Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Lubricating Composition and Method of Lubricating a Transmission
FIELD OF INVENTION
The present invention relates to a lubricating composition
comprising:(a) an oil of lubricating viscosity having a kinematic viscosity at
100 C of 2.8 to 3.6 cSt and a viscosity index of 104 to 130; (b) 1.2 to 5.0 wt
% of
at least one borated dispersant, wherein at least one borated dispersant is
further
functionalised with a sulphur or phosphorus moiety; (c) a calcium-containing
detergent present in an amount to deliver at least 110 ppm to 700 ppm of
calcium; (d) at least two phosphorus-containing compounds, wherein the
phosphorus-containing compounds are present in an amount to deliver 360 to 950
ppm of phosphorus to the lubricating composition, wherein at least 150 ppm of
the phosphorus is delivered by a C4_6 hydrocarbyl phosphite; and (e) 0.1 wt %
to
5 wt % of a linear polymer viscosity modifier having dispersant functionality.
The invention further provides a method of lubricating a transmission with the
lubricating composition disclosed wherein.
BACKGROUND OF THE INVENTION
[0001] Driveline transmissions especially automatic transmission fluids
(ATFs), present highly challenging technological problems and solutions for
satisfying the multiple and often conflicting lubricating and power
transmitting
requirements of modern automatic transmissions (including continuously
variable
transmissions of various types). Many additive components are typically
included
in an ATF, providing such performance characteristics as lubrication,
dispersancy,
friction control (for clutches), anti-wear durability (e.g., gear wear) and
pump
durability, fuel economy, anti-shudder performance, anti-corrosion and anti-
oxidation performance. However, over periods of use, the additive components
are consumed which may detrimentally damage transmissions.
[0002] US
5,578,236 (Srinivasan, published 26 November 1996) discloses a
power transmission fluid composition wherein said composition has on a
weight basis an oil-soluble boron content of about 0.001 to about 0.1%, an oil-
soluble phosphorus content of about 0.005 to about 0.2%, and either no metal
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additive content or an oil-soluble metal content as one or more metal-
containing additives of no more than about 100 ppm; wherein said composition
comprises: a) at least about 50 wt % based on the total weight of said
composition of one or more hydrotreated mineral oils in the range of about 55N
to about 125N; b) about 5 to about 40 wt % based on the total weight of said
composition of hydrogenated poly-.alpha.-olefin oligomer fluid having a
viscosity in the range of about 2 to about 6 cSt at 100 C; c) on an active
ingredient basis, about 5 to about 20 wt % based on the total weight of said
composition of an acrylic viscosity index improver having a permanent shear
stability index of 30 or less in the form of a solution in an inert solvent;
d) an
effective seal-swelling amount of at least one seal swell agent selected from
oil-soluble dialkyl esters, oil-soluble sulfones, and mixtures thereof; e) a
dispersant amount of at least one oil-soluble ashless dispersant; f) a
friction
modifying amount of at least one oil-soluble friction modifier; and g) oil-
soluble inhibitors selected from the group consisting of foam inhibitors,
copper
corrosion inhibitors, rust inhibitors, and oxidation inhibitors; with the
proviso
that said composition has (i) a Brookfield viscosity of 13,000 cP or less at -
40
C, (ii) a viscosity of at least 2.6 mPa.s at 150 C in the ASTM D-4683 method,
and (iii) a viscosity of at least 6.8 cSt at 100 C after 40 cycles in the
FISST of
ASTM D-5275.
[0003] US 2011-0239971 (Nelson, published 6 October, 2011) discloses a
method for improving copper corrosion performance of a lubricating oil
composition comprising (a) a major amount of a base oil of lubricating
viscosity; and (b) one or more dispersants containing one or more basic
nitrogen atoms, the method comprising adding to the lubricating oil
composition an effective amount of one or more copper corrosion performance
improving agents of the general formula Si-X4 or a hydrolysis product thereof,
wherein each X is independently a hydroxyl-containing group, hydrocarbyloxy-
containing group, acyloxy-containing group, amino-containing group,
monoalkyl amino-containing group or dialkyl amino-containing group.
[0004] EP 1 705 235 (Ozbalik, published 22 March 2006) discloses an
automatic transmission fluid composition comprising: (a) a major amount of a
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base oil; (b) one or more friction modifiers, wherein total nitrogen content
provided by the one or more friction modifiers is greater than or equal to
about
300 ppm; and (c) one or more ashless dispersants, wherein the total nitrogen
content provided by the one or more ashless dispersants is greater than or
equal
to about 500 ppm; wherein the automatic transmission fluid has a kinematic
viscosity at 100 C of from about 4 cSt to about 6.5 cSt and a Brookfield
viscosity at -40 C of from about 4,000 cP to about 20,000 cP.
[0005]
International Publication WO 2005/010134 (Sumiejski et at., 3
February 2005) discloses a lubricating composition containing (a) a
hydrocarbyl phosphite; (b)the condensation product of at least one fatty acid
with a polyamine; (c) a borate ester; (d) a borated dispersant; and (e) an oil
of
lubricating viscosity. The invention further relates to the use of the
composition in
automotive transmissions.
[0006]
International Publication WO 2007/127615 (Tipton et at., 8 November
2007) discloses a lubricating composition containing a polymer such as a star
polymer, a phosphorus-containing compound and a dispersant. The invention
further provides a method for lubricating a mechanical device using the
lubricating composition.
[0007]
International Publication WO 00/70001 (Ward, 23 November 2000)
discloses a method for lubricating a continuously variable transmission,
comprising supply thereto a composition comprising (a) an oil of lubricating
viscosity; (b) a dispersant; a detergent; or mixtures of (b) and (c) wherein
at
least one of the dispersant (b) and the detergent (c) is a borated species and
wherein the amount of boron is at least 250 parts per million, based on the
composition, and is present in an amount sufficient to impart improved
friction
and anti-seizure properties to said composition when employed in said
transmission. The
composition is also noted as useful for automatic
transmissions.
[0008] US
5,840,663 (Nibert et at., published 24 November 1998) discloses
a composition and method of improving the anti-shudder durability of a power
transmitting fluid comprising: a major amount of a lubricating oil; and an
anti-
shudder improving effective amount of an additive combination comprising: a
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reaction product of an isomerized alkenyl substituted succinic anhydride and a
polyamine, an oil-soluble alkyl phosphite, an ashless dispersant with alkyl
side
chains of greater than 1500 molecular weight; a nitrogen containing corrosion
inhibitor, and optionally, a metallic detergent which is a salt of an alkali,
or
alkaline earth metal. The anti-shudder durability of these fluids can be
further
improved by optionally incorporating overbased metallic detergents.
[0009] US 7,737,092 (Ward et at., published 11 August 2005) discloses
a
composition suitable for use as a lubricant for a transmission, comprising:
(a)
an oil of lubricating viscosity; (b) a dispersant; (c) a calcium detergent;
(d) a
magnesium detergent; and (e) an inorganic phosphorus compound; wherein at
least one of (b), (c), and (d) is borated. The formulations of Ward are
suitable
for use as fluids for transmissions, especially continuously variable
transmissions. Ward also discloses that continuously variable transmissions
(CVT) represent a radical departure from conventional automatic transmissions.
[0010] US 20020151441 (Srinivasan et at., published 17 October 2002)
discloses an automatic transmission fluid, comprising: a major amount of a
base oil, and a minor amount of an additive comprising at least about 0.10
weight % of a metal-containing detergent, a dispersant, and a mixture of at
least two different friction modifiers. The automatic transmission fluid has
anti-shudder durability, and friction durability.
[0011] US 20090305922 (Cha et at., published 10 December 2009)
discloses an automatic transmission lubricating oil composition, and
particularly to an automatic transmission lubricating oil composition
comprising an oil of lubricating viscosity, an ashless dispersant, an anti-
oxidant, a phosphorus-based anti-wear agent and a friction-modifier, wherein
more than 310 ppm of phosphorus is contained, thereby being useful for
lubricating or operating an automatic transmission comprising a transmission
clutch using a slip lock-up torque converter and a paper based clutch material
and a planetary gear system, especially six-speed automatic transmission.
[0012] US 20120277134 (Deshimaru, published 1 November 2012)
discloses a lubricating oil composition contains: at least one lubricating
base oil
selected from the group consisting of a mineral lubricating base oil and a
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synthetic lubricating base oil; (a) a neutral phosphorus compound; (b) at
least
one acid phosphorus compound selected from the group consisting of a specific
acid phosphate amine salt and a specific acid phosphite; and (c) a sulphur
compound. The lubricating oil composition may be an automatic transmission
1 fluid with a kinematic viscosity at 100- C of 5 mm2/s.
SUMMARY OF THE INVENTION
[0013] An objective of the present invention is to provide a
lubricating
composition capable of lubricating an automatic transmission. The lubricating
composition may be capable of providing at least one property including
friction control (for clutches), improved fuel economy, anti-wear durability
(e.g.,
gear wear) and pump durability, and anti-shudder performance. The lubricating
composition may for instance, be capable of providing improved fuel economy,
and anti-wear durability.
[0014] 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 characteristics of the composition or method under consideration.
[0015] As used herein the term "C4_6 hydrocarbyl phosphite" is
intended to
include both a mono- C4_6 hydrocarbyl phosphite and di- C4_6 hydrocarbyl
phosphite. Typically the C4_6 hydrocarbyl phosphite comprises a di- C4-6
hydrocarbyl phosphite.
[0016] As used herein the expression "(meth)acrylic", (meth)arylate"
and
related terms is intended to encompass both acrylic functionality as well as
methacrylic functionality. Typically the (meth)acrylic", (meth)arylate" and
related terms is intended to include a methacrylic or methacrylate.
[0017] The present invention in one embodiment may be a lubricating
composition comprising:
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(a) an oil of lubricating viscosity having a kinematic viscosity at 100 C of
2.8 to 3.6 cSt (mm2/s) and a viscosity index of 104 to 130;
(b) 1.2 to 5.0 wt % of at least one borated dispersant, wherein at least one
borated dispersant is further functionalised with a sulphur or phosphorus
moiety;
(c) a calcium-containing detergent, wherein the detergent is present in an
amount to deliver at least 110 ppm to 700 ppm of calcium;
(d) at least two phosphorus-containing compounds, wherein the
phosphorus-containing compounds are present in an amount to deliver 360 to 950
ppm of phosphorus to the lubricating composition, wherein at least 150 ppm of
the phosphorus is delivered by a C4_6 hydrocarbyl phosphite; and
(e) 0.1 wt % to 5 wt % of a linear polymer viscosity modifier having
dispersant functionality, wherein the linear polymer has a weight average
molecular weight of 5,000 to 25,000.
[0018] The
present invention in a different embodiment may be a
lubricating composition comprising:
(a) an oil of lubricating viscosity having a kinematic viscosity at 100 C of
2.8 to 3.6 cSt (mm2/s) and a viscosity index of 104 to 130;
(b) 1.2 to 5.0 wt % of at least one borated dispersant, wherein at least one
borated dispersant is further functionalised with a sulphur or phosphorus
moiety;
(c) a calcium-containing detergent, wherein the detergent is present in an
amount to deliver at least 160 ppm to 400 ppm of calcium;
(d) a at least two phosphorus-containing compounds, wherein the
phosphorus-containing compounds are present in an amount to deliver 525 to 800
ppm of phosphorus to the lubricating composition, wherein at least 150 ppm of
the phosphorus is delivered by a C4_6 hydrocarbyl phosphite; and
(e) 0.1 wt % to 5 wt % of a linear polymer viscosity modifier having
dispersant functionality, wherein the linear polymer has a weight average
molecular weight of 5,000 to 25,000.
[0019] The
lubricating composition of the present invention may further
comprise 0.1 wt % to 5 wt % of a (meth)acrylic polymer having star
architecture.
[0020] The
lubricating composition of the present invention may further
comprise 0.1 wt % to 5 wt % of a linear (meth)acrylic polymer viscosity
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modifier having dispersant functionality, wherein the linear polymer has a
weight
average molecular weight of greater than 25,000 to 400,000 (or to 350,000).
[0021] The amount of boron in the lubricant composition disclosed
herein
may be 150 to 400 parts per million by weight.
[0022] In one embodiment, the lubricating composition disclosed herein
further comprises 0.3 wt % to 1.2 wt % of an amine antioxidant.
[0023] In one embodiment, the lubricating composition disclosed herein
further comprises 0.5 wt % to 3.5 wt % of a friction modifier component
comprising at least two ashless friction modifiers.
[0024] In one embodiment, the lubricating composition disclosed herein
further comprises 0.3 wt % to 1.2 wt % of an amine antioxidant; and 0.5 wt %
to
3.5 wt % of a friction modifier component comprising at least two ashless
friction modifiers.
[0025] The lubricating composition disclosed herein may in one
embodiment of the invention have a kinematic viscosity at 100 C of 3.6 to 4.8
cSt (mm2/s); and a Brookfield viscosity at -40 C may be at most 6,800 cP
(mP a = s).
[0026] In one embodiment the invention provides a method of
lubricating an
automatic transmission comprising supplying to the automatic transmission a
lubricating composition disclosed herein.
[0027] In one embodiment the invention provides for the use of the
lubricating
composition disclosed herein to provide at least one of friction control (for
clutches), improved fuel economy, anti-wear durability (e.g., gear wear) and
pump durability, and anti-shudder performance for an automatic transmission.
[0028] The automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT), Toroidal
transmissions, continuously slipping torque converted clutches (CSTCC),
stepped automatic transmissions or dual clutch transmissions (DCT).
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present invention provides a method of lubricating an automatic
transmission and a lubricating composition as disclosed above.
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[0030] As used herein, the viscosity index is determined by employing
ASTM method D2270-10e1 .
[0031] As used herein, the kinematic viscosity at 100 C is measured by
the
methodology of ASTM D445-12.
[0032] As used herein, the Brookfield viscosity is measured by ASTM
D2983-09 at -40 C (Brookfield viscosity at -40 C).
Lubricating Composition
[0033] The lubricating composition may have a kinematic viscosity at
100 C
of 3.6 to 4.8 cSt (mm2/s), or 4.0 to 4.6 cSt (mm2/s), or 4.0 to 4.4 cSt
(mm2/s), or
4.0 to 4.2 cSt (mm2/s).
[0034] The lubricating composition may have a Brookfield viscosity at -
40 C
of at most 6,800 cP (mPa=s). The Brookfield viscosity at -40 C may be 3,000 to
6,800 cP (mPa=s).
[0035] The lubricating composition may have a kinematic viscosity at
100 C
of 3.6 to less than 4.5 cSt (mm2/s); and a Brookfield viscosity at -40 C may
be
3000 to at most 6,800 cP (mPa=s).
[0036] The lubricating composition may have a kinematic viscosity at
100 C
of 4.0 to 4.4 cSt (mm2/s); and a Brookfield viscosity at -40 C may be 3,000 to
6,800 cP (mPa=s).
Oils of Lubricating Viscosity
[0037] The oil of lubricating viscosity of the invention has a
kinematic
viscosity at 100 C of 2.8 to 3.6 cSt (mm2/s), or 2.9 to 3.5 cSt (mm2/s), or
3.0 to
3.4 cSt (mm2/s). The kinematic viscosity at 100 C is measured by the
methodology of ASTM D445-12. The oil of lubricating viscosity of the
invention may also be defined as an API Group II+ base oil. API Group II+ base
oils are known and described for example in SAE publication entitled "Design
Practice: Passenger Car Automatic Transmissions", fourth Edition, AE-29,
published 2012, page 12-9. US 8,216,448 also defines a API Group II+ as a
"Group II plus base oil" having a viscosity index greater than or equal to 110
and less than 120.
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[0038] The oil of lubricating viscosity of the invention may have a
viscosity
index (VI) of at 104 to 130, or least 105, or at least 110, or at least 115 to
130.
The viscosity index may be in the range of 104 to 125, or 110 to less than
120.
In one particular embodiment the oil of lubricating viscosity has a kinematic
viscosity at 100 C of 2.8 to 3.6 cSt (mm2/s) and a viscosity index of 110 to
less
than 120;
[0039] Examples of an oil of lubricating viscosity of the present
invention
include base oils sold under the registered trade names of S-Oil, Nexbase,
Yubase, Petrocanada, and Chevron neutral oil 11ORLV.
[0040] The oil of lubricating viscosity of the invention may be present at
60
wt % to 97.5 wt %, or 70 wt % to 95 wt %, or 80 wt % to 95 wt % of the
lubricating composition.
[0041] The oil of lubricating viscosity of the invention with a
kinematic
viscosity at 100 C of 2.8 to 3.6 cSt (mm2/s) may also be blended with a
conventional oil of lubricating viscosity (i.e., an oil of lubricating
viscosity
other than that defined by the present invention). The conventional oil of
lubricating viscosity may be defined as specified in the American Petroleum
Institute (API) Base Oil Interchangeability Guidelines. The five base oil
groups are as follows: Group I (sulphur content >0.03 wt %, and/or <90 wt %
saturates, viscosity index 80-120); Group II (sulphur content <0.03 wt %, and
>90 wt % saturates, viscosity index 80-120); Group III (sulphur content <0.03
wt %, and >90 wt % saturates, viscosity index >120); Group IV (all
polyalphaolefins (PA0s)); and Group V (all others not included in Groups I,
II,
III, or IV). The oil of lubricating viscosity comprises an API Group I, Group
II
(other than the oil of lubricating viscosity defined by the present
invention),
Group III, Group IV, Group V oil or mixtures thereof.
[0042] Often the conventional oil of lubricating viscosity is an API
Group I,
Group II (other than the oil of lubricating viscosity defined by the present
invention), Group III, Group IV oil or mixtures thereof Alternatively the
conventional oil of lubricating viscosity is often an API Group II (other than
the oil of lubricating viscosity defined by the present invention), Group III
or
Group IV oil or mixtures thereof
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[0043] In
one embodiment the conventional oil of lubricating viscosity may
be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as
other gas-to-liquid oils.
[0044] In
one embodiment the conventional oil of lubricating viscosity may
be an API Group IV oil. The amount of Group IV oil may be 0 wt % to 20 wt
%, or 0.1 wt % to 20 wt %, or 1 wt % to 15 wt %, or 5 to 10 wt % of the
lubricating composition.
[0045] 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
performance additives of the present invention.
[0046] The
lubricating composition may be in the form of a concentrate
and/or a fully formulated lubricant. If the performance additives of this
invention are 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 performance 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.
Detergent
[0047] The
lubricating composition includes a calcium-containing detergent.
The calcium-containing detergent is present in an amount to deliver 130 ppm to
600 ppm, or 160 ppm to 400 ppm of calcium.
[0048] The
calcium-containing detergent may be an overbased detergent, a
non-overbased detergent, or mixtures thereof. Typically the detergent may be
overbased.
[0049] The
preparation of the calcium-containing detergent is known in the
art. Patents
describing the preparation of overbased calcium-containing
detergents include U.S. patents 2,501,731; 2,616,905; 2,616,911; 2,616,925;
2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284;
and 3,629,109.
[0050] As
used herein the TBN values quoted and associated range of TBN is on
"an as is basis," i.e., containing conventional amounts of diluent oil.
Conventional
amounts of diluent oil typically range from 30 wt % to 60 wt % (often 40 wt %
to 55
wt %) of the detergent component.
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[0051] A more detailed description of the expressions "metal ratio",
TBN
and "soap content" are known to a person skilled in the art and explained in
standard textbook entitled "Chemistry and Technology of Lubricants", Third
Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219
to 220 under the sub-heading 7.2.5. Detergent Classification.
[0052] The calcium-containing detergent may be a non-overbased
detergent
(may also be referred to as a neutral detergent). The TBN of a non-overbased
may be 20 to less than 200, or 30 to 100, or 35 to 50 mg KOH/g. The TBN of a
non-overbased calcium-containing detergent may also be 20 to 175, or 30 to
100 mg KOH/g. When a non-overbased calcium-containing detergent is
prepared from a strong acid such as a hydrocarbyl-substituted sulphonic acid,
the TBN may be lower (for example 0 to 50 mg KOH/g, or 10 to 20 mg
KOH/g).
[0053] The calcium-containing detergent may be an overbased detergent,
which may have a TBN of greater than 200 mg KOH/g (typically 250 to 600, or
300 to 500 mg KOH/g).
[0054] The calcium-containing detergent may be formed by the reaction
of a
basic calcium compound and an acidic detergent substrate. The acidic detergent
substrate may include an alkyl phenol, an aldehyde-coupled alkyl phenol, a
sulphurised alkyl phenol, an alkyl aromatic sulphonic acid (such as, alkyl
naphthalene sulphonic acid, alkyl toluene sulphonic acid or alkyl benzene
sulphonic
acid), an aliphatic carboxylic acid, a calixarene, a salixarene, an alkyl
salicylic acid,
or mixtures thereof
[0055] The metal basic compound is used to supply basicity to the
detergent. The basic calcium compound is a compound of a hydroxide or oxide
of the metal.
[0056] The oxides and/or hydroxides may be used alone or in
combination.
The oxides or hydroxides may be hydrated or dehydrated, although hydrated is
typical. In one embodiment the basic calcium compound may be calcium
hydroxide, which may be used alone or mixtures thereof with other metal basic
compounds. Calcium hydroxide is often referred to as lime. In one
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embodiment the metal basic compound may be calcium oxide which may be
used alone or mixtures thereof with other metal basic compounds.
[0057] Collectively, when the alkyl phenol, the aldehyde-coupled alkyl
phenol,
and the sulphurised alkyl phenol are used to prepare a calcium-containing
detergent,
the detergent may be referred to as a calcium phenate. The calcium phenate may
be
an alkyl phenate, an aldehyde-coupled alkyl phenate, a sulphurised alkyl
phenate, or mixtures thereof.
[0058] The TBN of a calcium phenate may vary from less 200, or 30 to
175
typically 150 to 175) mg KOH/g for a neutral phenate to 200 or more to 500, or
210
to 400 (typically 230 to 270) mg KOH/g for an overbased phenate.
[0059] The alkyl group of a phenate (i.e., an alkyl phenate) may
contain 4 to 80,
or 6 to 45, or 8 to 20, or 9 to 15 carbon atoms.
[0060] In one embodiment the calcium-containing detergent may be a
sulphonate, or mixtures thereof. The sulphonate may be prepared from a mono-
or di- hydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl, or
bicyclopentadienyl) sulphonic acid, wherein the hydrocarbyl group may contain
6 to 40, or 8 to 35 or 9 to 30 carbon atoms.
[0061] The hydrocarbyl group may be derived from polypropylene or a
linear or branched alkyl group containing at least 10 carbon atoms. Examples
of a suitable alkyl group include branched and/or linear decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-
eicosyl, penta-eicosyl, hexa-eicosyl or mixtures thereof
[0062] In one embodiment the hydrocarbyl-substituted sulphonic acid
may
include polyprop ene benzenesulphonic acid and/or C16-C24 alkyl
benzenesulphonic acid, or mixtures thereof.
[0063] In one embodiment a calcium 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). In some embodiments the linear alkyl
group may be attached to the benzene ring anywhere along the linear chain of
the
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alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in
some
instances predominantly in the 2 position.
[0064] When neutral or slightly basic, a calcium sulphonate detergent
may
have TBN of less than 100, or less than 75, typically 20 to 50 mg KOH/g, or 0
to 20 mg KOH/g.
[0065] When overbased, a calcium sulphonate detergent may have a TBN
greater than 200, or 300 to 550, or 350 to 450 mg KOH/g.
[0066] The detergent may be borated or non-borated.
[0067] Chemical structures for sulphonates, and phenates detergents
are
known to a person skilled in the art. The standard textbook entitled
"Chemistry
and Technology of Lubricants", Third Edition, Edited by R. M. Mortier and S.
T. Orszulik, Copyright 2010, pages 220 to 223 under the sub-heading 7.2.6
provide general disclosures of said detergents and their structures.
[0068] In one embodiment the calcium-containing detergent may be an
overbased calcium sulphonate, an overbased calcium phenate, or mixtures
thereof Typically the detergent may be an overbased calcium sulphonate.
[0069] In one embodiment the calcium-containing detergent may be in a
mixture with a having zinc-, barium-, sodium-, or magnesium- containing
detergent. The zinc-, barium-, sodium-, or magnesium- containing detergent is
also well known in the art and described in the same references describing a
calcium-containing detergent. The TBN and metal ratios may however, differ
slightly. The zinc-, barium-, sodium-, or magnesium- containing detergent may
be a phenate, a sulphur-containing phenate, sulphonate, salixarate or
salicylate.
Typically a zinc-, barium-, sodium-, or magnesium- containing detergent may
be a magnesium phenate, a magnesium sulphur-containing phenate, or a
magnesium sulphonate.
Phosphorus-containing compound
[0070] The phosphorus-containing compounds may be an acid, salt or
ester;
and may be a friction modifier, an antiwear agent, an extreme pressure agent
or
mixtures thereof. In one embodiment the phosphorus-containing compounds
are in the form of a mixture of two or three, or two to four (typically two or
three) phosphorus-containing compounds.
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[0071] The phosphorus-containing compound may be metal-containing or
metal free (prior to being mixed with other components).
[0072] The phosphorus-containing compound may be present in an amount
to
deliver 400 ppm to 900 ppm, or 500 ppm to 850 ppm, or 525 ppm to 800 ppm of
phosphorus.
[0073] The phosphorus-containing compound may be derived from a
phosphoric acid, phosphorous acid, thiophosphoric acid, thiophosphorous acid,
or mixtures thereof.
[0074] The phosphorus-containing compound may be a non-ionic
phosphorus compound.
[0075] In one embodiment the phosphorus-containing compounds comprise
two or more (possibly up to four) non-ionic phosphorus compounds. Typically
the non-ionic phosphorus compound may have an oxidation of +3 or +5. The
different embodiments comprise phosphite ester, phosphate esters, or mixtures
thereof.
[0076] In one embodiment the phosphorus-containing compound comprises
a non-ionic phosphorus compound (a C4_6 hydrocarbyl phosphite) and an amine
salt of a phosphorus acid or ester.
[0077] The phosphorus-containing compound comprises a non-ionic
phosphorus compound that is a C4_6 hydrocarbyl phosphite, or mixtures thereof
The C4_6 hydrocarbyl phosphite of the invention includes those represented by
the formula:
R-0 H
\ /
P
IR-0 \
wherein each R" may be independently hydrogen or a hydrocarbyl group having 4
to 6 carbon atoms, typically 4 carbon atoms, with the proviso that at least
one of the
R" groups is hydrocarbyl. Typically the C4_6 hydrocarbyl phosphite comprises
dibutyl phosphite.
[0078] The C4_6 hydrocarbyl phosphite may deliver at least 175 ppm, or
at
least 200 ppm of the total amount of phosphorus delivered by the phosphorus-
containing compounds.
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[0079] The C4_6 hydrocarbyl phosphite may deliver at least 45 wt %, or
50
wt % to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the total
amount of phosphorus from the phosphorus-containing compound.
[0080] The phosphorus-containing compounds may comprise a second
phosphite whose formula is similar to that disclosed above, except R" may
contain 2 to 40, 8 to 24 or 11 to 20 carbon atoms, with the proviso that the
second phosphite is not a C4_6 hydrocarbyl phosphite. Examples of suitable
hydrocarbyl groups include propyl, dodecyl, butadecyl, hexadecyl, octadecyl,
propenyl, dodecenyl, butadecenyl, hexadeencyl, or octadecenylgroups.
[0081] As used herein the term "alk(en)yl" is intended to include moieties
that have an alkyl and/or alkenyl group.
[0082] In one embodiment the phosphorus-containing compounds include a
mixture of a C4_6 hydrocarbyl phosphite (typically dibutyl phosphite) and a
C12_
18 alk(en)yl hydrogen phosphite and optionally phosphoric acid.In different
embodiments the phosphoric acid is present or absent.
[0083] In one embodiment the phosphorus-containing compounds include a
mixture of a C4_6 hydrocarbyl phosphite (typically dibutyl phosphite) and a
C16_
18 alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite be may an
alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of
alkenyl hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment
the alk(en)yl hydrogen phosphite be may a mixture of alkenyl hydrogen
phosphite and alkyl hydrogen phosphite and optionally phosphoric acid. The
phosphoric acid may be present or absent.
[0084] In one embodiment the phosphorus-containing compounds include a
mixture of a C4_6 hydrocarbyl phosphite (typically dibutyl phosphite) and a
C11_
14 alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite be may an
alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of
alkenyl hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment
the alk(en)yl hydrogen phosphite may be a mixture of alkenyl hydrogen
phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.
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[0085] In
one embodiment the phosphorus-containing compounds include a
mixture of a C4_6 hydrocarbyl phosphite (typically dibutyl phosphite) and
phosphoric acid.
[0086] The
lubricating composition of the invention in one embodiment
includes a package that comprises a phosphorus-containing compound and a
non-ionic phosphorus compound that is a hydrocarbyl phosphite.
[0087] In
one embodiment the lubricating composition further comprises a
C8_20 hydrocarbyl phosphite, or a C12-18 hydrocarbyl phosphite, or C16-18
hydrocarbyl phosphite.
[0088] In different
embodiments the lubricating composition of the
invention may or may not contain phosphoric acid. In one embodiment the
lubricating composition further includes phosphoric acid.
Dispersant
[0089] The
borated dispersant of the invention may be a succinimide
dispersant, a Mannich dispersant, a polyolefin succinic acid ester, amide, or
ester-amide, or mixtures thereof. In
one embodiment the non-borated
dispersant may be a borated succinimide dispersant.
[0090] The
borated dispersant may be based upon a borated polyisobutylene
succinimide dispersant, wherein the polyisobutylene of the borated
polyisobutylene succinimide has a number average molecular weight of 750 to
2200, or 750 to 1350, or 750 to 1150.
[0091] The
borated dispersant may be used alone or as part of a mixture of
borated dispersants. If a mixture of borated dispersants is used, there may be
two
to five, or two to three or two borated dispersants.
[0092] A second
borated dispersant may also be a borated polyisobutylene
succinimide dispersant (provided it is chemically different from the first
borated
dispersant), wherein the polyisobutylene of the borated polyisobutylene
succinimide has a number average molecular weight of 750 to 2200, or 750 to
1350, or 750 to 1150.
[0093] The
lubricating composition containing one or more borated
dispersant may also further comprise a non-borated dispersant. The non-borated
may be a polyisobutylene succinimide, wherein the polyisobutylene of the
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borated polyisobutylene succinimide has a number average molecular weight of
750 to 2200, or 750 to 1350, or 750 to 1150.
[0094] The borated and non-borated polyisobutylene succinimide are
known
in the art and may be prepared with a polyisobutylene having a number average
molecular weight of 950.
[0095] The borated and non-borated dispersant may be formed by
reaction
of a substituted acylating agent with a polyamine (typically having two or
more
reactive sites). For example, the substituted acylating agent may be a
polyisobutylene succinic anhydride and the polyamine.
[0096] The polyamine may be an alkylenepolyamine. The alkylene-
polyamine may include an ethylenepolyamine, a propylenepolyamine, a
butylenepolyamine, or mixtures thereof. Examples of propylenepolyamine
include propylenediamine, dipropylenetriamine and mixtures thereof.
[0097] In one embodiment the polyamine is selected from the group
consisting of ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms and
mixtures thereof.
[0098] The borated and non-borated dispersant may be
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 non-borated dispersant prepared by a process that includes
an "ene" reaction may be a polyisobutylene succinimide having a carbocyclic
ring present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less
than 20 mole %, or 0 mole % of the dispersant molecules. The "ene" reaction
may have a reaction temperature of 180 C to less than 300 C, or 200 C to
250 C, or 200 C to 220 C.
[0099] The borated and non-borated 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
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produce a non-borated dispersant that is a polyisobutylene succinimide having
a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole %
(typically 100 mole %) of the dispersant molecules. Both the thermal and
chlorine-assisted processes are described in greater detail in U.S. Patent
7,615,521, columns 4-5 and preparative examples A and B.
[00100] The borated dispersant(s) of the present invention may be prepared in
such a way to have a N:CO ratio of 0.9:1 to 1.6:1, or 0.95:1 to 1.5:1, or 1:1
to
1:4.
[00101] The non-borated dispersant may have a carbonyl to nitrogen ratio
(CO:N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 1:1 to 1:10, or 1:1 to 1:5, or
1:1 to
1:2. In one embodiment the non-borated dispersant may have a CO:N ratio of
1:1 to 1:10, or 1:1 to 1:5, or 1:1 to 1:2.
[00102] The borated and non-borated dispersant may also be post-treated by
conventional methods by a reaction with any of a variety of agents. Among
these are urea, thiourea, dimercaptothiadiazoles, carbon disulphide,
aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic
anhydride, nitriles, epoxides, and phosphorus compounds.
[00103] The non-borated dispersant is typically present at 0.1 wt % to 10 wt
%, or 0.5 wt % to 7 wt %, or 1 wt % to 4 wt %, or 1.5 wt % to 3 wt % of the
lubricating oil composition.
[00104] The dispersant may be a reaction product prepared by heating
together: (a) a dispersant (such as a polyisobutylene succinimide) and (b) 2,5-
dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-
1,3,4-thiadiazole which is substantially insoluble in a hydrocarbon oil of
lubricating viscosity at 25 C, and further either (c) a borating agent or (d)
an
inorganic phosphorus compound, or both (c) and (d), said heating being
sufficient to provide a reaction product of (a), (b), and (c) or (d) which is
soluble in said hydrocarbon oil at 25 C.
[00105] The reaction product can typically contain 0.5 to 2.5 weight percent
sulfur derived from component (b), or 1 to 2 weight percent, or 1.25 to 1.5
weight percent sulfur. It can likewise contain 0.2 to 0.6 weight percent boron
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from component (c), or 0.3 to 1.1 percent phosphorus from component (d), or
such amounts from both components (c) and (d).
[00106] Borated dispersants may be prepared by borating using a variety of
agents selected from the group consisting of the various forms of boric acid
(including metaboric acid, HB02, orthoboric acid, H3B03, and tetraboric acid,
H2B407), boric oxide, boron trioxide, and alkyl borates. These agents are
described in more detail above. In one embodiment the borating agent is boric
acid which may be used alone or in combination with other borating agents.
[00107] The borated dispersant may be prepared by blending the boron
compound and a N-substituted long chain alkenyl succinimide and heating them
at a suitable temperature, typically 80 C to 250 C, 90 C to 230 C, or 100
C
to 210 C, until the desired reaction has occurred. An inert liquid may be
used
in performing the reaction. The liquid may include but are not limited to
toluene, xylene, chlorobenzene, dimethylformamide and mixtures thereof.
[00108] The borated dispersant may also be a product prepared by heating
together:
(i) a dispersant substrate;
(ii) 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-di-
mercapto-1,3,4-thiadiazole, or oligomers thereof;
(iii) a borating agent; and
(iv) optionally a dicarboxylic acid of an aromatic compound selected
from the group consisting of 1,3 diacids and 1,4 diacids; or
(v) optionally a phosphorus acid compound,
said heating being sufficient to provide a product of (i), (ii), (iii) and
optionally
(iv) or (v), which is soluble in an oil of lubricating viscosity.
[00109] The mixture of dispersant substrate, dicarboxylic acid of an aromatic
compound and the mercaptothiadiazole is treated with a borating agent and
optionally also with a phosphorus acid or anhydride. The components may be
combined and reacted in any order. In particular, the borating agent may be a
pre-treatment process or a post-treatment process. Thus, for instance, boric
acid (and optionally also phosphoric acid) may be reacted with a dispersant
substrate in one step, and thereafter the intermediate borated dispersant may
be
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reacted with the mercaptothiadiazole and the dicarboxylic acid of an aromatic
compound. Alternatively, the dispersant substrate, dicarboxylic acid of an
aromatic compound and mercapthothiadiazole may be first reacted, and then the
product treated with a borating agent (and optionally with phosphoric acid, a
phosphorus acid). In yet another variation, a phosphorylated succinimide
dispersant may be prepared by reacting a phosphorus acid with a hydrocarbyl-
substituted succinic anhydride to prepare a mixed anhydride-acid precursor,
and then reacting the precursor with a polyamine to form a phosphorus-
containing dispersant. The phosphorus-containing dispersant may thereafter be
reacted with the dicarboxylic acid of an aromatic compound and
mercaptothiadiazole; and with the borating agent.
[00110] The components are typically reacted by heating the borating agent
and optionally the phosphorus acid compound (together or sequentially) with
the remaining components, that is, with the dispersant substrate, dicarboxylic
acid of an aromatic compound and the dimercaptothiadiazole, although other
orders of reaction are possible, as described above. The heating will be at a
sufficient time and temperature to assure solubility of resulting product,
typically 80-200 C, or 90-180 C, or 120-170 C, or 150-170 C. The time of
reaction is typically at least 0.5 hours, for instance, 1-24 hours, 2-12
hours, 4-
10 hours, or 6-8 hours. The length of time required for the reaction is
determined in part by the temperature of the reaction, as will be apparent to
one
skilled in the art. Progress of the reaction is generally evidenced by the
evolution of H2S or water from the reaction mixture. Typically, the H2S is
derived from one or more of the sulphur atoms in the dimercaptothiadiazole.
[00111] The reaction product may typically contain 0.5 to 2.5 weight
percent
sulphur derived from component (iii), or 1 to 2 weight percent, or 1.25 to 1.5
weight percent sulphur. It may likewise contain 0.2 to 0.6 weight percent
boron from component (iv), or 0.3 to 1.1 percent phosphorus from component
(e), or such amounts from both components (iv) and (v).
[00112] The reaction may be conducted in a hydrophobic medium such as an
oil of lubricating viscosity which may, if desired, be retained in the final
product. The oil, however, should typically be an oil which does not itself
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react or decompose under conditions of the reaction. Thus, oils containing
reactive ester functionality are typically not used as diluent. Oils of
lubricating
viscosity are described in greater detail above.
[00113] In the absence of the dicarboxylic acid, the relative amounts of the
components which are reacted are, expressed as parts by weight prior to
reaction are typically 100 parts of (i) the dispersant, per 0.75 to 6 parts of
(ii)
the dimercaptothiadiazole or substituted dimercaptothiadiazole, and 0 or 0.01
to
7.5 parts of (iii) the borating agent, and 0.01 to 7.5 parts of (v) the
phosphorus
acid compound, provided that the relative amount of (iii) + (v) is at least
0.075
parts. In one embodiment the relative amounts are 100 parts of (i), 1.5 to 3
parts of (ii), 0 to 4.5 parts of (iii), and 0 to 4.5 parts of (v), provided
that (iii) +
(v) is at least 1.5 parts. In another embodiment, the relative amounts are 100
parts (i) : 1.5 to 2.2 parts (ii) : 3.7 to 4.4 parts (iii) : 1.5 to 4.4 parts
(v). The
amounts and ranges of the various components, in particular, (iii) and (v),
may
be independently combined so that there may be, for instance, 3.7 to 4.4 parts
of (iii) whether or not any of (v) is present, and likewise there may be 1.5
to 4.4
parts (v) whether or not any of (iii) is present.
[00114] When the dicarboxylic acid is present, relative amounts of the
components which are reacted are, expressed as parts by weight prior to
reaction are typically 100 parts of (i) the dispersant, per 5-5000 parts per
million of (ii) the dicarboxylic acid of an aromatic compound, 0.75 to 6 parts
of
(iii) the dimercaptothiadiazole or substituted dimercaptothiadiazole, and 0 to
7.5 parts of (iv) the borating agent and 0 to 7.5 parts of (v) the phosphorus
acid
compound, provided that the relative amount of (ii) + (iii) + (iv) + (v) is at
least
1.5 parts. In a one embodiment the relative amounts are 100 parts of (i), 1.5
to
6 parts of (ii), 5-1000 parts per million of (iii), 0 or 0.01 to 4.5 parts of
(iv), and
0 to 4.5 parts of (v), provided that (iii) + (iv) + (v) is at least 1.5 parts.
In
another embodiment, the relative amounts are 100 parts (i) : 1.5 to 5.0 parts
(ii)
: 25-500 parts per million (iii) : 3.7 to 4.4 parts (iv) : 0 to 4.4 parts (v).
The
amounts and ranges of the various components, in particular, (iv) and (v), may
be independently combined so that there may be, for instance, 3.7 to 4.4 parts
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of (iv) whether or not any of (v) is present, and likewise there may be 1.5 to
4.4
parts (v) whether or not any of (iv) is present.
The Dispersant Substrate
[00115] The product prepared by heating comprises a dispersant substrate.
The dispersant of the invention is well known and include a succinimide
dispersant (for example N-substituted long chain alkenyl succinimides), a
Mannich dispersant, an ester-containing dispersant, a condensation product of
a
fatty hydrocarbyl monocarboxylic acylating agent with an amine or ammonia,
an alkyl amino phenol dispersant, a hydrocarbyl-amine dispersant, a polyether
dispersant, a polyetheramine dispersant, a viscosity modifier containing
dispersant functionality (for example polymeric viscosity index modifiers
(VMs) containing dispersant functionality), or mixtures thereof Typically the
dispersant substrate is a succinimide, or mixtures thereof The dispersant
substrate may be a polyisobutylene succinimide.
[00116] In one embodiment the borated dispersant is prepared by reaction in
the presence of a 1,3-dicarboxylic acid or 1,4-dicarboxylic acid of an
aromatic
compound, or reactive equivalents thereof, or mixtures thereof, which is
reacted or complexed with the dispersant. The term "reactive equivalents
thereof' include acid halides, esters, amides or mixtures thereof The
"aromatic
component" is typically a benzene (phenylene) ring or a substituted benzene
ring,
although other aromatic materials such as fused ring compounds or heterocyclic
compounds are also contemplated. It is believed (without intending to be bound
by any theory) that the dicarboxylic acid aromatic compound may be bound to
the dispersant by salt formation or complexation, rather than formation of
covalently bonded structures such as amides, which may also be formed but
may play a less important role. Typically the presence of the dicarboxylic
acid
aromatic compound within the present invention is believed to impart corrosion
inhibition properties to the composition. Examples of suitable dicarboxylic
acids include 1,3-dicarboxylic acids such as isophthalic acid and alkyl
homologues such as 2-methyl isophthalic acid, 4-methyl isophthalic acid or 5-
methyl isophthalic acid; and 1,4-dicarboxylic acids such as terephthalic acid
and alkyl homologues such as 2-methyl terephthalic acid.
Other ring
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substituents such as hydroxy or alkoxy (e.g., methoxy) groups may also be
present in certain embodiments. In one embodiment the aromatic compound is
terephthalic acid.
[00117] In one embodiment the borated dispersant is prepared by reaction in
the presence of a dimercaptothiadiazole which is reacted as a part of the
"product prepared by heating." This is in addition to any
dimercaptothiadiazole
which may be present within a lubricating composition as a separate corrosion
inhibitor. Examples include 2,5-dimercapto-1,3-4-thiadiazole or a hydrocarbyl-
substituted 2,5-dimercapto-1,3-4-thiadiazole, or oligomers thereof. The
oligomers of hydro carbyl-
substituted 2,5 -dimercapto -1,3 -4-thiadiazo le
typically form by forming a sulphur-sulphur bond between 2,5-dimercapto-1,3-
4-thiadiazole units to form oligomers of two or more of said thiadiazole
units.
[00118] In one embodiment the borated dispersant is prepared by reaction in
the presence of a phosphorus acid compound. The phosphorus acid compound
may contain an oxygen atom and/or a sulphur atom as its constituent elements,
and is typically a phosphorus acid or anhydride. This component includes the
following examples: phosphorous acid, phosphoric acid, hypophosphoric acid,
polyphosphoric acid, phosphorus trioxide, phosphorus tetroxide, phosphorous
pentoxide (P205), phosphorotetrathionic acid (H3PS4), phosphoromonothionic
acid (H3P03S), phosphorodithionic acid (H3P02S2), phosphorotrithionic acid
(H3P02S3), and P2S5. Among these, phosphorous acid and phosphoric acid or
their anhydrides are typically used. A salt, such as an amine salt of a
phosphorus acid compound may also be used. It is also possible to use a
plurality of these phosphorus acid compounds together. The phosphorus acid
compound is often phosphoric acid or phosphorous acid or their anhydride.
[00119] The phosphorus acid compound may also include phosphorus
compounds with a phosphorus oxidation of +3 or +5, such as, phosphates,
phosphonates, phosphinates, or phosphine oxides. A more detailed description
for these suitable phosphorus acid compounds is described in US Patent
6,103,673, column 9, line 64 to column 11, line 8.
[00120] In one embodiment the phosphorus acid compound is an inorganic
phosphorus compound.
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[00121] The borated dispersant is typically present at 0.1 wt % to 10 wt %, or
0.5 wt % to 7 wt %, or 1 wt % to 4 wt % of the lubricating oil composition.
[00122] In one embodiment the dispersant package may comprise
(i) a non-borated dispersant that comprises a polyisobutylene
succinimide, wherein the polyisobutylene used to prepare the non-borated
dispersant has a number average molecular weight of 550 to 1150, or 750 to
1150, or 900 to 1000 (often commercially available with a number average
molecular weight of about 950); and
(ii) a borated dispersant that comprises a polyisobutylene succinimide,
wherein the polyisobutylene used to prepare the non-borated dispersant has a
number average molecular weight of 550 to 1150, or 750 to 1150, or 900 to
1000 (often commercially available with a number average molecular weight of
about 950).
[00123] In one embodiment the dispersant package may comprise:
(a) a non-borated dispersant that comprises a polyisobutylene
succinimide, wherein the polyisobutylene used to prepare the non-borated
dispersant has a number average molecular weight of 550 to 1150, or 750 to
1150, or 900 to 1000 (often commercially available with a number average
molecular weight of about 950); and
(b) the borated dispersant may also be a product prepared by heating
together:
(i) a dispersant substrate;
(ii) 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-di-
mercapto-1,3,4-thiadiazole, or oligomers thereof;
(iii) a borating agent; and
(iv) optionally a dicarboxylic acid of an aromatic compound selected
from the group consisting of 1,3 diacids and 1,4 diacids; or
(v) optionally a phosphorus acid compound,
said heating being sufficient to provide a product of (i), (ii), (iii) and
optionally
(iv) or (v), which is soluble in an oil of lubricating viscosity.
Viscosity Modifier
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[00124] As used herein ranges below for the viscosity modifier are measured
by GPC using polystyrene standards with a weight average molecular weight
ranging from 350 to 2,000,000.
[00125] The lubricating composition contains 0.1 wt % to 5 wt % (or 0.5 wt %
to 4 wt %) of a linear polymer having dispersant functionality. Compounds of
this type are known in the art and are considered different from dispersants
and
the molecular weights are lower than that of the linear polymer of the present
invention.
Linear Polymer
[00126] The lubricating composition of the invention in one embodiment
includes a linear polymer with a weight average molecular weight of 5,000 to
25,000, or 8000 to 20,000.
[00127] In one embodiment the linear polymer includes a poly(meth)acrylate,
or mixtures thereof. The linear polymer may be present in the compositions
described herein at 0.1 wt % to 5 wt %, or 0.1 wt % to 4 wt %, or 0.2 wt % to
3
wt %, or 0.5 wt % to 3 wt %, 0.5 wt % to 4 wt % of the lubricating
composition.
[00128] The linear polymer may have a composition that comprises a
poly(meth)acrylate polymer derived from a monomer composition
comprising:(a) 50 wt % to 95 wt %, or 60 wt % to 80 wt % of an alkyl
(meth)acrylate, wherein the alkyl group of the (meth)acrylate has 10 to 15
carbon atoms; (b) 1 wt % to 40 wt %, or 4 wt % to 35 wt % of an alkyl
(meth)acrylate, wherein the alkyl group of the (meth)acrylate has 1 to 9
carbon
atoms; (c) 1 wt % to 10 wt %, or 1 wt % to 8 wt % of a dispersant monomer,
(d) 0 wt % to 4 wt %, or 0 wt % to 2 wt %, or 0 wt % of a vinyl aromatic
monomer (typically styrene); and (e) 0 wt % to 9 wt %, or 0 wt % to 6 wt % of
an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 16
to
18 carbon atoms. In one embodiment the linear polymer may contain 0 wt % to
20 wt % of 16 to 18 alkyl (meth)acrylate.
[00129] The Star polymer may be derived from a monomer composition
comprising C12-15 alkyl (meth)acrylate (about 80 wt %), and about 20 wt % of a
mixture of monomers composed of methyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, and ethylene glycol di(meth)acrylate. a difunctional The
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linear polymer may be derived from a monomer composition comprising 2-
ethylhexyl (meth)acrylate (30 wt %), C12-15 alkyl (meth)acrylate (68.2 wt %),
and dimethylaminopropyl (meth)acrylate (1.8 wt %).
[00130] In one embodiment the linear polymer includes a poly(meth)acrylate
(typically a polymethacrylate) with units derived from a mixture of alkyl
(meth)acrylate ester monomers containing, (a) 8 to 24, or 10 to 18, or 12 to
15
carbon atoms in the alcohol-derived portion of the ester group and (b) 6 to
11, or
8 to 11, or 8 carbon atoms in the alcohol-derived portion of the ester group,
and
which have 2-(C1_4 alkyl)-substituents, and optionally, at least one monomer
selected from the group consisting of (meth)acrylic acid esters containing 1
to 7
carbon atoms in the alcohol-derived portion of the ester group and which are
different from (meth)acrylic acid esters (a) and (b), vinyl aromatic compounds
(or vinyl aromatic monomers); and nitrogen-containing vinyl monomer; provided
that no more than 60% by weight, or no more than 50% by weight, or no more
than 35% by weight of the esters contain not more than 10 carbon atoms in the
alcohol-derived portion of the ester group. The linear polymer of this type is
described in more detail in US 6,124,249, or EP 0 937 769 Al paragraphs [0019]
and [0031] to [0067]. (The "alcohol-derived portion" refers to the "-OR"
portion
of an ester, when written as R'C(=0)-OR, whether or not it is actually
prepared
by reaction with an alcohol.) Optionally, the linear polymer may further
contain
a third monomer. The third monomer may be styrene, or mixtures thereof. The
third monomer may be present in an amount 0% to 25% of the polymer
composition, or from 1% to 15% of the composition, 2% to 10% of the
composition, or even from 1% to 3% of the composition.
[00131] Typically, the mole ratio of esters (a) to esters (b) in the copolymer
ranges from 95:5 to 35:65, or 90:10 to 60:40, or 80:20 to 50:50.
[00132] The esters are usually aliphatic esters, typically alkyl esters. In
one
embodiment the ester of (a) may be a C12-15 alkyl (meth)acrylate and the ester
of (b) may be 2-ethylhexyl (meth)acrylate.
[00133] In one embodiment, the ester groups in ester (a) contain branched
alkyl groups. The ester groups may contain 2 to 65%, or 5 to 60% of the ester
groups having branched alkyl groups. The branched alkyl groups may be
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I3-branched and may contain 8 to 60, or 8 to 30, or 8 to 16 carbon atoms. For
examples branched alkyl groups may be derived from 2-ethylhexanol, 2-
butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or
mixtures thereof, or commercially available alcohols such as Isofol0 branched
Guerbet alcohols available from Sasol.
[00134] The C1_4 alkyl substituents may be methyl, ethyl, and any isomers of
propyl and butyl.
[00135] The weight average molecular weight of the linear
poly(meth)acrylate may be 45,000 or less, or 35,000 or less, or 25,000 or
less, or
8000 to 25,000, or, 10,000 to 35,000, or 12,000 to 20,000.
[00136] The linear polymer viscosity modifier having dispersant functionality
may be used as a sole dispersant viscosity modifier present at 0.5 wt % to 4
wt %
of a linear (meth)acrylic polymer viscosity modifier having dispersant
functionality, wherein the linear polymer has a weight average molecular
weight
of 5,000 to 25,000, or 10,000 to 20,000, and wherein oil the of lubricating
viscosity has a kinematic viscosity at 100 C of 2.8 to 3.1 cSt (mm2/s) and a
viscosity index of 104 to 130.
[00137] The lubricating composition in one embodiment may contain only two
linear polymer viscosity modifiers having dispersant functionality, wherein
the
linear polymer has a weight average molecular weight of 5,000 to 25,000, or
10,000 to 20,000,
[00138] In one embodiment the lubricating composition of the invention
includes a viscosity modifier comprises a star polymer and linear polymer
described herein.
[00139] In one embodiment the lubricating composition may comprise 0.1
wt% to 4 wt % (or 0.2 wt % to 3 wt %) of a linear (meth)acrylic polymer
viscosity modifier having dispersant functionality, wherein the linear polymer
has a weight average molecular weight of greater than 25,000 to 400,000 (or to
350,000) or 30,000 to 150,000. The linear (meth)acrylic polymer a weight
average molecular weight of greater than 25,000 to 400,000 (or to 350,000) may
be considered chemically similar to the linear (meth)acrylic polymer a weight
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average molecular weight of 5,000 to 25,000 except the weight average
molecular weight is different.
[00140] The lubricating composition may comprise a linear polymer viscosity
modifier having dispersant functionality comprises:0.1 wt % to 4 wt % (or 0.2
wt
% to 3 wt %) of a linear (meth)acrylic polymer viscosity modifier having
dispersant functionality, wherein the linear polymer has a weight average
molecular weight of 10,000 to 20,000; and 0.1 wt % to 4 wt % (or 0.2 wt % to 3
wt %) of a linear (meth)acrylic polymer viscosity modifier having dispersant
functionality, wherein the linear polymer has a weight average molecular
weight
of greater than 20,000 to 250,000 (or 30,000 to 150,000).
[00141] The lubricating composition may comprise a linear polymer viscosity
modifier having dispersant functionality comprises 0.1 wt % to 4 wt % (or 0.2
wt
% to 3 wt %) of a linear (meth)acrylic polymer having dispersant functionality
wherein the linear polymer has a weight average molecular weight of 5,000 to
25,000 or 10,000 to 20,000, and the composition further comprises 0.1 wt % to
4
wt % (or 0.2 wt % to 3 wt %) of a (meth)acrylic polymer having star
architecture.
[00142] A detailed description of the star polymer disclosed herein may also
be described in WO 2007/127660 (published on 8 November 2007, by Baker et
at. and assigned to The Lubrizol Corporation), paragraphs [0021] to [0061].
Baker discloses composition and methods of preparation of a variety of star
polymers.
[00143] In different embodiments the star polymer may contain greater than
50 wt %, or 55 wt % or more, or 70 wt % or more, or 90 wt % or more, or 95 wt
%
or more, or 100 wt % of a non-diene monomer (that is to say, non-diene monomer
units or units derived from polymerisation of one of more non-diene monomers).
Examples of diene monomers include 1,3-butadiene or isoprene. In contrast,
examples of a non-diene of the present invention may include styrene,
(meth)acrylates, acrylates, or mixtures thereof. In one embodiment the star
polymer may be a polymer derived from (meth)acrylates, or mixtures thereof,
and
is free of styrene.
[00144] As described hereinafter the molecular weight of the viscosity
modifier has been determined using known methods, such as GPC analysis
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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 star polymer Chemistry", Cornell University Press 91953),
Chapter
VII, pp 266-315; or (ii) "Macromolecules, an Introduction to star polymer
Science",
F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312. As
used herein the weight average and number average molecular weights of the
polymers of the invention are obtained by integrating the area under the peak
corresponding to the star polymer of the invention, which is normally the
major high
molecular weight peak, excluding peaks associated with diluents, impurities,
uncoupled star polymer chains and other additives.
[00145] The (meth)acrylic polymer having star architecture has three or more
arms that comprise a poly(meth)acrylate polymer is derived from a monomer
composition comprising: (a) 50 wt % to 100 wt % of an alkyl (meth)acrylate,
wherein the alkyl group of the (meth)acrylate has 12 to 15 carbon atoms;(b) 0
wt %
to 40 wt % of an alkyl (meth)acrylate, wherein the alkyl group of the
(meth)acrylate
has 1 to 9 carbon atoms; (c) 0 wt % to 10 wt % of a dispersant monomer, (d) 0
wt %
to 5 wt %, or 0 wt % to 2 wt %, or 0 wt % of a vinyl aromatic monomer
(typically
styrene); and (e) 0 wt % to 20 wt %, or 0 wt % to 10 wt %, or 0 wt % of an
alkyl
(meth)acrylate, wherein the alkyl group of the (meth)acrylate has 16 to 18
carbon
atoms.
[00146] The (meth)acrylic polymer having star architecture may have three or
more arms that comprise a poly(meth)acrylate polymer is derived from a monomer
composition comprising:(a) 60 wt % to 95 wt % of an alkyl (meth)acrylate,
wherein
the alkyl group of the (meth)acrylate has 12 to 15 carbon atoms;(b) 5 wt % to
30 wt
% of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate
has 1 to
9 carbon atoms; (c) 0 wt % to 10 wt % of a dispersant monomer, (d) 0 wt % to 5
wt
%, or 0 wt % to 2 wt %, or 0 wt % of a vinyl aromatic monomer (typically
styrene);
and(e) 0 wt % to 20 wt %, or 0 wt % to 10 wt %, or 0 wt % of an alkyl
(meth)acrylate, wherein the alkyl group of the (meth)acrylate has 16 to 18
carbon
atoms.
[00147] The star polymer may have a weight average molecular weight of
100,000 to 1,300,000, or 125,000 to 1,000,000, or 150,000 to 950,000, or
200,000 to
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800,000. As used herein the shear stability index (SSI) of the star polymer
may be
determined by a 20 hour KRL test (Volkswagen Tapered Bearing Roller Test). The
test procedure is set out in both CEC-L-45-99 or equivalent test method DIN
51350-
6-KRL/C.
[00148] The star polymer SSI may be in the range of 0 to 100, or 0 to 80, or 0
to
60, or 0 to 50, 0 to 20, or 0 to 15, or 0 to 10, or 0 to 5. An example of a
suitable
range for the SSI includes 1 to 5, 10 to 25, or 25 to 65.
[00149] The star polymer may be a homopolymer or a copolymer, that is, its
arms may be homopolymeric or copolymeric (i.e., containing two or more
monomer types). In one embodiment the star polymer may be a copolymer.
The star polymer may be a star polymer having a random, tapered, di-block, tri-
block or multi-block architecture. Typically the star polymer has random or
tapered architecture.
[00150] The star polymer may have arms that may have a block-arm
architecture, or hetero-arm architecture, or tapered-arm architecture. Tapered-
arm architecture has a variable composition across the length of a star
polymer
arm. For example, the tapered arm may be composed of, at one end, a
relatively pure first monomer and, at the other end, a relatively pure second
monomer. The middle of the arm is more of a gradient composition of the two
monomers.
[00151] The hetero-arm, or "mikto-arm," star polymers contain arms
which may vary from one another either in molecular weight, composition, or
both, as described in Hsieh et al. (Chapter 13 (pp. 333-368) of "Anionic
Polymerization, Principles and Practical Applications" by Henry Hsieh and
Roderic
Quirk (Marcel Dekker, Inc, New York, 1996) (hereinafter referred to as Hsieh
et
al.). For example, a portion of the arms of a given star polymer may be of one
polymeric type and a portion of a second polymeric type. More complex
hetero-arm star polymers may be formed by combining portions of three or
more polymeric arms with a coupling agent. In one embodiment hetero-arm
stars may be prepared by combining several batches of polymers with living
characteristics prior to linkage and core formation.
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[00152] The above-described monomers, as used in the disclosed technology for
formation of the "arm" portion of the polymers, are based on methacrylic acid
rather than acrylic acid. In certain embodiments, methacrylic polymers have
better
low temperature properties than do acrylic polymers. In general, the amount of
acrylic monomers present in the reaction mixture to form the polymer arms or
in
the resulting polymer arms themselves may be 0 to 5 mole % , or 0.001 to 2
mole
% or 0.01 to 1 mole percent or 0.05 to 0.5 mole percent, or less than 0.1 mole
percent.
[00153] The star polymer with branched, comb-like, radial or star
architecture may have 2 or more arms, or 5 or more arms, or 7 or more arms, or
10 or more arms, for instance 12 to 100, or 14 to 50, or 16 to 40 arms. The
star
polymer with branched, comb-like, radial or star architecture may have 120
arms or less, or 80 arms or less, or 60 arms or less.
[00154] The star polymer may be obtained/obtainable from a controlled
radical polymerisation technique. Examples of a
controlled radical
polymerisation technique include RAFT, ATRP or nitroxide mediated
processes. The star polymer may also be obtained/obtainable from anionic
polymerisation processes. In one embodiment the star polymer may be
obtained/obtainable from RAFT, ATRP or anionic polymerisation process. In
one embodiment the star polymer may be obtained/obtainable from RAFT or
ATRP polymerisation process. In one embodiment the star polymer may be
obtained/obtainable from a RAFT polymerisation process.
[00155] RAFT or ATRP polymerization process are preferred to other
polymerization techniques when preparing star polymers because polar vinyl
monomers, including (meth)acrylates and (meth)acrylamides may be prone to side
reactions during anionic polymerisation, making anionic polymerization less
desirable.
[00156] Methods of preparing polymers using ATRP, RAFT or nitroxide-
mediated techniques are disclosed in the example section of International
Publication WO 2006/047398, see examples 1 to 47.
[00157] 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), ATRP (Chapter 11, pages 523 to 628) and RAFT
(Chapter 12, pages 629 to 690) 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 at.").
[00158] The discussion of the star polymer mechanism of ATRP
polymerisation is shown on page 524 in reaction scheme 11.1, page 566
reaction scheme 11.4, reaction scheme 11.7 on page 571, reaction scheme 11.8
on page 572 and reaction scheme 11.9 on page 575 of Matyjaszewski et at. 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
6,391,996, or paragraphs 61 to 65 of International Publication WO
2006/047398.
[00159] In RAFT polymerisation, chain transfer agents are important. A
more detailed review of suitable chain transfer agents is found in paragraphs
[0066] to [0071] of International Publication WO 2006/047398. In one
embodiment a suitable RAFT chain transfer agent includes 2-dodecylsulphanyl-
thiocarbonylsulphany1-2-methyl-propionic acid butyl ester, cumyl
dithiobenzoate
or mixtures thereof. A discussion of the star polymer mechanism of RAFT
polymerisation is shown on page 664 to 665 in section 12.4.4 of Matyjaszewski
et at.
[00160] The star polymers may be prepared by techniques known in the art to
prepare either core-first or arm-first approaches. Typically the star polymer
is
prepared by an "arm-first" approach using RAFT or ATRP (typically RAFT)
polymerization techniques.
[00161] The (meth)acrylic polymer having star architecture may be prepared
from known monomers such as alkyl (meth)acrylate. Alkyl (meth)acrylates
include, for example, compounds derived from saturated alcohols, such as
methyl
(meth)acrylate, butyl (meth)acrylate, 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-butylheptyl (meth)acrylate,
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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-methyltridecyl (meth)acrylate,
tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl
(meth)acrylate,
2-methylhexadecyl (meth)acrylate, heptadecyl (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 cycloalkyl (meth)acrylates, such
as
3-vinyl-2-butylcyclohexyl (meth)acrylate or bornyl (meth)acrylate.
[00162] 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 (meth)acrylate (by transesterification) with long-
chain
fatty alcohols, in which reaction a mixture of esters such as (meth)acrylate
with
alkyl 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); Epal0 610 and Epal0 810 of Ethyl Corporation;
Linevol0 79, Linevol0 911 and Dobano10 25 L of Shell AG; Liar) 125 of
Condea Augusta, Milan; Dehydad0 and Lorol0 of Henkel KGaA (now Cognis)
as well as Linopol0 7-11 and Acropol0 91 of Ugine Kuhlmann, as well as
Isofol0 branched Guerbet alcohols from Sasol.
[00163] In one embodiment the star polymer may be further functionalised in
the core or the polymeric arms with a nitrogen-containing monomer. The
nitrogen-containing monomer may be referred to as a dispersant monomer. The
nitrogen-containing monomer may include a vinyl-substituted nitrogen
heterocyclic monomer, a dialkylamino alkyl (meth)acrylate monomer, a
dialkylaminoalkyl (meth)acrylamide monomer, a tertiary-(meth)acrylamide
monomer, ureido (meth)acrylate, or mixtures thereof
[00164] In one embodiment the core or polymeric arms further comprise a
(meth)acrylamide or a nitrogen containing (meth)acrylate monomer. Examples
of a suitable nitrogen-containing vinyl monomer include
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N,N-dimethylacrylamide, N-vinyl carbonamides such as N-vinyl-formamide,
vinyl pyridine, N-vinylacetoamide, N-vinyl-n-propionamides, N-vinyl
hydroxyacetoamide, N-vinyl imidazole, N-vinyl pyrrolidinone, N-vinyl
caprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylamino ethyl-
(meth)acrylate (DMAEMA), dimethylaminobutylacrylamide, dimethylamine-
propyl(meth)acrylate (DMAPMA),
dimethylamine-propyl-acrylamide,
dimethylaminopropylmethacrylamide, dimethylaminoethyl-acrylamide, or
mixtures thereof. A
dispersant monomer may also be oxygen-containing
compound. The
oxygen-containing compound may include hydroxyalkyl
(meth)acrylates such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl
(meth)acrylate, 2 -hydro x yethyl (meth)acrylate, 2 -
hydroxypropyl
(meth)acrylate, 2,5-dimethy1-1,6-hexanediol (meth)acrylate, 1,10-decanediol
(meth)acrylate, carbonyl-containing (meth)acrylates such as 2-carboxyethyl
(meth)acrylate, carboxymethyl (meth)acrylate,
oxazolidinylethyl
(meth)acrylate, N-(methacryloyloxy)formamide, acetonyl (meth)acrylate, N-
methacryloylmorpholine, N-methacryloy1-2 -pyrro lidinone, N-(2-
methacryloyloxyethyl)-2-pyrro lidinone, N-(3
-methacryloyloxypropy1)-2 -
pyrro lidinone, N - (2 -methacryloyloxyp entade cy1)-2 -pyrro lidinone,
N-(3 -
methacryloyloxyheptadecy1)-2-pyrrolidinone; glycol di(meth)acrylates such as
ethylene glycol di(meth)acrylate, 1,4-butanediol (meth)acrylate, 2-butoxyethyl
(meth) acryl at e, 2 -ethoxyethoxymethyl (m eth) acryl ate , 2 -
ethoxyethyl
(meth)acrylate, or mixtures thereof
[00165] Other examples of suitable non-carbonyl oxygen containing
compounds capable of being incorporated into the copolymer include
(meth)acrylates of ether alcohols, such as tetrahydrofurfuryl (meth)acrylate,
vinyloxyethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1-
butoxypropyl (meth)acrylate, 1-methyl-(2-vinyloxy)ethyl (meth)acrylate, cyclo-
hexyloxymethyl (meth)acrylate, methoxymethoxyethyl (meth)acrylate,
b enzyloxymethyl (m eth)a cryl ate , furfuryl (meth)acrylate, 2 -butoxyethyl
(meth) acryl at e, 2 -ethoxyethoxymethyl (m eth) acryl
ate , 2 -ethoxyethyl
(meth)acrylate, allyloxymethyl (meth)acrylate, 1-ethoxybutyl (meth)acrylate,
methoxymethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, ethoxymethyl
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(meth)acrylate and ethoxylated (meth)acrylates which typically have 1 to 20,
or
2 to 8, ethoxy groups, or mixtures thereof.
[00166] The star polymer may be prepared from a bifunctional monomer
divinylb enzene, dip entaerythritol hexamethacrylate, dip
enta erythritol
hexaacrylate, tripentaerythritol
octamethacrylate, tripentaerythritol
octaacrylate, pentaerythritol tetraacrylate, pentaerythritol
tetramethacrylate,
bis-acrylates and methacrylates of polyethylene glycols of molecular weight
200-4000, polycaprolactonediol diacrylate, pentaerythritol triacrylate,
pentaerythritol trimethacrylate,
1,1,1 -trimethylolpropane triacrylate,
pentaerythritol diacrylate, pentaerythritol tetraacrylate, ethylene glycol
dimethacrylate, triethylene glycol diacrylate, triethylene glycol
dimethacrylate,
1,1,1-trimethylolpropane trimethacrylate, hexamethylenediol diacrylate or
hexamethylenediol dimethacrylate or an alkylene bis-(meth)acrylamide.
Typically the bifunctional monomer comprises a bifunctional methacrylate
monomer.
[00167] The linear or star (meth)acrylate may contain 0 wt % to 30 wt % or 0
wt % to 20 wt % of a C1-C10, or C1-C8 acrylate group. The acrylate groups may
for instance be ethyl acrylate or 2-ethylhexyl acrylate.
[00168] The lubricating composition of the present invention may further
comprise 0.1 wt % to 5 wt % (0.1 wt % to 4 wt % or 0.2 wt % to 3 wt %) of a
polymer having comb architecture.
[00169] The polymer having comb architecture may be a comb polymer
comprising, in the main chain, repeat units which are derived from polyolefin-
based macromonomers, and repeat units which are derived from low molecular
weight monomers selected from the group consisting of styrene monomers
having from 8 to 17 carbon atoms, alkyl(meth)acrylates having from 1 to 15
carbon atoms in the alcohol group, vinyl esters having from 1 to 11 carbon
atoms in the acyl group, vinyl ethers having from 1 to 10 carbon atoms in the
alcohol group, (di)alkyl fumarates having from 1 to 10 carbon atoms in the
alcohol group, (di)alkyl maleates having from 1 to 10 carbon atoms in the
alcohol group, and mixtures of these monomers, wherein the molar degree of
branching is in the range from 0.1 to 10 mol % and the comb polymer
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comprises a total of at least 80% by weight, based on the weight of the repeat
units, which are derived from polyolefin-based macromonomers, and repeat
units which are derived from low molecular weight monomers selected from
the group consisting of styrene monomers having from 8 to 17 carbon atoms,
alkyl(meth)acrylates having from 1 to 15 carbon atoms in the alcohol group,
vinyl esters having from 1 to 11 carbon atoms in the acyl group, vinyl ethers
having from 1 to 10 carbon atoms in the alcohol group, (di)alkyl fumarates
having from 1 to 10 carbon atoms in the alcohol group, (di)alkyl maleates
having from 1 to 10 carbon atoms in the alcohol group, and mixtures of these
monomers.
[00170] In one embodiment the polymer having comb architecture may have
a glass transition temperature in the range from -30 to 100 C.
[00171] The polymer having comb architecture may have repeat units which
are derived from polyolefin-based macromonomers have a number-average
molecular weight in the range from 500 to 10 000 g/mol.
[00172] The polymer having comb architecture may have at least 90% by
weight of repeat units which are derived from polyolefin-based
macromonomers and repeat units which are derived from low molecular weight
monomers selected from the group consisting of styrene monomers having from
8 to 17 carbon atoms, alkyl(meth)acrylates having from 1 to 15 carbon atoms in
the alcohol group, vinyl esters having from 1 to 11 carbon atoms in the acyl
group, vinyl ethers having from 1 to 10 carbon atoms in the alcohol group,
(di)alkyl fumarates having from 1 to 10 carbon atoms in the alcohol group,
(di)alkyl maleates having from 1 to 10 carbon atoms in the alcohol group, and
mixtures of these monomers.
[00173] The polymer having comb architecture may have a molar degree of
branching is- in the range from 0.8% to 6.0%, or 0.8% to 3.4%.
[00174] The polymer having comb architecture may have the iodine number
of less than or equal to 0.2 g per g of comb polymer.
[00175] The polymer having comb architecture may have the repeat units
derived from polyolefin-based macromonomers which are derived from
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monomers selected from the group consisting of C2-C10-alkenes and/or C4-
C10-alkadienes .
[00176] The repeat units may be derived from polyolefin-based
macromonomers which comprise at least 80% by weight of groups which are
derived from monomers selected from the group consisting of C2-C10-alkenes
and/or C4-C10-alkadienes, based on the weight of the repeat units derived from
polyolefin-based macromonomers.
[00177] The polymer having comb architecture may have the repeat units
derived from polyolefin-based macromonomers comprising groups which are
derived from non-olefinic monomers selected from the group of styrenes,
(meth)acrylates, vinyl esters, vinyl ethers, fumarates and maleates.
[00178] The repeat units may be derived afe from polyolefin-based
macromonomers comprising at most 20% by weight of groups which are
derived from non-olefinic monomers selected from the group of styrenes,
(meth)acrylates, vinyl esters, vinyl ethers, fumarates and maleates, based on
the
weight of the repeat units.
[00179] The polymer having comb architecture may have repeat units derived
from polyolefin-based macromonomers having a melting point of less than or
equal to -10 C.
[00180] The polymer having comb architecture may have repeat units which
are derived from styrene, and repeat units which are derived from n-butyl
methacrylate. The repeat units may be derived from styrene, and repeat units
which are derived from n-butyl acrylate.
[00181] The polymer having comb architecture may have repeat units which
are derived from methyl methacrylate and repeat units which are derived from
n-butyl methacrylate.
[00182] The polymer having comb architecture may have a weight-average
molecular weight in the range from 50,000 to 500,000 g/mol.
[00183] The process to prepare the polymer having comb architecture may be
continuous or batch-wise, typically batch-wise.
[00184] The process to prepare the polymer having comb architecture may be
carried out in the absence or presence of a solubilizing carrier medium,
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typically in the presence of a solubilizing carrier medium. When present, the
carrier medium is selected from the group of the base oil and/or the aromatic
hydrocarbons.
[00185] A more detailed description of the comb polymer is described in
US2008/194443. The comb polymer may also be prepared as is disclosed in
paragraphs [0142] to [0160] of US2008/194443. A more detailed description of
the comb polymer is described in US2008/194443. The comb polymer may
also be prepared as is disclosed in paragraphs [0142] to [0160] of
US2008/194443.
Friction Modifier
[00186] The lubricating composition of the present invention may optionally
contain at least two friction modifiers. Useful friction modifiers for the
present
invention are described below.
[00187] In one embodiment the friction modifier may be formed by the
condensation of the hydroxyalkyl compound with an acylating agent or an
amine. A more detailed description of the hydroxyalkyl compound is described
in US Patent Application 60/725360 (filed on October 11, 2005, inventors
Bartley, Lahiri, Baker and Tipton) in paragraphs 8, 19-21. The friction
modifier disclosed in US Patent Application 60/725360 may be an amide
represented by the formula R1R2N-C(0)R3, wherein R1 and R2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and R3 is a
hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the
condensation of said hydroxyalkyl group, through a hydroxyl group thereof,
with an acylating agent. Preparative Examples are disclosed in Examples 1 and
2 (paragraphs 68 and 69). In one embodiment the amide of a hydroxylalkyl
compound is prepared by reacting glycolic acid, that is, hydroxyacetic acid,
HO-CH2-COOH with an amine.
[00188] In one embodiment the friction modifier may be a secondary or
tertiary amine being represented by the formula R4R5NR6, wherein R4 and R5
are each independently an alkyl group of at least 6 carbon atoms and R6 is
hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an
amine-containing alkyl group. A more detailed description of the friction
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modifier is described in US Patent Application 05/037897 in paragraphs 8 and
19 to 22.
[00189] In one embodiment the friction modifier may be derived from the
reaction of a carboxylic acid or a reactive equivalent thereof with an
aminoalcohol, wherein the friction modifier contains at least two hydrocarbyl
groups, each containing at least 6 carbon atoms. An example of such a friction
modifier includes the reaction product of isostearic acid or an alkyl succinic
anhydride with tris-hydroxymethylaminomethane. A more detailed description
of such a friction modifier is disclosed in International Publication
W004/007652) in paragraphs 8 and 9 to 14.
[00190] The friction modifier includes fatty amines, borated glycerol esters,
fatty acid amides, non-borated fatty epoxides, borated fatty epoxides,
alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of
fatty
acids, fatty imidazolines, metal salts of alkyl salicylates (may also be
referred
to as a detergent), metal salts of sulphonates (may also be referred to as a
detergent), condensation products of carboxylic acids or polyalkylene-
polyamines, or amides of hydroxyalkyl compounds.
[00191] In one embodiment the friction modifier includes a fatty acid ester of
glycerol. The final product may be in the form of a metal salt, an amide, an
imidazoline, or mixtures thereof. The fatty acids may contain 6 to 24, or 8 to
18 carbon atoms. The fatty acids may branched or straight-chain, saturated or
unsaturated. Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic,
isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, and linolenic
acids,
and the acids from the natural products tallow, palm oil, olive oil, peanut
oil,
corn oil, and Neat's foot oil. In one embodiment the fatty acid is oleic acid.
When in the form of a metal salt, typically the metal includes zinc or
calcium;
and the products include overbased and non-overbased products. Examples are
overbased calcium salts and basic oleic acid-zinc salt complexes which may be
represented by the general formula Zn4Oleate60. When in the form of an
amide, the condensation product includes those prepared with ammonia, or with
primary or secondary amines such as diethylamine and diethanolamine. When
in the form of an imidazoline, the condensation product of an acid with a
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diamine or polyamine such as a polyethylenepolyamine. In one embodiment
the friction modifier is the condensation product of a fatty acid with C8 to
C24
atoms, and a polyalkylene polyamine, and in particular, the product of
isostearic acid with tetraethylenepentamine.
[00192] In one embodiment the friction modifier includes those formed by
the condensation of the hydroxyalkyl compound with an acylating agent or an
amine. A more detailed description of the hydroxyalkyl compound is described
in WO 2007/0044820 paragraphs 9, and 20-22. The friction modifier disclosed
in W02007/044820 includes an amide represented by the formula
R12R13N_c(0)R145
wherein R12 and R13 are each independently hydrocarbyl
groups of at least 6 carbon atoms and R14 is a hydroxyalkyl group of 1 to 6
carbon atoms or a group formed by the condensation of said hydroxyalkyl
group, through a hydroxyl group thereof, with an acylating agent. Preparative
Examples are disclosed in Examples 1 and 2 (paragraphs 72 and 73 of
W02007/044820). In one embodiment the amide of a hydroxylalkyl compound
is prepared by reacting glycolic acid, that is, hydroxyacetic acid,
HO-CH2-COOH with an amine.
[00193] In one embodiment the friction modifier includes a secondary or
I
tertiary amine being represented by the formula R-5R-16 NR17 , wherein R15 and
R16 are each independently an alkyl group of at least 6 carbon atoms and R17
is
hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an
amine-containing alkyl group. A more detailed description of the friction
modifier is described in US Patent Application 2005/037897 in paragraphs 8
and 19 to 22.
[00194] In one embodiment the friction modifier includes a reaction product
of a di-cocoalkyl amine (or di-cocoamine) with glycolic acid. The friction
modifier includes compounds prepared in Preparative Examples 1 and 2 of WO
2008/014319.
[00195] In one embodiment the friction modifier includes those derived from
the reaction product of a carboxylic acid or a reactive equivalent thereof
with
an aminoalcohol, wherein the friction modifier contains at least two
hydrocarbyl groups, each containing at least 6 carbon atoms. An example of
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such a friction modifier includes the reaction product of isostearic acid or
an
alkyl succinic anhydride with tris-hydroxymethylaminomethane. A more
detailed description of such a friction modifier is disclosed in US Patent
Application 2003/22000 (or International Publication W004/007652) in
paragraphs 8 and 9 to 14.
[00196] In one embodiment the friction modifier includes an alkoxylated
alcohol. A detailed description of suitable alkoxylated alcohols is described
in
paragraphs 19 and 20 of US Patent Application 2005/0101497. The
alkoxylated amines are also described in US Patent 5,641,732 in column 7, line
15 to column 9, line 25.
[00197] In one embodiment the friction modifier includes a hydroxyl amine
compound as defined in column 37, line 19, to column 39, line 38 of US Patent
5,534,170. Optionally the hydroxyl amine includes borated as such products
are described in column 39, line 39 to column 40 line 8 of US Patent
5,534,170.
[00198] In one embodiment the friction modifier includes an alkoxylated
amine e.g., an ethoxylated amine derived from 1.8 % EthomeenTM T-12 and
0.90 % TomahTm PA-1 as described in Example E of US Patent 5,703,023,
column 28, lines 30 to 46. Other suitable alkoxylated amine compounds
include commercial alkoxylated fatty amines known by the trademark
"ETHOMEEN" and available from Akzo Nobel. Representative examples of
these ETHOMEENTm materials is ETHOMEENTm C/12 (bis[2-hydroxyethy1]-
co co -amine); ETHOMEENTm C/20
(polyoxyethylene [10] cocoamine);
ETHOMEENTm S/12 (bis[2-hydroxyethyl]soyamine); ETHOMEENTm T/12
(bis[2-hydroxyethyl] -tallow-amine); ETHOMEENTm T/15 (polyoxyethylene-
[5 ]tallowamine); ETHOMEENTm 0/12 (bis[2-hydroxyethyl]oleyl-amine);
ETHOMEENTm 18/12 (bis [2¨hydroxyethyl]octadecylamine); and
ETHOMEENTm 18/25 (polyoxyethylene[15]octadecylamine). Fatty amines and
ethoxylated fatty amines are also described in U.S. Patent 4,741,848.
[00199] In one embodiment the friction modifier includes a polyol ester as
described in US Patent 5,750,476 column 8, line 40 to column 9, line 28.
[00200] In one embodiment the friction modifier includes a low potency
friction modifier as described in US Patent 5,840,662 in column 2, line 28 to
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column 3, line 26. US Patent 5,840,662 further discloses in column 3, line 48
to column 6, line 25 specific materials and methods of preparing the low
potency friction modifier.
[00201] In one embodiment the friction modifier includes a reaction product
of an isomerised alkenyl substituted succinic anhydride and a polyamine as
described in US Patent 5,840,663 in column 2, lines 18 to 43. Specific
embodiments of the friction modifier described in US Patent 5,840,663 are
further disclosed in column 3, line 23 to column 4, line 35. Preparative
examples are further disclosed in column 4, line 45 to column 5, line 37 of US
Patent 5,840,663.
[00202] In one embodiment the friction modifier includes an
alkylphosphonate mono- or di- ester sold commercially by Rhodia under the
trademark Duraphos0 DMODP.
[00203] The condensation of a fatty acid and a polyamine of the invention
typically result in the formation of at least one compound selected from
hydrocarbyl amides, hydrocarbyl imidazolines and mixtures thereof In one
embodiment the condensation products are hydrocarbyl imidazolines. In one
embodiment the condensation products are hydrocarbyl amides. In one
embodiment the condensation products are mixtures of hydrocarbyl
imidazolines and hydrocarbyl amides. Typically the condensation product is a
mixture of hydrocarbyl imidazolines and hydrocarbyl amides.
[00204] The fatty acid of the invention may be derived from a hydrocarbyl
carboxylic acid. The hydrocarbyl group may be alkyl, cycloalkyl, or aryl,
although alkyl is typical, and the hydrocarbyl groups may be linear or
branched. Typically the fatty acid contains 8 or more, 10 or more, more 13 or
14 or more carbon atoms (including the carbon of the carboxy group).
Typically the fatty acid contains 8 to 30, 12 to 24, or 16 to 18 carbon atoms.
Other suitable carboxylic acids may include the polycarboxylic acids or
carboxylic acids or anhydrides having from 2 to 4 carbonyl groups, typically
2.
The polycarboxylic acids may include succinic acids and anhydrides and Diels-
Alder reaction products of unsaturated monocarboxylic acids with unsaturated
carboxylic acids (such as acrylic, methacrylic, maleic, fumaric, crotonic and
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itaconic acids). The fatty carboxylic acids include fatty monocarboxylic acids
containing 8 to 30, 10 to 26, or 12 to 24 carbon atoms.
[00205] Examples of suitable fatty acids may include caprylic acid, capric
acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acid
and, tall
oil acids. In one embodiment the fatty acid is stearic acid, which may be used
alone or in combination with other fatty acids.
[00206] The polyamines of the invention may be acyclic or cyclic, preferably
acyclic; and linear or branched, preferably linear.
[00207] In one embodiment the polyamines may be alkylenepolyamines
selected from the group consisting of ethylenepolyamines,
propylenepolyamines, butylenepolyamines and mixtures thereof. Examples of
propylenepolyamines may include propylenediamine and dipropylenetriamine.
[00208] Particularly useful ethylenepolyamines are selected from the group
consisting of ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, N-(2-aminoethyl)-N'-[2-[(2-
aminoethyl)amino]ethy1]-1,2-ethanediamine, polyamine still bottoms and
mixtures thereof.
[00209] In one embodiment the polyamines may bea,I3-diaminoalkanes.
Suitable a,13-diaminoalkanes may include diaminopropanes, diaminobutanes or
mixtures thereof. Specific diaminoalkanes are selected from the group
consisting of N-(2 -amino ethyl)-1,3 -prop ane diamine, 3,3' -di amino-N-
methyldipropylamine, tris(2 -amino ethyl)amine , N,N-bis(3 -aminopropy1)-1,3 -
propane diamine, N,N'-1,2-ethanediylbis-(1,3-propane diamine) and mixtures
thereof
[00210] In one embodiment other polyamines may include
di-(trimethylene)triamine, pip erazine, diaminocyclohexanes and mixtures
thereof
[00211] One or both friction modifiers may in one embodiment be nitrogen-
containing compounds, typically both friction modifiers are nitrogen-
containing.
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[00212] In one embodiment one of friction modifiers is the condensation
product of a fatty acid with C8 to C24 atoms, and a polyalkylene polyamine,
and in particular, the product of isostearic acid with tetraethylenepentamine.
[00213] The mixture of at least two friction modifiers may be present at 0.1
wt % to 1 wt %, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt %
to 1.0 wt %, of the lubricating composition
Antioxidant
[00214] In one embodiment the lubricating composition of the invention
includes an amine antioxidant. The amine antioxidant may be a phenyl-a-
naphthylamine (PANA) or a hydrocarbyl substituted diphenylamine, or mixtures
thereof The hydrocarbyl substituted diphenylamine may include mono- or di-
C4 to C16-, or C6 to C12-, or C9- alkyl diphenylamine. For example the
hydrocarbyl substituted diphenylamine may be octyl diphenylamine, or di-octyl
diphenylamine, dinonyl diphenylamine, typically dinonyl diphenylamine.
[00215] When present the amine antioxidant may be present at 0.2 wt % to
1.2 wt %, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt % or 0.5 wt % to 0.8
wt %, of the lubricating composition.
[00216] The lubricating composition be optionally include at least one other
antixodiant that is known and includes sulphurised olefins, hindered phenols,
molybdenum dithiocarbamates, and mixtures thereof.
[00217] The hindered phenol antioxidant often contains a secondary butyl
and/or a tertiary butyl group as a sterically hindering group. The phenol
group
is often further substituted with a hydrocarbyl group 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-butylphenol, or 4-dodecy1-2,6-di-tert-butylpheno1. In one embodiment
the hindered phenol antioxidant may be an ester and may include, e.g.,
IrganoxTM L-135 from C ib a, or butyl 3 -
(3 55 -di-tert-buty1-4 -
hydro x yp henyl)prop ano ate .
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[00218] If present, the secondary antioxidant may be present at 0.1 wt % to 1
wt %, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt % to 1.0 wt
%, of the lubricating composition.
[00219] Optionally the lubricating composition may further contain other
performance additives. Other performance additives include corrosion
inhibitors, foam inhibitors, pour point depressants, demulsifiers, metal
deactivators or seal swell agents.
[00220] Corrosion inhibitors include 1-amino-2-propanol, amines, triazole
derivatives including tolyl triazole, dimercaptothiadiazole derivatives,
octylamine octanoate, condensation products of dodecenyl succinic acid or
anhydride and/or a fatty acid such as oleic acid with a polyamine.
[00221] Foam inhibitors that may be useful in the compositions of the
invention include polysiloxanes, copolymers of ethyl acrylate and 2-
ethylhexylacrylate and optionally vinyl acetate; demulsiflers including
fluorinated
polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides,
polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
[00222] Pour point depressants that may be useful in the compositions of the
invention include polyalphaolefins, esters of maleic anhydride-styrene
copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
[00223] Demulsifiers include trialkyl phosphates, and various polymers and
copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof
[00224] Metal deactivators include derivatives of benzotriazoles (typically
tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles
or
2-alkyldithiobenzothiazoles. The metal deactivators may also be described as
corrosion inhibitors.
[00225] Seal swell agents include sulfolene derivatives, Exxon Necton37TM
(FN 1380) and Exxon Mineral Seal Oi1TM (FN 3200).
[00226] The following examples provide illustrations of the invention. These
examples are non-exhaustive and are not intended to limit the scope of the
invention.
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EXAMPLES
Lubricants: Invention and Reference Lubricating Oil Compositions
[00227] Four Inventive fluids (INV1 to INV4) are prepared as summarized
below by adding to the named base oil (or oil of lubricating viscosity) 13.85
wt
% of an additive package described below. The base oil of each inventive
lubricant has a kinematic viscosity at 100 C in the range of 2.8 to 3.6 cSt
(mm2/s) and a viscosity index of between 110, and less than 120.
INV1 INV2 INV3 INV4
Base Oil
3 mm2/s Ultra S-3 oil 84 100 100 100
8 mm2/s Ultra S-8 oil 16 0 0 0
Borated succinimide 1.83 1.83 1.83 1.83
dispersant (wt %)
overbased calcium- 170 170 170 170
containing sulphonate
detergent (delivering
ppm of calcium)
A mixture of 0.33 0.33 0.33 0.33
phosphoru-containing
antiwear agents
Total amount of 356 ppm 356 ppm 356 ppm 356 ppm
Phosphorus from
dibutyl phosphite (
ppm)
Total amount of 689 689 689 689
Phosphorus in
lubricant ( ppm)
Mixture of amine- 1.17 1.17 1.17 1.17
containing friction
modifiers (wt %)
Star poly(meth) 0.27 0.85 0.25 0
acrylate copolymer
having Mw of about
300,000
Linear dispersant 0.62 0.94 1.48 0.62
poly(meth)acrylate
copolymer having Mw
of about 15,000
Other additives (wt %) 4.24 4.24 4.24 4.24
Footnote:
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Ultra S-3 oil and S-8 oil are both API Group II+ base oils having a viscosity
index of between 110 and less than 120.
The mixture of antiwear agents comprises phosphoric acid, dibutyl phosphite,
and a dihydrocarbyl C16-18 hydrogen phosphite (wherein the hydrocarbyl
groups are a mixture of alkyl and alkenyl groups).
The mixture of friction modifiers includes between 3 and 6 friction modifiers.
The other additives treated at 4.24 wt % include a mixture of phenolic and
aminic antioxidants, a carboxylic acid ester, borate esters, corrosion
inhibitors,
pour point depressants, antifoam agents, seal swell agents, and diluent oil.
The linear polymer may be derived from a monomer composition comprising
methyl methacrylate (14.1 wt %), 2-ethylhexyl methacrylate (4.7 wt %), C12-15
alkyl methacrylate (75.1 wt %), and ethylene glycol dimethacrylate (6.1 wt %).
The weight average molecular weight of the linear polymer is 15,000.
A comparative example is evaluated based upon a Ford Type A
MERCONOLV ATF and Shell ATFTm134FE
[00228] Each lubricant INV1 to INV4, and the comparative ATF are assessed
by comparing CAFE figures using a 2011 Ford Fusion AT (6HP6) using the
following procedures described below.
[00229] ASTM D2882 Pump Test: This procedure assesses lubricant antiwear
properties using an electric motor driven Vickers 104-C vane pump. The weight
loss of the pump vanes and cam rings are recorded after 100 hours of
continuous operation, followed by visual inspection for scoring and scuffing.
[00230] The Falex wear/EP test described in ASTM D-3233 is used to assess
the friction, wear and extreme pressure (EP) properties of a lubricating
fluid. A
rotating steel journal is run between two stationary steel V-blocks immersed
in
the test fluid. Load is applied to V-blocks in 250-lbf (1112 N) increments
with
the load maintained constant for 1 minute at each load increment until failure
to
maintain torque or by seizure of the blocks against the pin. The test was
conducted with fluid temperatures of 100 & 150 C.
[00231] The results obtained for the Falex EP test and the pump test are:
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Vane Pump Test
Lubricant Cam Ring Wear Vane weight loss Total mass loss
loss (mg) (mg) (mg)
INV1 1.0 0.1 1.1
INV2 1.0 0.4 1.4
INV3 1.8 0.4 2.2
INV4 2.0 0.8 2.8
Mercon LV 835.4 4.6 840
ATF 134FE 2598.6 23.2 2621.8
Falex EP Test (Result passing load based upon 2 tests)
100 C 150 C
INV1 680 510
INV2 737 510
INV3 680 567
INV4 624 454
Mercon LV 567 340
ATF 134FE 680 397
[00232] The lubricating compositions are then evaluated by determining the
kinematic and Brookfield viscosities (by employing ASTM methods D445 at 40
C and 100 C (kinematic viscosity at 40 C, KV40 and 100 C, KV100) and
D2983 at -40 C (Brookfield viscosity at -40 C, BV-40) respectively). The
results obtained are also shown in the table. The results obtained for each
lubricant are as follows:
Lubricant KV40 KV100 BV-40 Base
Oil Viscosity at
(mm2/s) (mm2/s) (mm2/s) 100 C (mm2/s)
INV1 20 4.51 4900 3.55
INV2 18.85 4.5 3710 3.1
INV3 17.61 4.17 3600 3.1
INV4 16.46 3.91 2470 3.1
MerconOLV 28.91 5.92 9860 Unknown
ATFTm 134FE 17.38 4.19 5070 Unknown
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[00233] Overall the data indicates that the lubricating composition of the
present invention has reduced wear as measured by Vane pump test, higher
passing load as measured by 150 C Falex wear test, while maintaining a low
lubricant viscosity.
[00234] Inventive Examples 5 to 11 (INV5 to INV12) are prepared in a
similar way to INV1, except lubricating composition of each lubricant is
summarized as follows:
INV5 INV6 INV7 INV8 INV9 INV10
Borated succinimide 1.83 1.83 1.83 1.83 1.83 1.83
dispersant
(wt %)
overbased calcium- 170 170 170 170 170 170
containing
sulphonate detergent
(delivering ppm of
calcium)
A mixture of 0.33 0.33 0.33 0.33 0.33 0.33
phosphorus-
containing antiwear
agents
Total amount of 356 356 356 356 356 356
Phosphorus from PPm PPm PPm PPm PPm PPm
dibutyl phosphite
(PPm)
Total amount of 689 689 689 689 689 689
Phosphorus in
lubricant ( ppm)
Mixture of amine- 1.17 1.17 1.17 1.17 1.17 1.17
containing friction
modifiers (wt %)
Linear dispersant 0.78 0.30 0 0 0 0
polymeth acrylate
copolymer (HLW)
Star polymeth 0 0 0.31 0.31 0.31 0.31
acrylate copolymer
Linear dispersant
polymeth acrylate 0.62 0.62 0.62 0.62 0.62 0,62
copolymer
Other additives (wt 4.24 4.24 4.24 4.24 4.24 4.24
%)
Base Oil Balance to 100 wt % of 3 mm2/s
Ultra S-3 oil
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Footnote:
The linear dispersant poly(meth)acrylate is derived from a monomer
composition comprising 2-ethylhexyl (meth)acrylate (30 wt %), C12-15 alkyl
(meth)acrylate (68.2 wt %), and dimethylaminopropyl (meth)acrylate (1.8 wt
%).
The star polymers of INV7 to INV10 have a weight average molecular weight
of about 540,000; 740,000; 920,000; and 1,200,000 respectively. The star
polymers are prepared from a monomer mix methacrylate described below. The
star polymers are prepared by RAFT polymerization process.
INV C12-15 C1-C9 Difunctional
Mononer
7 81 19 E
8 81 19 E
9 81 19 E
10 81 19 E
E = Ethylene glycol dimethacrylate.
INV C12- C1-C9 Acrylate Difunctional
C15 Monomer* Monomer
11 80 19 1.0
12 70 30 0 E
Footnote:
* is 2 Ethylhexylacrylate
The linear dispersant polymethacrylate copolymer (HLW) is a second
dispersant viscosity modifier. The HLW of INV5 has a weight average
molecular weight of 15,000; and is derived from a monomer mix of 68.2 wt %
C12-15 alkyl methacrylate, 30 wt % of 2-ethylhexylmethacrylate; and 1.8 wt %
of dimethylaminopropyl (meth)acrylate.
The mixture of antiwear agents comprises phosphoric acid, dibutyl phosphite,
and a dihydrocarbyl C16-18 hydrogen phosphite (wherein the hydrocarbyl
groups are a mixture of alkyl and alkenyl groups).
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The mixture of friction modifiers includes between 3 and 6 friction modifiers.
The other additives treated at 4.24 wt % include a mixture of phenolic and
aminic antioxidants, a carboxylic acid ester, borate esters, corrosion
inhibitors,
pour point depressants, antifoam agents, seal swell agents, and diluent oil.
[00235] INV5 to INV10 are evaluated for viscometric properties and
summarized below:
Lubricant KV40 KV100 BV-40
(mm2/s) (mm2/s) (mm2/s)
INV5 17.55 4.12 4010
INV6 17.31 4.08 3720
INV7 18.26 4.28 3940
INV8 18.22 4.28 4200
INV9 18.27 4.32 4230
INV10 18.42 4.37 4450
[00236] 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
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
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other than carbon in a ring or chain otherwise composed of carbon atoms.
Heteroatoms include sulphur, oxygen, nitrogen, and encompass substituents as
pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,
preferably
no more than one, non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group; typically, there will be no non-
hydrocarbon substituents in the hydrocarbyl group.
[00237] It is known that some of the materials described above may interact
in the final formulation, so that the components of the final formulation may
be
different from those that are initially added. The products formed thereby,
including the products formed upon employing lubricant composition of the
present invention in its intended use, may not be susceptible of easy
description. Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present invention
encompasses lubricant composition prepared by admixing the components
described above.
[00238] Each of the documents referred to above is incorporated herein by
reference. 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 are normally understood to be
present in the commercial grade. However, the amount of each chemical
component is presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise indicated. It
is to be understood that the upper and lower amount, range, and ratio limits
set
forth herein may be independently combined. Similarly, the ranges and
amounts for each element of the invention may be used together with ranges or
amounts for any of the other elements.
[00239] While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will
52
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PCT/US2014/037774
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.
53
