspect equal to or less
than
550 ppm and in yet another aspect equal to or less than 500 ppm of the
composition. In one embodiment of the invention the phosphorus is present
from 200 ppm or 300 ppm to 475 ppm or 580 ppm or even 780 ppm.
[0015] Often the composition has a total ash content as determined by ASTM
D-874 of below 1.5 wt %, in one aspect equal to or less than 1.1 wt %, in
another
aspect equal to or less than 1.0 wt %, in yet another aspect equal to or less
than
0.8 wt % and in yet another aspect equal to or less than 0.5 wt % of the
composition. In one embodiment the total ash content is present from 0.1 wt %
or 0.2 wt % to 0.6 wt % or 0.7 wt%.
Detergent Package
[0016] The detergent package contains a metal salixarate and optionally at
least one detergent other than the metal salixarate. The other detergent
compounds are well known in the art and are often selected from the group
consisting of a sulphonate, a phenate, a sulphurised phenate, a carboxylate, a
phosphate, a saligenin, and an alkylsalicylate. Saligenin chemistry is
disclosed
in more detail in US Patent Number 6,310,009. Phenate, alkylsalicylate and
phosphate chemistry is disclosed in "Chemistry and Technology of Lubricants,"
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Edited by R.M. Mortier and S.T. Orszulik, 2' Edition, Chapter 3, section
3.2.2,
page 82 to 85, Copyright 1997. Sulphonate chemistry is disclosed in "Chemistry
and Technology of Lubricants," Edited by R.M. Mortier and S.T. Orszulik, 2nd
Edition, Chapter 3, section 3.2.1, page 77 to 82, Copyright 1997.
[0017] Often the detergent compounds will be in the form of a metal salt or
metal salts. In one aspect of the invention the metal is selected from an
alkali
metal or alkaline earth metal such as magnesium, calcium, potassium or sodium
or mixtures thereof. Suitable examples of a metal detergent include a
magnesium saligenin, a calcium saligenin, a calcium alkylsalicylate, a
magnesium alkylsalicylate, a calcium sulphonate, a magnesium sulphonate or
mixtures thereof. In one embodiment the other detergent compound is a
magnesium saligenin.
[0018] The detergent package often contains the metal of the metal salt
present at 50 ppm to 1200 ppm, in one aspect 75 ppm to 1000 ppm, in another
aspect 120 ppm to 800 ppm and in yet another aspect 150 ppm to 700 ppm, for
example, about 225 ppm, about 275 ppm, about 325 ppm, about 400 ppm, or
about 550 ppm or less.
[0019] The detergent package is often present on an oil free basis at 0.01 to
20, in one aspect 0.05 to 15, in another aspect 0.1 to 12, in another aspect
0.15 to
8 and in yet another aspect 0.25 to 4 weight percent of the composition. In
one
aspect the detergent contains the metal salixarate present at 10 wt % or more
of
the detergent package, in another aspect 20 wt % or more of the detergent
package and in another aspect 30 wt % or more of the detergent package. In one
aspect the metal salixarate is present at 0.25 to 4 weight percent of the
composition.
Salixarate Salt Detergent
[0020] The substrate of the metal salixarate of the invention is often
represented by a substantially linear compound comprising at least one unit of
the formulae (I) or (II):
(R2)i
(I)
COOR3
Or
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(OH)f
(R4)g
each end of the compound having a terminal group of formulae (III) or (IV):
(OH)f
(R2)i
U
(R4)g
COOR3
(11I) (W)
such groups being linked by divalent bridging groups, which may be the same or
different for each linkage; wherein in formulas (I)-(IV) fin one aspect is 1,
2 or
3, in another aspect 1 or 2; U is ¨OH, -NH2 -NHR1, -N(R1)2 or mixtures
thereof,
' R1 is a hydrocarbyl group containing 1 to 5 carbon atoms; R2 is hydroxyl or
a
hydrocarbyl group and j is 0, 1, or 2; R3 is hydrogen or a hydrocarbyl group;
R4
is a hydrocarbyl group or a substituted hydrocarbyl group; g is 1, 2 or 3,
provided at least one R4 group contains 8 or more carbon atoms; and wherein
the
molecules on average contain at least one of unit (I) or (III) and at least
one of
unit (II) or (IV) and the ratio of the total number of units (I) and (III) to
the total
number of units of (II) and (IV) in the composition is 0.1:1 to 2:1.
[0021] The U group in formulae (i) and (iii) may be located in one or more
positions ortho, meta, or para.' to the -COOR3 group. In one embodiment of the
invention, the U group is located ortho to the -COOR3 group. When the U group
is a ¨OH group, formulae (i) and (iii) are derived from 2-hydroxybenzoic acid
(often called salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid or
mixtures thereof. When U is a ¨NH2 group, formulae (i) and (iii) are derived
from 2-aminobenzoic acid (often called anthranilic acid), 3-aminobenzoic acid,
4-aminobenzoic acid or mixtures thereof.
[0022] The divalent bridging group, which may be the same or different in
each occurrence, includes -CH2- (methylene bridge) and -CH2OCH2- (ether
bridge), either of which may be derived from an aldehyde such as formaldehyde
or a formaldehyde equivalent (e.g., paraform, formalin), ethanal or propanal.
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[0023] The metal of the metal salixarate is often mono-valent, di-valent or
mixtures thereof. In one aspect of the invention the metal is selected from an
alkali metal or alkaline earth metal such as magnesium, calcium, potassium or
sodium or mixtures thereof.
[0024] It is believed that a significant fraction of salixarate molecules
(prior
to neutralisation) may be represented on average by the following formula:
0 OH OH OH OH 0
HO OH
HOOH
R5 R5
wherein each R5 may be the same or different, and are hydrogen or an alkyl
group, provided at least one R5 is alkyl. In one embodiment, R5 is a
polyisobutene group (especially of molecular weight 200 to 1,000, or 550).
Significant amounts of di-or trinuclear species may also be present containing
one salicylic end group of formula (III). The salixarate detergent may be used
alone or with other detergents.
[0025] Salixarate derivatives and methods of their preparation are described
in greater detail in U.S. patent number 6,200,936 and PCT Publications WO
01/56968 and WO 03/18728.
Dispersant Package
[0026] The dispersants of the invention are often derived from N-substituted
long chain alkenyl succinimides. The invention requires at least 2
dispersants,
one with a high Total Base Number and one with a high Total Acid Number.
Generally dispersants with a high TAN number have a carbonyl to nitrogen ratio
of 1 or higher, in one aspect 1.2 or higher, in another aspect 1.4 or higher
and in
yet another aspect 1.45 or higher, for example 1.5. Generally dispersants with
a
high TBN number have a carbonyl to nitrogen ratio of less than 1, in one
aspect
0.94 or lower, in another aspect 0.88 or lower and in another aspect 0.8 or
lower,
for instance 0.77. The carbonyl to nitrogen ratio is to be calculated on a
molar
basis, that is, the ratio of moles of carbonyl functionality (e.g., -C(0)0- )
to the
moles of nitrogen functionality (e.g., amine nitrogens).
[0027] The dispersant package is often present on an oil free basis at 0.01 to
30, in one aspect 0.5 to 25, in another aspect 1.5 to 20 and in yet another
aspect 3
to 15 weight percent of the composition. Often the dispersant with a high
Total
Base Number is present at lower concentration than the dispersant with a high
Total Acid Number. Alternatively the amount of dispersant with a high Total
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Acid Number and a high Total Base Number is equal. In yet another alternative
the dispersant with a high Total Acid Number is often present at lower
concentration than the dispersant with a high Total Base Number. Often the
dispersant present in the greater quantity is present at greater than 50% of
the
amount of dispersant present in the package, in one aspect greater than 55% of
the amount of dispersant present in the package, in yet another aspect greater
than 60% of the amount of dispersant present in the package. For example the
dispersant present in the greater quantity may be present from 61% to 95% of
the
dispersant, in one aspect 62% to 90% of the dispersant and in yet another
aspect
63% to 85% of the dispersant present in the package. In one aspect the ratio
of
high TAN dispersant to high TBN dispersant is 1:1 to 15:1, in another aspect
2:1
to 10:1 and in another aspect 3:1 to 6:1. In certain embodiments the mixture
of
dispersants has a TAN which is at least 15% or at least 20% of the TBN of the
mixture of dispersants, for example, 15 to 30% of the TBN. In certain
embodiments the TBN/TAN ratio for the mixture of dispersants is 3:1 to 7:1.
[0028] The N-substituted long chain alkenyl succinimides have a variety of
chemical structures and include a mono-succinimide and/or a di-succinimide.
Often the long chain alkenyl group will have number average molecular weight
of 350 to 10,000, in one aspect 400 to 7000, in another aspect 500 to 5000 and
in
yet another aspect 500 to 4000. In one embodiment the long chain alkenyl group
is a polyisobutylene group, which has a number average molecular weight from
800 to 1600 and in another embodiment from 1600 to 3000. The succinimide is
often prepared by the condensation of a hydrocarbyl-substituted acylating
agent
(e.g., hyd.rocarbyl-substituted succinic anhydride) with a polyamine or an
amino
alcohol, often a polyalkylene polyamine or poly(ethyleneamine) such as
triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or, in
one embodiment, polyamine still bottoms.
[0029] N-substituted long chain alkenyl succinimides dispersant additives and
their preparation are disclosed, for instance, in US Patent Numbers 3,361,673,
3,401,118 and 4,234,435.
[0030] Other dispersants may also be present. One class of suitable
dispersants include Mannich bases, which are the reaction products of alkyl
phenols in which the alkyl group typically contains at least 30 carbon atoms
with
aldehydes (especially formaldehyde) and amines (especially polyalkylene
polyamines) and are described in more detail in U.S. Patent 3,634,515.
[0031] Another class of ashless dispersant is high molecular weight esters.
These materials are similar to the above-described succinimides except that
they
may be seen as having been prepared by reaction of a hydroca'rbyl acylating
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agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or
sorbitol. Such materials are described in more detail in U.S. Patent
3,381,022.
[0032] Other dispersants include polymeric dispersant additives, which are
generally hydrocarbon-based polymers which contain polar functionality to
impart dispersancy characteristics to the polymer.
[0033] Dispersants may also be post-treated by reaction with any of a variety
of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon
disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted
succinic
anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds.
References detailing such treatment are listed in U.S. Patent 4,654,403. (The
carbonyl to nitrogen ratio herein is calculated prior to any such post-
treatment.)
[0034] There are two commonly employed processes for making N-
substituted long chain alkenyl succinimide dispersants. These differ in the
method by which a polyalkylene (typically polyisobutylene, but also copolymers
including ethylene copolymer) substituent is prepared and by which it is
affixed
to a mono- or diacid or anhydride moiety, especially a succinic anhydride
moiety
or its reactive equivalent. In a conventional process (a), isobutylene is
polymerised in the presence of AlC13 to produce a mixture of polymers
comprising predominantly tri-substituted olefin and tetra-substituted olefin
end
groups, with only a very small amount (for instance, less than 20 percent) of
chains containing a terminal vinylidene group. In an alternative, "chlorine-
free"
or "thermal" process (b), isobutylene is polymerised in the presence of BF3
catalyst to produce a mixture of polymers comprising predominantly (for
instance, at least 70 percent) terminal vinylidene groups, with smaller
amounts
of tetra-substituted end groups and other structures. These materials,
sometimes
referred to as "high vinylidene PIB," are also described in U.S. Patent
6,165,235.
Generally a dispersant with a carbonyl to nitrogen ratio of 1 or higher; or a
dispersant with a carbonyl to nitrogen ratio of less than 1 may be prepared
using
either process.
[0035] Amines which may be used in preparing dispersants include those
with at least one reactive N-H group. Suitable examples of an amine are
selected
from the group consisting of an amine compound containing only a single
reactive amino group per molecule; (ii) a polyamine; (iii) an aminoalcohol;
(iv) a
cyclic amine; and (v) mixtures of (i) to (iv).
[0036] In one embodiment the polyamine is an alkylenepolyamine often
selected from the group consisting of an ethylenepolyamine, a
propylenepolyamine, a butylenepolyamine and mixtures thereof. Examples of a
propylenepolyamine include propylenediamine, dipropylenetriamine or mixtures
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thereof. An especially useful class of amine is derived from an
ethylenepolyamines, selected from the group consisting of ethylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyamine still bottoms and mixtures thereof.
[0037] In one embodiment the polyamine includes a a,13-diaminoalkane or
mixtures thereof. Suitable examples of the a,f3-diaminoalkane include a
diaminopropane, a diaminobutane or mixtures thereof. Especially useful
examples of a diaminoalkanes include those selected from the group consisting
of N-(2-aminoethyl)-1,3-propane diamine, 3,3'-diamine-N-methyldipropylamine,
tris(2-aminoethyl)amine, N,N-bis(3-aminopropy1)-1,3-propane diamine, N,N'-
1,2-ethanediylbis-(1,3-propane diamine) and mixtures thereof.
[0038] In one embodiment another polyamine includes
di-(trimethylene)triamine, piperazine, diaminocyclohexanes or mixtures
thereof.
[0039] Aminoalcohols suitable for the invention contain 1 to 6 and in one
aspect 1 to 3 hydroxy groups; and 1 to 8 and in one aspect 1 to 2 amine
groups.
When the amine is an aminoalcohol, the amine is often selected from the group
consisting of ethanolamine, isopropanolamine, diethanolamine, triethanolamine,
diethylethanolamine, dimethylethanolamine, dibutylethanolamine, 3-amino-1,2-
prop anedi ol ; serinol; 2-amino-2-methyl- 1,3 -prop anedi ol ; tri s (hydrox
ymeth y1)-
aminomethane; 1-amino-l-deoxy-D-sorbitol; diethanol amine;
diisopropanolamine; N-methyl-N,N-diethanol amine; triethanolamine;
N,N,N,NI-tetraki s(2-hydroxypropypethylenediamine, 2-amino-2-methyl-1-
propanol, 2-dimethyl amino-meth y1-1 -prop an edi ol, 2-amino-2-ethy1-1,3-
propanediol, 2- amino-2-methy1-1 ,3-propanediol, 2-amino-1 -butanol
and
mixtures thereof.
Antioxidant Package
[0040] The hindered phenol suitable for the invention is often represented
by
the formula:
R6
HO (W)
E
R7
wherein R6 and R7 are independently branched or linear alkyl groups containing
in one aspect 1 to 24, in another aspect 4 to 18, and in yet another aspect 4
to 12
carbon atoms; and E is hydrogen, a hydrocarbyl group, a bridging group linking
to a second aromatic group, an ester-containing group, or mixtures thereof.
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[0041] R6 and R7 may be either straight or branched chain and suitable
examples include secondary butyl and tertiary butyl.
[0042] In one embodiment, the hindered phenol of formula (VI) suitable for
the invention are esters or acids represented by the formula:
R6
= HO CH2CH2C (0) OR8 (VIa)
R7
wherein R6 and R7 are as defined above and R8 is hydrogen, a hydrocarbyl group
or mixtures thereof. When R8 is a hydrocarbyl group, R8 is often selected from
the
group consisting of butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl,
sec-
hexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and mixtures
thereof.
[0043] In one embodiment, the hindered phenol of formula (VI) suitable for
the invention contains a bridging group. Examples of suitable bridging groups
include an alkylene bridge or an ether bridge, often containing 1 to 8, in one
aspect 1 to 6, in another aspect 1 to 4 and in yet another aspect 1 to 2
carbon
atoms. Examples of a suitable bridge group include -CH2-, -CH2CH2-,
-CH2OCH2- and -CH2CH2OCH2CH2-.
[0044] When present, the hindered phenol with a bridging group is often
represented by the formula:
R6 R6
HI 411 Y- OH (Vlb)
R7 R7
wherein R6 and R7 are defined above and Y is a bridging group. Examples of a
methylene-bridged hindered phenol include 4,4:-methylene-bis-(6-tert-butyl-o-
cresol), 4,4:-methylene-bis-(2-tert-amyl-o-cresol) and 4,4:-methylene-bis-(2,6-
di-
tertbutylphenol).
[0045] The hindered phenol of the invention also includes compounds
represented by the formula:
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OH OH
R7
(VII)
wherein R6 and R7, E and Y are defined above. Examples of a suitable
methylene-bridged hindered phenol of formula (VII) include 2,2'-methylene-bis-
(4-methyl-6-tert-butylphenol), and 2,2 -methylene-bis-(4-ethyl-6-tert-
butylphenol), 2,2'-methylene-bis-(4-propy1-6-tert-butylphenol).
[0046] The antioxidant package is often present on an oil free basis at 0.01
to
20, in one aspect 0.1 to 15, in another aspect 0.5 to 10 and in yet another
aspect 1
to 5 weight percent of the composition. In one aspect at least 50 wt % of the
antioxidant package is a hindered phenol. In one aspect the hindered phenol is
present at 0.2 to 3 weight percent of the composition; alternatively 0.01 to
15 or
0.05 to 10 or 0.1 to 5 or 0.5 to 4 weight percent..
Oils of Lubricating Viscosity
[0047] The lubricating oil composition of the present invention may be added
to an oil of lubricating viscosity. The oil includes natural and synthetic
oils, oil
derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined
and re-refined oils, or mixtures thereof.
[0048] Unrefined oils are those obtained directly from a natural or
synthetic
source generally without (or with little) further purification treatment.
[0049] Refined oils are similar to the unrefined oils except they have been
further treated in one or more purification steps to improve one or more
properties. Purification techniques are known in the art and include solvent
extraction, secondary distillation, acid or base extraction, filtration,
percolation
and the like.
[0050] Re-refined oils are also known as reclaimed or reprocessed oils, and
are obtained by processes similar to those used to obtain refined oils and
often
are additionally processed by techniques directed to removal of spent
additives
and oil breakdown products.
[0051] Natural oils useful in making the inventive lubricants include animal
oils, vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils
such as
liquid petroleum oils and solvent-treated or acid-treated mineral lubricating
oils
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of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils
derived from coal or shale or mixtures thereof.
[0052] Synthetic lubricating oils are useful and include hydrocarbon oils such
as polymerised and interpolymerised olefins (e.g., polybutylenes,
polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-
octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g.
dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-
benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls);
alkylated diphenyl ethers and alkylated diphenyl sulphides and the
derivatives,
analogs and homologs thereof or mixtures thereof.
[0053] Other synthetic lubricating oils include but are not limited to polyol
esters, liquid esters of phosphorus-containing acids (e.g., tricresyl
phosphate,
trioctyl phosphate, and the diethyl ester of decane phosphonic acid), and
polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch
reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons
or waxes.
[0054] Oils of lubricating viscosity may also be defined as specified in the
American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The
five base oil groups are as follows: Group I (sulphur content >0.03 wt %,
and/or
<90 wt % saturates, viscosity index 80-120); Group II (sulphur content <0.03
wt
%, and >90 wt % saturates, viscosity index 80-120); Group III (sulphur content
<0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all
polyalphaolefins (PAO's)); and Group V (all others not included in Groups I,
II,
III, or IV). The oil of lubricating viscosity is selected from the group
consisting
of an API Group I, II, III, IV, V oil and mixtures thereof; in one aspect an
API
Group II, III, IV or V oil and mixtures thereof; and in yet another aspect an
API
Group III, IV or V oil and mixtures thereof. If the oil of lubricating
viscosity is
an API Group II, III, IV or V oil there may be up to a maximum of 20 wt %, in
one aspect up to a maximum of 10 wt %, in anther aspect up to a maximum of 5
wt % and in yet another aspect up to a maximum of 1.5 wt % of the lubricating
oil an API Group I oil.
[0055] Examples of suitable API Group III oils include NexbaseTM 3050,
NexbaseTM 3043, NexbaseTM 3060, PA0-6, PriolubeTm 1976, YubaseTM 4,
YubaseTM 6, and SheJJTM XHVI 5.2.
[0056] The oil of lubricating viscosity is often present at up to 99.97, in
one
aspect up to 99.69, in another aspect up to 97.75 and in yet another aspect up
to
95.5 weight percent of the composition. The composition is often classed as a
SAE XW-Y lubricating oil, wherein X is 0 or 5; and Y is 20, 30, 40 or 50.
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[0057] If the present invention 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 each of the above-mentioned dispersant, as well as other
components,
to diluent oil is often 80:20 to 10:90 by weight.
Other Performance Additives
[0058] The composition of the invention optionally further includes other
performance additives. The other performance additives selected from the group
consisting of antioxidants other than component (c), corrosion inhibitors,
antiwear agents, friction modifiers, viscosity modifiers, antiscuffing agents,
foam inhibitors, demulsifiers, pour point depressants, seal swelling agents
and
mixtures thereof.
[0059] The total combined amount of the other performance additives present
on an oil free basis is often from 0 to 25, in one aspect 0.01 to 20, in
another
aspect 0.05 to 15 and in yet another aspect 0.1 to 10 weight percent of the
composition. Although one or more of the other performance additives may be
present, it is common for the other performance additives to be present in
different amounts relative to each other.
Friction Modifiers
[0060] When present in the invention, the friction modifier may be a
monoester of a polyol and an aliphatic carboxylic acid, often an acid
containing
12 to 24 carbon atoms. Often the monoester of a polyol and an aliphatic
carboxylic acid is in the form of a mixture with a sunflower oil or the like,
which
may be present in the friction modifier mixture from 5 to 95, in one aspect 10
to
90, in another aspect 20 to 85 and in yet another aspect 20 to 80 weight
percent
of said mixture.
[0061] Polyols include diols, triols, and alcohols with higher numbers of
alcoholic OH groups. Polyhydric alcohols include ethylene glycols, including
di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri-
and
tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol;
arabitol;
mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and
pentaerythritols, including di- and tripentaerythritol. Often the polyol is
diethyl-
ene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or
dipentaerythritol.
[0062] The aliphatic carboxylic acids which form the esters are those acids
containing 12 to 24 carbon atoms. Acids containing straight chain hydrocarbyl
groups containing 12 to 24 carbon atoms are often used, for instance, 14 to 20
or
16 to 18 carbon atoms. Such acids may be used in combination with acids with
more or fewer carbon atoms as well. Generally the acid is a monocarboxylic
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acid. Examples of carboxylic acids include dodecanoic acid, stearic acid,
lauric
acid, behenic acid, and oleic acid.
[0063] The esters used in the present invention are in particular the
monoesters of such polyols and such carboxylic acids. Often the ester is
glycerol
monooleate. It is to be understood that glycerol monooleate, as is the case
with
other such materials, in its commercially available grade, is a mixture which
includes such materials as glycerol, oleic acid, other long chain acids,
glycerol
dioleate, and glycerol trioleate. The commercial material is believed to
include
60 + 5 percent by weight of the chemical species "glycerol monooleate," along
with 35 + 5 percent glycerol dioleate, and less than 5 percent trioleate and
oleic
acid. The amounts of the monoesters, described below, are calculated based on
the actual, corrected, amount of polyol monoester present in any such mixture.
[0064] Other friction modifiers that are suitable for the invention include
fatty amines, fatty phosphites, fatty acid amides, fatty epoxides, alkoxylated
fatty
amines, metal salts of fatty acids, sulphurised olefins, fatty imidazolines,
condensation products of carboxylic acids and polyalkylene-polyamines, amine
salts of alkylphosphoric acids.
Other Antioxidants
[0065] Optionally the invention includes an antioxidant other than a hindered
phenol, such as, a diphenylamine antioxidant, a molybdenum dithiocarbamate, a
sulphurised olefin, or mixtures thereof. Diphenylamine antioxidant additives
often contain in one aspect 6 or fewer, in another aspect 4 or fewer and in
yet
another aspect 3 or fewer hydrocarbyl groups such as 1 or 2. Each hydrocarbyl
group often contains in one aspect 1 to 24, in another aspect 2 to 18 and in
yet
another aspect 4 to 12 carbon atoms. In one embodiment of the invention the
composition contains a diphenylamine antioxidant.
[0066] Examples of suitable diphenylamine antioxidants include octyl
diphenylamine, nonyl diphenylamine, bis-octyl diphenylamine, and bis-nonyl
diphenylamine.
Viscosity Modifiers
[0067] Optionally the invention contains a viscosity modifier. Viscosity
modifiers are known and include polymeric materials including hydrogenated
styrene-butadiene rubbers, an olefin copolymer, hydrogenated styrene-isoprene
polymers, hydrogenated radical isoprene polymers, polymethacrylate acid
esters,
polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl conjugated diene
copolymers, polyalkylmethacrylates, esters of maleic anhydride-styrene
copolymers or mixtures thereof.
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[0068] Often polymethacrylate viscosity modifiers include copolymers of (a)
a methacrylic acid ester containing 9 to 30 carbons in the ester group, (b) a
methacrylic acid ester containing 7 to 12 carbons in the ester group wherein
the
ester group contains a 2-(C1..4 alkyl)-substituent and optionally (c) at least
one
monomer selected from the group consisting of a methacrylic acid ester
containing from 2 to 8 carbon atoms in the ester group and which are different
from methacrylic acid esters used in (a) and (b) above. A more detailed
description of polymethacrylate viscosity modifiers is disclosed in US Patent
Number 6,124,249.
[0069] Often viscosity modifiers derived from an olefin copolymer backbone
contain in one aspect 2 to 4, in another aspect 2 to 3 and in yet another
aspect 2
different olefin monomers. The olefin monomers often contain in one aspect 2
to
20, in another aspect 2 to 10, in yet another aspect 2 to 6 and in yet another
aspect 2 to 4 carbon atoms.
[0070] The olefin copolymer often contains an ethylene monomer and at least
one other comonomer derived from an alpha-olefin having the formula
H2C=CHR8, wherein R8 is a hydrocarbyl group, in one aspect an alkyl radical
containing 1 to 18, in one aspect 1 to 10, in another aspect 1 to 6 and in yet
another aspect 1 to 3 carbon atoms. The hydrocarbyl group includes an alkyl
radical that has a straight chain, a branched chain or mixtures thereof.
Examples
of a suitable comonomer include propylene, 1-butene, 1-hexene, 1-octene, 4-
methylpentene-1, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene,
1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene or
mixtures thereof. Examples of the olefin copolymers include ethylene-propylene
copolymers, ethylenebutene-1 copolymers and mixtures thereof.
[0071] In one embodiment of the invention the optional viscosity modifier is
a mixture of 2 or more olefin containing copolymers. For example a mixture of
2 copolymers derived from (A) a copolymer comprising 45 to 85 % by weight of
units derived from ethylene, having a Mw of 50,000 to 300,000, Mw/Mn less
than 3, and a melting point of 0 C to 60 C; and (B) a block copolymer
comprising a vinyl aromatic comonomer moiety and a second comonomer
moiety.
[0072] The copolymer (A) is often prepared by copolymerising ethylene and
other monomers, usually propylene.
[0073] Among the monomers which may be used to prepare the (B)
copolymers of the present inventions are 1,3-butadiene, 1,2-pentadiene, 1,3-
pentadiene, isoprene, 1,5-hexadiene, and 2-chloro-1,3 butadiene, and aromatic
olefins such as styrene, oc-methyl styrene, ortho-methyl styrene, meta-methyl
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styrene, para-methyl styrene, and para-t-butyl styrene, and mixtures thereof.
Other comonomers may be included in the mixture and in the polymer, which do
not substantially change the character of the resulting polymer.
[0074] Suitable styrene/isoprene hydrogenated copolymers are available
commercially from Infineum under the trade names InfineumTM SV140
(formerly ShellvisTM 40) (M, ca. 200,000), InfineumTM SF150 (M, ca. 150,000)
and InfineumTM SV160 (M, ca. 150,000), as well as from Septon Company of
America (Kuraray Group) under the trade names SeptonTM 1020 (Mw, ca.
150,000) and SeptonTM 1001 (M, ca. 200,000). Suitable styrene/1,3-butadiene
hydrogenated random block copolymers are available from BASF under the trade
name GlissoviscalTM (M, ca. 160,000-220,000). A more detailed description of
certain of these polymers and their manufacture is found in U.S. Patent
5,747,433, see column 3 lines 56 through column 8 line 62. A more detailed
description of the mixture of the 2 or more olefin containing copolymers is
given
in US Patent Application 60/458666, now PCT Application WO 04/087849.
[0075] Optionally the viscosity modifier copolymers are further grafted with
an unsaturated dicarboxylic acid anhydride or derivatives thereof and an amine
to form a dispersant viscosity modifier (often referred to as DVM), thus
named,
because they also exhibit dispersant properties.
Antiwear Agent
[0076] The invention optionally includes an antiwear agent such as a metal
hydrocarbyl dithiophosphate often represented by the formula:
P\ M' (VIII)
R9--0
wherein R9 and R1 are independently hydrogen, hydrocarbyl groups or mixtures
thereof, provided that at least one of R9 and R1 is a hydrocarbyl group,
often
containing in one aspect 1 to 30, in another aspect 2 to 20 and in yet another
aspect 2 to 15 carbon atoms.
[0077] M' is a metal, and n is an integer equal to the available valence of
M'.
M' is mono- or di- or tri- valent, in one aspect M' is divalent and in another
aspect a divalent transition metal. In one embodiment M' is zinc. In one
embodiment M' is calcium. In one embodiment M' is barium. Examples of a
metal hydrocarbyl dithiophosphate include zinc dihydrocarbyl dithiophosphates
(often referred to as ZDDP, ZDP or ZDTP).
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[0078] Optionally the invention further contains a borate ester
antiwear agent.
The borate ester may be prepared by the reaction of a boron compound and at
least
one compound selected from epoxy compounds, halohydrin compounds,
epihalohydrin compounds, alcohols and mixtures thereof. Often the alcohols
include
monohydric alcohols, dihydric alcohols, trihydric alcohols or higher alcohols.
[0079] Boron compounds suitable for preparing the borate ester include
the
various forms selected from the group consisting of boric acid (including
metaboric acid, HBO2, orthoboric acid, H3B03, and tetraboric acid, H2B407),
boric oxide, boron trioxide and alkyl borates. The borate ester may also be
prepared from boron halides.
[0080] The borate ester formed by the reaction of a boron compound and
an
epoxy compound may be represented by at least one compound derived from the
formulae:
R12-0 R140
OR15
B-0¨R11 R170¨B ¨ 0¨B¨ OR"
R13-0 (IX) (X)
OH
(IR 8
R 21 0 le
B 0
B
0 0 0
0
R20B
B-0R19
0 R22 (
0
R23
(MI)
(XI)
OR25
HO
(XIV)
nOH
R24
0R27 R26
wherein R11, R12 and R13 may be hydrogen or hydrocarbyl groups provided at
least one, in one aspect at least two of R11, R12 and K-13 are
hydrocarbyl groups.
In one embodiment, R11 is a hydrocarbyl group; and R12 and R13 are hydrogen.
In one embodiment, R11 and R12 are hydrocarbyl groups and R13 is hydrogen. In
one embodiment R11, R12 and R13 are all hydrocarbyl groups. The hydrocarbyl
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WO 2005/061682 PCT/US2004/040895
groups may be alkyl, aryl or cycloalkyl when any 2 adjacent R groups are
connected in a ring.
[0081] Often there is no upper limit on the number of carbon atoms in the
hydrocarbyl groups, but a practical limit is 500, in one aspect 400, in
another
aspect 200 and in yet another aspect 100 or 60. For example the number of
carbon atoms present in R11, R12 and R13 may be 1 to 60, or 1 to 40 or even 1
to
30 carbon atoms, provided the total number of carbon atoms in R11, R12 and R13
is 9 or more, in one aspect 10 or more, in another aspect 12 or more and in
yet
another aspect 14 or more.
[0082] R14 to R2 inclusive may be hydrogen or hydrocarbyl groups, provided
at least one of R14 to R17 and/or R18 to R2 is a hydrocarbyl group. R21 to
R26
inclusive are independently hydrogen or a hydrocarbyl group, although it is
common for at least one of R21 to R26 to be a hydrocarbyl group; and R27 may
be
hydrogen or a hydrocarbyl group, although it is common for R27 to be hydrogen.
The hydrocarbyl group definition for R14 to R27 inclusive is the same as the
definition given for R11, R12 and R13.
[0083] Examples of groups suitable for R11 to R27 inclusive include isopropyl,
n-butyl, isobutyl, amyl, 2-pentenyl, 4-methyl-2-pentyl, 2-ethyl-1-hexyl,
2-ethylhexyl, heptyl, isooctyl, nonyl, decyl, undecyl, dodecenyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl
and
eicosyl groups.
[0084] Suitable examples of the optional borate ester include tripropyl
borate,
tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl
borate,
trinonyl borate and tridecyl borate. Borate ester compounds are discussed in
more detail in European Patent 976 814.
[0085] The composition of the invention optionally contains antiwear agent
additives other than a metal hydrocarbyl dithiophosphate including phosphoric
acid esters or salts thereof; phosphites; and phosphorus-containing carboxylic
esters, ethers, and amides or mixtures thereof. Often phosphoric acid esters
contain a hydrocarbyl ester group with 4 to 40, in one aspect 4 to 30 and in
another aspect 6 to 24 carbon atoms. In one embodiment the hydrocarbyl ester
group is alkyl and in another embodiment the hydrocarbyl group is aryl.
[0086] Other optional performance additives include, for example, corrosion
inhibitors octylamine octanoate, condensation products of dodecenyl succinic
acid
or anhydride and a fatty acid such as oleic acid with a polyamine; metal
deactivators including derivatives of benzotriazoles, 1,2,4-triazoles,
benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles;
foam
inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and
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optionally vinyl acetate; demulsifiers including trialkyl phosphates,
polyethylene
glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-
propylene
oxide) polymers; pour point depressants including esters of maleic anhydride-
styrene, polymethacrylates, polyacrylates or polyacrylamides; and seal swell
agents including Exxon Necton37TM (FN 1380) and Exxon Mineral Seal Oil (FN
3200); may also be used in the composition of the invention.
Process
[0087] The invention further provides a process for the preparation of a
composition as described above.
[0088] Components (a)-(d) are often mixed sequentially, separately for the
composition of the invention, although two or more of the components may also
be mixed simultaneously. The mixing conditions are often 15 C to 130 C, in
one aspect 20 C to 120 C and in another aspect 25 C to 110 C; and for a period
of time in the range 30 seconds to 48 hours, in one aspect 2 minutes to 24
hours,
in another aspect 5 minutes to 16 hours and in yet another aspect 10 minutes
to 5
hours; and at pressures in the range 86 kPa to 266 kPa (650 mm Hg to 2000 mm
Hg), in one aspect 91 kPa to 200 kPa (690 mm Hg to 1500 mm Hg), and in
another aspect 95 kPa to 133 kPa (715 mm Hg to 1000 mm Hg).
[0089] The process optionally includes mixing other optional performance
additives as described above. The optional performance additives are often
added sequentially, separately or as a concentrate.
Industrial Application
[0090] The composition of the present invention is useful as a lubricant in
internal combustion engines, for example diesel fuelled engines, gasoline
fuelled
engines, natural gas fuelled engines or a mixed gasoline/alcohol fuelled
engines.
[0091] In one embodiment of the invention provides a Method for lubricating
an internal combustion engine, comprising supplying thereto a lubricant
comprising the composition as described herein. The use of the composition of
the invention is capable of imparting at least one or more of improved engine
cleanliness, improved detergency, decreased sludge formation, decreased wear,
decreased bore polishing and decreased oil consumption.
[0092] The following examples provide an illustration of the invention.
These examples are non exhaustive and are not intended to limit the scope of
the
invention.
EXAMPLES
Reference Example 1 =
[0093] Reference Example 1 is a 5W-30 lubricating oil containing on an oil
free basis about 6% of succinimide dispersants, with the high TAN dispersant
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WO 2005/061682 PCT/US2004/040895
present in higher quantity than the high TBN dispersant; on an oil free basis
about 2.8 wt % hindered phenol antioxidant; and a detergent package containing
an alkylsalicylate (AC60C commercially available from Infineum) present on
an oil free basis at about 1.1 wt %. The lubricating oil has a phosphorus
content
of 480 ppm and a sulphated ash content of 0.49 wt %.
Example 1
[0094] Example 1 is the same as Reference Example 1, except the detergent
package containing alkylsalicylate is replaced by a calcium sulphonate
detergent
and a calcium salixarate detergent (each commercially available from The
Lubrizol Corporation) together present on an oil free basis at about 1.1 wt %.
Reference Example 2
[0095] Reference Example 2 is the same as Example 1, except the high TAN
dispersant is used alone.
Reference Example 3
[0096] Reference Example 3 is the same as Reference Example 1, except the
detergent package containing alkylsalicylate is replaced by a calcium
sulphonate
and a calcium phenate.
Example 2
[0097] Example 2 is the same as Reference Example 1, except the detergent
package containing alkylsalicylate is replaced by calcium sulphonate, a
calcium
phenate and a calcium salixarate.
Preparative Example A
[0098] Blends are prepared of a 50:50 mixture by weight of an ethylene-
propylene copolymer (Polymer A) and a styrene/isoprene hydrogenated
copolymer (Polymer B), each of which are commercially available viscosity
modifiers. Polymer A is first dissolved in a 150N mineral oil containing 0.1%
of
a butylated hydroxytoluene (BHT) antioxidant. The antioxidant is added to the
mineral oil at room temperature. Polymer A, which is in a pellet from, is
slowly
added to the oil while it is being heated and stirred under high agitation.
After all
the polymer A has been added, the oil is continued to be heated to 130 C and
is
maintained at that temperature until all the Polymer A pellets are fully
dissolved.
Polymer B, which is also in a pellet form, is then added to the oil with
strong
agitation at 130 C until all of Polymer B is fully dissolved. The blends are
maintained at 130 C under strong agitation for an additional two hours to
ensure
that all the polymers are fully soluble.
Example 3
[0099] Example 3 is a 5W-30 lubricating oil containing on an oil free basis
about 6% of succinimide dispersants, with a high TAN dispersant present in
20
CA 02549095 2012-06-13
Ø
higher quantity than the high TBN dispersant; on an oil free basis about 2.8%
hindered phenol antioxidant; and a detergent package containing only a calcium
salixarate on an oil free basis at 1.2 wt % and an olefin copolymer viscosity
modifier present on an oil free basis at about 1 wt %. The lubricating oil has
a
phosphorus content of 480 ppm and a sulphated ash content of 0.44 wt %.
Example 4
10100] Example 4 is the same as Reference Example 4, except the viscosity
modifier is the product of Preparative Example A.
Reference Example 4
[0101] Reference Example 4 is the same as Reference Example 3, except the
composition contains an antioxidant package with a hindered phenol and a
diphenylamine. The detergent package is present at about 1.1 wt %. The
lubricating oil has a phosphorus content of 760 ppm and an ash content of 0.76
wt
%.
Example 5
[0102] Example 5 is the same as Reference Example 4, except the detergent
package present at 0.8 wt% contains a calcium sulphonate, a calcium phenate
and a
calcium salixarate instead of alkylsalicylate.
Reference Example 5
[0103] Reference Example 5 is a is a 5W-30 lubricating oil containing on an
oil free basis about 6% of succinimide dispersants with a high TAN dispersant
present in higher quantity than the high TBN dispersant; on an oil free basis
about
0.65% hindered phenol antioxidant; and a detergent package containing only a
magnesium saligenin on an oil free basis at 0.9- wt %. The lubricating oil has
a
magnesium content of 400 ppm, a phosphorus content of 1300 ppm, an ash content
of 1.65 wt %.
Example 6
[0104] Example 6 is 5W-40 lubricating oil containing on an oil free basis
about 11.9% of succinimide dispersants with a high TAN dispersant present in
higher quantity than the high TBN dispersant; on an oil free basis about 3%
hindered phenol antioxidant; and a detergent package containing a calcium
salixarate and a magnesium saligenin, present together on an oil free basis at
1.0 wt
%. The lubricating oil has a magnesium content of 100 ppm, a phosphorus
content
of 500 ppm, a sulphated ash content of 0.97 wt %.
Test 1: Cleanliness Test
[0105] A piston engine cleanliness test is carried out based on the
Coordinating European Council (CEC) test method CEC L-78-T-99. The results are
21
CA 02549095 2012-06-13
based on a merit rating and higher numbers indicate better piston cleanliness.
The
results obtained are:
Table 1: TDi Piston Cleanliness Ratings
Example Rating
Reference Example 1 57
Reference Example 2 56
Example 1 60
Reference Example 3 55
Example 2 60
Example 3 53
Example 4 65
[0106] The results from Table 1 indicate that the combination of a high TAN
dispersant and a high TBN dispersant (in Example 1) have improved piston
cleanliness compared with Reference Examples 2 with only one dispersant.
[0107] Comparing Example 1 and Reference Example 1 indicates that a (a)
dispersant package with a high TAN dispersant, a high TBN dispersant detergent
package containing a salixarate; and a hindered phenol antioxidant package
improves piston cleanliness compared with a detergent package free of
salixarate.
Likewise comparing Example 2 and Reference Example 3 again indicates the
piston
cleanliness properties of the composition of the invention.
[0108] Comparing Example 3 and Reference Example 4 indicates that the
composition of the invention has piston cleanliness properties even in the
presence
of viscosity modifiers.
Test 2: Sludge and Wear Test
[0109] A sludge test M111ESL is carried out based on the Coordinating
European Council (CEC) test method CEC-L-53-T-95. The test conditions used are
conditions E of the test method. The test produces a sludge rating and the
average
engine Cam-wear scar (tm). The higher the sludge rating results the less
sludge is
formed in the engine and the lower wear scar values indicate decreased engine
wear.
The results obtained are:
Table 2: M111ESL Sludge and Wear Test Data
Example Sludge Rating Cam wear scar (gm)
Reference Example 4 9.0 3.3
Example 5 9.3 3.0
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CA 02549095 2012-06-13
[0110] The results indicate the composition of the invention decreases
sludge
formation and engine wear.
Test 3 MB OM 441 LA Heavy Duty Diesel Cleanliness Test
[0111] The heavy duty diesel cleanliness test MB OM 441 LA is carried out
based on the Coordinating European Council (CEC) test method CEC-L-52-T-97.
The test produces engine cleanliness data and data associated with engine
durability.
The results obtained are:
Table 3: MB OM 441 LA Test Data
Reference Example 5 Example 6
Average Engine Sludge (rating) 9.5 9.5
Piston Cleanliness Rating (rating) 34.6 (Fail) 40.0
General Deposit Cleanliness 1.8 1.9
(demerit)
Average Wear scar (demerit) 1.9 2.0
Bore Polishing (%) 2.5 0.6
Average Cylinder Wear (mm) n/a 0.0009
Ring Sticking 2 Piston Rings 0.9 0.17
(ASF)
Specific Oil Consumption (g/h) 111.49 (Fail) 77.7
Boost Pressure Loss (Total %) -2.87 -3.4
[0112] The results indicate the composition of the invention has improved
piston cleanliness, decreased bore polishing and decreased oil consumption
compared with the reference example. Other measurements shown in Table 3 are
within acceptable limits.
[0113] Overall the composition of the invention improves engine
cleanliness,
improves detergency, decreases sludge formation, decrease wear, decreased bore
polishing and decreased oil consumption.
[0114] In this specification the terms "hydrocarbyl substituent" or
"hydrocarbyl group," as used herein are used in its ordinary sense, which is
well-
known to those skilled in the art. Specifically, it refers to a group
primarily
composed of carbon and hydrogen atoms and attached to the remainder of the
molecule through a carbon atom and which does not exclude the presence of
other
atoms or groups in a proportion insufficient to detract from the molecule
having a
predominantly hydrocarbon character. In general, no more than two, in one
aspect
no more than one, non-hydrocarbon substituent will be present for every ten
carbon
atoms in the hydrocarbyl group; typically, there will be no non-
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CA 02549095 2012-06-13
hydrocarbon substituents in the hydrocarbyl group. A more detailed definition
of
the terms "hydrocarbyl substituent" or "hydrocarbyl group," is provided in US
Patent Number 6,583,092.
[0115] Except in the Examples, or where otherwise explicitly indicated, all
numerical quantities in this description specifying amounts of materials,
reaction
conditions, molecular weights, number of carbon atoms, and the like, are to be
understood as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as being a
commercial grade material which may contain the isomers, by-products,
derivatives,
and other such materials which are normally understood to be present in the
commercial grade. However, the amount of each chemical component is presented
exclusive of any solvent or diluent oil, which may be customarily present in
the
commercial material, unless otherwise indicated. It is to be understood that
the
upper and lower amount, range, and ratio limits set forth herein may be
independently combined. Similarly, the ranges and amounts for each element of
the
invention may be used together with ranges or amounts for any of the other
elements. As used herein, the expression "consisting essentially of" permits
the
inclusion of substances that do not materially affect the basic and novel
characteristics of the composition under consideration.
24
