Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Composition Containing a Block Copolymer and a Method of Lubricating an
Internal Combustion Engine
FIELD OF INVENTION
[0001] The invention provides a lubricating composition containing an oil
of lubricating viscosity and a block copolymer. The invention further relates
to
a method of lubricating an internal combustion engine by lubricating the
engine
with the lubricating composition. The invention further relates to the use of
the
block copolymer as an emulsifier and/or pour point depressant.
BACKGROUND OF THE INVENTION
100021 Lubricants are often exposed to contaminant amounts of water. The
contaminant amounts of water are believed to be caused by ingress of water
through equipment seals during operation, or from combustion by-products that
pass into the crankcase via blow-by. The water may form a second layer in the
lubricant. Typically to reduce the formation of the second layer emulsifiers
and/or dispersants are employed. If the water concentration becomes high
enough, an emulsion results. If the emulsion is unstable, the contaminant
water
may then cause additional difficulties such as corrosion. The corrosion may be
from copper or lead bearings, or iron.
[0003] In addition to the need for an emulsifier, lubricant base oils may
also
contain waxy components. Waxes may agglomerate and cause accumulation of
crystals in a lubricant. When this occurs, problems arising include reduced
low
temperature oil pumpability, poorer cold temperature properties or reduced
fuel
economy. Accordingly, in one embodiment it may also be desirable to employ
a pour point depressant that reduces wax agglomeration.
[0004] In flexible fuel vehicles (FFVs) the internal combustion engine is
designed to run on gasoline or a blend of up to 85% ethanol (E85). Except for
a few engine and fuel system modifications, they are identical to gasoline-
only
models. Traditionally, dispersants are designed to stabilise contaminants in
the
engine oil of gasoline-fuelled cars. Fuelling with E85 introduces the
potential
to transform the engine oil into a milky emulsion. In order to overcome the
formation of an unstable milky emulsion, it would be desirable to employ an
emulsifier.
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[0005] International publication W02006/047393 discloses linear and star
RAFT polymers as viscosity index improvers in a variety of lubricants. The
RAFT polymers may have a variety of architectures including diblock
copolymers. All of polymers are derived from C12-15 alkyl (meth)acrylates.
There is no disclosure or teaching of linear or star polymers having
emulsifier
and/or pour point depressant properties.
[0006] US Patent Application 2006/0189490 discloses a lubricating
composition containing base oil and at least one additive having friction-
modifying properties. The additive is a linear diblock copolymer which
includes hydrophobic segments P and polar segments D, said hydrophobic
segments being obtained by polymerisation of monomer compositions which
comprises 0 to 40 % of C1_5 alkyl (meth)acrylates, 50 to 100 % of C6_10 alkyl
(meth)acrylates, and 0 to 50 A of a polar group containing ester, thioester
or
amide functionality. All of the examples disclose C12-15 alkyl
(meth)acrylates.
There is no disclosure or teaching of linear or star polymers having
emulsifier
and/or pour point depressant properties.
SUMMARY OF THE INVENTION
[0007] The inventors of this invention have discovered that a lubricating
composition containing a block copolymer and method as disclosed herein is
capable of providing acceptable levels of at least one of (i) emulsifying
properties, and (ii) pour point depressant properties. In one embodiment the
lubricating composition containing the block copolymer provides both
emulsifying properties and pour point depressant properties.
[0008] As used herein, the term "polar" in the state of the art is used in
the
ordinary sense of the word and is also known to mean hydrophilic.
[0009] In one embodiment the invention provides a lubricating composition
comprising an oil of lubricating viscosity and a diblock copolymer, wherein
the
diblock copolymer comprises:
(a) a hydrophobic first block having C1_30 alkyl (meth)acrylic units,
wherein at least 50 wt % of the C130 alkyl (meth)acrylic units are C1215 alkyl
(meth)acrylic units, and up to 50 wt % of the C1_10 alkyl (meth)acrylic units
are
C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the
C1_30
alkyl (meth)acrylic units have an average total number of carbon atoms of at
least 8; and
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(b) a second block having (meth)acrylic units which further have a non-
carbonyl heteroatom-containing group providing a polar group to such units,
whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
first block.
[0010] The second block having (meth)acrylic units which further have a
non-
carbonyl heteroatom-containing group providing a polar group to such units,
whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
first block, may also be described as a second block having (meth)acrylic
units
further having a heteroatom group providing a polar group.
MOM In one embodiment the invention provides a lubricating composition
comprising an oil of lubricating viscosity and a diblock copolymer, wherein
the
diblock copolymer comprises:
(a) a hydrophobic first block having C1_30 alkyl (meth)acrylic units,
wherein at least 50 wt % of the C1_30 alkyl (meth)acrylic units are C12_15
alkyl
(meth)acrylic units, and up to 50 wt % of the C1_30 alkyl (meth)acrylic units
are
C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the
C1_30
alkyl (meth)acrylic units have an average total number of carbon atoms of at
least 8; and
(b) a second block having (meth)acrylic units which further have a non-
carbonyl heteroatom-containing group providing a polar group to such units,
whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
first block.
[0012] In one embodiment the invention provides a diblock copolymer
product (and optionally a lubricating composition) obtained/obtainable by a
process comprising:
(1) contacting:
(i) a free radical initiator;
(ii) a chain transfer agent (typically containing a thiocarbonyl
thio group useful in RAFT polymerisation processes); and
(iii) one or more C10 alkyl (meth)acrylic monomer units,
wherein at least 50 wt % of the C1_30 alkyl (meth)acrylic monomer units
contain C12-15 alkyl (meth)acrylic units, and up to 50 wt % of the Ci_3o
alkyl (meth)acrylic units are C16_2o alkyl (meth)acrylic units, with the
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proviso that alkyl groups of the C1_30 alkyl (meth)acrylic units have an
average total number of carbon atoms of at least 8, to form a polymer;
wherein the process of step (1) is typically a controlled radical or other
living
polymerisation process with living characteristics (for instance a controlled
radical polymerisation process); and at least about 50 wt % of the polymer
chains from step (1) contain a reactive end group capable of reacting with a
polyvalent coupling agent;
(2) optionally contacting the polymer of step (1) with a polymerisation
inhibitor;
(3) contacting the polymer of step (1) or step (2) with one or more
(meth)acrylic units typically at least 50 wt % or at least 75 wt % of the said
units further containing a heteroatom-containing group; and
(4) optionally mixing the polymer of step (3) with an oil of lubricating
viscosity to form a lubricating composition.
[0013] In different embodiments the Ci6_20 alkyl (meth)acrylic units may
be
C16-18 alkyl (meth)acrylic units, or C18-20 alkyl (meth)acrylic units. The C16-
20
alkyl (meth)acrylic units may also contain up to 10 wt % (or typically up to 5
wt %) of C14 alkyl (meth)acrylic units. In one embodiment the C16-20 alkyl
(meth)acrylic units may be in the form of a mixture of (meth)acrylic
compounds having alkyl groups containing 16 to 20, or 16 to 18 carbon atoms.
[0014] In the process described above, the first step of the process may
be
performed in the presence of a mineral oil, synthetic oil, hexane, toluene,
tetrahydrofuran, or other known polymerisation solvents.
[0015] In one embodiment the invention provides a diblock copolymer
product (and optionally a lubricating composition) obtained/obtainable by a
process comprising:
(I) contacting:
(i) a free radical initiator;
(ii) a chain transfer agent (typically containing a thiocarbonyl
thio group useful in RAFT polymerisation processes); and
(iii) with one or more (meth)acrylic units typically at least 50 wt
% or at least 75 wt % of the said units further having a heteroatom-
containing group,
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wherein the process of step (1) is typically a controlled radical or other
living
polymerisation process with living characteristics; and at least about 50 wt %
of the polymer chains from step (1) contain a reactive end group capable of
reacting with a polyvalent coupling agent;
(2) optionally contacting the polymer of step (1) with a
polymerisation inhibitor;
(3) contacting the polymer of step (1) or step (2) with one or
more C1_30 alkyl (meth)acrylic monomer units, wherein at least 50 wt %
of the C1_30 alkyl (meth)acrylic monomer units contain C12-15 alkyl
(meth)acrylic units, and up to 50 wt % of the C1_30 alkyl (meth)acrylic
units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl
groups of the C1_30 alkyl (meth)acrylic units have an average total
number of carbon atoms of at least 8, to form a polymer; and
(4) optionally mixing the polymer of step (3) with an oil of
lubricating viscosity to form a lubricating composition.
[0016] In the process described above, the first step of the process may
be
performed in the presence of a solvent such as toluene or tetrahydrofuran.
[0017] The processing temperatures, pressures and reagents are known to a
person skilled in the art of controlled radical polymerisation techniques.
References describing such materials include W02006/047393 and the various
references disclosed herein below in the description of the diblock copolymer.
[0018] In one embodiment the invention provides block copolymer obtained
(or obtainable) by the process described above.
[0019] In one embodiment the invention provides a method of lubricating a
flexible fuel vehicle (flex fuel vehicle or FFV) internal combustion engine
comprising supplying to the engine a lubricating composition comprising an oil
of lubricating viscosity and a block copolymer, wherein the block copolymer
comprises:
(a) a hydrophobic first block having C1_30 alkyl (meth)acrylic units, with
the proviso that alkyl groups of the C130 alkyl (meth)acrylic units have an
average total number of carbon atoms of at least 8; and
(b) a second block having (meth)acrylic units which further have a non-
carbonyl heteroatom-containing group providing a polar group to such units,
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whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
first block.
[0020] A person skilled in the art will appreciate that the flexible fuel
vehicle may be fuelled with gasoline typically containing 5 wt % to 85 wt %,
or
vvrt % up to 85 wt %, or 15 wt % to up to 85 wt % alcohol. The alcohol may
for instance be ethanol.
[0021] The hydrophobic first block may contain 0 wt % to 5 wt % of a
hydrophilic monomer (i.e., units derived from a monomer with a polar group
such as a monomer containing a heteroatom group derived from a nitrogen or
oxygen containing group. Monomers of this type are discussed in more detail
below. In one embodiment the hydrophobic first block may contain 0 wt % a
hydrophilic monomer.
[0022] In one embodiment the invention provides a method of lubricating an
internal combustion engine comprising supplying to the engine a lubricating
composition comprising an oil of lubricating viscosity and a block copolymer,
wherein the block copolymer comprises:
(a) a hydrophobic first block having C1_30 alkyl (meth)acrylic units,
wherein at least 50 wt % of the C1_30 alkyl (meth)acrylic units are C12_15
alkyl
(meth)acrylic units, and up to 50 wt % of the Ci_30 alkyl (meth)acrylic units
are
C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the
C1_30
alkyl (meth)acrylic units have an average total number of carbon atoms of at
least 8; and
(b) a second block having (meth)acrylic units which further have a non-
carbonyl heteroatom-containing group providing a polar group to such units,
whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
first block.
[0023] In one embodiment the invention provides for the use of a block
copolymer comprising:
(a) a hydrophobic first block having C1_30 alkyl (meth)acrylic units, with
the proviso that alkyl groups of the C130 alkyl (meth)acrylic units have an
average total number of carbon atoms of at least 8; and
(b) a second block having (meth)acrylic units which further have a non-
carbonyl heteroatom-containing group providing a polar group to such units,
whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
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first block providing a polar group such that the block copolymer may be an
emulsifier and/or pour point depressant.
[0024] In one embodiment the invention provides for the use of a block
copolymer comprising:
(a) a hydrophobic first block having C1_30 alkyl (meth)acrylic units,
wherein at least 50 wt % of the C1_30 alkyl (meth)acrylic units are C12_15
alkyl
(meth)acrylic units, and up to 50 wt % of the C1_20 alkyl (meth)acrylic units
are
C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the
Ci_30
alkyl (meth)acrylic units have an average total number of carbon atoms of at
least 8; and
(b) a second block having (meth)acrylic units which further have a non-
carbonyl heteroatom-containing group providing a polar group to such units,
whereby said second block exhibits greater hydrophilicity than does the
hydrophobic
first block such that the block copolymer may be an emulsifier and/or pour
point
depressant.
[0025] Typically the block copolymer may be an emulsifier and/or pour
point
depressant in an internal combustion engine.
[0026] Pour point depressant properties typically occur when the block
copolymer contains C16_2o alkyl (meth)acrylic units.
100271 Emulsifier properties may occur for any block copolymer composition
of
the present invention.
[0028] Emulsifier and pour point depressant properties typically occur
when
the diblock block copolymer contains C16-2o alkyl (meth)acrylic units, and C12-
15 alkyl (meth)acrylic units.
[0029] The internal combustion engine may be operated on gasoline, diesel,
biofuels, ethanol, or mixtures thereof. In one embodiment the internal
combustion
engine may be operated on a mixture of gasoline and ethanol. The internal
combustion engine may be referred to as a flexible fuel vehicle engine.
[0030] Typically the block copolymer disclosed herein may be a linear
diblock
copolymer.
[0031] In one embodiment the lubricating composition may be further
characterised as having at least one of (i) a sulphur content of 0.8 wt % or
less,
(ii) a phosphorus content of 0.2 wt % or less, or (iii) a sulphated ash
content of
2 wt % or less.
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[0032] In one embodiment the lubricating composition may be further
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
1.5
wt % or less.
[0033] In one embodiment the lubricating composition further includes at
least one of a friction modifier, a viscosity modifier, an antioxidant, an
overbased detergent, a succinimide dispersant, a pour point depressant, or
mixtures thereof.
[0034] In one embodiment the lubricating composition further includes a
viscosity modifier and an overbased detergent.
[0035] In one embodiment the lubricating composition further includes an
overbased detergent and a succinimide dispersant.
[0036] In one embodiment the invention provides a method for lubricating
an
engine oil comprising supplying to the engine a lubricating composition as
disclosed herein.
[0037] The block copolymer may be used at 0.01 wt % to 0.5 wt %, or 0.05
to 0.3 wt % of the lubricating composition disclosed herein.
DETAILED DESCRIPTION OF THE INVENTION
[0038] The present invention provides a lubricating composition and a
method for lubricating a mechanical device as disclosed above. Typically the
mechanical device may be an internal combustion engine.
Block Copolymer
[0039] As used herein the term "(meth)acrylic units" includes both acrylic
and
methacrylic units and the units are derived from an appropriate monomer. The
(meth)acrylic units typically include methacrylates, acrylates,
methacrylamides,
acrylamides, or mixtures thereof.
[0040] As described hereinafter the molecular weight of the block
copolymer has been determined using known methods, such as GPC analysis
using polystyrene standards. Methods for determining molecular weights of
polymers are well known. The methods are described for instance: (i) P.J.
Flory,
"Principles of Polymer Chemistry", Cornell University Press 91953), Chapter
VII,
pp 266-315; or (ii) "Macromolecules, an Introduction to Polymer Science", F.
A.
Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312.
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[0041] The block
copolymer may be a diblock, a triblock, or a higher block
copolymer.
[0042] The diblock
copolymer may have a AB composition, where A is a
hydrophobic unit, and B is a hydrophilic unit.
[0043] The
triblock copolymer may have ABA or BAB, ABA', or BAB',
where A and B are defined above, and A' and B' represent hydrophobic and
hydrophilic units different from A and B respectively.
[0044] Each block
may be a tapered copolymer, a random copolymer, a
sequential copolymer, or may have a random or sequential distribution of two
or more monomer units.
[0045] The weight
average molecular weight of the block copolymer may be
in the range of 1000 to 400,000, or 1000 to 150,000, or 15,000 to 100,000.
[0046] The weight
ratio of the second block to the first block may be in the
range of 1:2 to 1:100, or 1:4 to 1:30, or 1:6 to 1:18.
[0047] The length
of the first block to the second block may have a ratio of
10:1 to 1:10, or 6:1 to 1:2.
[0048] The C1_30
alkyl (meth)acrylic units may be derived from an alkyl
(meth)acrylate.
[0049] The alkyl
(meth)acrylate includes for example compounds derived
from saturated alcohols, such as methyl methacrylate, butyl methacrylate,
2-methylpentyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-butyloctyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl
(meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-tert-butyl-
heptyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate,
undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)-
acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyl-
trid ecyl (meth)acryl ate, tetradecyl (meth )acrylate , pentad ecyl (m
eth)acryl ate,
hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl
(meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl
(meth)acryl ate, 5-ethyl octad ecyl (m
eth)acryl ate, 3-isopropyloctadecyl -
(meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl
(meth)acrylate, cetyleicosyl (meth)acrylate, stearyleicosyl (meth)acrylate,
docosyl (meth)acrylate and/or eicosyltetratriacontyl (meth)acrylate; (meth)-
acrylates derived from unsaturated alcohols, such as oleyl (meth)acrylate; and
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cycloalkyl (meth)acrylates, such as 3-viny1-2-butylcyclohexyl (meth)acrylate
or
bornyl (meth)acrylate.
[0050] The alkyl (meth)acrylates with long-chain alcohol-derived groups
may be obtained, for example, by reaction of a (meth)acrylic acid (by direct
esterification) or methyl methacrylate (by transesterification) with long-
chain
fatty alcohols, in which reaction a mixture of esters such as (meth)acrylate
with
alcohol groups of various chain lengths is generally obtained. These fatty
alcohols include Oxo Alcohol 7911, Oxo Alcohol 7900 and Oxo Alcohol
1100 of Monsanto; Alphano10 79 of ICI; Nafol0 1620, Alfol0 610 and Alfol0
810 of Condea (now Sasol); Epalt 610 and Epal(R) 810 of Ethyl Corporation;
Linevol0 79, Linevol0 911 and Dobano10 25 L of Shell AG; Lial0 125 of
Condea Augusta, Milan; Dehydad0 and Lorol0 of Henkel KGaA (now Cognis)
as well as LinopoW 7-11 and Acropolt 91 of Ugine Kuhlmann.
[0051] In one embodiment the block copolymer may be a methacrylate
polymer.
[0052] The hydrophobic first block may contain 70 wt % or more, or 80 wt
% or more of the C1_30 alkyl (meth)acrylic units containing C12-15 alkyl
(meth)acrylic units.
[0053] The hydrophobic first block may contain up to 30 wt %, or up to 20
wt % of the C1_30 alkyl (meth)acrylic units containing C16-20 alkyl
(meth)acrylic
units.
[0054] In one embodiment the hydrophobic first block contains C1_30 alkyl
(meth)acrylic units, wherein at least 70 wt % of the C1_30 alkyl (meth)acrylic
units may be C12-15 alkyl (meth)acrylic units, and up to 30 wt % of the C1_30
alkyl (meth)acrylic units are Ci6_20 alkyl (meth)acrylic units, with the
proviso
that alkyl groups of the C1_30 alkyl (meth)acrylic units have an average total
number of carbon atoms of at least 8 (or at least 10 carbon atoms).
[0055] In one embodiment the hydrophobic first block contains C1_30 alkyl
(meth)acrylic units, wherein at least 80 wt % of the Ci_30 alkyl (meth)acrylic
units may be C1215 alkyl (meth)acrylic units, and up to 20 wt % of the Ci 30
alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the
proviso
that alkyl groups of the C1_30 alkyl (meth)acrylic units have an average total
number of carbon atoms of at least 8 (or at least 10 carbon atoms).
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[0056] In one embodiment the hydrophobic first block contains C1_10 alkyl
(meth)acrylic units, wherein at least 50 wt % to 99 wt % of the C1_30 alkyl
(meth)acrylic units are C12_15 alkyl (meth)acrylic units, and 1 up to 50 wt %
of
the C1_30 alkyl (meth)acrylic units are C16_20 alkyl (meth)acrylic units, with
the
proviso that alkyl groups of the C1_30 alkyl (meth)acrylic units have an
average
total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
[0057] In one embodiment the hydrophobic first block contains C1_30 alkyl
(meth)acrylic units, wherein at least 75 wt % to 95 wt % of the C1_30 alkyl
(meth)acrylic units are C12_15 alkyl (meth)acrylic units, and 5 up to 25 wt %
of
the C1_30 alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with
the
proviso that alkyl groups of the C1_30 alkyl (meth)acrylic units have an
average
total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
[0058] In one embodiment the hydrophobic first block contains Ci_30 alkyl
(meth)acrylic units, wherein at least 80 wt % to 95 wt % of the C1_30 alkyl
(meth)acrylic units are C12_15 alkyl (meth)acrylic units, and 1 up to 20 wt %
of
the C1_30 alkyl (meth)acrylic units are C16_2o alkyl (meth)acrylic units, with
the
proviso that alkyl groups of the Ci_30 alkyl (meth)acrylic units have an
average
total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
[0059] The second block having (meth)acrylic units have a heteroatom-
containing group providing the polar group, with the heteroatom including
sulphur, nitrogen, non-carbonyl oxygen, phosphorus, or mixtures thereof. In
one embodiment the heteroatom may be nitrogen. The term "non-carbonyl
oxygen" is not meant to exclude the presence of a carbonyl oxygen, but rather
to indicate that if such is present , there will also be a heteroatom that is
not a
carbonyl oxygen (that is, neither an oxygen atom of an aldehyde, ketone or
either oxygen atoms of a carboxylic acid or ester).
[0060] In one embodiment the copolymer of the invention further includes a
heteratom group derived from a nitrogen or oxygen containing group. The
group may be derived from a nitrogen or oxygen containing compound capable
of being incorporated during copolymerisation.
[0061] The nitrogen or oxygen containing group may be derived from an
aminoalkyl (meth)acrylamide or a nitrogen containing (meth)acrylate monomer
that may be represented by the formula:
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R2 CH2
Z
R2
\R1/0
wherein
Q is hydrogen or methyl and, in one embodiment, Q is methyl;
Z is an N-H group or an NR2 group or 0 (oxygen);
each R2 is independently hydrogen or a hydrocarbyl group containing 1
to 8, or 1 to 4 carbon atoms;
each RI is independently hydrogen or a hydrocarbyl group containing 1
to 2 carbon atoms and, in one embodiment, each R1 is hydrogen; and
g is an integer in ranges including 1 to 6, or 1 to 3.
[0062] Examples of suitable nitrogen-containing compounds capable of
being incorporated into the copolymer include N,N-dimethylacrylamide,
N-vinyl carbonamides (such as, N-vinyl-formamide, N-vinylacetoamide,
N-vinyl propionamides, N-vinyl hydroxyacetoamide, vinyl pyridine, N-vinyl
imidazole, N-vinyl pyrrolidinone, N-vinyl caprolactam, dimethylaminoethyl
acrylate, dimethylaminoethyl methacrylate, dimethylaminobutylacrylamide,
dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, dimethyl-
aminopropylacrylamide, dimethyl aminopropylmethacryl amide, dimethylamino-
ethylacrylamide or mixtures thereof.
[0063] In one embodiment the heteratom group derived from a nitrogen
containing group may include dimethylaminoethyl acrylate, dimethyl-
aminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylamino-
propyl acrylate, dimethylaminopropylacrylamide, dimethylaminopropyl-
methacrylamide, nitrites of (meth)acrylic acid and other nitrogen-containing
(meth)acrylates, such as N-(methacryloyloxyethyl)diisobutyl ketimine, N-
(methacryloyloxyethyl)dihexadecyl ketimine, methacryloylamidoacetonitrile,
2-methacryloyloxyethylmethylcyanamide, cyanomethyl methacrylate, or
mixtures thereof.
[0064] Examples of suitable non-carbonyl oxygen containing compounds
capable of being incorporated into the copolymer include hydroxyalkyl
(meth)acrylates such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl
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methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-
dimethyl- 1,6-hexanediol (meth)acrylate, 1, 10- de
cane diol (meth)acrylate,
carbonyl-containing methacrylates such as 2-carboxyethyl methacrylate,
carboxymethyl methacrylate, oxazolidinylethyl methacryl ate, N-(methacryloyl-
oxy)formamide, acetonyl methacrylate, N-methacryloylmorpholine, N-
methacryloy1-2-pyrrolidinone, N-(2-methacryloyloxyethyl)-2-pyrrolidinone, N-
(3 -m ethacryloyloxypropy1)-2-pyrroli dinon e, N-(2-m ethacryl oyl
oxypentadecy1)-
2-pyrrolidinone, N-(3-methacryloyloxyheptadecy1)-2-pyrrolidinone; glycol
dimethacrylates such as 1,4-butanediol methacrylate, 2-butoxyethyl
methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate,
or mixtures thereof.
[0065] Other
examples of suitable non-carbonyl oxygen containing
compounds capable of being incorporated into the copolymer include
methacrylates of ether alcohols, such as tetrahydrofurfuryl methacrylate,
vinyloxyethoxy ethyl methacrylate, methoxyethoxyethyl methacrylate, 1-
butoxypropyl methacrylate, 1-methyl-(2-vinyloxy)ethyl methacrylate, cyclo-
hexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxy-
methyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-
ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl
methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-
ethoxyethyl methacrylate, ethoxymethyl methacrylate and ethoxylated (meth)-
acrylates which typically have 1 to 20, or 2 to 8, ethoxy groups, or mixtures
thereof.
[0066] The block
copolymer may be obtained/obtainable from controlled
radical or other living polymerisation techniques such as RAFT (Reversible
Addition Fragmentation Transfer), ATRP (Atom Transfer Radical
Polymerisation), nitroxide-mediated and anionic. These
polymerisation
techniques are known to a person skilled in the art.
[0067] Anionic polymerisation processes may be useful when the
heteroatom of the second block contains a nitrogen heteroatom (from an amine)
when steps are taken to quench the amine during polymerisation. Such
techniques are known to a person skilled in the art.
[0068] More
detailed descriptions of polymerisation mechanisms and
related chemistry is discussed for nitroxide-mediated polymerisation (Chapter
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10, pages 463 to 522) of in the Handbook of Radical Polymerization, edited by
Krzysztof Matyjaszewski and Thomas P. Davis, 2002, published by John Wiley
and Sons Inc (hereinafter referred to as "Matyjaszewski et al.").
[0069] In one embodiment the controlled radical polymerisation process
employed to prepare the block copolymer may be a RAFT process. A detailed
description of RAFT processes is described in W02006/047393 (see whole
document for reagents, and reference to linear polymers) or US Patent
Application 2006/0189490 (see paragraphs [0128] to [0131].
[0070] In one embodiment the controlled radical polymerisation process
employed to prepare the block copolymer may be an ATRP process. In ATRP
polymerisation, groups that may be transferred by a radical mechanism include
halogens (from a halogen-containing compound) or various ligands. A more
detailed review of groups that may be transferred is described in US Patent
6,391,996, or paragraphs 61 to 65 of US Patent Application 2005/038146.
Another detailed description of ATRP processes is described in US Patent
Application 2006/0189490 (sec paragraphs [0102] to [0126]).
[0071] More detailed descriptions of polymerisation mechanisms and
related chemistry is discussed for ATRP (Chapter 11, pages 523 to 628) and
RAFT (Chapter 12, pages 629 to 690) in Matyjaszewski et al.
[0072] In one embodiment the controlled radical polymerisation process
may be a RAFT process.
[0073] In RAFT polymerisation, chain transfer agents are important. A
more detailed review of suitable chain transfer agents is found in paragraphs
66
to 71 of US Patent Application US 2005/038146.
[0074] In one embodiment a suitable RAFT chain transfer agent includes
2-Dodecylsulphanylthiocarbonylsulphany1-2-methyl-propionic acid butyl ester,
cumyl dithiobenzoate or mixtures thereof.
Oils of Lubricating Viscosity
[0075] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil derived from
hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined and re-
refined oils and mixtures thereof.
[0076] Unrefined oils are those obtained directly from a natural or
synthetic
source generally without (or with little) further purification treatment.
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[0077] 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.
[0078] 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.
[0079] Natural oils useful in making the inventive lubricants include
animal
oils, vegetable oils (e.g., castor oil), mineral lubricating oils such as
liquid
petroleum oils and solvent-treated or acid-treated mineral lubricating oils of
the
paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived
from coal or shale or mixtures thereof.
[0080] Synthetic lubricating oils are useful and include hydrocarbon oils
such as polymerised and interpolymerised olefins (typically hydrogenated)
(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); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl
ethers and alkylated diphenyl sulphides and the derivatives, analogs and
homologs thereof or mixtures thereof.
[0081] Other synthetic lubricating oils include polyol esters (such as
Prolube03970), diesters, liquid esters of phosphorus-containing acids (e.g.,
tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane
phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may 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.
[0082] 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 %,
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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 (PA0s)); and Group V (all others not included
in Groups I, IT, III, or IV). The oil of lubricating viscosity includes an API
Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof.
Often the oil of lubricating viscosity is an API Group I, Group IT, Group III,
Group IV oil or mixtures thereof.
[0083] The amount of the oil of lubricating viscosity present is typically
the
balance remaining after subtracting from 100 wt (Yo the sum of the amount of
the compound of the invention and the other performance additives.
[0084] The lubricating composition may be in the form of a concentrate
and/or a fully formulated lubricant. If the lubricating composition of the
invention comprising the additives disclosed herein above 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
[0085] The composition optionally includes other performance additives.
The other performance additives comprise at least one of metal deactivators,
viscosity modifiers, detergents, friction modifiers, antiwear agents,
corrosion
inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure
agents,
antioxidants, foam inhibitors, demulsifiers, emulsifiers (other than the block
copolymer of the invention), pour point depressants (other than the block
copolymer of the invention), seal swelling agents and mixtures thereof.
Typically, fully-formulated lubricating oil will contain one or more of these
performance additives.
[0086] In one embodiment the lubricating composition of the invention
further includes at least one of a friction modifier, a viscosity modifier, an
antioxidant, an overbased detergent, a succinimide dispersant, or mixtures
thereof.
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[0087] In one
embodiment the lubricating composition of the invention
further includes at least one of a viscosity modifier, an antioxidant, an
overbased detergent, a succinimide dispersant, or mixtures thereof.
Detergents
[0088] In one
embodiment the lubricating composition further includes
known neutral or overbased detergents. Suitable detergent substrates include
ph enates, sulphur containing phenates, sulphonates, salixarates, salicylates,
carboxylic acid, phosphorus acid, mono- and/or di- thiophosphoric acids, alkyl
phenols, sulphur coupled alkyl phenol compounds, or saligenins. Various
overbased detergents and their methods of preparation are described in greater
detail in numerous patent publications, including W02004/096957 and
references cited therein. The detergent substrate may be salted with a metal
such as calcium, magnesium, potassium, sodium, or mixtures thereof.
[0089] In one
embodiment the overbased detergent is selected from the
group consisting of phenates, sulphur containing phenates, sulphonates,
salixarates, salicylates, and mixtures thereof. Typically the selected
overbased
detergent include calcium or magnesium phenates, sulphur containing phenates,
sulphonates, salixarates, saliginens, salicylates, or mixtures thereof.
[0090] In one
embodiment the detergent may be a calcium salicylate. In one
embodiment the detergent may be a calcium sulphonate. In one embodiment
the invention the detergent may be a mixture of a calcium sulphonate and a
calcium salicylate.
[0091] In one
embodiment the detergent may be a calcium phenate. In one
embodiment the detergent may be a calcium sulphonate. In one embodiment
the invention the detergent may be a mixture of a calcium sulphonate and a
calcium phenate.
[0092] When the
lubricating composition is not lubricating a 2-stroke
marine diesel engine the detergent may be present (on an oil free basis i.e.,
an
actives basis) at 0 wt % to 10 wt %, or 0.1 wt % to 8 wt %, or 1 wt % to 4 wt
%
of the lubricating composition. When the lubricating composition is
lubricating
a 2-stroke marine diesel engine the amount of detergent (on an oil free basis
i.e., an actives basis)may be 0 wt % to 40 wt %, or 2 wt % to 35 wt %, or 5 wt
(Yo to 30 wt % of the lubricating composition.
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Dispersants
[0093] Dispersants are often known as ashless-type dispersants because,
prior to mixing in a lubricating oil composition, they do not contain ash-
forming metals and they do not normally contribute any ash forming metals
when added to a lubricant and polymeric dispersants. Ashless type dispersants
are characterised by a polar group attached to a relatively high molecular
weight hydrocarbon chain. Typical ashless dispersants include N-substituted
long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl
succinimides include polyisobutylene succinimide with number average
molecular weight of the polyisobutylene substituent in the range 350 to 5000,
or 500 to 3000. Succinimide dispersants and their preparation are disclosed,
for instance in US Patent 3,172,892 or US Patent 4,234,435. Succinimide
dispersants are typically the imide formed from a polyamine, typically a
pa ly(ethyleneamine).
[0094] In one embodiment the invention further includes at least one
dispersant which is a polyisobutylene succinimide derived from a
polyisobutylene with number average molecular weight in the range 350 to 5000,
or 500 to 3000. The polyisobutylene succinimide may be used alone or in
combination with other dispersants.
[0095] In one embodiment the invention further includes at least one
dispersant derived from polyisobutylene succinic anhydride, an amine and zinc
oxide to form a polyisobutylene succinimide complex with zinc. The
polyisobutylene succinimide complex with zinc may be used alone or in
combination.
[0096] Another class of ashless dispersant includes Mannich bases.
Mannich dispersants are the reaction products of alkyl phenols with aldehydes
(especially formaldehyde) and amines (especially polyalkylene polyamines).
The alkyl group typically contains at least 30 carbon atoms.
[0097] The dispersants may also be post-treated by conventional methods by
a reaction with any of a variety of agents. Among these are boron, urea,
thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones,
carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic
anhydride, nitrites, epoxides, and phosphorus compounds.
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[0098] The
dispersant (typically a polyisobutylene succinimide) may have a
high total base number or the dispersant may have 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). In one embodiment the dispersant may be in a mixture of (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.
[0099] The
dispersant may be present (on an oil free basis i.e., an actives
basis) at 0 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %,
or 1 wt % to 6 wt % of the lubricating composition.
Antioxidants
[0100] Antioxidant
compounds are known and include for example,
sulphurised olefins, alkylated diphenylamines (typically di-nonyl
diphenylamine, octyl diphenylamine, di-octyl diphenylamine), hindered
phenols, molybdenum compounds (such as molybdenum dithiocarbamates), or
mixtures thereof. Antioxidant
compounds may be used alone or in
combination. The antioxidant may be present in ranges (on an oil free basis
i.e., an actives basis) of 0 wt % to 20 wt %, or 0.1 wt % to 10 wt %, or 1 wt
%
to 5 wt %, of the lubricating composition.
[0101] 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-methy1-2,6-di-tert-butylpheno1, 4-ethyl-2,6-di-tert-
butylphenol,
4-propy1-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-
dodecy1-2,6-di-tert-butylphenol. In one embodiment the hindered phenol
antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba.
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A more detailed description of suitable ester-containing hindered phenol
antioxidant chemistry is found in US Patent 6,559,105.
[0102] In one embodiment the lubricating composition further includes a
molybdenum compound.
[0103] The molybdenum compound is selected from the group consisting of
molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine
salts of molybdenum compounds, and mixtures thereof.
[0104] Suitable examples of molybdenum dithiocarbamates which may be
used as an antioxidant include commercial materials sold under the trade names
such as Molyvan 8221m, Molyvanrm A and Molyvan 8551'm from R. T.
Vanderbilt Co., Ltd., and Adeka SakuraLubeTM S-100, S-165 S-515, S-600 and
S-710 from Adeka ; and mixtures thereof.
[0105] When present, the molybdenum compound may provide 5 ppm to
1000 ppm, or 20 ppm to 300 ppm of molybdenum to the lubricating
composition.
Viscosity Modifiers
[0106] Viscosity modifiers include hydrogenated copolymers of maleic
anhydride-(alpha olefin) copolymers, styrene-butadiene, ethylene-propylene
copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers,
hydrogenated isoprene polymers, polymethacrylates, polyacrylates, polyalkyl
styrenes, hydrogenated alkenyl arene conjugated diene copolymers, polyolefins,
esters of maleic anhydride-styrene copolymers.
Dispersant Viscosity Modifiers
[0107] Dispersant viscosity modifiers (often referred to as DVM), include
functionalised polyolefins, for example, ethylene-propylene copolymers that
have been functionalized with an acylating agent such as maleic anhydride and
an amine; polymethacrylates functionalised with an amine, or esterified
styrene-maleic anhydride copolymers reacted with an amine.
Antiwear Agents
[0108] In one embodiment the lubricating composition further includes an
antiwear agent.
[0109] The additional antiwear agent may be either ashless or ash-forming.
Typically ashless antiwear agents do not contain metal, whereas ash-forming do
contain metal.
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[0110] The antiwear agent
may be present (on an oil free basis i.e., an
actives basis) in ranges including 0 wt % to 15 wt %, or 0 wt % to 10 wt %, or
0.05 wt % to 5 wt %, or 0.1 wt % to 3 wt % of the lubricating composition.
[0111] In one embodiment
the lubricating composition further includes a
phosphorus-containing antiwear agent. Typically the phosphorus-containing
antiwear agent may be present in an amount to deliver the ranges of phosphorus
described below in the subject matter under the sub-heading "Industrial
Application".
[0112] Examples of
suitable antiwear agents include phosphate esters,
sulphuriscd olefins, sulphur-containing anti-wear additives including metal
dihydrocarbyldithiophosphates (such as primary or secondary zinc
dialkyldithiophosphates, Or molybdenum
dialkyldithiophosphates),
molybdenum thiocarbamate-containing compounds including thiocarbamate
esters, alkylene-co up led thiocarbamates, and bis(S-alkyldithiocarbamyl)
disulphides.
[0113] Examples of
suitable zinc dialkyldithiophosphates include those
disclosed in PCT Publication WO 2008011339 (entitled "Method
of Lubricating
an Internal Combustion Engine and Improving the Efficiency of the Emissions
Control System of the Engine") or in pcp Publication WO 2008011338
(entitled
"Lubricating Oil Composition and Method of Improving Efficiency of
Emissions Control System"). Both applications claim priority from July 17,
2006. The zinc dialkyldithiophosphates or zinc dialkylphosphates may in one
embodiment be defined as a zinc salt of a mixture of phosphorus-containing
compounds represented by the formula:
ji
R3-0 //h
H
wherein in formula, J1 and J2 are independently S or 0, and R3 and R4 may be
independently hydrocarbyt groups, the average total number of carbon atoms in
R' plus R4 for the mixture of phosphorus-containing compounds being at least
9.5; wherein R3 and R4 are characterised in that (i) 4 to 70 mole percent of
such
groups contain 2 to 4 carbon atoms and (ii) 30 to 96 mole percent such groups
contain 5 to 12 carbon atoms; and wherein, in less than 8 mole percent of the
molecules of the formula in the mixture of phosphorus-containing compounds,
each of R3 and R4 contain 2 to 4 carbon atoms and in greater than 11 mole
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percent of the molecules of the formula in said mixture R3 has 2 to 4 carbon
atoms and R4 has 5 to 12 carbon atoms; and wherein, within the formula, the
average total number of hydrogen atoms in R3 and R4 on carbon atoms located
beta to the 0 atoms is at least 7.25.
[0114] The dithiocarbamate-containing compounds may be prepared by
reacting a dithiocarbamate acid or salt with an unsaturated compound. The
dithiocarbamate containing compounds may also be prepared by simultaneously
reacting an amine, carbon disulphide and an unsaturated compound. Generally,
the reaction occurs at a temperature of 25 C to 125 C. US Patents 4,758,362
and 4,997,969 describe dithiocarbamate compounds and methods of making
them.
[0115] Examples of suitable olefins that may be sulphurised to form an
sulphurised olefin include propylene, butylene, isobutylene, pentene, hexane,
heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene,
tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene,
nonodecene, eicosene or mixtures thereof. in one embodiment, hexadecene,
heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures
thereof and their dimers, trimers and tetramers are especially useful olefins.
Alternatively, the olefin may be a Diels-Alder adduct of a diene such as
1,3-butadiene and an unsaturated ester, such as butylacrylate.
[0116] Another class of sulphurised olefin includes fatty acids and their
esters. The fatty acids are often obtained from vegetable oil or animal oil
and
typically contain 4 to 22 carbon atoms. Examples of suitable fatty acids and
their esters include triglycerides, oleic acid, linoleic acid, palmitoleic
acid or
mixtures thereof. Often, the fatty acids are obtained from lard oil, tall oil,
peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures
thereof.
in one embodiment fatty acids and/or ester are mixed with olefins.
Extreme Pressure Agents
[0117] Extreme Pressure (EP) agents that are soluble in the oil include
sulphur- and chlorosulphur-containing EP agents, chlorinated hydrocarbon EP
agents and phosphorus EP agents. Examples of such EP agents include
chlorinated wax; organic sulphides and poly sulphides such as
dibenzyldisulphide, bis¨(chlorobenzyl) disulphide, dibutyl tetrasulphide,
sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised
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dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts;
phosphosulphurised hydrocarbons such as the reaction product of phosphorus
sulphide with turpentine or methyl oleate; phosphorus esters such as the
dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl
phosphite, dioleyl phosphite, di-2-ethylhexyl phosphite, didodecyl phosphite,
di C12-
14 alkyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene
substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithio-
carbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl-
phosphoric acids, including, for example, the amine salt of the reaction
product of a
dialkyldithiophosphoric acid with propylene oxide; and mixtures thereof.
Friction Modifiers
[0118] In one embodiment the lubricating composition further includes a
friction modifier, or mixtures thereof. Typically the friction modifier may be
present (on an oil free basis i.e., an actives basis) in ranges including 0 wt
% to
wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 4 wt %.
[0119] Examples of suitable friction modifiers include long chain fatty
acid
derivatives of amines, esters, or epoxides; fatty imidazolines such as
condensation products of carboxylic acids and polyalkylene-polyamines; amine
salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl
tartrimides; or
fatty alkyl tartramides.
[0120] Friction modifiers may also encompass materials such as fatty alkyl
tartrates; fatty alkyl tartrimides, sulphurised fatty compounds and olefins,
molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sun-
flower oil or monoester of a polyol and an aliphatic carboxylic acid (all
these
friction modifiers may also be described as antioxidants or antiwear agents).
[0121] In one embodiment the friction modifier friction modifier is
selected
from the group consisting of long chain fatty acid derivatives of amines,
esters,
or epoxides; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl
tartrami des .
[0122] In one embodiment the friction modifier may be a long chain fatty
acid
ester (previously described above as an ashless antiwear agent). In one
embodiment
the long chain fatty acid ester may be a mono-ester, e.g., a monoglyceride,
and in
one embodiment the long chain fatty acid ester may be a (tri)glyceride.
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Other Additives
[0123] Other performance
additives such as corrosion inhibitors include
those described in paragraphs 5 to 8 of US Publication 20090156446 (filed
on
October 25, 2004 McAfee and Boyer as named inventors), octylamine
octanoate, condensation products of dodecenyl succinic acid or anhydride and a
fatty acid such as oleic acid with a polyaminc. In one embodiment the
corrosion inhibitors include the Synalox corrosion inhibitor. The Synalox
corrosion inhibitor is typically a homopolymer or copolymer of propylene
oxide. The Synalox corrosion inhibitor is described in more detail in a
product brochure with Form No. 118-01453-0702 AMS, published by The Dow
Chemical Company. The product brochure is entitled "SYNALOX Lubricants,
High-Performance Polyglycols for Demanding Applications."
[0124] Metal deactivators
including derivatives of benzotriazoles (typically
tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazolcs, benzimid-
azoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam
inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and
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
may be useful. Foam inhibitors that may be useful in the compositions of the
invention include copolymers of ethyl acrylate and 2-ethythexylacrylate and
optionally vinyl acetate; demulsifiers including trialkyl phosphates,
polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene
oxide-propylene oxide) polymers.
[0125] Pour point
depressants that may be useful in the compositions of the
invention include polyalphaolefins, esters of maleic anhydride-styrene
copolymers, fumarate ester-vinyl acetate copolymers, polyalkyl(meth)acrylates,
polyalkylacrylates or polyalkylacrylamides.
Industrial Application
[01261 In one embodiment
the mechanical device is an internal combustion
engine.
[0127] In one embodiment
the internal combustion engine may be a diesel
fueled engine, a gasoline fueled engine, a natural gas fueled engine or a
mixed
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gasoline/alcohol fueled engine. In one embodiment the internal combustion
engine may be a diesel fueled engine and in one embodiment a gasoline fueled
engine.
[0128] 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.
[0129] As used herein the components of the internal combustion engine
include all of the parts of the engine derived from metal lubricated by an
engine
lubricant. This includes for example, cylinder liners, camshafts, pistons,
bearings, oil coolers etc.
[0130] In one embodiment the internal combustion engine contains
components ferric (i.e., ferrous) components. The ferric components include
Fe, FeO, Fe304 or other materials containing iron.
[0131] In one embodiment the internal combustion engine contains
components of an aluminium-alloy. The aluminium-alloy includes aluminium
silicates, aluminium oxides, or other ceramic materials. In one embodiment the
aluminium-alloy is an aluminium-silicate surface.
[0132] The lubricating 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 0.1 wt % or less, or 0.085 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 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
The total sulphated ash content may be 2 wt % or less, or 1.5 wt % or less, or
1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less.
In
one embodiment the sulphated ash content may be 0.05 wt % to 0.9 wt %, or
0.1 wt % to 0.2 wt % to 0.45 wt %.
[0133] In one embodiment the lubricating composition may be an engine
oil, wherein the lubricating composition may be characterised as having (i) a
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sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.08 wt % or
less, and (iii) a sulphated ash content of 1.5 wt % or less.
[0134] In one embodiment the lubricating composition may be suitable for a
2-stroke or a 4-stroke marine diesel internal combustion engine. In one
embodiment the marine diesel combustion engine is a 2-stroke engine.
[0135] The block copolymer of the invention may also be used in a variety
of lubricants requiring emulsifiers and/or pour point depressants. The block
copolymer of the invention may be an emulsifier and/or pour point depressant
in driveline devices, industrial gears, hydraulic devices, off-highway mobile
equipment such as farm tractors, greases, metalworking fluids and fuels. For
each of these devices the lubricant formulation may, as a person skilled in
the
art will appreciate, change due to the different additives and treat rates
commonly employed in each lubricant type. None the less, the block
copolymer is believed to function as an emulsifier and/or pour point
depressant.
[0136] Driveline devices include gearboxes, axle gears, traction drive
transmissions, automatic transmissions or manual transmissions.
[0137] Automatic transmissions include continuously variable transmissions
(CVT), infinitely variable transmissions (IVT), Torroidal transmissions,
continuously slipping torque converted clutches (CSTCC), stepped automatic
transmissions or dual clutch transmissions (DCT).
[0138] The following examples provide illustrations of the invention.
These examples are non-exhaustive and are not intended to limit the scope of
the invention.
EXAMPLES
[0139] Preparative Example 1 (EX1): is a diblock copolymer of (C12_15-
alkyl
methacrylate and 2-ethylhexylmethacrylate)-b-dimethylaminoethyl meth-
acrylate. The diblock copolymer is prepared by charging reagents into a 4-
necked flask equipped with a nitrogen inlet, thermocouple and a heating
mantle. The reagents added include 99.2 g of C12-15-alkyl methacrylate, 48 g
of
2-ethylhexylmethacrylate, 5.04 g of a chain transfer agent (dodecyl-
trithiocarbonate butyl ester), 0.87 g of Trigonox021 initiator and 41.48 g of
PA0-4 diluent oil. The flask is stirred and purged with nitrogen for 30
minutes. The nitrogen flow rate is 0.028 m3/hr (or 1 SCFH). The flask is then
heated to 90 C and the nitrogen flow is reduced to 0.014 m3/hr (or 0.5 SCFH)
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and held for 150 minutes. The flask is then charged with 12.8 g of
dimethylaminoethyl methacrylate. The flask is held for a further 3 hours at 90
C, before cooling. The product is a viscous liquid.
[0140] Preparative
Example 2 (EX2): is a diblock copolymer of (Cu-is-alkyl
methacrylate and 2-ethylhexylmethacrylate)-b-dimethylaminoethyl meth-
acrylate. 111.6 g of
C12-15-alkyl methacrylate, 54 g of 2-ethylhexyl-
methacrylate, and 0.97 g of Trigonox 21 initiator are blended to form a blend.
About one third of the blend is charged into a 4-necked flask equipped with a
nitrogen inlet, thermocouple and a heating mantle. 5.67 g of a chain transfer
agent (dodecyl-trithiocarbonate butyl ester) is then added to the flask.
[0141] The flask
is stirred and purged with nitrogen for 30 minutes. The
nitrogen flow rate is 0.028 M3/hr (or 1 SCFH). The flask is then heated to 80
C and the nitrogen flow is reduced to 0.014 m3/hr (or 0.5 SCFH) and the
remaining two thirds of the blend is added over a period of 90 minutes. The
flask is maintained at 80 C and held for 150 minutes. The flask is then
charged with 14.4 g of dimethylaminoethyl methacrylate. The flask is held for
a further 150 minutes at 80 C, before cooling. The product is a viscous
liquid.
[0142] Preparative
Example 3 (EX3): is a diblock copolymer of (C12-15-alkyl
methacrylate and CI 6-1 - alkyl methacrylate)-b-dimethylaminoethyl meth-
acrylate. 1500 g of C12_15-alkyl methacrylate, 260 g of C16_18-alkyl meth-
acrylate (the Ci6_18-a1ky1 methacrylate also contains up to 5 wt % C14-alkyl
methacrylate and up to 2 wt % C20-alkyl methacrylate), and 3 g of
Trigonox021 initiator are blended to form a blend. About one third of the
blend is charged into a 4-necked flask equipped with a nitrogen inlet,
thermocouple and a heating mantle. 17.5 g of a chain transfer agent (dodecyl-
trithiocarbonate butyl ester) is then added to the flask.
[0143] The flask
is stirred and purged with nitrogen for 30 minutes. The
nitrogen flow rate is 0.056 M3/hr (or 2 SCFH). The flask is then heated to 80
C and the nitrogen flow is reduced to 0.014 ms/hr (or 0.5 SCFH) and the
remaining two thirds of the blend is added over a period of 90 minutes. The
flask is maintained at 80 C and held for 15 hours. The flask is then charged
with 240 g of dimethylaminoethyl methacrylate. The flask is held for at 90 C
for 2 hours. Three separate charges (each 1 g) of Trigonox(R)21 initiator are
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added over a period of 5 hours. The product is a viscous liquid before
dilution
with diluent oil to form a 40 % polymer mixture in oil.
[0144] Preparative Example 4 (EX4): is a diblock copolymer prepared by a
process similar to EX3, except the final polymer is a block copolymer of (C12-
15-alkyl methacrylate and C16_18-alkyl methacrylate)-b-(dimethylaminoethyl
methacrylate and methylmethacrylate). The methyl methacrylate is added
concurrently with dimethylaminoethyl methacrylate. The ratio of the weight
percent of C12-15-alkyl methacrylate to C16-i8-alkyl methacrylate is 85:15
(the
C16-18-alkyl methacrylate also contains up to 5 wt % C14-alkyl methacrylate
and
up to 2 wt (Yo C20-alkyl methacrylate). The ratio of the weight percent of
dimethylaminoethyl methacrylate to methylmethacrylate is 91:9. The ratio
weight percent of hydrophobic block to the second block containing a polar
group is 87:13. The product is a viscous liquid before dilution with diluent
oil
to form a 50 % polymer mixture in oil.
[0145] Comparative Preparative Example 1 (CP1): is a random polymer of
C12-15-alkyl methacrylate, 2-ethylhexylmethaerylate, and dimethylaminoethyl
methacrylate. The random polymer is prepared by charging reagents into a 4-
necked flask equipped with a nitrogen inlet, thermocouple and a heating
mantle. The reagents added include 99.2 g of C12-15-alkyl methacrylate, 48 g
of
2-ethylhexylmethacrylate, 12.8 g of dimethylaminoethyl methacrylate, 5.04 g
of a chain transfer agent (dodecyl-trithiocarbonate butyl ester), 0.87 g of
Trigonox021 initiator and 41.48 g of PA0-4 diluent oil. The flask is then
heated to 90 C as is described in EX1.
[0146] In the following lubricant examples and comparative lubricant
examples, the listed amount of the products from the preparative example or
comparative preparative example, as the case may be, includes the amount of
diluent oil reported to be added or included therein.
[0147] Comparative Lubricant Example 1 (CLC1) is a SAE 5W-30 engine
lubricant.
[0148] Comparative Lubricant Example 2 (CLC2) is a 5W-30 engine
lubricant similar to CLC1, except it further contains 0.05 wt % of the product
of CP1.
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[0149] Comparative Lubricant Example 3 (CLC3) is a 5W-30 engine
lubricant similar to CLC1, except it further contains 0.12 wt % of the product
of CP1.
[0150] Comparative Lubricant Example 4 (CLC4) is a oil mixture of 80 wt
% of ExxonMobil Group II EHCTm-45, with viscosity of 4.6 mm2/s at 100 C and
20 wt % of ExxonMobil Group II EHCTm-60, with viscosity of 6.0 mm2/s at 100
C.
[0151] Lubricant Example 1 (LC1) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.05 wt % of the product of EX1.
[0152] Lubricant Example 2 (LC2) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.12 wt % of the product of EX1.
[0153] Lubricant Example 3 (LC3) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.05 wt % of the product of EX2.
[0154] Lubricant Example 4 (LC4) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.12 wt % of the product of EX2.
[0155] Lubricant Example 5 (LC5) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.07 wt % of the product of EX3.
[0156] Lubricant Example 6 (LC6) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.16 wt % of the product of EX3.
[0157] Lubricant Example 7 (LC7) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.06 wt % of the product of EX4.
[0158] Lubricant Example 8 (LC8) is a 5W-30 engine lubricant similar to
CLC1, except it further contains 0.15 wt % of the product of EX4.
[0159] Lubricant Example 9 (LC9) is similar to CLC4, except it contains
0.26 wt % of the product of EX2.
[0160] Lubricant Example 10 (LC10) is similar to CLC4, except it contains
0.35 wt % of the product of EX3.
[0161] Lubricant Example 11 (LC11) is similar to CLC4, except it contains
0.35 wt % of the product of EX4.
Testing
[0162] Lubricant examples LC1 to LC8 and comparative Lubricant
examples CLC1 to CLC3 are evaluated in the following ASTM tests D445,
D4684-07 and D5985-02. The lubricants are also evaluated in Chrysler's FFV
emulsion stability test.
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[0163] ASTM D445 relates to measurement of kinematic viscosity (units
mm2/s) at 100 C.
[0164] ASTM D4684-07 (Mini-Rotary Viscometer or MRV) relates to the low-
temperature pumpability of an engine lubricating oil. Yield stress and low-
shear-
rate viscosity are measured after cooling at controlled rates over a period
exceeding 45 hour to a final test temperature between -10 C and -40 C. The
units are Centipoise (cP) or mPa-s.
[0165] D5985-02 covers the determination of pour point of petroleum
products by an automatic instrument that continuously rotates the test
specimen
against a suspended detection device during cooling of the test specimen.
[0166] The Chrysler FFV emulsion stability test involves the steps of
combining 10 volume % E85 fuel, 10% water, and 80% fully formulated engine
oil and mixing them in a Waring blender. The resultant emulsion is stored in
graduated cylinders at 0 C and room temperature (25 C) for 24 hours. At the
end of the test, the volume percent oil (% oil), percent emulsion (% emul),
and
percent water (% H20) are recorded. Typically, a formulated oil is considered
to pass the FFV test if %H20 at both 0 C and room temperature is zero.
[0167] The results obtained for the tests described above are as follows:
Test D445 D4684-07 (at -35 C)
CLC1 10.33 32400
CLC2 10.62 30900
CLC3 10.60 32300
LC1 n/m n/m
LC2 n/m n/m
LC3 10.54 30500
LC4 10.54 31300
LC5 10.45 44500
LC6 10.43 66000
LC7 10.65 36300
LC8 10.66 46500
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Chrysler FFV at 0 C Chrysler FFV at 25 C
% oil % emul % H20 % oil % emul % H20
CLCI 86 0 14 85 0 15
CLC2 87 0 13 84 0 16
CLC3 88 0 12 84 0 15
LC1 n/m n/m n/m 12 88 0
LC2 n/m n/m n/m 3 97 0
LC3 18 82 0 52 48 0
LC4 6 94 0 15 85 0
LC5 7 94 0 3 97 0
LC6 23 77 0 1 99 0
LC7 9 91 0 40 60 0
LC8 5 95 0 26 74 0
Footnote to the tables:
n/m indicates a data point not measured
101681 Examples CLC4 and LC9 to LC11 are analysed for pour point
performance by the methodology of ASTM method D5985-02. The results
obtained are as follows:
Example Pour Point ( C) No Flow Point ( C)
CLC4 -18 -19.9
LC9 -18 -21
LC10 -30 -30.1
LC11 -30 -30.1
101691 Overall the results obtained for the block copolymer of the present
invention indicate that the polymer has emulsifying properties and/or pour
point depressant properties.
101701 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 lubricating composition of the
present invention in its intended use, may not be susceptible of easy
description. Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present invention
encompasses lubricating composition prepared by admixing the components
described above.
31
[0171]
Except in the Examples, or where otherwise explicitly indicated, all
numerical quantities in this description specifying amounts of materials, reac-
tion 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 arc 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. Multiple groups represented by the
same symbol in the formulae described above, may be the same or different.
[0172] As used herein the "C1_30 alkyl (meth)acrylic units" relate to
product
formed by the polymerisation of C1_30 alkyl (meth)acrylic monomer. The C1_30
alkyl (meth)acrylic units may then be used to form the block(s) as described
herein above. Reference to the percentage of C1_30 alkyl (meth)acrylic units
is
considered as a mole percent.
[01731 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:
(i) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-,
aliphatic-,
and alicyclic-substituted aromatic substituents, as well as cyclic
substituents
wherein the ring is completed through another portion of the molecule (e.g.,
two substituents together form a ring);
(ii) substituted hydrocarbon substituents, that is, substituents containing
non-hydrocarbon groups which, in the context of this invention, do not alter
the
predominantly hydrocarbon nature of the substituent (e.g., halo (especially
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chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso,
and sulphoxy);
(iii) hetero substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this invention, contain
other than carbon in a ring or chain otherwise composed of carbon atoms, and
encompass substituents as pyridyl, furyl, thienyl and imidazolyl; and
(iv) heteroatoms, including sulphur, oxygen, and nitrogen. In general,
no more than two, preferably no more than one, non-hydrocarbon substituent
will be present for every ten carbon atoms in the hydrocarbyl group;
typically,
there will be no non-hydrocarbon substituents in the hydrocarbyl group.
[0174] 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.
33
