Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
LUBRICATING COMPOSITION CONTAINING AN
OXYALKYLATED HYDROCARBYL PHENOL
FIELD OF INVENTION
[0001] The
disclosed technology provides lubricating composition comprising: an oil
of lubricating viscosity, a p-dodecylphenol-free detergent, and an
oxyalkylated
hydrocarbyl phenol, wherein the oxyalkylated hydrocarbyl phenol is substituted
with at
least one aliphatic hydrocarbyl group of 1 to 250 carbon atoms (or 20 to 220,
or 30 to 150
carbon atoms), and wherein the oxyalkylated hydrocarbyl phenol is
substantially free of
aromatic hydrocarbyl groups. The disclosed technology further relates to a
method of
lubricating a mechanical device (such as an internal combustion engine) with
the
lubricating composition. The disclosed technology further relates to the use
of the of the
lubricating composition in a passenger car internal combustion engine to
improve control
of at least one of the following (i) fuel economy, (ii) corrosion, (iii)
cleanliness, and
(iv) bore wear.
BACKGROUND OF THE DISCLOSED TECHNOLOGY
[0002]
Detergents and dispersants are known to assist in maintaining reduced
amounts of deposits on engine components. The lubricant industry has a number
of
engine tests used to evaluate lubricant's ability to handle deposits and
sludge including
the Sequence VG, Sequence JIG, Volkswagen TDI, Caterpillar 1N, and Mercedes
Benz
0M501LA.
[0003]
With recent changes to engine specifications there is an increasing demand on
the lubricant to reduce deposits, especially soot deposits that are known to
accumulate in
diesel engines but not gasoline engines. For instance, the ILSAC GF-5
specification
requires a 4.0 piston merit rating in the Sequence IIIG (vs. 3.5 for GF-4).
[0004] US
3,933,662 (Lowe, published 20 January 1976) discloses mono-ester
polyalkoxylated compounds combined with alkaline earth metal carbonates
dispersed in a
hydrocarbon medium to provide lubricating compositions of superior acid
neutralizing
capability and rust inhibition in internal combustion engines. The internal
combustion
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engine tested is a Sequence JIB gasoline engine. The Sequence JIB gasoline
engine test
evaluates valve guide rust and pitting.
[0005] US
4,402,845 (Zoleski et al., published 6 September 1983) discloses improved
spreadability of marine diesel cylinder oils by the incorporation therein of a
polyethylene
glycol of the formula: R-CH20-(CH2CH20).H wherein n ranges from 7 to 40 and R
is an
alkyl group containing from 11 to 15 carbon atoms.
[0006] US
4,438,005 (Zoleski et al., published 20 March, 1984) discloses improved
spreadability of marine diesel engine cylinder lubricants by the incorporation
therein of a
spreadability improving amount of at least one polyoxyethylene ester of the
formula
disclosed therein: wherein n ranges from 18 to 22 and R is an alkyl group
having 11 to 17
carbon atoms in the chain.
[0007] US
4,479,882 (Zoleski et al., published 30 October, 1984) discloses improved
spreadability of marine diesel cylinder oils by the incorporation therein of a
spreadability
improving amount of a polyethoxylated phenoxy compound having the formula
disclosed
therein: wherein R is an aliphatic hydrocarbyl group having from 5 to 70
carbon atoms
and n ranges from 14 to 30.
[0008] US
4,493,776 (Rhodes, published 15 January, 1985) discloses a lubricating
composition with improved rust and corrosion inhibition comprising an additive
that is a
combination of (A) R I 0 [C2H40],F1 and/or
R20[C11-160]yfl with
(B) R30[C2H40][C1H60]yH and/or R40[C3H60][C2H40],H, wherein RI-, R2, R3 and R4
are hydrocarbyl radicals selected from alkyl, aryl, alkaryl, and arylalkyl
groups or
combinations thereof having from about 10 to about 24 carbon atoms; and
wherein x and
y may vary independently in the range from 3 to about 15. The additives are
hydroxyl-
terminated.
[0009] US 4,973,414
(Nerger et al., published 27 November, 1990) discloses
monofunctional polyethers having hydroxyl groups contain, as built-in terminal
groups or
monomers, (a) 1 to 30% by weight of one or more C4- to C24-alkylmonophenols,
(b) 1 to
30% by weight of one or more C8- to C24-monoalkanols, (c) 1 to 30% by weight
of one
or more C10- to C20-1,2-epoxyalkanes and (d) 45 to 80% by weight of propylene
oxide
or a lower alkylene oxide mixture consisting mainly of propylene oxide the sum
of
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components (a) to (d) adding up to 100% by weight, and have average molecular
weights
of 600 to 2,500.
[0010]
Polyalkoxylated compounds are also disclosed in US 2,681,315 (Tongberg,
published 15 June, 1954) and US 2,833,717 (Whitacre, published 6 May, 1958)
teaching
lubricating oil compositions containing poly(oxyethylene)alkylphenols useful
as rust or
corrosion-inhibiting additives.
[0011] US
2,921,027 (Brennan 12 January, 1960) teaches poly(oxyethylene)sorbitan
fatty acid ester as a rust inhibitor.
[0012] 1,2-
poly(oxyalkylene)glycol lubricating compositions are disclosed in
US 2,620,302 (Harle, published 2 December 1952), US 2,620,304 (Stewart et al.,
published 2 December, 1952), and US 2,620,305 (Stewart et al., published 2
December,
1952).
[0013] US
2011/0239978 (Dambacher et al, published 6 October 2011) discloses a
lubricating composition that contains as an additive component, an oil-soluble
mixture of
oxyalkylated hydrocarbyl phenol condensates wherein the oxyalkyl groups have
the
formula -(R'0)n- where R' is an ethylene, propylene or butylene group; and n
is
independently from 0 to 10; wherein less than 45 mole % of the phenolic
functional
groups of the condensates are non-oxyalkylated; and more than 55 mole % of the
phenolic functional groups of the condensates are mono-oxyalkylated.
[0014] Research
Disclosure RD 417045 (Anon, published 10 January 1999) describes
ethoxylated methylene-bridged alkyl phenols as detergents.
SUMMARY OF THE DISCLOSED TECHNOLOGY
[0015] The
objectives of the disclosed technology include providing a lubricating
composition which results in improved control of at least one of the following
(i) fuel
economy, (ii) corrosion, (iii) cleanliness (typically control of deposits,
typically
control/reduction of soot), and (iv) bore wear in an internal combustion
engine, a gasoline
or diesel passenger car internal combustion engine (typically a diesel
passenger car
internal combustion engine).
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[0016] As
used herein, reference to the amounts of additives present in the lubricating
composition disclosed are quoted on an oil free basis, i.e., amount of
actives, unless
otherwise indicated.
[0017] As
used herein, the transitional term "comprising", which is synonymous with
"including", "containing", or "characterized by", is inclusive or open-ended
and does not
exclude additional, un-recited elements or method steps. However, in each
recitation of
"comprising" herein, it is intended that the term also encompass, as
alternative
embodiments, the phrases "consisting essentially of" and "consisting of',
where
"consisting of' excludes any element or step not specified and "consisting
essentially of'
permits the inclusion of additional un-recited elements or steps that do not
materially
affect the basic and novel, and essential characteristics of the composition
or method
under consideration.
[0018] As
used herein the term "oxyalkylated hydrocarbyl phenol" is intended to
include un-substituted and substituted compounds that have a hydroxyl group
directly
bonded aromatic group (within the definition of Hiickel Rule 47r+2 electrons)
such as
phenol, or ortho-, meta- or para- methyl phenol i.e., cresol.
[0019] In
one embodiment the disclosed technology provides a lubricating
composition comprising: an oil of lubricating viscosity, a p-dodecylphenol-
free detergent
and an oxyalkylated hydrocarbyl phenol, wherein the oxyalkylated hydrocarbyl
phenol is
substituted with at least one aliphatic hydrocarbyl group of 1 to 250 carbon
atoms (or 20
to 220, or 30 to 150 carbon atoms), and wherein the oxyalkylated hydrocarbyl
phenol is
substantially free of aromatic hydrocarbyl groups.
[0020] In
one embodiment the disclosed technology provides a lubricating
composition characterised as having at least one of (i) a sulphur content of
0.2 wt % to
0.4 wt % or less, (ii) a phosphorus content of 0.08 wt % to 0.15 wt %, and
(iii) a
sulphated ash content of 0.5 wt % to 1.5 wt % or less.
[0021] In
one embodiment the disclosed technology provides a lubricating
composition characterised as having (i) a sulphur content of 0.5 wt % or less,
(ii) a
phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of
0.5 wt % to
1.5 wt % or less.
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[0022] The
lubricating composition may have a SAE viscosity grade of XW-Y,
wherein X may be 0, 5, 10, or 15; and Y may be 16, 20, 30, or 40.
[0023] In
one embodiment the disclosed technology provides a method of lubricating
an internal combustion engine comprising supplying to the internal combustion
engine a
lubricating composition of a lubricating disclosed herein.
[0024] The
internal combustion engine may have a steel surface on a cylinder bore, a
cylinder block, or a piston ring.
[0025] The
internal combustion engine may be a heavy duty diesel internal
combustion engine.
[0026] The heavy
duty diesel internal combustion engine may have a "technically
permissible maximum laden mass" over 3,500 kg. The engine may be a compression
ignition engine or a positive ignition natural gas (NG) or LPG (liquefied
petroleum gas)
engine. The internal combustion engine may be a passenger car internal
combustion
engine. The passenger car engine may be operated on unleaded gasoline.
Unleaded
gasoline is well known in the art and is defined by British Standard BS EN
228:2008
(entitled "Automotive Fuels ¨ Unleaded Petrol ¨ Requirements and Test
Methods").
[0027] In
one embodiment the passenger car internal combustion engine may have a
reference mass not exceeding 2610 kg. The passenger car internal combustion
engine
may be a gasoline or diesel passenger car internal combustion engine
(typically a diesel
passenger car internal combustion engine).
[0028] In
one embodiment the lubricating composition disclosed herein comprises
the p-dodecylphenol-free detergent may be present at 3 wt % to 8 wt% or 3 wt %
to
5 wt % and the oxyalkylated hydrocarbyl phenol disclosed herein may be present
at
0.1 wt (N) to 5 wt %, or 0.1 wt % to 1.5 wt % of the lubricating composition.
Typically a
lubricating composition of this type may be used as a heavy duty diesel
internal
combustion engine lubricant.
[0029] In
one embodiment the lubricating composition disclosed herein comprises
the p-dodecylphenol-free detergent present at 0.15 wt % to less than 3 wt %,
or 0.2 to
1 wt % and the oxyalkylated hydrocarbyl phenol is present at 0.1 wt % to 5 wt
%, or
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0.1 wt % to 1.5 wt % of the lubricating composition. Typically a lubricating
composition
of this type may be used as a passenger car internal combustion engine
lubricant.
[0030] The disclosed technology may also provide for a method of
controlling soot
formation in a 4-stroke compression ignition engine or a positive ignition
natural gas
(NG) or LPG engine comprising supplying to the engine a lubricating
composition
disclosed herein.
[0031] In one embodiment the disclosed technology provides for the use
of the
oxyalkylated hydrocarbyl phenol and p-dodecylphenol-free detergent disclosed
herein in
a lubricating composition provide at least one of (i) control of fuel economy,
(ii) control
of corrosion, (iii) cleanliness (typically control of deposits, typically
control/reduction of
soot), and (iv) control of bore wear in an internal combustion engine.
Typically the
internal combustion engine is a diesel passenger car internal combustion
engine.
[0032] In one embodiment the disclosed technology provides for the use
of the
oxyalkylated hydrocarbyl phenol disclosed herein in a lubricating composition
for a
diesel passenger car internal combustion engine to control soot deposit
formation.
DETAILED DESCRIPTION OF THE DISCLOSED TECHNOLOGY
[0033] The disclosed technology provides a detergent, a process to
prepare a
detergent, a lubricating composition, a method for lubricating an internal
combustion
engine and the use as disclosed above.
p-Dodecylphenol-Free Detergent
[0034] As used herein the term "p-dodecylphenol-free detergent" is
intended to
include a detergent when in a lubricating composition that comprises less than
0.2 wt %,
or less than 0.1 wt %, or even less than 0.05 wt % of a phenate detergent
derived from
p-dodecylphenol (also referred to as PDDP).
[0035] As referred to herein, the TBN is measured using ASTM D2986-11.
[0036] In one embodiment the p-dodecylphenol-free detergent does not
include a
phenate or salicylate detergent derived from an alkyl phenol (or salicyclic
acid) having an
alkyl group of tetrapropenylphenol.
[0037] The p-dodecylphenol-free detergent may include a sulphonate
detergent, or a
salicyclatc or phenate detergent that may typically be derived from p-
hydrocarbyl
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phenols other than p-dodecylphenol. The phenates and salicylates may be
neutral or
overbased. The overbased phenates and salicylates typically have a total base
number of
180 to 450 TBN. The phenate detergent includes a sulphur-coupled phenate, an
alkylene-
coupled phenate, or mixtures thereof.
[0038] The p-
dodecylphenol-free detergent is known in the art, as are the processes to
prepare them.
[0039] In
one embodiment the p-dodecylphenol-free detergent includes a phenate
detergent that may typically be derived from p-hydrocarbyl phenols other than
p-dodecylphenol. Alkylphenols of this type may be coupled with sulphur and
overbased,
coupled with aldehyde and overbased, or carboxylated to form salicylate
detergents.
Suitable alkylphenols include those alkylated with oligomers of propylene,
i.e. tetrapropenylphenol (i.e. p-dodecylphenol or PDDP) and
pentapropenylphenol.
Suitable alkylphenols also include those alkylated with oligomers of butene,
especially
tetramers and pentamers of n-butenes. Other suitable alkylphenols include
those alkylated
with alpha-olefins, isomerized alpha-olefins, and polyolefins such as
polyisobutylene.
[0040] In
one embodiment, the lubricant composition comprises a phenate detergent
that is not derived from PDDP. In one embodiment the lubricating composition
comprises a phenate detergent prepared from PDDP, wherein the phenate
detergent
contains less than 1.0 wt % unreacted PDDP, or less than 0.5 wt % unreacted
PDDP, or
substantially free of PDDP.
[0041] In
one embodiment the p-dodecylphenol-free detergent consists of a
magnesium or calcium sulphonate detergent (typically a calcium sulphonate
detergent).
The sulphonate detergent may be neutral, or overbased.
[0042]
Overbased detergents are known in the art. Overbased materials, otherwise
referred to as overbased or superbased salts, are generally single phase,
homogeneous
Newtonian systems characterized by a metal content in excess of that which
would be
present for neutralization according to the stoichiometry of the metal and the
particular
acidic organic compound reacted with the metal. The overbased materials are
prepared by
reacting an acidic material (typically an inorganic acid or lower carboxylic
acid, typically
carbon dioxide) with a mixture comprising an acidic organic compound, a
reaction
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medium comprising at least one inert, organic solvent (mineral oil, naphtha,
toluene,
xylene, etc.) for said acidic organic material, a stoichiometric excess of a
metal base, and
a promoter such as a calcium chloride, acetic acid, phenol or alcohol. The
acidic organic
material will normally have a sufficient number of carbon atoms to provide a
degree of
solubility in oil. The amount of "excess" metal (stoichiometrically) is
commonly
expressed in terms of metal ratio. The term "metal ratio" is the ratio of the
total
equivalents of the metal to the equivalents of the acidic organic compound. A
neutral
metal salt has a metal ratio of one. A salt having 4.5 times as much metal as
present in a
normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The
term "metal
ratio" is also explained in standard textbook entitled "Chemistry and
Technology of
Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik,
Copyright 2010,
page 219, sub-heading-7.25.
[0043] The
overbased sulphonate detergent may be present at 0.1 wt % to 10 wt %, or
0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %.
[0044] For example
in a heavy duty diesel engine the detergent may be present at
2 wt % to 3 wt % of the lubricating composition. For a passenger car engine
the detergent
may be present at 0.2 wt % to 1 wt % of the lubricating composition. In one
embodiment,
an engine lubricating composition comprises at least one overbased sulphonate
detergent
with a metal ratio of at least 3, or at least 8, or at least 15. In one
embodiment, the
overbased sulphonate detergent may be present in an amount to deliver total
base number
(TBN) of at least 3 mg KOH/g to the lubricating composition or at least 4 mg
KOH/g, or
at least 5 mg KOH/g to the lubricating composition; the overbased sulphonate
detergent
may deliver 3 to 10 mg KOH/g, or 5 to 10 mg KOH/g to the lubricating
composition.
[0045]
Overbased sulphonate detergents typically have a total base number of 250 to
600, or 300 to 500. Overbased detergents are known in the art.
[0046] In
one embodiment the sulphonate detergent may be a predominantly linear
alkylbenzene sulphonate detergent having a metal ratio of at least 8 as is
described in
paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted
as
US 7,407,919). Linear alkyl benzenes may have the benzene ring attached
anywhere on
the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof. The
predominantly
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linear alkylbenzene sulphonate detergent may be particularly useful for
assisting in
improving fuel economy. In one embodiment, the sulphonate detergent may be a
branched alkylbenzene sulphonate detergent. Branched alkylbenzene sulphonate
may be
prepared from isomerized alpha olefins, oligomers of low molecular weight
olefins, or
combinations thereof. Typically oligomers include tetramers, pentamers, and
hexamers of
propylene and butylene. In one embodiment the sulphonate detergent may be a
metal salt
of one or more oil-soluble alkyl toluene sulphonate compounds as disclosed in
paragraphs [0046] to [0053] of US Patent Application 2008/0119378.
[0047] The overbased metal-containing detergent may also include
"hybrid"
detergents formed with mixed surfactant systems including phenate and/or
sulphonate
components, e.g., ph en ate/sal i cylates, su 1ph on ate/ph en ates, su 1phon
ate/s al i cyl ates,
sulphonates/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
sulphonate/phenate
detergent is employed, the hybrid detergent would be considered equivalent to
amounts
of distinct phenate and sulphonate detergents introducing like amounts of
phenate and
sulphonate soaps, respectively.
Oxyalkylated Hydrocarbyl Phenol
[0048] The oxyalkylated hydrocarbyl phenol may be represented by the
formula:
(R2 \
(R4 /- 0 __ R3
_____________________________________ 0 _______
2 /n
wherein
each R2 may be independently hydrogen or a hydrocarbyl group of 1 to 6 carbon
atoms;
R3 may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl
group
represented by -C(=0)R5,
R5 may be a hydrocarbyl group of 1 to 24 carbon atoms;
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each R4 may be independently a hydrocarbyl group of 1 to 250 carbon atoms
(typically
wherein at least one R4 contains 20 to 220, or 30 to 150, 35 to 140, or 40 to
96 carbon
atoms);
n = 1 to 20, or 1 to 10; and
m = 1 to 3.
[0049] The oxyalkylated hydrocarbyl phenol may be represented by the
formula:
( R2 \
(R4),,c/-) 0 __ R3
_____________________________________ 0 _______
2
wherein
one R2 may be methyl, and the second R2 may be hydrogen;
R3 may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl
group
represented by -C(=0)R5,
R5 may be a hydrocarbyl group of 1 to 24 carbon atoms;
each R4 may be a hydrocarbyl group of 20 to 220, or 30 to 150, 35 to 140, or
40 to 96
carbon atoms;
n = 1 to 20, or 1 to 10; and
m= 1.
[0050] The oxyalkylated hydrocarbyl phenol may be represented by the
formula:
(R2 \
(R4)m / ________________________
_____________________________________ 0 _______________ R3
Jn
wherein
one R2 may be methyl, and the second R2 may be hydrogen;
R3 may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl
group
represented by -C(=0)R5,
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R5 may be a hydrocarbyl group of 1 to 24 carbon atoms;
R4 may be a hydrocarbyl group of 1 to 220 carbon atoms, wherein at least one
R4
comprises a polyalk(en)yl group containing 30 to 150, 35 to 140, or 40 to 96,
35 to 140,
or 35 to 96 carbon atoms;
n = 1 to 8, or 2 to 8; and
m=1.
[0051] The oxyalkylated hydrocarbyl phenol may be represented by the
formula:
(R4)m /- (R2 0 \ R3
_____________________________________ 0 _______
2 in
wherein
one R2 may be methyl, and the second R2 may be hydrogen;
R3 may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl
group
represented by -C(=0)R5,
R5 may be a hydrocarbyl group of 1 to 24 carbon atoms;
each a hydrocarbyl group of 1 to 220 carbon atoms comprises a polyisobutenyl
group
containing 35 to 140, or 35 to 96 carbon atoms;
n= 1 to 8, or 2 to 8 (or 3 to 5); and
m= 1.
[0052] The R4 group of each of the formulae above may be located in
the para-
position relative to the oxyalkylated group, and the resultant formula may be
represented
by structure:
R2
R4
= \ R3
2 in
wherein variables R2 to R5, n, and m are defined previously.
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[0053] In
one embodiment the oxyalkylated hydrocarbyl phenol of the disclosed
technology may be represented by the formula:
R4
= 0 R2 \ R3
2
wherein R4 may be a polyolefinic group such as a polypropenyl or a
polyisobutenyl group
(typically a polyisobutenyl group), and variables R2, R3, R5, and n are
defined previously.
The polyisobutenyl group may have a number average molecular weight of 350 to
2500,
or 550 to 2300, or 750 to 1150. In one embodiment the polyisobutenyl group has
a
number average molecular weight of 950-1000. The polypropenyl group may have a
number average molecular weight of 740 to 1200, or 800-850. In one embodiment
the
polypropenyl group has a number average molecular weight of 825.
[0054] In
one embodiment the oxyalkylated hydrocarbyl phenol of the disclosed
technology may be represented by the formula:
4
= -()) R3 R
2
wherein R4 may be a polyolefinic group such as a polypropenyl or a
polyisobutenyl group
(typically a polyisobutenyl group), and variables R2, R3, R5, and n, are
defined
previously. The polyisobutenyl group may have a number average molecular
weight of
350 to 2500, or 550 to 2300, or 750 to 1150. In one embodiment the
polyisobutenyl
group has a number average molecular weight of 950-1000.
[0055] The
oxyalkylated group of the oxyalkylated hydrocarbyl phenol has formula
¨(R10)11¨, wherein R1 may be an ethylene, propylene, butylene group, or
mixtures
thereof; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2
to 5.
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[0056] The
oxyalkylated group of the oxyalkylated hydrocarbyl phenol may be either
a homopolymer or copolymer or oligomers thereof If the oxyalkylated group is
in the
form of a copolymer, or oligomer thereof, the oxyalkylated group may have
either
random or block architecture.
[0057] In one
embodiment the oxyalkylated group (or RI- may be a propylene, or
butylene group i.e., the oxyalkylated group does not require an ethylene
group. If an
ethylene group is present the oxyalkylate group may be a copolymer, or
oligomer thereof
with either propylene or butylene oxide i.e., blocks of (i) -CH2 CH20- with
(ii) -CH2CH2CH2CH20- or -CH2CH(CH3)CH20- or -CH2CH(CH3)0-.
[0058] In one
embodiment the oxyalkylated group may be based upon propylene
oxide.
[0059] The
oxyalkylated hydrocarbyl phenol may be prepared by reacting a
hydrocarbyl substituted phenol with an alkylene oxide (typically ethylene
oxide,
propylene oxide or butylene oxide), optionally in the presence of a base
catalyst.
Typically the reaction occurs in the presence of a base catalyst.
[0060] The
base catalyst may include sodium chloroacetate, sodium hydride or
potassium hydroxide.
[0061] The
aliphatic hydrocarbyl group (also represented by R4) may be linear or
branched, typically with at least one branching point. The aliphatic
hydrocarbyl group
typically has one, although it may in some embodiments be desirable to have to
R4
groups, with the second group being methyl. If a second R4 group is present
and is
methyl, then the oxyalkylated hydrocarbyl phenol is a cresol.
[0062] In
different embodiments the oxyalkylated hydrocarbyl phenol of the
disclosed technology 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. Typically
the
oxyalkylated hydrocarbyl phenol may be present in an amount from 0.1 to 1.5 wt
% of
the lubricating composition.
Oils of Lubricating Viscosity
[0063] The
lubricating composition comprises an oil of lubricating viscosity. Such
oils include natural and synthetic oils, oil derived from hydrocracking,
hydrogenation,
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and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof. A
more
detailed description of unrefined, refined and re-refined oils is provided in
International
Publication W02008/147704, paragraphs [0054] to [0056] (a similar disclosure
is
provided in US Patent Application 2010/197536, see [0072] to [0073]). A more
detailed
description of natural and synthetic lubricating oils is described in
paragraphs [0058] to
[0059] respectively of W02008/147704 (a similar disclosure is provided in US
Patent
Application 2010/197536, see [0075] to [0076]). Synthetic oils may also be
produced by
Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch
hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-
Tropsch
gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
[0064]
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). In one embodiment the oil of
lubricating
viscosity may be an API Group II, Group III, Group IV oil, or mixtures
thereof.
[0065] 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
compound of the
disclosed technology and the other performance additives.
[0066] The
lubricating composition may be in the form of a concentrate and/or a fully
formulated lubricant. If the lubricating composition of the disclosed
technology
(comprising the additives disclosed herein) is in the form of a concentrate
which may be
combined with additional oil to form, in whole or in part, a finished
lubricant), the ratio
of the of these additives to the oil of lubricating viscosity and/or to
diluent oil include the
ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
Other Performance Additives
[0067] A
lubricating composition may be prepared by adding the oxyalkylated
hydrocarbyl phenol described herein to an oil of lubricating viscosity,
optionally in the
presence of other performance additives (as described herein below).
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[0068] The
lubricating composition of the disclosed technology may further include
other additives. In one embodiment the disclosed technology provides a
lubricating
composition further comprising at least one of a dispersant, an antiwear
agent, a
dispersant viscosity modifier, a friction modifier, a viscosity modifier, an
antioxidant, a
foam inhibitor, a demulsifier, a pour point depressant or mixtures thereof. In
one
embodiment the disclosed technology provides a lubricating composition further
comprising at least one of a polyisobutylene succinimide dispersant, an
antiwear agent, a
dispersant viscosity modifier, a friction modifier, a viscosity modifier
(typically an olefin
copolymer such as an ethylene-propylene copolymer), an antioxidant (including
phenolic
and aminic antioxidants), an overbased detergent (including overbased
sulphonates and
ph en ates), or mixtures thereof.
[0069] The
lubricating composition may further include a dispersant, or mixtures
thereof. The dispersant may be a succinimide dispersant, a Mannich dispersant,
a
succinamide dispersant, a polyolefin succinic acid ester, amide, or ester-
amide, or
mixtures thereof. In one embodiment the disclosed technology does include a
dispersant
or mixtures thereof. The dispersant may be present as a single dispersant. The
dispersant
may be present as a mixture of two or more (typically two or three) different
dispersants,
wherein at least one may be a succinimide dispersant.
[0070] The
succinimide dispersant may be derived from an aliphatic polyamine, or
mixtures thereof. The aliphatic polyamine may be aliphatic polyamine such as
an
ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures
thereof. In
one embodiment the aliphatic polyamine may be ethylenepolyamine. In one
embodiment
the aliphatic polyamine may be chosen from ethylenediamine,
diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine
still
bottoms, and mixtures thereof.
[0071] In
one embodiment the dispersant may be a polyolefin succinic acid ester,
amide, or ester-amide. For instance, a polyolefin succinic acid ester may be a
polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A
polyolefin
succinic acid ester-amide may be a polyisobutylene succinic acid reacted with
an alcohol
(such as pentaerythritol) and an amine (such as a diamine, typically
diethyleneamine).
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[0072] The
dispersant may be an N-substituted long chain alkenyl succinimide. An
example of an N-substituted long chain alkenyl succinimide is polyisobutylene
succinimide. Typically the polyisobutylene from which polyisobutylene succinic
anhydride is derived has a number average molecular weight of 350 to 5000, or
550 to
3000 or 750 to 2500. Succinimide dispersants and their preparation are
disclosed, for
instance in US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552,
3,381,022,
3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511,
4,234,435,
Re 26,433, and 6,165,235, 7,238,650 and EP Patent Application 0 355 895 A.
[0073] The
dispersants may also be post-treated by conventional methods by a
reaction with any of a variety of agents. Among these are boron compounds
(such as
boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulphide,
aldehydes,
ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted
succinic
anhydrides, maleic anhydride, nitrites, epoxides, and phosphorus compounds. In
one
embodiment the post-treated dispersant is borated. In one embodiment the post-
treated
dispersant is reacted with dimercaptothiadiazoles. In one embodiment the post-
treated
dispersant is reacted with phosphoric or phosphorous acid. In one embodiment
the post-
treated dispersant is reacted with terephthalic acid and boric acid (as
described in US
Patent Application US2009/0054278.
[0074] In
one embodiment the dispersant may be borated or non-borated. Typically a
borated dispersant may be a succinimide dispersant. In one embodiment, the
ashless
dispersant is boron-containing, i.e., has incorporated boron and delivers said
boron to the
lubricant composition. The boron-containing dispersant may be present in an
amount to
deliver at least 25 ppm boron, at least 50 ppm boron, or at least 100 ppm
boron to the
lubricant composition. In one embodiment, the lubricant composition is free of
a boron-
containing dispersant, i.e. delivers no more than 10 ppm boron to the final
formulation.
[0075] The
dispersant may be prepared/obtained/obtainable from reaction of succinic
anhydride by an "ene" or "thermal" reaction, by what is referred to as a
"direct alkylation
process." The "ene" reaction mechanism and general reaction conditions are
summarised
in "Maleic Anhydride", pages 147-149, Edited by B.C. Trivedi and B.C.
Culbertson and
Published by Plenum Press in 1982. The dispersant prepared by a process that
includes an
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"ene" reaction may be a polyisobutylene succinimide having a carbocyclic ring
present
on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole
%, or
0 mole % of the dispersant molecules. The "ene" reaction may have a reaction
temperature of 180 C to less than 300 C, or 200 C to 250 C, or 200 C to 220 C.
[0076] The
dispersant 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 a dispersant that is a polyisobutylene succinimide having
a
carbocyclic ring present on 50 mole (N) or more, or 60 to 100 mole A of the
dispersant
molecules. Both the thermal and chlorine-assisted processes are described in
greater
detail in U.S. Patent 7,615,521, columns 4-5 and preparative examples A and B.
[0077] The
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.
[0078] The
dispersant may be present at 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or
0.5 wt % to 9 wt %, or 1 wt % to 8.5 wt % of the lubricating composition.
[0079] In
one embodiment the lubricating composition may be a lubricating
composition further comprising a molybdenum compound. The molybdenum compound
may be an antiwear agent or an antioxidant. The molybdenum compound may be be
chosen from 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, 5 ppm to 300 ppm, or 20 ppm to 250 ppm of
molybdenum.
[0080] Antioxidants include sulphurised olefins, diarylamines, alkylated
diarylamines, hindered phenols, molybdenum compounds (such as molybdenum
dithiocarbamates), hydroxyl thioethers, or mixtures thereof. In one embodiment
the
lubricating composition includes an antioxidant, or mixtures thereof. The
antioxidant may
be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt
%, or
0.5 wt % to 3 wt %, or 0.3 wt % to 1.5 wt % of the lubricating composition.
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[0081] 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
ph enyln apthyl amines.
[0082] The
hindered phenol antioxidant often contains a secondary butyl and/or a
tertiary butyl group as a sterically hindering group. The phenol group may be
further
substituted with a hydrocarbyl group (typically linear or branched alkyl)
and/or a
bridging group linking to a second aromatic group. Examples of suitable
hindered phenol
antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-
butylphenol, 4-ethyl-
2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-butylphenol or 4-buty1-2,6-di-
tert-butyl-
phenol, or 4-dodecy1-2,6-di-tert-butylphenol. In one embodiment the hindered
phenol
antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba.
A more
detailed description of suitable ester-containing hindered phenol antioxidant
chemistry is
found in US Patent 6,559,105.
[0083]
Examples of molybdenum dithiocarbamates, which may be used as an
antioxidant, include commercial materials sold under the trade names such as
Vanlubc
822'm and Molyvan'm A from R. T. Vanderbilt Co., Ltd., and Adcka Sakura-Lube
'm
S-100, S-165, S-600 and 525, or mixtures thereof
[0084] In one
embodiment the lubricating composition further includes a viscosity
modifier. The viscosity modifier is known in the art and may include
hydrogenated
styrene-butadiene rubbers, ethylene-propylene copolymers, polymethacrylates,
polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene
polymers,
polyalkyl styrenes, polyolefins, esters of maleic anhydride-olefin copolymers
(such as
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those described in International Application WO 2010/014655), esters of maleic
anhydride-styrene copolymers, or mixtures thereof.
[0085] The
dispersant viscosity modifier may include functionalised polyolefins, for
example, ethylene-propylene copolymers that have been functionalised with an
acylating
agent such as maleic anhydride and an amine; polymethacrylates functionalised
with an
amine, or styrene-maleic anhydride copolymers reacted with an amine. More
detailed
description of dispersant viscosity modifiers are disclosed in International
Publication
W02006/015130 or U.S. Patents 4,863,623; 6,107,257; 6,107,258; 6,117,825; and
US 7,790,661. In one embodiment the dispersant viscosity modifier may include
those
described in U.S. Patent 4,863,623 (see column 2, line 15 to column 3, line
52) or in
International Publication W02006/015130 (see page 2, paragraph [0008] and
preparative
examples are described paragraphs [0065] to [0073]). In one embodiment the
dispersant
viscosity modifier may include those described in U.S. Patent US 7,790,661
column 2,
line 48 to column 10, line 38.
[0086] In one
embodiment the lubricating composition of the disclosed technology
further comprises a dispersant viscosity modifier. The dispersant viscosity
modifier may
be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt %,
or 0.2 wt %
to 1.2 wt % of the lubricating composition.
[0087] In
one embodiment the friction modifier may be be chosen from long chain
fatty acid derivatives of amines, long chain fatty esters, or derivatives of
long chain fatty
epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty
alkyl tartrates;
fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty
glycolamides.
The friction modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt
%, or
0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.
[0088] As used
herein the term "fatty alkyl" or "fatty" in relation to friction modifiers
means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon
chain.
[0089]
Examples of suitable friction modifiers include long chain fatty acid
derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines
such as
condensation products of carboxylic acids and polyalkylene-polyamines; amine
salts of
alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty
alkyl tartramides;
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fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty
epoxides;
glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty
amines; borated
alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including
tertiary
hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal
salts of
alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation
products of
carboxylic acids and polyalkylene polyamines; or reaction products from fatty
carboxylic
acids with guanidine, aminoguanidine, urea, or thiourea and salts thereof
[0090]
Friction modifiers may also encompass materials such as sulphurised fatty
compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates, sunflower oil or soybean oil monoester of a polyol and an
aliphatic
carboxylic acid.
[0091] In
one embodiment the friction modifier may be a long chain fatty acid ester.
In another embodiment the long chain fatty acid ester may be a mono-ester and
in another
embodiment the long chain fatty acid ester may be a triglyceride.
[0092] The
lubricating composition optionally further includes at least one antiwear
agent. Examples of suitable antiwear agents include titanium compounds,
tartaric acid
derivatives such as tartrate esters, amides or tartrimides, oil soluble amine
salts of
phosphorus compounds, sulphurised olefins, metal dihydrocarbyldithiophosphates
(such
as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite),
phosphonates,
thiocarbamate-containing compounds, such as thiocarbamate esters,
thiocarbamate
amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-
alkyldithiocarbamyl) disulphides.
[0093] 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.
[0094] The
lubricating composition may further include a phosphorus-containing
antiwear agent. Typically the phosphorus-containing antiwear agent may be a
zinc
dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium
phosphate
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salts, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art.
The
antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or
0.5 wt %
to 0.9 wt % of the lubricating composition.
[0095]
Another class of additives includes oil-soluble titanium compounds as
disclosed in US 7,727,943 and US2006/0014651. The oil-soluble titanium
compounds
may function as antiwear agents, friction modifiers, antioxidants, deposit
control
additives, or more than one of these functions. In one embodiment the oil
soluble
titanium compound may be a titanium (IV) alkoxidc. The titanium alkoxide may
be
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 may be titanium (IV) isopropoxide. In one embodiment, the titanium
alkoxide
may be 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 may
be oleic acid.
[0096] In one
embodiment, the oil soluble titanium compound may be a titanium
earboxylate. In one embodiment the titanium (IV) carboxylate may be titanium
neodecanoate.
[0097]
Foam inhibitors that may be useful in the compositions of the disclosed
technology include polysiloxanes, copolymers of ethyl acrylate and 2-
ethylhexylacrylate
and optionally vinyl acetate; demulsifiers including fluorinated
polysiloxanes, trialkyl
phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides
and
(ethylene oxide-propylene oxide) polymers.
[0098]
Pour point depressants that may be useful in the compositions of the disclosed
technology include polyalphaolefins, esters of maleic anhydride-styrene
copolymers,
poly(meth)acryl ates, polyacryl ates or polyacryl amides.
[0099]
Demulsifiers include trialkyl phosphates, and various polymers and
copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof
different from the non-hydroxy terminated acylated polyalkylene oxide of the
disclosed
technology.
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[0100] Metal deactivators include derivatives of benzotriazoles (typically
tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles
or 2-alkyl-
dithiobenzothiazoles. The metal deactivators may also be described as
corrosion
inhibitors.
[0101] Seal swell
agents include sulpholene derivatives Exxon Necton37TM
(FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
[0102] An
engine lubricating composition in different embodiments may have a
composition as disclosed in the following table:
Additive Embodiments (wt %)
A
oxyalkylated hydrocarbyl phenol 0.01 to 5 0.05 to 3 0.1 to
1.5
p-Dodecylphenol-Free Detergent 0.1 to 9 3 to 8 3 to 5
Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to
2
Dispersant 0 to 12 0 to 8 0.5 to 6
Antioxidant 0.1 to 13 0.1 to 10 0.5 to 5
Antiwear Agent 0.1 to 15 0.1 to 10 0.3 to 5
Friction Modifier 0.01 to 6 0.05 to 4 0.1 to 2
Viscosity Modifier 0 to 10 0.5 to 8 Ito 6
Any Other Performance Additive 0 to 10 0 to 8 0 to 6
Oil of Lubricating Viscosity Balance to Balance to Balance
to
100% 100% 100%
Industrial Application
[0103] In
one embodiment the disclosed technology provides a method of lubricating
an internal combustion engine. The engine components may have a surface of
steel or
aluminium.
[0104] An
aluminium surface may be derived from an aluminium alloy that may be a
eutectic or a hyper-eutectic aluminium alloy (such as those derived from
aluminium
silicates, aluminium oxides, or other ceramic materials). The aluminium
surface may be
present on a cylinder bore, cylinder block, or piston ring having an aluminium
alloy, or
aluminium composite.
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[0105] The
internal combustion engine may or may not have an exhaust gas
recirculation system. The internal combustion engine may be fitted with an
emission
control system or a turbocharger. Examples of the emission control system
include diesel
particulate filters (DPF), or systems employing selective catalytic reduction
(SCR).
[0106] In one
embodiment the internal combustion engine may be a diesel fueled
engine (typically a heavy duty diesel engine), a gasoline fueled engine, a
natural gas
fueled engine, a mixed gasoline/alcohol fueled engine, or a hydrogen fueled
internal
combustion engine. In one embodiment the internal combustion engine may be a
diesel
fueled engine and in another embodiment a gasoline fueled engine. Diesel
fueled engines
may be fueled with a mixture of conventional diesel fuel and bio-derived
diesel fuel
(i.e. bio-diesel). In one embodiment the diesel engine fuel may comprise 5
volume
percent to 100 volume percent bio-diesel (i.e. B5 to b100); in one embodiment
the diesel
fuel comprises 5 volume percent to 50 volume percent bio-diesel or 8 volume
percent to
30 volume percent bio-diesel. In one embodiment the diesel fuel is
substantially free of
(i.e. contains less than 1 volume percent) bio-diesel. In one embodiment the
internal
combustion engine may be a heavy duty diesel engine. In one embodiment, the
internal
combustion engine may be a gasoline direct injection (GDI) engine. When the
internal
combustion engine is a gasoline engine, and the oxyalkylated group of the
oxyalkylated
hydrocarbyl phenol of the disclosed technology has formula -(R10)0-, wherein
R1 is
ethylene, propylene, butylene group, or mixtures thereof, with the proviso
that if R1
comprises ethylene groups the resultant oxyalkylated hydrocarbyl phenol is a
random or
block copolymer derived from ethylene glycol and either (i) propylene glycol
or
(ii) butylene glycol; and n is independently from 1 to 50, or 1 to 20.
[0107] The
internal combustion engine may be a 2-stroke or 4-stroke engine. Suitable
internal combustion engines include marine diesel engines, aviation piston
engines,
low-load diesel engines, and automobile and truck engines. The marine diesel
engine may
be lubricated with a marine diesel cylinder lubricant (typically in a 2-stroke
engine), a
system oil (typically in a 2-stroke engine), or a crankcase lubricant
(typically in a
4-stroke engine). In one embodiment the internal combustion engine is a 4-
stroke engine,
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and is a compression ignition engine or a positive ignition natural gas (NG)
or LPG
engine.
[0108] The
lubricant composition for an internal combustion engine may be suitable
for any engine lubricant irrespective of the sulphur, phosphorus or sulphated
ash (ASTM
D-874) content. The sulphur content of the engine oil lubricant may be 1 wt %
or less, or
0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment
the sulphur
content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt
%. The
phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt %
or less, or
0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt
% or less, or
0.05 wt % or less. In one embodiment the phosphorus content may be 0.04 wt %
to
0.12 wt %. In one embodiment the phosphorus content may be 100 ppm to 1 000
ppm, or
200 ppm to 600 ppm. The total sulphated ash content may be 0.3 wt % to 1.2 wt
%, or
0.5 wt % to 1.2 wt % or 1.1 wt % of the lubricating composition. In one
embodiment the
sulphated ash content may be 0.5 wt % to 1.2 wt % of the lubricating
composition. The
TBN (as measured by ASTM D2896) of the engine oil lubricant may be 5 mg KOH/g
to
15 mg KOH/g, or 6 mg KOH/g to 12 mg KOH/g, or 5 mg KOH/g to 10 mg KOH/g, or
7 mg KOH/g to 10 mg KOH/g.
[0109] In
one embodiment the lubricating composition may be an engine oil, wherein
the lubricating composition may be characterised as having at least one of (i)
a sulphur
content of 0.5 wt % or less, (ii) a phosphorus content of 0.12 wt % or less,
and (iii) a
sulphated ash content of 0.5 wt % to 1.1 wt % of the lubricating composition.
[0110] As
used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is
used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it
refers to a group having a carbon atom directly attached to the remainder of
the molecule
and having predominantly hydrocarbon character. Examples of hydrocarbyl groups
include: hydrocarbon substituents, including aliphatic, alicyclic, and
aromatic
substituents; substituted hydrocarbon substituents, that is, substituents
containing non-
hydrocarbon groups which, in the context of this disclosed technology, do not
alter the
predominantly hydrocarbon nature of the substituent; and hetero substituents,
that is,
substituents which similarly have a predominantly hydrocarbon character but
contain
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other than carbon in a ring or chain. A more detailed definition of the term
"hydrocarbyl
substituent" or "hydrocarbyl group" is described in paragraphs [0118] to
[0119] of
International Publication W02008147704, or a similar definition in paragraphs
[0137] to
[0141] of published application US 2010-0197536.
[0111] The
following examples provide illustrations of the disclosed technology.
These examples are non-exhaustive and are not intended to limit the scope of
the
disclosed technology.
EXAMPLES
[0112]
Inventive Preparative Example A (1 equivalents of ethylene oxide to
1 equivalent of polyisobutylene phenol): Polyisobutylene (950 Mn) phenol (600
g) and
KOH pellets (5 g) are charged to the vessel. The vessel is purged 6 times with
Nitrogen
(0-30 psi) then pressurised to 10 psi. The contents are heated to 130 C with
stirring and
the vessel is repressurised to 10 psi. Ethylene oxide (20.33 g) is added over
4 hours.
Purged cylinder lines and allowed pressure to drop to 12 psi (8 hours).
Discharged 626 g
of a golden liquid.
[0113]
Inventive Preparative Example B (1 equivalents of propylene oxide to
1 equivalent of polyisobutylene phenol): Polyisobutylene (950 Mn) phenol (600
g) and
KOH pellets (5 g) are charged to the vessel. The vessel is purged 6 times with
Nitrogen
(0-30 psi) then pressurised to 10 psi. The contents are heated to 120 C with
stirring and
the vessel is repressurised to 10 psi. Propylene oxide (26.81 g) is added over
2 hours.
Purged cylinder lines and allowed pressure to drop to 12 psi (8 hours).
Discharged 632 g
of a golden liquid.
[0114]
Inventive Preparative Example C (2 equivalents of ethylene oxide to
1 equivalent of polyisobutylene phenol): Polyisobutylene (950 Mn) phenol (600
g) and
potassium hydroxide pellets (5 g) are charged to a pressurised vessel. The
vessel is
purged 6 times with nitrogen (0-30 psi) then pressurised to 10 psi. The
contents are
heated to 130 C with stirring and the vessel is re-pressurised to 10 psi.
Ethylene oxide
(40.66g ) is added over 4 hours. The vessel is then depressurised over 8
hours. The
product yield is 646 g of a yellow liquid.
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[0115]
Inventive Preparative Example D (2 equivalents of propylene oxide to
1 equivalent of polyisobutylene phenol): Polyisobutylene (950 Mn) phenol (600
g) and
KOH pellets (5 g) are charged to the vessel. The vessel is purged 6 times with
Nitrogen
(0-30 psi) then pressurised to 10 psi. The contents are heated to 120 C with
stirring and
the vessel is repressurised to 10 psi. Propylene oxide (53.61 g) is added over
2 hours.
Purged cylinder lines and allowed pressure to drop to 12 psi (8 hours).
Discharged 659 g
of a yellow liquid.
[0116]
Inventive Preparative Example F (5 equivalents of propylene oxide to
1 equivalent of polyisobutylene phenol): Polyisobutylene (950 Mn) phenol (550
g) and
KOH pellets (4.5 g) are charged to the vessel. The vessel is purged 6 times
with Nitrogen
(0-30 psi) then pressurised to 10 psi. The contents are heated to 120 C with
stirring and
the vessel is repressurised to 10 psi. Propylene oxide (122.86 g) is added
over 4 hours.
Purged cylinder lines and allowed pressure to drop to 12 psi (8 hours).
Discharged 678 g
of a yellow liquid.
[0117] Inventive
examples A, B, C, D, and F through V are prepared in a similar
fashion and are summarized in Table 1.
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Table 1 ¨ Examples of Oxyalkylated phenols
PIB phenol Alkylene EO:PO:BO Degree of
Oxide Ratio* Alkoxylation
Example A PP-1 E0 1:0:0 1
Example B PP-1 PO 0:1:0 1
Example C PP-1 EO 1:0:0 2
Example D PP-1 PO 0:1:0 2
Example E PP-1 EO 1:0:0 5
Example F PP-1 PO 0:1:0 5
Example G PP-1 PO 0:1:0 10
Example H PP-1 BO 0:0:1 5
Example I PP-1 EO/PO 1:1:0 5
Example J PP-1 EO/B0 1:0:1 5
Example K PP-1 PO/B0 0:1:1 5
Example L PP-1 EO/P0/130 1:1:1 5
Example J PP-1 EO/B0 1:0:2 10
Example L PP-2 PO 0:1:0 2
Example M PP-2 PO 0:1:0 5
Example N PP-2 E0 1:0:0 2
Example 0 PP-2 E0 1:0:0 5
Example P PP-2 BO 0:0:1 5
Example Q PP-2 EO/PO 1:1:0 5
Example R PP-2 EO/B0 1:0:1 5
Example S PP-2 PO/B0 0:1:1 5
Example T PP-2 EO/P0/130 1:1:1 5
Example U PP-3 PO 0:1:0 5
Example V PP-4 PO 0:1:0 5
PP-1: 4-Alkylphenol where alkyl is 1000Mn Pib;
PP-2: 4-Alkylphenol where alkyl is 550Mn Pib;
PP-3: 4-Alkylphenol where alkyl is 1500Mn Pib;
PP-4: 4-Alkylphenol where alkyl is 2000Mn Pib;
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*Mixtures represent feed ratios
[0118] A set
of 5W-40 engine lubricants suitable for use in light duty diesel engines
are prepared in Group III base oil of lubricating viscosity containing the
additives
described above as well as conventional additives including polymeric
viscosity modifier,
ashless succinimide dispersant, overbased detergents, antioxidants
(combination of
phenolic ester, diarylamine, and sulphurized olefin), zinc
dialkyldithiophosphate (ZDDF'),
as well as other performance additives as follows (Table 2 and 3).
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Table 2 - Lubricating Compositions
BL1 CEX EX1 EX2 EX3 EX4 EX5 EX6
Base Oil Balance to 100%
PP-1 1
Example A 1
Example B 1
Example C 1
Example D 1
Example E 1
Example F 1
Calcium
1.35 1.35 1.35 1.35 1.35 1.35 1.35
1.35
Sulphonatel
Calcium
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Phenate2
ZDDP3 0.5 - 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Antioxidant4 2 2 2 2 2 2 2 2
Dispersant5 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9
Viscosity
1.23 1.23 1.23 1.23 1.23 1.23 1.23
1.23
Modifier6
Additional
0.36 0.36 0.36 0.36 0.36 0.36 0.36
0.36
additives'
%Phosphorus 0.045 0.045 0.045 0.045 0.045 0.045 0.045 0.045
%Sulphur 0.18 0.18 0.18 0.18 0.18 0.18 0.18
0.18
I Mixture of overbased calcium sulphonate detergents
2 Mixture of calcium phen ate detergents derived from p-dodeylphenol
3 Secondary ZDDP derived from mixture of C3 and C6 alcohols
4 Combination of phenolic and atylarnine antioxidants
5 Succinimide dispersant derived from polyisobutylene
6 Styrene-diene block copolymer
7 Additional additives include friction modifier, anti-foam agents, and
pourpoint depressants
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Table 3 ¨ 5W-30 Lubricating Compositions
BL2 BL3 EX7
Base Oil Balance to 100%
Example F 0 0 1.5
Calcium Sulphonatel 0.91 0.91 0.91
ZDDP2 0.86 0.86 0.86
Antioxidant3 1.2 1.75 1.75
Dispersant4 3.02 3.02 3.02
Viscosity Modificr5 0.57 0.57 0.57
Additional additives 0.26 0.26 0.26
%Phos 0.076 0.076 0.076
%Sulphur 0.21 0.21 0.21
1 Overbased calcium alkylbenzene sulphonate detergent
2 Secondary ZDDP derived from mixture of C3 and C6 alcohols
3 Combination of phenolic and arylarnine antioxidants
4 Succinimide dispersant derived from polyisobutylene
5 Olefin copolyiner
6 Additional additives include friction modifier, anti-foam agents, and
pourpoint depressants
[0119] The
formulations are evaluated in both bench oxidation-deposit tests as well
as a fired engine test designed to evaluate deposit control of lubricants.
[0120] The
lubricating compositions are tested in a Panel Coker heated to 325 C,
with a sump temperature of 105 C, and a splash/bake cycle of 120 s/45 s. The
airflow is
350 ml/min, with a spindle speed of 1000 rpm and the test lasts for 4 hours.
The oil is
splashed onto an aluminum panel which is then optically rated by computer.
Performance
ranges from 0% (black panel) to 100% (clean panel).
[0121] The
lubricating compositions are also evaluated in the Volkswagen (VW) TDI
engine test. The test procedure follows the PV1452 and CEC L-78-T-99 methods
as laid
out in the ACEA oil sequences. This engine test rates lubricants on piston
cleanliness
(merit) and ring sticking.
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Table 4- Deposit Engine Test
BL2 EX7 Difference
VW TDI Piston Merit 54 61 7
[122] The lubricating compositions are also evaluated in the Sequence
IIIG engine
test following the test procedure of ASTM D7320-14 (entitled Standard Test
Method for
Evaluation of Automotive Engine Oils in the Sequence IIIG, spark-ignition
engine. The
test measures oxidation, and weighted piston deposits (WPD). Typically better
results
are obtained for samples having a higher rating. The results obtained are:
Table 5- Deposit Engine Test
BL3 EX7 Difference
IIIG WPD 4.1 5.8 1.7
[123] The disclosed technology is capable of at least one of (i) control of
fuel
economy, (ii) control of corrosion, (iii) cleanliness (typically control of
deposits,
typically control/reduction of soot), and (iv) control of bore wear, typically
in a passenger
car internal combustion engine.
[124] It is known that some of the materials described above may interact
in the
final formulation, so that the components of the final formulation may be
different from
those that are initially added. The products formed thereby, including the
products
formed upon employing lubricant composition of the disclosed technology in its
intended
use, may not be susceptible of easy description. Nevertheless, all such
modifications and
reaction products are included within the scope of the disclosed technology;
the disclosed
technology encompasses lubricant composition prepared by admixing the
components
described above.
[125] 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
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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 disclosed
technology may be used together with ranges or amounts for any of the other
elements.
[0126]
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the specification.
Therefore, it is to be
understood that the invention disclosed herein is intended to cover such
modifications as
fall within the scope of the appended claims.
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