[0001] This invention relates to a lubricant oil composition and a method of lubricating
a gearbox or operating an apparatus having a gearbox wherein the gearbox comprises
a rolling element.
BACKGROUND
[0002] Industrial manufacturing facilities and processes use apparatus and robots for manufacturing
processes, which have gearboxes requiring lubrication. Depending upon manufacturer
design requirements, gearboxes can be lubricated with grease or lubricant oils. For
oil-lubricated gearboxes, the demands for lubricants are particular and include sludge-
free and leak-free performance for an extended period of time with a target of 20,000
hours, particularly in robot gearboxes and especially in the automotive sector.
[0003] Commercial offerings of oils for robot gearboxes tend to suffer from a number of
disadvantages, which mean that they tend not to be capable of meeting the industry
requirement of 20,000 hours of uninterrupted operation.
[0004] Such disadvantages include poor elastomer compatibility which results in degradation
of elastomer forming seals in gearboxes as well as characteristics which result in
wear of metal gear components. This can result in leaks of oil from the gearbox which,
in many robot applications are problematic and in car manufacture, especially where
cleanliness is critical, can be considered catastrophic failures.
[0005] Whilst mineral oil-based lubricant formulations are used, there is increasing demand
for synthetic oil-based formulations to meet longevity requirements. Synthetic oils
having a poly-alpha-olefin base oil have the potential for greater longevity, but
suffer from poorer solubility of additive components.
[0006] Gear boxes for manufacturing apparatus such as robots, as well as for wind turbines,
also have rolling elements within them that have a different set of wear and performance
requirements to other gearboxes.
[0007] WO 2016/124293 A1 discloses the use of an oil-soluble mono-, di-, or tri-glyceride of at least one
hydroxy polycarboxylic acid, or a derivative thereof, as an anti-camshaft-wear additive
in a non-aqueous lubricant composition and/or in a fuel composition.
[0008] There is thus a need for a synthetic gear oil formulation that provides stability
and longevity, is compatible with seal elastomers, has effective anti- wear properties,
particularly in systems with rolling elements, is not prone to sludge formation and
has excellent performance characteristics. The present inventor has developed compositions
that addresses one or more of the above problems.
SUMMARY OF INVENTION
[0009] According to a first aspect of the invention, there is provided a lubricant composition
suitable for use as a lubricant for gearboxes comprising a rolling element, comprising:
a base oil composition of lubricating viscosity; and an additive composition comprising
a molybdenum dialkyldithiocarbamate and an organic friction modifier selected from
an oil-soluble mono-, di- or tri-glyceride of at least one hydroxyl polycarboxylic
acid, or an ether or an ester derivative thereof, which lubricant composition has
no more than 0.1% by weight of molybdenum dithiophosphate.
[0010] Also disclosed herein but not encompassed within the present claims is an additive
composition for use in a lubricant composition defined above, the additive composition
comprising a molybdenum dialkyldithiocarbamate and an organic friction modifier such
as an oil- soluble mono-, di- or tri-glyceride of at least one hydroxyl polycarboxylic
acid, or a derivative thereof.
[0011] In a lubricant composition defined above, the base oil composition may comprise a
functionally modified poly-alpha-olefin, a poly-alpha-olefin and optionally an additive
carrier.
[0012] In a second aspect of the invention, there is provided a synthetic gear oil composition
suitable for use as a lubricant for gearboxes comprising a rolling element, comprising:
a base oil composition comprising a modified poly alpha olefin; and an additive composition
comprising a molybdenum dialkyldithiocarbamate and an organic friction modifier selected
from an oil-soluble mono-, di- or tri-glyceride of at least one hydroxyl polycarboxylic
acid, or an ether or ester derivative thereof.
[0013] In a third aspect of the invention, there is provided a use of a lubricant or gear
oil composition as defined above as a lubricant for gearboxes comprising a rolling
element.
[0014] Disclosed herein but not encompassed within the present claims is a kit for manufacture
of a lubricant, the kit comprising a base oil composition optionally as defined above
an additive pack or additive concentrate optionally having the additive composition
as defined above.
[0015] In a fourth aspect of the invention, there is provided a method of lubricating a
gearbox comprising a rolling element, the method comprising supplying to a gearbox
comprising a rolling element an oil of lubricating viscosity having the lubricating
composition as defined above.
[0016] In a fifth aspect of the invention, there is provided a method of operating an apparatus
having a gearbox comprising a rolling element, the method comprising supplying to
the gearbox a lubricating oil of lubricating viscosity having a composition as defined
above.
DETAILED DESCRIPTION
[0017] The invention, according to a first aspect is directed to a lubricant composition
suitable for use as a lubricant for gearboxes comprising a rolling element. The lubricant
composition comprises a base oil composition and an additive composition. The base
oil composition should be such to provide a lubricating viscosity or the lubricating
viscosity once the additive composition is added. The base oil composition makes up
the major part of the lubricant composition, by which it is meant more than 50% by
weight. The additive composition comprises a molybdenum dialkyldithiocarbamate and
an organic friction modifier which is an oil-soluble mono-, di- or tri-glyceride of
at least one hydroxyl polycarboxylic acid, or an ether or an ester derivative thereof.
[0018] The lubricant composition of the present invention finds particular application as
a lubricant composition for robotics and robotic gearboxes, industrial gears and wind
turbine gears and especially for gearboxes having a rolling element (such as a spherical
bearing or a cylindrical bearing). The present invention addresses a particular problem
concerning lubricants in such applications, in particular the need for longevity,
good elastomer compatibility and good anti-wear properties. Embodiments of the invention
also demonstrate excellent protection against leaks and sludge.
[0019] Any suitable molybdenum dialkyldithiocarbamate may be used (including dinuclear and
trinuclear molybdenum species).
[0020] The molybdenum dialkyldithiocarbamate may be provided in an amount, in terms of molybdenum,
of from 100 to 5000 ppm, preferably from 500 to 3000 ppm and more preferably from
750 to 1500 ppm. In one embodiment, molybdenum dialkyldithiocarbamate provided in
the lubricant composition in an amount, in terms of molybdenum, of from 800 to 1300
ppm. In a particular embodiment, a molybdenum dialkyldithiocarbamate may be provided
in an amount of from 0.1 to 5% by weight of the lubricant composition, and preferably
in an amount of from 0.5 to 3% by weight of the lubricant compositions and more preferably,
in certain compositions from 0.75 to 1.5% by weight of the lubricant composition.
[0021] The molybdenum dialkyldithiocarbamate may be provided in the lubricant composition
in an amount, in terms of molybdenum, of from 100 to 5000 ppm, preferably from 500
to 3000 ppm and more preferably from 750 to 1500 ppm. In one embodiment, molybdenum
dialkyldithiocarbamate provided in the lubricant composition in an amount, in terms
of molybdenum, of from 800 to 1300 ppm. The organic friction modifier may be a metal-free
organic friction modifier. Preferably the organic friction modifier is free from sulphur
and/or phosphorus. Suitable organic friction modifiers may include, but are not limited
to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether
amines, amine oxides, amidoamines, nitriles, imines, amino guanidines, alkanolamides,
glycerol esters, and olefins, sunflower oil and other naturally occurring plant or
animal oils, dicarboxylic acid esters, esters or partial esters of a polyol and one
or more aliphatic or aromatic carboxylic acids, and the like. The organic friction
modifier used in the compositions of the present invention may comprise one or a combination
of organic friction modifiers defined herein.
[0022] Suitable organic friction modifiers may contain hydrocarbyl groups that are selected
from straight chain, branched chain, or aromatic hydrocarbyl groups or mixtures thereof,
and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon
and hydrogen or hetero atoms such as nitrogen or oxygen. The hydrocarbyl groups may
range from about 12 to about 25 carbon atoms. In some embodiments the organic friction
modifier may be a long chain fatty acid ester. In an embodiment the long chain fatty
acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The organic friction
modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty
epoxide derivative, or a long chain imidazoline.
[0023] Other suitable organic friction modifiers may include organic, ashless (metal-free),
nitrogen-free organic friction modifiers. Such organic friction modifiers may include
esters formed by reacting carboxylic acids and anhydrides with alkanols and generally
include a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an
oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction
modifier is known generally as glycerol monooleate (GMO) which may contain mono-,
di-, and tri-esters of oleic acid. Other suitable friction modifiers are described
in
U.S. 6,723,685.
[0024] Suitable organic friction modifiers may be aminic organic friction modifiers which
include amines or polyamines. Such compounds can have hydrocarbyl groups that are
linear, either saturated or unsaturated, or a mixture thereof and may contain from
about 12 to about 25 carbon atoms. Further examples of suitable organic friction modifiers
include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl
groups that are linear, either saturated, unsaturated, or a mixture thereof. They
may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines
and ethoxylated ether amines. The amines and amides may be used as such or in the
form of an adduct or reaction product with a boron compound such as a boric oxide,
boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate. Other suitable
organic friction modifiers are described in
U.S. 6,300,291.
[0025] Preferably, the organic friction modifier may be present in amount of up to about
10% by weight of the lubricant composition, preferably up to about 5% by weight.
Preferably, the organic friction modifier is present in an amount of from about 0.1%
by weight to about 4% by weight and more preferably up to about 1% by weight of the
lubricant composition.
[0026] The organic friction modifier may comprise an organic ashless nitrogen-free friction
modifier and preferably is glycerol monooleate (GMO). According to this embodiment,
the lubricant composition and the additive composition comprise the molybdenum dialkyldithiocarbamate
and GMO, preferably in the aforementioned amounts.
[0027] In another particular embodiment, the organic friction modifier may further comprise
fatty acid amide having from about 12 to about 25 carbon atoms and preferably is oleylamide.
According to this embodiment the lubricant composition and the additive composition
comprise the molybdenum dialkyldithiocarbamate and oleylamide, preferably in the aforementioned
amounts.
[0028] In accordance with the present invention, the organic friction modifier is and/or
the lubricant composition and additive - composition comprises an oil-soluble mono-,
di- or tri- glyceride of at least one hydroxyl polycarboxylic acid, or an ether or
an ester derivative thereof.
[0029] The lubricant composition of one aspect of the invention comprises a base oil composition
of lubricating viscosity; and an additive composition comprising a molybdenum dialkyldithiocarbamate
and an oil-soluble mono-, di- or tri-glyceride of at least one hydroxyl polycarboxylic
acid, or an ether or an ester derivative thereof.
[0030] Disclosed herein is an additive composition for use in a lubricant composition defined
above, comprising a molybdenum dialkyldithiocarbamate and an oil-soluble mono-, di-
or tri-glyceride of at least one hydroxyl polycarboxylic acid, or an ether or an ester
derivative thereof.
[0031] The oil-soluble mono-, di- or tri-glyceride of at least one hydroxyl polycarboxylic
acid, or an ether or an ester derivative thereof may be provided in an amount of up
to 5% by weight of the lubricant composition, preferably from 0.1 to 2.5% by weight
of the lubricant composition, more preferably 0.25to 1% by weight of the lubricant
composition.
[0032] In one embodiment, the oil-soluble mono-, di- or tri-glyceride of at least one hydroxyl
polycarboxylic acid, or an ether or an ester derivative thereof is provided in a percent
by weight ratio relative to the molybdenum dialkyldithiocarbamate in the range from
1:3 to 3: 1, more preferably 1 :3 to 1 :1, still more preferably in the range 1 :2
to 2:3.
[0033] The additive composition allows a lubricant composition to be produced that has excellent
longevity and provides a high performance oil. The present composition allows this
longevity and performance to be achieved with very little or reduced molybdenum dialkyldithiophosphate
content or no molybdenum dialkyldithiophosphate. The composition comprises no more
than 0.1% molybdenum dialkyldithiophosphate, still more preferably no more than 0.05
% molybdenum dialkyldithiophosphate and most preferably the additive composition is
absent molybdenum dialkyldithiophosphate.
[0034] In a preferred embodiment, the lubricant composition and the additive composition
further comprises, in addition to the oil-soluble mono-, di- or tri-glyceride of at
least one hydroxyl polycarboxylic acid, or an ether or an ester derivative thereof
described above, a long chain fatty amide, and more preferably comprises oleylamide,
which may optionally be in the amount of up to 1% by weight of the lubricant composition,
preferably in the amount of up to 0.5% by weight of the lubricant composition and
more preferably in the amount of from 0.05 to 0.25% by weight of the lubricant composition.
Optionally, oleylamide may be provided in a weight percent ratio relative to the oil-soluble
mono-, di- or tri- glyceride of at least one hydroxyl polycarboxylic acid, or an ether
or an ester derivative thereof in the range of from 1: 10 to 1:1, more preferably
from 1:6 to 1:4 and most preferably about 1:5.
[0035] The lubricant composition and additive composition may further comprise further additive
components, which may include other anti-wear additives (but preferably not an organometallic
dithiophosphate anti-wear additive, especially not zinc or molybdenum based organometallic
dithiophosphate anti-wear additives), dispersants, dispersant viscosity modifiers,
detergents, corrosion inhibitors, anti-oxidants, anti-foaming agents, or other additives.
Such further additive components further make up no more than 5% and more preferably
no more than 3% by weight of the lubricant composition.
[0036] In one particular embodiment, there are no further dispersant additives used in the
composition of the invention.
[0037] The additive composition may make up a proportion of the lubricant composition of
up to 20% by weight, more preferably of up to 10% by weight and more preferably of
between 2.5 and 7.5% by weight, e.g. from 3% to 6% by weight.
[0038] As used herein, an additive concentrate comprises an additive composition and an
additive carrier which may typically be a polar base oil and preferably comprises
part of a base oil composition. Typically an additive concentrate provides a stable
concentrate that can be made up to a lubricant composition by addition of appropriate
base oils.
[0039] An additive composition, as used herein, comprises components other than a base oil
composition.
[0040] A lubricant composition having an additive composition such as that defined above
has improved properties useful in gear oils, especially for robot gear and gear having
a rolling element, such as low wear, reduced sludge formation. These properties reduce
the risk of catastrophic failure and allow that the lubricant composition meets the
longevity requirements of these applications. An aspect of the invention is thus directed
to the use of a lubricant composition as defined above for gear boxes having a rolling
element, especially robot gearboxes or wind turbine gears.
[0041] Disclosed herein but not forming part of the present invention is an additive pack
for later blending with a base oil composition or base stock to produce the lubricant
composition locally. Optionally, the additive pack may be provided as a concentrate,
which may comprise a portion of the base oil composition to be used, such as defined
above, or one component base stock of the base oil, such as, for example, an alkylated
naphthalene. An additive concentrate may, for example, comprise the additive composition
in a weight percent ratio in the range 1:5 to 5:1, preferably from 1:2 to 3:1, more
preferably from 1:1 to 1:2 for later dilution to the desired amount in a lubricant
composition for use.
[0042] The molybdenum dialkyldithiocarbamate (MoDTC) may be any suitable MoDTC. For example,
it can be a compound of Formula 1 below:

where R
1 to R
4 denote alkyl groups and X
1 to X
4 each denote a sulphur atom or an oxygen atom.
[0043] Preferably, the MoDTC is a compound of Formula 2 below:

where R
1 to R
4 denote alkyl groups.
[0044] The alkyl groups R
1 to R
4 in the molybdenum dialkyldithiocarbamates of Formula 1 and Formula 2 are preferably
each independently lipophilic groups of 1 to 30 carbons, and it is preferable that
at least one or two of these four lipophilic groups is a secondary lipophilic group.
Preferably, the alkyl groups R
1 to R
4 are C8 to C13 branched secondary lipophilic groups. The molybdenum dialkyldithiocarbamate
may be provided in the lubricant composition in an amount, in terms of molybdenum,
of from 100 to 5000 ppm, preferably from 500 to 3000 ppm and more preferably from
750 to 1500 ppm. In one embodiment, molybdenum dialkyldithiocarbamate provided in
the lubricant composition in an amount, in terms of molybdenum, of from 800 to 1300
ppm.
[0045] A molybdenum dialkyldithiocarbamate used in accordance with the present invention
may preferably have an elemental analysis value for molybdenum of from 9.5 to 10.5
mass %.
[0046] In one embodiment in which the molybdenum dialkyldithiocarbamate has an elemental
analysis value for molybdenum of 10 mass %, the molybdenum dialkyldithiocarbamate
may be provided in an amount of from 0.1 to 5% by weight of the lubricant composition,
and preferably in an amount of from 0.5 to 3% by weight of the lubricant compositions
and more preferably, in certain compositions from 0.75 to 1.5% by weight of the lubricant
composition.
[0047] The content of molybdenum dialkyldithiocarbamate in a lubricating oil composition
can be determined by carrying out an elemental analysis using an ICP (Inductively
Coupled Plasma atomic emission spectroscopy, hereinafter referred to sometimes as
ICP) analysis apparatus. The amount of molybdenum can also be measured by the ICP
method.
[0048] Weight % amounts of molybdenum dialkyldithiocarbamates and weight ratios of other
components to molybdenum dialkyldithiocarbamates as used herein are based upon molybdenum
dialkyldithiocarbamate compounds (that is, compositions of molybdenum dialkyldithiocarbamate
compounds) having a molybdenum content of 10 wt%. Thus, in using molybdenum dialkyldithiocarbamate
compositions having a different wt% content of molybdenum, such values are adapted
accordingly.
[0049] As mentioned above, combinations of organic friction modifiers may be used.
[0050] The organic friction modifier is or comprises an oil-soluble mono-, di- or tri-glyceride
of at least one hydroxyl polycarboxylic acid, or an ether or an ester derivative thereof.
[0051] Any suitable oil-soluble mono-, di- or tri-glyceride of at least one hydroxyl polycarboxylic
acid, or an ether or an ester derivative thereof may be used.
[0052] Preferably, the hydroxy polycarboxylic acid has at least one hydroxy group or derivative
(for example ether or ester) thereof, which is in an alpha position with respect to
a carboxylic moiety.
Each hydroxy polycarboxylic acid may independently have from 4 to 22 carbon atoms,
for example 4 to 15 carbon atoms. The oil-soluble mono-, di-, or triglyceride of at
least one hydroxy polycarboxylic acid or derivative thereof may suitably have from
16 to 80 carbon atoms. The number of carbon atoms in the glyceride may affect its
solubility in oil of lubricating viscosity and/or in liquid fuel.
[0053] By oil-soluble is meant that the glyceride is soluble in an oil of lubricating viscosity
in a friction modifying and/or anti-wear amount, for example in an amount by weight
of at least 200 ppm in an oil of lubricating viscosity. The solubility may be determined
at ambient temperature, for example at 20° C. Preferably, the oil-soluble glyceride
is soluble at 0° C. The solubility may be determined at atmospheric pressure.
[0054] Suitable hydroxy polycarboxylic acids include: citric acid (also sometimes called
3- carboxy-3 -hydroxy pentanedioic acid; 2-hydroxypropane- 1,2, 3 -tricarboxylic acid;
or 3-hydroxypentanedioic acid-3 -carboxylic acid); tartaric acid (also sometimes called
2,3-dihydroxybutanedioic acid; or 2,3-dihydroxysuccinic acid); malic acid (also sometimes
called hydroxybutanedioic acid); monohydroxy trimesic acid; and hydrogenated monohydroxy
trimesic acid (sometimes also called 1,3,5-tricarboxy, 2-hydroxy cyclohexane).
[0055] The oil-soluble mono-, di-, or tri-glyceride of at least one hydroxy polycarboxylic
acid, or an ether or an ester derivative thereof may be a di-, or tri-glyceride which
is a glyceride of at least one hydroxy polycarboxylic acid and at least one second
carboxylic acid which is a saturated, mono-unsaturated or poly-unsaturated, branched
or linear, monocarboxylic or polycarboxylic acid having 4 to 22 carbon atoms, or a
derivative thereof.
[0056] The second carboxylic acid may be saturated, mono-unsaturated or poly-unsaturated.
Suitably, the second carboxylic acid is unsaturated. The second carboxylic acid may
be branched or linear. The second carboxylic acid may be monocarboxylic or polycarboxylic
acid. If the second carboxylic acid is a polycarboxylic acid, the derivative of the
glyceride may be an ester of the second carboxylic acid group.
[0057] Suitable saturated second carboxylic acids include caproic acid, caprylic acid, capric
acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid.
Suitable unsaturated second carboxylic acids include oleic acid, linoleic acid, linolenic
acid, myristoleic acid, palmitoleic acid, sapienic acid, eracic acid (also known as
cis-13- docosenoic acid) and brassidic acid.
[0058] Preferably, the glyceride is a glyceride of citric acid and oleic acid, a glyceride
of citric acid and linoleic acid or a mixture thereof.
[0059] The mono-, di-, or tri-glyceride of at least one hydroxy polycarboxylic acid or derivative
thereof may be represented by the Formula 3:

wherein RO, OR' and OR" independently represent:- OH; a saturated, mono-unsaturated
or poly-unsaturated, branched or linear, monocarboxylic or polycarboxylic group having
from 4 to 22 carbon atoms or an ether or an ester thereof; a hydroxy polycarboxylic
acid moiety or an ether and/or ester thereof provided that at least one of RO, OR'
and OR" is a hydroxy polycarboxylic acid moiety or an ether and/or ester thereof.
[0060] Preferably, in Formula 3, at least one of RO, OR' and OR" is a hydroxy polycarboxylic
acid moiety or an ether and/or ester thereof and at least one of RO, OR' and OR" is
a saturated, mono-unsaturated or poly-unsaturated, branched or linear, monocarboxylic
or polycarboxylic group having from 4 to 22 carbon atoms or an ester thereof.
[0061] Preferably in Formula 3, the hydroxy polycarboxylic moiety acid has at least one
hydroxy group or derivative (for example ether or ester) thereof which is in an alpha
position with respect to a carboxylic moiety.
[0062] In Formula 3, each hydroxy polycarboxylic moiety may independently have from 4 to
22 carbon atoms. In formula 3, the hydroxy polycarboxylic moiety may be derivable
from acids including for example citric acid, tartaric acid, malic acid, monohydroxy
trimesic acid and hydrogenated monohydroxy trimesic acid.
[0063] In Formula 3, when present, each saturated, branched or linear, monocarboxylic or
polycarboxylic group having from 4 to 22 carbon atoms or an ester thereof may be derivable
from saturated carboxylic acids or their halide equivalents. Suitable saturated carboxylic
acids include for example, caproic acid, caprylic acid, capric acid, lauric acid,
myristic acid, palmitic acid, stearic acid and arachidic acid. In Formula 3, when
present, each mono-unsaturated or poly-unsaturated, branched or linear, monocarboxylic
or polycarboxylic group having from 4 to 22 carbon atoms or an ester thereof may be
derivable from unsaturated carboxylic acids or their halide equivalents. Suitable
mono-unsaturated acids include for example, oleic acid, myristoleic acid, palmitoleic
acid, sapienic acid, erucic acid and brassidic acid. Suitable polyunsaturated acids
include for example linoleic acid and linolenic acid.
[0064] The glyceride may be a glyceride of at least one hydroxy polycarboxylic acid and
a saturated C4 to C22 polycarboxylic acid, or an ether or an ester derivative thereof.
The polycarboxylic acid may be branched or linear. The glyceride may be a glyceride
of at least one hydroxy polycarboxylic acid and a mono-unsaturated or polyunsaturated
C4 to C22 polycarboxylic acid, or an ether or an ester derivative thereof. The polycarboxylic
acid may be branched or linear. The glyceride may be a glyceride of at least one hydroxy
polycarboxylic acid and a saturated C4 to C22 monocarboxylic acid, or an ether or
an ester derivative thereof. The monocarboxylic acid may be branched or linear. Suitable
saturated C16 monocarboxylic acids include palmitic acid. Suitable saturated C18 monocarboxylic
acids include stearic acid. The glyceride may be a glyceride of at least one hydroxy
polycarboxylic acid and a mono-unsaturated or polyunsaturated C4 to C22 monocarboxylic
acid, or an ether or an ester derivative thereof. The unsaturated monocarboxylic acid
may be branched or linear. The glyceride may be a glyceride of at least one hydroxy
polycarboxylic acid and an unsaturated C18 monocarboxylic acid, or an ether or an
ester derivative thereof. The monocarboxylic acid may be branched or linear. Suitable
hydroxy polycarboxylic acids include citric acid. The glyceride additive may be a
glyceride of citric acid and an unsaturated C18 monocarboxylic acid, or an ether or
an ester derivative thereof. Suitable unsaturated C18 monocarboxylic acids include
oleic acid and linoleic acid.
[0065] The glyceride may be a citric acid ester of a mono-glyceride of a saturated, mono-
unsaturated or polyunsaturated, branched or linear, monocarboxylic or polycarboxylic
C4 to C22 carboxylic acid, suitably a C16 or C18 carboxylic acid for example, palmitic
acid, stearic acid, oleic acid or linoleic acid. The glyceride may be a citric acid
ester of monoglyceride made from vegetable oil, for example sunflower and/or palm
oil. The glyceride may be a citric acid ester of mono-glyceride made from edible,
refined sunflower and palm based oil. Preferably, the glyceride is a glyceride of
citric acid and oleic acid, a glyceride of citric acid and linoleic acid or a mixture
thereof. A suitable source of glycerides of citric acid with oleic acid and/or linoleic
acid is GRINSTED CITREM SP70 (Trade Mark) which is available from Danisco DuPont.
GRINSTED CITREM SP70 is believed to be a citric acid ester of mono-glyceride made
from edible, refined sunflower and palm based oil. GRINSTED CITREM SP70 is also believed
to comprise at least one diglyceride having the Formula 4:

wherein- Y- represents a C16 hydrocarbyl moiety which is mono- or di-unsaturated.
[0066] Thus, diglycerides having Formula 4 include a glyceride of citric acid and oleic
acid and a glyceride of citric acid and linoleic acid. This corresponds to a structure
of Formula 3 in which (i) RO represents a carboxyl group having 18 carbon atoms, which
may be derivable from oleic acid and/or linoleic acid, (ii) OR' represents a hydroxyl
moiety, and (iii) OR" represents a hydroxy polycarboxylic acid moiety, which may be
derivable from citric acid.
[0067] The glyceride may be an ester of citric acid with a partial glyceride, for example
mono- or di-glyceride or mixtures thereof, which have free hydroxyl groups. Suitable
partial glycerides include those derived from fatty acids with 12 to 18 carbon atoms,
including for example those derived from coconut oil fatty acids and palm oil fatty
acids. Examples include Lamegin
® ZE 306, Lamegin
® ZE 609 and Lamegin
® ZE 618 (Cognis Deutschland GmbH & Co. KG). Thus the glyceride may be a citric acid
ester of the monoglyceride of hydrogenated tallow fatty acid, for example Lamegin
® ZE 309, or an ester of diacetyl tartaric acid with monoglyceride of hydrogenated
tallow fatty acid, for example Lamegin
® DW 8000, or citric acid ester based on sunflower oil fatty acid monoglyceride, for
example Lamegin
® ZE 609 FL. Such esters are described for example in
US 5,770,185 and
US 2010/0087319.
[0068] The derivative of the glyceride may be an ester of the at least one hydroxy polycarboxylic
acid moiety. The ester may be an ester of a carboxylic acid moiety of the hydroxy
polycarboxylic acid. Each carboxylic acid moiety of the hydroxyl polycarboxylic acid
may be independently derivatisable as an ester. The ester derivative may be a hydrocarbyl
ester, in which the hydrocarbyl moiety may have from 4 to 22 carbon atoms. The hydrocarbyl
moiety may be an alkyl moiety which may have from 4 to 22 carbon atoms. The hydrocarbyl
moiety may comprise one or more hetero atoms for example nitrogen and/or oxygen.
[0069] The derivative of the glyceride may be an ether or an ester of the hydroxyl moiety
of the hydroxy polycarboxylic acid. If more than one hydroxy moiety is present in
the mono-, di-, or tri-glyceride of at least one hydroxy polycarboxylic acid, each
hydroxyl moiety may independently be derivatisable as an ether or an ester. Each ether
may be a hydrocarbyl ether. The hydrocarbyl moiety of each ether may independently
have from 1 to 22 carbon atoms, more suitably from 1 to 18 carbon atoms. The hydrocarbyl
moiety of each ether may independently be an alkyl moiety. The alkyl moiety of each
ether may independently have from 1 to 22 carbon atoms, more suitably from 1 to 18
carbon atoms. The hydrocarbyl moiety of each ether may independently comprise one
or more hetero atoms for example nitrogen and/or oxygen. Each ester may independently
be a hydrocarbyl ester. The hydrocarbyl moiety of each ester may have from 4 to 22
carbon atoms. The hydrocarbyl moiety of each ester may independently be an alkyl moiety.
The alkyl moiety of each ester may independently have from 4 to 22 carbon atoms. The
hydrocarbyl moiety of each ester may independently comprise one or more hetero atoms
for example nitrogen and/or oxygen.
[0070] If the saturated, mono-unsaturated or polyunsaturated, branched or linear carboxylic
acid having 4 to 22 carbon atoms is a polycarboxylic acid, the derivative of the glyceride
may be an ester of a carboxylic acid moiety of one or more of the at least one saturated,
mono-unsaturated or poly-unsaturated, branched or linear, polycarboxylic acid having
from 4 to 22 carbon atoms, if present. Each ester may independently be a hydrocarbyl
ester. The hydrocarbyl moiety of each ester may independently have from 4 to 22 carbon
atoms. The hydrocarbyl moiety may be an alkyl moiety. The alkyl moiety of each ester
may independently have from 4 to 22 carbon atoms. The hydrocarbyl moiety of each ester
may independently comprise one or more hetero atoms for example nitrogen and/or oxygen.
[0071] The oil-soluble mono-, di-, or tri-glycerides of at least one hydroxy polycarboxylic
acid and derivatives thereof may be made by methods known in the art. The di- and
tri-glycerides may be made by partial hydrolysis of a fat to produce a mono-glyceride
followed by esterification with a hydroxy polycarboxylic acid. The mono-glycerides
may be made by esterification of glycerol with a hydroxy polycarboxylic acid. Hydrocarbyl
ether derivatives may be made from corresponding hydrocarbyl halides.
[0072] As mentioned above, the lubricant composition and additive composition may further
comprise further additive components.
[0073] Examples of further additive components include dispersants (metallic and non-metallic),
dispersant viscosity modifiers, detergents (metallic and non-metallic), viscosity
index improvers, viscosity modifiers, pour point depressants, rust inhibitors, corrosion
inhibitors, anti-oxidants, anti-foaming agents, seal swell agents, extreme pressure
and/or anti-wear additives (including non-metallic, phosphorus containing, non-phosphorus
containing, sulphur containing, non-sulphur containing extreme pressure additives
and phosphorus- and sulphur-containing hydrocarbons), surfactants, demulsifiers, anti-seizure
agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents
and metal deactivators.
[0074] Dispersants (also called dispersant additives) help hold solid and liquid contaminants
for example resulting from oxidation of the lubricant composition during use, in suspension
and thus reduce sludge flocculation, precipitation and/or deposition for example on
lubricated surfaces. They generally comprise long-chain hydrocarbons, to promote oil-solubility,
and a polar head capable of associating with material to be dispersed. Examples of
suitable dispersants include oil soluble polymeric hydrocarbyl backbones each having
one or more functional groups which are capable of associating with particles to be
dispersed. The functional groups may be amine, alcohol, amine-alcohol, amide or ester
groups. The functional groups may be attached to the hydrocarbyl backbone through
bridging groups. More than one dispersant may be present in the additive concentrate
and/or lubricant composition. Optionally the composition is absent such dispersants.
[0075] Examples of suitable ashless dispersants include oil soluble salts, esters, amino-esters,
amides, imides and oxazolines of long chain hydrocarbon-substituted mono- and polycarboxylic
acids or anhydrides thereof; thiocarboxylate derivatives of long chain hydrocarbons;
long chain aliphatic hydrocarbons having polyamine moieties attached directly thereto;
Mannich condensation products formed by condensing a long chain substituted phenol
with formaldehyde and polyalkylene polyamine; Koch reaction products and the like.
Examples of suitable dispersants include derivatives of long chain hydrocarbyl-substituted
carboxylic acids, for example in which the hydrocarbyl group has a number average
molecular weight of up to 20000, for example 300 to 20000, 500 to 10000, 700 to 5000
or less than 15000. Examples of suitable dispersants include hydrocarbyl-substituted
succinic acid compounds, for example succinimide, succinate esters or succinate ester
amides and in particular, polyisobutenyl succinimide dispersants. The dispersants
may be borated or non-borated.
[0076] Additionally or alternatively, dispersancy may be provided by polymeric compounds
capable of providing viscosity index improving properties and dispersancy. Such compounds
are generally known as dispersant viscosity improver additives or multifunctional
viscosity improvers. Examples of suitable dispersant viscosity modifiers may be prepared
by chemically attaching functional moieties (for example amines, alcohols and amides)
to polymers which tend to have number average molecular weights of at least 15000,
for example in the range 20000 to 600000 (for example as determined by gel permeation
chromatography or light scattering methods). Examples of suitable dispersant viscosity
modifiers and methods of making them are described in
WO 99/21902,
WO2003/099890 and
WO2006/099250. More than one dispersant viscosity modifier may be present in the additive concentrate
and/or lubricant composition.
[0077] Detergents (also called detergent additives) may help reduce high temperature deposit
formation for example on metallic surfaces within machinery, including for example
high-temperature varnish and lacquer deposits, by helping to keep finely divided solids
in suspension in the lubricant composition. Detergents may also have acid-neutralising
properties. Ashless (that is non-metal containing) detergents may be present. Metal-containing
detergent comprises at least one metal salt of at least one organic acid, which is
called soap or surfactant. Detergents may be overbased in which the detergent comprises
an excess of metal in relation to the stoichiometric amount required to neutralise
the organic acid. The excess metal is usually in the form of a colloidal dispersion
of metal carbonate and/or hydroxide. Examples of suitable metals include Group I and
Group 2 metals, more suitably calcium, magnesium and combinations thereof, especially
calcium. More than one metal may be present.
[0078] Examples of suitable organic acids include sulphonic acids, phenols (sulphurised
or preferably sulphurised and including for example, phenols with more than one hydroxyl
group, phenols with fused aromatic rings, phenols which have been modified for example
alkylene bridged phenols, and Mannich base-condensed phenols and saligenin-type phenols,
produced for example by reaction of phenol and an aldehyde under basic conditions)
and sulphurised derivatives thereof, and carboxylic acids including for example, aromatic
carboxylic acids (for example hydrocarbyl-substituted salicylic acids and sulphurised
derivatives thereof, for example hydrocarbyl substituted salicylic acid and derivatives
thereof). More than one type of organic acid may be present.
[0079] Additionally or alternatively, non-metallic detergents may be present. Suitable non-metallic
detergents are described for example in
U.S. Pat. No. 7,622,431.
[0080] More than one detergent may be present in the lubricant composition and/or additive
concentrate.
[0081] Viscosity Index Improvers/Viscosity Modifiers Viscosity index improvers (also called
viscosity modifiers, viscosity improvers or VI improvers) impart high and low temperature
operability to a lubricant composition and facilitate it remaining shear stable at
elevated temperatures whilst also exhibiting acceptable viscosity and fluidity at
low temperatures.
[0082] Examples of suitable viscosity modifiers include high molecular weight hydrocarbon
polymers (for example polyisobutylene, copolymers of ethylene and propylene and higher
alpha-olefins); polyesters (for example polymethacrylates); hydrogenated poly(styrene-co-butadiene
or isoprene) polymers and modifications (for example star polymers); and esterified
poly(styrene-co-maleic anhydride) polymers. Oil-soluble viscosity modifying polymers
generally have number average molecular weights of at least 15000 to 1000000, preferably
20000 to 600000 as determined by gel permeation chromatography or light scattering
methods.
[0083] Viscosity modifiers may have additional functions as multifunction viscosity modifiers.
More than one viscosity index improver may be present.
[0084] Pour point depressants (also called lube oil improvers or lube oil flow improvers),
lower the minimum temperature at which the lubricant will flow and can be poured.
Examples of suitable pour point depressants include C8 to C18 dialkyl fumarate/vinyl
acetate copolymers, methacrylates, polyacrylates, polyarylamides, polymethacrylates,
polyalkyl methacrylates, vinyl fumarates, styrene esters, condensation products of
haloparaffm waxes and aromatic compounds, vinyl carboxylate polymers, terpolymers
of dialkyfumarates, vinyl esters of fatty acids and allyl vinyl ethers, wax naphthalene
and the like.
[0085] More than one pour point depressant may be present.
[0086] Rust inhibitors generally protect lubricated metal surfaces against chemical attack
by water or other contaminants. Examples of suitable rust inhibitors include non-ionic
polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, polyoxyalkylene
polyols, anionic alky sulphonic acids, metal phenolates, basic metal sulphonates,
fatty acids and amines. Preferably the rust inhibitor is not a zinc dithiophosphate.
[0087] More than one rust inhibitor may be present.
[0088] Corrosion inhibitors (also called anti-corrosive agents) reduce the degradation of
metallic parts contacted with the lubricant composition. Examples of corrosion inhibitors
include phosphosulphurised hydrocarbons and the products obtained by the reaction
of phosphosulphurised hydrocarbon with an alkaline earth metal oxide or hydroxide,
non-ionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles,
triazoles and anionic alkyl sulphonic acids. Examples of suitable epoxidised ester
corrosion inhibitors are described in
US2006/0090393.
[0089] More than one corrosion inhibitor may be present.
[0090] Antioxidants (sometimes also called oxidation inhibitors) reduce the tendency of
oils to deteriorate in use. Evidence of such deterioration might include for example
the production of varnish-like deposits on metal surfaces, the formation of sludge
and viscosity increase. Examples of suitable antioxidants include alkylated diphenylamines,
N-alkylated phenylenediamines, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamines,
dimethylquinolines, trimethyldihydroquinolines and oligomeric compositions derived
therefrom, hindered phenolics (including ashless (metal-free) phenolic compounds and
neutral and basic metal salts of certain phenolic compounds), aromatic amines (including
alkylated and non-alkylated aromatic amines), sulphurised alkyl phenols and alkali
and alkaline earth metal salts thereof, alkylated hydroquinones, hydroxylated thiodiphenyl
ethers, alkylidenebisphenols, thiopropionates, metallic dithiocarbamates, 1,3,4-dimercaptothiadiazole
and derivatives, oil soluble copper compounds (for example, copper dihydrocarbyl thio-
or thio-phosphate, copper salts of a synthetic or natural carboxylic acids, for example
a C8 to C18 fatty acid, an unsaturated acid or a branched carboxylic acid, for example
basic, neutral or acidic Cu(I) and/or Cu(II) salts derived from alkenyl succinic acids
or anhydrides), alkaline earth metal salts of alkylphenolthioesters, suitably having
C5 to C12 alkyl side chains, calcium nonylphenol sulphide, barium t-octylphenyl sulphide,
dioctylphenylamine, phosphosulphised or sulphurised hydrocarbons, oil soluble phenates,
oil soluble sulphurised phenates, calcium dodecylphenol sulphide, phosphosulphurised
hydrocarbons, sulphurised hydrocarbons, phosphorus esters, low sulphur peroxide decomposers
and the like.
[0091] More than one anti-oxidant may be present. More than one type of anti-oxidant may
be present.
[0092] Anti-foams (sometimes also called anti-foaming agents) retard the formation of stable
foams. Examples of suitable anti-foam agents include silicones, organic polymers,
siloxanes (including poly siloxanes and (poly) dimethyl siloxanes, phenyl methyl siloxanes),
acrylates and the like.
[0093] More than one anti-foam may be present.
[0094] Seal swell agents (sometimes also called seal compatibility agents or elastomer compatibility
aids) help to swell elastomeric seals for example by causing a reaction in the fluid
or a physical change in the elastomer. Examples of suitable seal swell agents include
long chain organic acids, organic phosphates, aromatic esters, aromatic hydrocarbons,
esters (for example butylbenzyl phthalate) and polybutenyl succinic anhydride.
[0095] More than one seal swell agent may be present.
[0096] Examples of other additives which may be present in the lubricant composition and/or
additive concentrate include extreme pressure and/or anti-wear additives (including
non-metallic, phosphorus containing, non-phosphorus containing, sulphur containing,
non-sulphur containing extreme pressure additives and phosphorus- and sulphur-containing
hydrocarbons), surfactants, demulsifiers, anti-seizure agents, wax modifiers, lubricity
agents, anti-staining agents, chromophoric agents and metal deactivators.
[0097] The base oil composition used in the present aspect preferably makes up at least
75% by weight of the lubricant composition, more preferably at least 80%, still more
preferably at least 85%, still more preferably at least 90%. More preferably still,
the base oil composition makes up from 92 to 97% by weight, such as at least 94%.
[0098] The base oil composition may be any suitable base oil and may selected from mineral
oils, synthetic oils, vegetable and animal oils and mixtures thereof used in conventional
lubricating oils as appropriate. Specific examples thereof include base oils of groups
I, II, III, IV or V in the API (American Petroleum Institute) standard in base oil
categories according to API standard 1509, "
ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", April 2007 version, 16
th edition Appendix E, as set out in Table 1.
Table 1
Group |
Saturated hydrocarbon content (% by weight) ASTM D2007 |
|
Sulphur content (% by weight) ASTM D2622 or D4294 or D4927 or 03120 |
|
Viscosity Index ASTM D2270 |
I |
<90 |
and/or |
>0.03 |
and |
≧80 and <120 |
II |
≧90 |
and |
≦0.03 |
and |
≧80 and <120 |
III |
≧90 |
and |
≦0.03 |
and |
≧120 |
IV |
polyalpha olefins |
V |
all base stocks not in Groups I, II, III or IV |
[0099] Group I, Group II and Group III base stocks may be derived from mineral oils. Group
I base stocks are typically manufactured by known processes comprising solvent extraction
and solvent dewaxing, or solvent extraction and catalytic dewaxing. Group II and Group
III base stocks are typically manufactured by known processes comprising catalytic
hydrogenation and/or catalytic hydrocracking, and catalytic hydroisomerisation. A
suitable Group I base stock is AP/E core 150, available from ExxonMobil. Suitable
Group II base stocks are EHC 50 and EHC 110, available from ExxonMobil. Suitable group
III base stocks include Yubase 4 and Yubase 6 available for example, from SK Lubricants.
Suitable Group V base stocks are ester base stocks, for example Priolube 3970, available
from Croda International plc. Suitable Group IV base stocks include hydrogenated oligomers
of alpha olefins. Suitably, the oligomers may be made by free radical processes, Zeigler
catalysis or by cationic Friedel-Crafts catalysis. Poly-alpha-olefin base stocks may
be derived from C8, C10, C12, C14 olefins and mixtures of one or more thereof. In
one embodiment, the poly-alpha-olefin base stock may be derived from C10 and C12 olefins.
[0100] The lubricant composition and the oil of lubricating viscosity may comprise one or
more base oil and/or base stock which is/are natural oil, mineral oil (sometimes called
petroleum-derived oil or petroleum-derived mineral oil), non-mineral oil and mixtures
thereof. Natural oils include animal oils, fish oils, and vegetable oils. Mineral
oils include paraffinic oils, naphthenic oils and paraffinic-naphthenic oils. Mineral
oils may also include oils derived from coal or shale.
[0101] Suitable base oils and base stocks may be derived from processes such as chemical
combination of simpler or smaller molecules into larger or more complex molecules
(for example polymerisation, oligomerisation, condensation, alkylation, acylation).
[0102] Suitable base stocks and base oils may be derived from gas-to-liquids materials,
coal-to-liquids materials, biomass-to-liquids materials and combinations thereof.
[0103] Preferably, the base oil is a synthetic base oil comprising a poly-alpha-olefin component.
[0104] There is provided, in a preferred embodiment for use in the lubricant composition
of the first aspect of the present invention, a base oil comprising a modified poly-alpha-olefin.
Any suitable amount of the modified poly-alpha-olefin may be used and it may comprise
5 to 95% by weight of the total composition, more preferably 10 to 90% by weight and
optionally from 30 to 88% by weight. Preferably, the base oil according to this embodiment
is a synthetic base oil and more preferably comprises a conventional poly-alpha-olefin.
Optionally, the base oil further comprises one or more additive carriers, which may
be typically selected from other base stocks such as Group V base stocks, optionally
polymeric or non-polymeric base stocks and optionally having a polar component. Preferably
the additive carrier is not elastomer shrinking and more preferably is elastomer swelling.
[0105] A modified poly-alpha-olefin may preferably be a functionalised poly-alpha olefin,
preferably functionalised with a relatively polar functional group, such as an ester
group. Preferably, the olefin to ester ratio in the modified poly-alpha-olefin is
in the range from 20:1 to 1:1. A modified poly-alpha-olefin, as used herein, is preferably
obtainable and preferably obtained by co-polymerisation of one or more alpha-olefin
monomers with a monomer having a relatively polar functional group, e.g. an olefinic
monomer having or adapted to have a relatively polar functional group. The modified
poly-alpha-olefin preferably comprises a co-polymer of one or more alpha-olefin monomers
with ester (e.g. an alkyl ester of an acid, such as an alkyl ester of a dicarboxylic
acid) and preferably an olefinic alkyl ester. Other ester functional groups may include
butanedioic and succinic anhydride. One example of the modified poly-alpha-olefin
is a co-polymer of an alpha-olefin monomer (e.g. with a dodecene chain length) with
an olefinic alkyl esters, for example with an olefinic alkyl ester having a decene
olefin chain length and in a ratio of alpha olefin monomer and functionalised monomer
in the range 3:2 to 5:1, preferably 2:1 to 3:1 and preferably in a randomised copolymer.
Examples of commercially available modified poly-alpha-olefins include but are not
limited to Aria
™ WTP 40 or a Ketjenlube
™ grade such as Ketjenlube
™ 240.
[0106] Preferably, the modified poly-alpha-olefin is selected from a kinematic viscosity
at 100°C of 40 cSt or 100 cSt or thereabout. For use in robot gears, it is preferred
that the modified poly-alpha-olefin has a kinematic viscosity at 100°C of 40 cSt or
thereabout. For use in wind turbines or industrial gear, it is preferred that the
modified poly-alpha-olefin has a kinematic viscosity at 100°C of 100 cSt or thereabout.
[0107] Any suitable poly-alpha-olefin may be used, but preferably a relatively low viscosity
poly-alpha-olefin (by which it is meant low viscosity relative to the modified poly-alpha-olefin),
such as a PAO 8. Optionally, the poly-alpha-olefin may be or may include or comprise
a high viscosity poly-alpha-olefin, such as a high viscosity conventional poly-alpha-olefin
(e.g. conventional PAO 40 and/or 100) and/or a metallocene poly-alpha-olefin (e.g.
metallocene PAO 50 and/or 135).
[0108] Particular base stocks may be selected and particular base oils may be formulated
to provide any suitable viscosity grade of base oil, as required. The lubricant composition
may have any suitable viscosity grade (defined by kinematic viscosity at 40°C), such
as from 60 to 700 cSt, more preferably 68 to 680 cSt.
[0109] In one preferred embodiment, the base oil may comprise the modified poly-alpha-olefin
and poly-alpha-olefin in a weight ratio of 25:75 to 85:15, more preferably from 40:60
to 80:20, optionally 50:50 or a greater proportion of the modified poly-alpha-olefin,
such as in the range 60:40 to 75:25. A ratio of about 70:30 may be provided in one
embodiment. Preferably, according to this embodiment, the modified poly-alpha olefin
has a kinematic viscosity at 100°C of 40 cSt or thereabout and is suitable for use
in formulating a lubricating composition with a viscosity grade defined by a kinematic
viscosity of 150 cSt at 40°C and is preferably for use in robotic gears. The modified
poly-alpha-olefin and poly-alpha-olefin may make up the major part of the base oil
composition and preferably at least 60% by weight of the base oil composition, more
preferably at least 75% by weight of the base oil composition. More preferably, it
makes up at least 85% of the base oil composition and optionally at least 90%.
[0110] A preferred base oil composition comprises one or more additive carriers. The additive
carriers preferably serve to increase the polarity of the base oil and may preferably
be used as the base stock component of an additive concentrate. Such additive carrier
may be a Group V base stock. Preferably the additive carrier is a relatively polar
base stock. Optionally, an additive carrier may have a kinematic viscosity at 40°C
of from 20 to 40 cSt, preferably 25-35 cSt. The additive carrier may be, for example,
selected from alkylated naphthalene, alkyl benzene or low viscosity esters, preferably,
alkylated naphthalene or low viscosity alkylbenzene is used. A low viscosity ester
may be for example a diisodecyl adipate (DIDA) or a diiso tridecyl adipate (DITA),
which may be present in the base oil in an amount of up to 20% by weight, but more
preferably up to 15% by weight and still more preferably up to 10% by weight and in
any case at least 5% by weight. Preferably, the additive carrier comprises (and still
more preferably is) an alkylated naphthalene and is provided in an amount of up to
25% by weight of the base oil composition, preferably up to 15%. The alkylated naphthalene
is preferably provided in an amount of at least 5%, preferably at least 7.5% and preferably
in an amount up to 12%, more preferably 10% of the base oil composition.
[0111] Base oil compositions of the present embodiment are particular advantageous in lubricant
compositions of the present invention in that they provide a stable lubricant composition
that can provide longevity, are less liable to sludge, and are capable of effectively
solubilising an additive composition such as that defined above. The base oil composition
of the present embodiment also provides excellent elastomer compatibility properties.
[0112] The base oil according to a preferred embodiment may enable for the lubricant composition
a viscosity of from 130 to 170 cSt at 40°C, more preferably 135 to 165 cSt at 40°C.
[0113] In a preferred embodiment of the invention, a lubricant composition is provided as
a synthetic gear oil composition suitable for use as a lubricant for gearboxes comprising
a rolling element, comprising a base oil composition comprising a modified poly-alpha-
olefin such as that defined above; and an additive composition comprising a molybdenum
dialkyldithiocarbamate and an oil-soluble mono-, di- or tri-glyceride of at least
one hydroxyl polycarboxylic acid, or an ether or an ester derivative thereof, which
has no more than 0.1% by weight of molybdenum dithiophosphate.
EXAMPLES
[0114] Lubricant compositions were prepared for comparison with commercially available lubricant
oils and subject to a number of performance tests to compare the performance as gear
oils, particularly as robot gear oils. In particular, tests were provided for wear,
including a gear wear test, a bearing gear performance test and elastomer compatibility
tests.
[0115] The performance or wear tests carried out are summarised below.
[0116] FZG test: this test is a well-known test designed to test wear performance of a lubricating
oil at the interface of a set of gears. For this test, gears are loaded through a
torsional coupling that is set to known load conditions or stages. The gears are rotated
by a variable speed electric motor. Fluid temperature is controlled by heating and/or
cooling elements. The test evaluates gear tooth face scuffing resistance of fluids
using A profile gears. A rig is operated at 1450 rpm through up to 12 progressive
load stages at 15 minute intervals. Standard tests are run at a fluid temperature
of 90°C. Gear teeth are inspected after each load stage for scuffing. The test was
carried out according to the test method defined in ISO14635-1. Load carrying capacity
before failure was identified by failure stage and determined as pass/fail. A fail
was considered failure to reach failure stage 12 or greater under the test conditions.
The evaluation of failure condition is when cumulative scratch width on the gear exceeds
20 mm. This is indicative of scuffing wear.
[0117] FE8 test: the FE8 test is recognised within the industry and a good means of evaluating
bearing gear performance. Both rolling and sliding lubrication conditions are present
in the same test and so the test is particularly suited at testing performance of
a lubricant for use in gears having rolling elements. Two steps of the FE8 test were
carried out. In step 1, wear and torque performance are measured and can be used to
evaluate performance of a lubricant composition. In step 2, long term integrity of
the product is examined. Test pieces, including rollers and washers, were visually
examined to assess for surface finish.
[0118] The FE8 tests were carried out consistent with DIN-51819-3. Test duration and loss
of weight of bearing components are used to classify the aptitude of the lubricant.
The test bearings used are cylindrical roller thrust bearings 81212 with brass cage.
One bearing consists of 15 cylindrical rolling elements, a brass cage, a housing washer
and a shaft washer. The material of the washers and rolling elements is usual bearing
steel 100Cr6 and the material of the cage is CuZn40. The bearings are manufactured
by FAG, Schweinfurt. An advantage of using a cylindrical bearing in an anti-wear test
is that there is a high amount of slippage (maximum 14.8%) and so anti-wear requirements
on lubricant is high.
[0119] In the FE8 test, the test bench is equipped with two cylindrical roller thrust bearings.
The test bearings are strained with a disc spring package to provide the axial test
force. A heat shield heats the test head by convection heating and a radial fan is
used to reduce temperature if required.
[0120] For FE8 step 1, a load of 80 kN is applied with a 7.5 rpm speed at 80°C, over 80
hours. A 4 litre oil reservoir is used with a 0.1 litre/minute flow rate per bearing.
Wear of bearings is measured in terms of weight loss of roller sets, rings and cage.
Less than 30 mg wear of the roller sets is considered acceptable under the DIN-51819-3
methodology.
[0121] For FE8 step 2, a load of 80 kN is applied with 75 rpm speed at 70°C, over 800 hours.
Again a 4 litre oil reservoir is used with a 0.1 litre/minute flow rate per bearing.
[0122] As elastomer compatibility testing, condition of both elastomers and the oil after
the elastomer compatibility tests was assessed, to be able to provide an assessment
of sludge formation as an elastomer compatibility component. Two static elastomer
compatibility tests were carried out: elastomer material 72NBR902 was tested at 95°C
over 1008 hours (referred to as the NBR test) and an elastomer material 75FKM585 was
tested at 120°C over 1008 hours (referred to as the FKM test). In each case change
in mass, volume, shore A hardness, tensile strength and rupture elongation were measured
in percentage terms relative to a reference. The NBR and FKM tests were carried out
in line with ISO 1817. The used oil from the NBR and FKM tests was visually assessed
for colour change relative to a fresh oil and sludge formation to further characterise
elastomer compatibility.
Example 1
[0123] Sample lubricant oil formulations were prepared by providing a base oil comprising
a mixture of base stocks and blending therewith an additive composition comprising
at least an anti-wear agent and other additives in a diluent (the diluent being one
of the base stocks). The formulations are summarised in Table 2 below:
Table 2: sample lubricant compositions (wt % content)
Sample No: |
|
S1 |
S2 |
S3 |
| S4 |
S5 |
| S6 |
Base oil |
PAO 8 |
|
25 |
25 |
28 |
28 |
28 |
28 |
Modified PAO (commercially available as Aria WTP 40) |
|
60 |
60 |
60 |
60 |
60 |
60 |
Alkylated naphthalene |
|
11.132 |
10.532 |
7.897 |
7.997 |
8.397 |
8.497 |
Sub-total |
|
96.132 |
95.532 |
95.897 |
95.997 |
96.397 |
96.497 |
Additive composition |
MoDTC |
|
1.25 |
1.25 |
0.9 |
0.9 |
0.9 |
0.9 |
Phenolic antioxidant |
|
0.095 |
0.095 |
0.095 |
0.095 |
0.095 |
0.095 |
Aminic antioxidant |
|
0.095 |
0.095 |
0.095 |
0.095 |
0.095 |
0.095 |
Yellow metal passivator |
|
0.008 |
0.008 |
0.008 |
0.008 |
0.008 |
0.008 |
Metal-containing detergent, e.g. Calcium |
|
1.695 |
1.695 |
1.68 |
1.68 |
1.68 |
1.68 |
S+P EP/AW booster, aliphatic, C3-C8 |
|
0.095 |
0.095 |
0.095 |
0.095 |
0.095 |
0.095 |
S+P anti-wear booster, aromatic |
|
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
Corrosion protector |
|
0.09 |
0.09 |
0.09 |
0.09 |
0.09 |
0.09 |
Anti-foam |
|
0.04 |
0.04 |
0.04 |
0.04 |
0.04 |
0.04 |
Sub-total |
|
3.868 |
3.868 |
3.503 |
3.503 |
3.503 |
3.503 |
Oil soluble glyceride of hydroxyl polycarboxylic acid |
|
0 |
0.5 |
0.5 |
0.5 |
0 |
0 |
Oleylamide |
|
0 |
0.1 |
0.1 |
0 |
0.1 |
0 |
Sub-total |
|
0 |
0.6 |
0.6 |
0.5 |
0.1 |
0 |
TOTAL |
|
100.000 |
100.000 |
100.000 |
100.000 |
100.000 |
100.000 |
Example 2
[0124] The samples S1 to S6 were then subjected to anti-wear performance and elastomer compatibility
tests. In particular, the FZG and FE8 step 1 and step 2 tests for anti-wear and the
NBR and FKM elastomer tests as described above. The post-test oil was checked visually
for sludge and there was a surface finish examination carried out with a laser microscope.
Results of the tests on the samples S 1 to S6 are set out in Table 3 below.
Table 3: anti-wear performance and elastomer compatibility tests
Sample No: |
S1 |
S2 |
S3 |
S4 |
S5 |
S6 |
Anti-wear performance |
FZG |
>12 |
>12 |
12 |
- |
- |
- |
FE8 Step 1 wear [mg] |
39 |
5 |
<1 |
2 |
60 |
26 |
FE8 Step 2 wear [mg] |
- |
3 |
3 |
- |
- |
- |
FE8 Step 2 sludge |
- |
None |
None |
- |
- |
- |
Elastomer compatibility |
NBR 902 [% changes relative to the reference] |
Mass change |
0.7 |
1.6 |
0.2 |
0.0 |
-0.2 |
- |
Volume change |
-0.1 |
1.3 |
0.1 |
-0.8 |
-1.2 |
- |
Hardness change |
4.3 |
5 |
3 |
4 |
5 |
- |
Tensile Strength change |
-0.3 |
-3.3 |
8.0 |
-3.0 |
-5.1 |
- |
Rupture Elongation change |
-65.8 |
-64.5 |
-30.6 |
-48.3 |
-52.0 |
- |
Sludge |
none |
none |
none |
None |
none |
- |
FKM 585 [% changes relative to the reference] |
Mass change |
0.2 |
0.3 |
0.2 |
- |
- |
- |
Volume change |
0.7 |
0.6 |
0.5 |
- |
- |
- |
Hardness change |
1 |
1 |
0.0 |
- |
- |
- |
Tensile Strength change |
-1.8 |
1.8 |
5.0 |
- |
- |
- |
Rupture Elongation change |
-8.3 |
-18.5 |
-17.8 |
- |
- |
- |
Sludge |
none |
none |
none |
- |
- |
- |
Surface finish |
Ra [nm] |
66 |
34 |
' 38 |
- |
- |
- |
Rz [nm] |
738 |
539 |
396 |
- |
- |
- |
[0125] In the later tests carried out (S5 and S6), FZG and other tests were not completed
where the FE8 Step 1 wear test demonstrated poor anti-wear performance for use in
long-lived robot gear oils.
[0126] A significant improvement in anti-wear can be demonstrated by the inclusion of the
oil soluble glyceride of hydroxyl polycarboxylic acid as illustrated by the significant
improvement in FE8 Step 1 wear test results for samples S2, S3 and S4 (which contained
the oil soluble glyceride of hydroxyl polycarboxylic acid) compared with S 1, S5 and
S6 (which did not).
[0127] As can be seen from the data in Table 3, the use of the blend of modified PAO and
PAO along with an alkylated naphthalene provides generally adequate elastomer compatibility
in all the samples. All the samples were sludge free. Further for each of the samples
(where data was obtained), the measures for mass change, volume change and hardness
change were within acceptable bounds. Generally very good elastomer compatibility
was achieved in sample S3 and significantly better than other samples, such as S2
(differs in proportions of MoDTC and alkylated naphthalene), in terms of rupture elongation
change for the NBR elastomer compatibility test as well as tensile strength change.
It is clear that formulations such as S2, S3 and S4 having a MoDTC in combination
with an oil soluble glyceride of hydroxyl polycarboxylic acid can provide long-lived
robot gear oils with very good elastomer compatibility and excellent anti-wear properties,
including for gears with a rolling element.
1. Eine Schmiermittelzusammensetzung, die als ein Schmiermittel für Getriebe, die einen
Wälzkörper beinhalten, geeignet ist, die Folgendes beinhaltet: eine Basisölzusammensetzung
mit Schmierviskosität; und eine Additivzusammensetzung, die ein Molybdän-Dialkyldithiocarbamat
und ein öllösliches Mono-, Di- oder Triglycerid mindestens einer Hydroxylpolycarbonsäure
oder ein Ether- oder ein Esterderivat davon beinhaltet, wobei die Schmiermittelzusammensetzung
nicht mehr als 0,1 Gewichts-% Molybdändithiophosphat aufweist.
2. Schmiermittelzusammensetzung nach Anspruch 1, wobei das Molybdän-Dialkyldithiocarbamat
in einer Menge, im Hinblick auf Molybdän, von 500 bis 3000 ppm der Schmiermittelzusammensetzung,
bevorzugt von 750 bis 1500 ppm der Schmiermittelzusammensetzung, bereitgestellt wird.
3. Schmiermittelzusammensetzung nach Anspruch 1 oder 2, wobei das öllösliche Mono-, Di-
oder Triglycerid mindestens einer Hydroxylpolycarbonsäure oder ein Ether- oder Esterderivat
davon in einer Menge von 0,1 bis 2,5 Gewichts-% der Schmiermittelzusammensetzung,
bevorzugt 0,25 bis 1 Gewichts-% der Schmiermittelzusammensetzung, bereitgestellt wird
und/oder das öllösliche Mono-, Di- oder Triglycerid mindestens einer Hydroxylpolycarbonsäure
oder ein Ether- oder Esterderivat davon in einem Gewichtsprozentverhältnis relativ
zu dem Molybdän-Dialkyldithiocarbamat im Bereich von 1:3 bis 1:1, bevorzugter im Bereich
von 1:2 bis 2:3, bereitgestellt wird.
4. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, in der Molybdän-Dithiophosphat
fehlt.
5. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Additivzusammensetzung
ferner ein Fettsäureamid mit 12 bis 25 Kohlenstoffatomen, wie etwa Oleylamid, in einer
Menge von bis zu 1 Gewichts-% der Schmiermittelzusammensetzung beinhaltet.
6. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Additivzusammensetzung
einen Anteil der Schmiermittelzusammensetzung von bis zu 10 Gewichts-%, bevorzugt
von 2,5 bis 7,5 Gewichts-%, ausmacht.
7. Schmiermittelzusammensetzung nach einem der Ansprüche 1 bis 6, wobei die Basisölzusammensetzung
ein funktionell modifiziertes Polyalphaolefin, ein Polyalphaolefin und optional einen
Additivträger beinhaltet.
8. Schmiermittelzusammensetzung nach Anspruch 7, wobei das modifizierte Polyalphaolefin
ein mit einer Estergruppe funktionalisiertes Polyalphaolefin ist, wobei das modifizierte
Polyalphaolefin bevorzugt ein Copolymer eines Alphaolefinmonomers mit einem Ester
ist, wobei das modifizierte Polyalphaolefin bevorzugt ein Copolymer eines Alphaolefinmonomers
mit einem olefinischen Alkylester mit einer Decen-Olefinkettenlänge und in einem Verhältnis
von Alphaolefinmonomer und funktionalisiertem Monomer im Bereich von 3:2 bis 5:1 ist.
9. Schmiermittelzusammensetzung nach Anspruch 8, wobei das modifizierte Polyalphaolefin
ein Copolymer eines Alphaolefinmonomers mit einem olefinischen Anhydrid ist, wobei
das olefinische Anhydrid bevorzugt ein olefinisches Bernsteinsäure- oder Maleinsäureanhydrid
ist.
10. Schmiermittelzusammensetzung nach einem der Ansprüche 7 bis 9, wobei das Polyalphaolefin
und modifizierte Polyalphaolefin den größten Teil der Basisölzusammensetzung, bevorzugt
mindestens 75 Gewichts-% der Basisölzusammensetzung, ausmachen.
11. Schmiermittelzusammensetzung nach einem der Ansprüche 7 bis 10, wobei die Basisölzusammensetzung
einen oder mehrere Additivträger beinhaltet.
12. Eine synthetische Getriebeölzusammensetzung, die als ein Schmiermittel für Getriebe,
die einen Wälzkörper beinhalten, geeignet ist, die Folgendes beinhaltet: eine Basisölzusammensetzung,
die ein modifiziertes Polyalphaolefin beinhaltet; und eine Additivzusammensetzung,
die ein Molybdän-Dialkyldithiocarbamat und ein öllösliches Mono-, Di- oder Triglycerid
mindestens einer Hydroxylpolycarbonsäure oder ein Ether- oder Esterderivat davon beinhaltet,
die nicht mehr als 0,1 Gewichts-% von Molybdändithiophosphat aufweist.
13. Verwendung einer Schmiermittel- oder Getriebeölzusammensetzung nach einem der Ansprüche
1 bis 6 und 12 als ein Schmiermittel für Getriebe, die einen Wälzkörper beinhalten.
14. Ein Verfahren zum Schmieren eines Getriebes oder Betreiben einer Vorrichtung, die
das Getriebe aufweist, wobei das Getriebe einen Wälzkörper beinhaltet, wobei das Verfahren
das Versorgen eines Getriebes, das einen Wälzkörper beinhaltet, mit einem Öl mit Schmierviskosität
beinhaltet, das die Schmierzusammensetzung nach einem der Ansprüche 1 bis 6 oder 12
aufweist.