Note: Descriptions are shown in the official language in which they were submitted.
1
LUBRICATING COMPOSITIONS INCLUDING MIXTURES OF FRICTION MODIFIERS COMPRIS-
ING AN N-SUBSTITUTED OXALIC ACID BISAMIDE OR AMIDE-ESTER CONTAINING AT
LEAST TWO HYDROCARBYL GROUPS, AND AN AMIDE OR THIOAMIDE
BACKGROUND
[0001] The disclosed technology relates to additives and fluids for
transmissions such
as automatic transmission fluids.
[0002] In the automatic transmission marketplace, where there is rapid
engineering
change driven by the desire to reduce weight and increase transmission
capacity, there is
a desire for automatic transmission fluids that exhibit a high static
coefficient of friction
for improved clutch holding capacity. Continuously slipping torque converter
clutches,
for instance, impose exacting friction requirements on automatic transmission
fluids
(ATFs). The fluid must have a good friction versus sliding speed relationship,
or an ob-
jectionable phenomenon called shudder will occur in the vehicle. Transmission
shudder
is a self-excited vibrational state commonly called "stick-slip" or "dynamic
frictional vi-
bration" generally occurring in slipping torque converter clutches. The
friction charac-
teristics of the fluid and material system, combined with the mechanical
design and con-
trols of the transmission, determine the susceptibility of the transmission to
shudder.
Plotting the measured coefficient of friction ( ) versus sliding speed (V),
commonly
called a -V curve, has been shown to correlate to transmission shudder. Both
theory
and experiments support the region of positive to slightly negative slope of
this -V
curve to correlate to good anti-shudder performance of transmission fluids. A
fluid
which allows the vehicle to operate without vibration or shudder is said to
have good
"anti-shudder" performance. The fluid should maintain those characteristics
over its ser-
vice lifetime. The longevity of the anti-shudder performance in the vehicle is
commonly
referred to as "anti-shudder durability." The variable speed friction tester
(VSFT)
measures the coefficient of friction with respect to sliding speed simulating
the speeds,
loads, and friction materials found in transmission clutches and correlates to
the perfor-
mance found in actual use. The procedures are well documented in the
literature; see for
example Society of Automotive Engineers publication #941883. It is also
desirable to
obtain good torque capacity in an automatic transmission with wet clutches by
providing
a lubricant with good frictional performance.
[0003] The combined requirements of high static coefficient of friction
and durable
positive slope are often incompatible with traditional ATF friction modifier
technology
which is extremely well described in the patent literature. Many of the
commonly used
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friction modifiers result in a low static coefficient of friction and are not
durable enough
on positive slope to be of sufficient use.
[0004] U.S. Patent 8,691,740, Vickerman et al., April 8, 2014, discloses
a composi-
tion suitable for use as a friction modifier for an automatic transmission,
comprising
an N-substituted oxalic acid bisamide or amide-ester containing at least two
hydro-
carbyl groups of 12 to 22 carbon atoms. Other, supplemental friction modifiers
may
also be present. Other materials that may also be present include antiwear
agents such
as, among others, various long-chain derivatives of hydroxy carboxylic acids,
such as
tartrates, tartramides, tartrimides, and citrates.
[0005] U.S. Patent 8,148,306, Bartley et al., April 3, 2012, discloses
products of
amines with hydroxy acid as friction modifiers suitable for automatic
transmission flu-
ids. An example is an amide or thioamide represented by the formula
R1R2N C(X)R3 wherein X is 0 or S, 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.
[0006] U.S. Patent 8,450,255, Sumiejski et al., May 28, 2013, discloses
a friction
modifier comprising at least two hydrocarbyl groups attached to a polar group
or atom
(e.g., a nitrogen atom), the friction modifier being (a) the reaction product
of at least one
carboxylic acid or equivalent with at least one aminoalcohol, (b) the reaction
product of
at least one carboxylic acid or equivalent with at least one polyamine, (c) an
amide or
thioamide represented by the formula R1R2N¨C(X)R3 wherein X is 0 or S, R1 and
R2
are each independently hydrocarbyl groups of at least about 6 carbon atoms,
and RI is a
hydroxyalkyl group of 1 to about 6 carbon atoms or a group formed by the
condensation
.. of the hydroxyalkyl group, through a hydroxyl group thereof, with an
acylating agent,
(d) at least one tertiary amine containing two hydrocarbyl groups and a
polyhydroxyl-
containing alkyl group or a polyhydroxyl-containing alkoxyalkyl group, or (e)
a mixture
of two or more of (a), (b), (c) and (d).
SUMMARY
[0007] The disclosed technology provides a composition comprising: (a) an
oil of
lubricating viscosity; (b) 0.05 to 3.0 percent by weight (or 0.1 to 2 or 0.3
to 1 or about
0.7%) of an N-substituted oxalic acid bisamide or amide-ester containing at
least two
hydrocarbyl groups of about 12 to about 22 (or 12 to 20 or 12 to 18 or 12 to
16 or 12 to
14 or 14 to 20 or 14 to 18 or 14 to 16) carbon atoms carbon atoms; and (c)
0.05 to 3.0
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percent by weight (or 0.1 to 2 or 0.3 to 1 or about 0.7%) of an amide or
thioamide repre-
sented by the formula R1R2N-C(X)R1 wherein X is 0 or S, R1 and R2 are each
inde-
pendently hydrocarbyl groups of at least 6 (or 8 to 24 or 10 to 18) carbon
atoms, and R3 is
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.
[0008] In one embodiment the composition further comprises (d) 1 to 6
percent by
weight (or 2 to 5.5 or 3 to 5 percent) of a dispersant component, comprising
one or more
succinimide dispersants, said dispersant component containing 0.05 to 1
percent by
weight (or 0.1 to 0.5 or 0.2 to 0.4 percent) boron and having a TBN (oil free)
of 40 to
90 (or 45 to 70 or 50 to 68).
[0009] It is desirable for an automatic transmission fluid to have a
high quasi-static
friction (described in greater detail below), ideally higher than the commonly
attained
value of about 0.092, without increasing the static friction (again described
in greater de-
tail below) to a value greater than about 0.135. Moreover, it is desired that
these values be
stable over time, that is, that they show minimal decrease in friction
coefficient from the
value at 500 test cycles extending out to 2500 or 10,000 cycles. The good
performance
should ideally persist over the range of transmission operating temperatures.
Meeting
these goals will help provide a fluid that has the properties of good torque
capacity, an-
tishudder performance, and durability. The materials of the present invention
will be suit-
able for meeting one or more of these objectives.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Various features and embodiments will be described below by way
of non-
limiting illustration.
[0011] One component which is used in certain embodiments of the
disclosed tech-
nology is an oil of lubricating viscosity. Such oils include natural and
synthetic oils,
oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined,
refined
and re-refined oils and mixtures thereof.
[0012] Unrefined oils are those obtained directly from a natural or
synthetic source
generally without (or with little) further purification treatment.
[0013] Refined oils are similar to the unrefined oils except they have been
further
treated in one or more purification steps to improve one or more properties.
Purifica-
tion techniques are known in the art and include solvent extraction, secondary
distilla-
tion, acid or base extraction, filtration, percolation and the like.
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[0014] Re-refined oils are also known as reclaimed or reprocessed oils,
and are ob-
tained by processes similar to those used to obtain refined oils and often are
additionally
processed by techniques directed to removal of spent additives and oil
breakdown prod-
ucts.
[0015] Natural oils useful in making the inventive lubricants include
animal oils, veg-
etable oils (e.g., castor oil,), mineral lubricating oils such as liquid
petroleum oils and sol-
vent-treated or acid-treated mineral lubricating oils of the paraffinic,
naphthenic or mixed
paraffinic-naphthenic types and oils derived from coal or shale or mixtures
thereof
[0016] Synthetic lubricating oils are useful and include hydrocarbon
oils such as pol-
ymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes,
propylene-
isobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes),
and mix-
tures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes,
dinonylben-
zenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls,
alkylated
polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl
ethers
and alkylated diphenyl sulfides and the derivatives, analogs and homologs
thereof or
mixtures thereof
[0017] Other synthetic lubricating oils include polyol esters (such as
Pri-
olube 3970), dicsters, liquid esters of phosphorus-containing acids (e.g.,
tricresyl phos-
phate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid),
or polymeric
tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions
and typi-
cally may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one
embodi-
ment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic
procedure as
well as other gas-to-liquid oils.
[0018] Oils of lubricating viscosity may also be defined as specified in
the American
Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five
base oil
groups are as follows: Group I (sulfur content >0.03 wt %, and/or <90 wt %
saturates,
viscosity index 80-120); Group II (sulfur content <0.03 wt %, and >90 wt %
saturates,
viscosity index 80-120); Group III (sulfur 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
may also be an
API Group II+ base oil, which term refers to a Group II base oil having a
viscosity index
greater than or equal to 110 and less than 120, as described in SAE
publication "Design
Practice: Passenger Car Automatic Transmissions", fourth Edition, AE-29, 2012,
page
12-9, as well as in US 8,216,448, column 1 line 57.
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[0019] The oil of lubricating viscosity may be an API Group IV oil, or
mixtures
thereof, i.e., a polyalphaolefin. The polyalphaolefin may be prepared by
metallocene
catalyzed processes or from a non-metallocene process.
[0020] The oil of lubricating viscosity comprises an API Group I, Group
II, Group
5 III, Group IV, Group V oil or mixtures thereof.
[0021] Often the oil of lubricating viscosity is an API Group I, Group
II, Group II+,
Group III, Group IV oil or mixtures thereof. Alternatively the oil of
lubricating viscosity
is often an API Group II, Group II+, Group III or Group IV oil or mixtures
thereof. Al-
ternatively the oil of lubricating viscosity is often an API Group II, Group
II+, Group III
oil or mixtures thereof.
[0022] The amount of the oil of lubricating viscosity present is
typically the balance
remaining after subtracting from 100 wt % the sum of the amount of the
additive as de-
scribed herein above, and the other performance additives.
[0023] The lubricating composition may be in the form of a concentrate
and/or a
fully formulated lubricant. If the lubricating composition of the invention is
in the form
of a concentrate (which may be combined with additional oil to form, in whole
or in
part, a finished lubricant), the ratio of the of components of the invention
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.
[0024] The present technology provides, as one component, an N-substituted
oxalic
acid bisamide or amide-ester containing at least two hydrocarbyl groups of 12
to 22 car-
bon atoms. In certain embodiments, the compound does not contain a primary
amine
group. (This may be absent in any of the embodiments whatever the detailed
chemical
nature, and in the presence or absence of other components.) This material is
useful as a
friction modifier, particularly for lubricating automatic transmissions. This
component,
as the bisamide, may be represented by the formula
0
m /R3
R4
0
[0025] In this structure at least two of the Rs are independently groups
comprising a
hydrocarbyl group of 1 to 22 carbon atoms and up to two of the R groups are
hydrogen
or a hydrocarbyl group of 10 or fewer carbon atoms. In other embodiments, one
or more
of the R groups may independently contain 12 to 20 or 12 to 18 or 12 to 16 or
12 to 14
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or 14 to 20 or 14 to 18 or 14 to 16 carbon atoms. If there are two hydrocarbyl
groups of
12 to 22 carbon atoms, they may be both on the same nitrogen or they may be on
differ-
ent nitrogen atoms; that is, either R3 and R4 or alternatively Wand R4 may be
hydrogen.
The hydrocarbyl groups may be the same or different within a given molecule or
within
a mixture of molecules in the overall composition.
[0026] Since at least two of the groups RI, R2, R3 and R4 comprise a
hydrocarbyl group
of 12 to 22 carbon atoms, such groups may be such a hydrocarbyl group, for
instance, an al-
kyl group of 12 to 22 carbon atoms. Alternatively, such groups may comprise
such a hydro-
carbyl group as a part of a larger structure. That is, such groups may have
the general struc-
ture such as R5R6N-R9¨ where one or both of the R5 and R6 are hydrocarbyl
groups of 12 to
22 carbons and optionally one of the R5 and R6 may be hydrogen or a shorter
hydrocarbyl
group. R9 would be a hydrocarbylene linking group, such as methylene,
ethylene, propyl-
ene, or butylene, and in some cases a 1-3-propylene group. In certain
embodiments the alkyl
groups of 12 to 22 carbon atoms may contain both linear and cyclic species,
e.g., up to 20
percent cyclic species.
[0027] In some embodiments, therefore, the substituted oxalic acid
bisamide may
comprise a material of the structure about in which two of the groups R1, R2,
R4, and R4
are independently alkyl groups of 12 to 22 carbon atoms. Such materials may
have a
structure such as
0
R1 --NH2
R2
0
wherein each R1 and R2 is independently an alkyl group of, for example, 12 to
18 carbon
atoms. Such a material may be obtained or obtainable by known methods such as
the
process of reacting a dialkylamine with an alkyl oxamate such as ethyl
oxamate.
[0028] In another embodiment, the N-substituted oxalic acid bisamide or
amide-ester
comprises an amide-ester represented by the formula:
0
R1
J-T-0
N
R2
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In this embodiment, each R1 and R2 may independently be a hydrocarbyl group of
12 to
22 carbon atoms, as defined elsewhere herein, and R1 may be a hydrocarbyl
group of 1
to 22 carbon atoms. In certain embodiments, R1 is methyl, ethyl, n-propyl,
isopropyl, n-
butyl, sec-butyl, isobutyl, or t-butyl.
[0029] Long chain monoalkyl and dialkyl amines are commercially available.
The
hydrocarbyl group or groups of the amines may be described as long chain
hydrocarbyl
groups, by which is meant generally hydrocarbyl groups containing 12 to 22
carbon at-
oms. For monoalkyl amines, that is, primary amines, the hydrocarbyl group may
com-
prise a mixture of individual groups on different molecules having a variety
of carbon
numbers falling generally within the range of 12 to 22 carbon atoms, although
molecules
with hydrocarbyl groups falling outside this range may also be present. If a
mixture of
hydrocarbyl groups is present, they may be primarily of even carbon number
(e.g., 12,
14, 16, 18, 20, or 22) as is characteristic of groups derived from many
naturally-occur-
ring materials, or they may be a mixture of even and odd carbon numbers or,
alterna-
tively, an odd carbon number or a mixture of odd numbers. They may be
branched, lin-
ear, or cyclic and may be saturated or unsaturated, or combinations thereof.
In certain
embodiments the hydrocarbyl groups may contain 16 to 18 carbon atoms, and some-
times predominantly 16 or predominantly 18. Specific examples include mixed
"coco"
groups, that is, cocoalkyl groups, from cocoamine (predominantly C12 and C14
amines)
and mixed "tallow" groups, that is, tallowalkyl groups, from tallowamine
(predomi-
nantly C16 and C18 groups), and isostearyl groups. The tallow groups may
optionally be
hydrogenated. Likewise, dialkyl amines, that is, secondary amine, are
commercially
available, which may have one long chain alkyl group as described above and
one short
chain alkyl group of 1 to 10 carbon atoms, or which may have two long chain
alkyl
groups. Examples of the latter include dicocoamine (available as Armeen 2CTm),
and
ditallowamine. Others, such is isostearyl-coco amine may be synthesized
generally as
described for preparative example B below.
[0030] It is also contemplated that two or more of the groups R', R2,
R3, and R4 may
be independently N-hydrocarbyl-substituted or di-substituted aminoalkyl groups
wherein the hydrocarbyl substituent or substituents contain 12 to 22 carbon
atoms and
the alkyl moieties contain 1 to 4 carbon atoms. A formula representing this
general
structure may be represented by
8
0 R7
R5 H 1
R8
1 H
R6 0
wherein R5 and le are independently a hydrocarbyl group of about 12 to about
22 car-
bon atoms and le and le are independently hydrogen or a hydrocarbyl group of 1
to 22
carbon atoms, e.g., a hydrocarbyl group of 10 or fewer carbon atoms or a
hydrocarbyl
group of about 12 to about 22 carbon atoms. Diamines suitable for preparing
such prod-
ucts include those in the DuomeenTM series, available from Akzo, having a
general
structure such as
R5
NN NH2
,
R6
Such polyamines may be prepared by the addition of the monoamine leleNH to
acrylo-
nitrile, to prepare the alkyl nitrile amine,
R5
R6 NN N
V
followed by catalytic reduction of the nitrile group using, e.g., H2 over Pd/C
catalyst, to
give the diamine.
[0031] In a related embodiment, the N-substituted oxalic acid bisamide or
amide-es-
ter may comprise an amide-ester represented by the formula:
0
R5.--------_______---
N N...- ----Rio
1 H
R6 0
wherein R5 and le are independently hydrocarbyl groups of 12 to 22 carbon
atoms as
.. defined above and le may be a hydrocarbyl group of 1 to 22 carbon atoms,
such as me-
thyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl.
[0032] Some specific examples of the materials for this component of the
disclosed
technology include those represented by the following structures:
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0 0
Coco-, Coco
Coco- Isostearyl
(I) 0 (II) 0
0
Coco
Coco
(III) 0
0 Tallow
Tallow
0
Tallow
(IV)
0
Coco
NN O¨C2H5
(V) Coc
0
Tallow 0¨CH3
(VI) tallow
where coco and tallow are as defined above and isostearyl represents the
carbon archi-
tecture of isostearic acid.
[0033] The bisamides disclosed herein may be prepared by known
techniques such
as reaction of the appropriate amine with oxalic acid or a reactive equivalent
thereof,
such as ethyl oxamide or dimethyl oxalate, as illustrated in the preparative
examples of
U.S. Patent 8,691,740. The amide-esters may be prepared by reaction of the
appropriate
amine with a dialkyl oxalate, using a controlled amount of amine
(approximating 1:1 mo-
lar ratio) or by reacting the amine with the half ester-half chloride (e.g.,
ethyl 2-chloro-2-
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oxo-acetate). Minor amounts of the amide-esters may be formed along with the
prepara-
tion of the bisamides, and the relative amounts may be adjusted by known
techniques.
[0034] The amount of the oxalic acid bisamide or amide ester in a fully
formulated
lubricant may be 0.05 to 3 percent by weight, or 0.1 to 2 percent or 0.3 to 1
percent or
5 about 0.7 percent by weight.
[0035] Another component of the disclosed technology, component (c) is
an amide or
thioamide (at least one amide or thioamide) represented by the formula
R1R2N-C(X)R3 wherein X is 0 or S, R1 and R2 are each independently hydrocarbyl
groups of at least about 6 (or 8 to 24 or 10 to 18) carbon atoms, and R3 is
hydroxyalkyl
10 group of 1 to about 6 carbon atoms or a group formed by the condensation
of said hy-
droxyalkyl group, through a hydroxyl group thereof, with an acylating agent.
This com-
ponent can be viewed as the condensation product of a secondary amine with a
hydroxy
acid or thioacid (described below), which can also serve as a friction
modifier. The
amine will contain substituent hydrocarbyl groups, for example, alkyl groups.
The
amine may be represented by the formula R1R2NH wherein R1 and R2 are each inde-
pendently a hydrocarbyl group of at least 6 carbon atoms (e.g., 6 to 30 carbon
atoms or
8 to 24 carbon atoms or 10 to 20 or 10 to 18 or 12 to 16). The R1 and R2
groups may be
linear or branched, saturated or unsaturated, aliphatic, aromatic, or mixed
aliphatic and
aromatic. In certain embodiments they are alkyl groups and in particular
linear alkyl
groups. The R1 and R2 groups may be the same or different. A commercial
example of a
suitable amine is sold under the trade name Armeen 2CTM, which is believed to
have two
C12 alkyl groups. In one embodiment the amine comprises di-cocoalkyl amine or
homol-
ogous amines. Di-cocoalkyl amine (or di-cocoamine) is a secondary amine in
which the
two R groups in the above formula are predominantly C12 groups (although
amounts of
Cg through C18 are generally also present), derived from coconut oil. In
certain embodi-
ments, one both of the groups R1 and R2 may be 2-ethylhexyl groups. In one
embodi-
ment, the amine moiety (or "substituted nitrogen moiety") R1R2N¨ of the amide
or thio-
amide comprises a (2-ethylhexyl)(hydrogenated tallow) amine moiety, where the
"hy-
drogenated tallow" moiety is derived from tallow, having predominantly C18
groups. It
is understood that commercially available dialkylamines will contain certain
amounts of
monoalkylamines and/or trialkylamines, and products formed from such
commercial
materials are contemplated to be within the scope of the present inventions
(recognizing
that any trialkylamine component would not be expected to be reactive to form
an am-
ide.)
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[0036] The amide or thioamide of the present invention may be viewed as
a conden-
sation product of the above-described amine with a hydroxy acid or hydroxy
thioacid or
reactive equivalent thereof. In the instance where X is 0, the amide is a
derivative of a
hydroxy acid which can be represented by the formula R3COOH. In the hydroxy
acid (or
hydroxy thioacid, as the case may be) R3 is a hydroxyalkyl group of 1 to 6
carbon atoms
or a group formed by the condensation of such hydroxyalkyl group, through the
hydroxyl
group thereof, with an acylating agent (which may include a sulfur-containing
acylating
agent). That is, the ¨OH group on R3 is itself potentially reactive and may
condense with
additional acidic materials or their reactive equivalents to form, e.g.,
esters. Thus, the
hydroxy acid may be condensed, for instance, with one or more additional
molecules of
acid such as glycolic acid. An example of a suitable hydroxy acid is glycolic
acid, that is,
hydroxyacetic acid, HO-CH2-COOH. Glycolic acid is readily commercially
available, ei-
ther in substantially neat form or as a 70% solution in water. When R3
contains more than
1 carbon atom, the hydroxy group may be on the 1 carbon (a) or on another
carbon in the
chain (e.g., 13 or co). The carbon chain itself may be linear, branched, or
cyclic.
[0037] The amount of component (c) in the compositions of the present
invention
can be 0.05 to 3.0 percent by weight of the finished fluid formulation.
Alternative
amounts include 0.1 percent to 2 percent, or 0.3 percent to 1 percent, or
about 0.7 per-
cent by weight. In a concentrate, the amounts will be proportionately higher.
[0038] Another component that may be present is a dispersant component,
which
may comprise either a single dispersant species or multiple dispersant
species. The dis-
persant may be described as "other than a compound as described above" in the
event
that some of the compounds described above may exhibit some dispersant
characteris-
tics. Examples of "carboxylic dispersants," as an example, arc described in
many U.S.
Patents including the following: 3,219,666, 3,316,177, 3,340,281, 3,351,552,
3,381,022,
3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511,
4,234,435,
Re 26,433, and 6,165,235.
[0039] Succinimide dispersants, a species of carboxylic dispersants, are
prepared by
the reaction of a hydrocarbyl -substituted succinic anhydride (or reactive
equivalent
thereof, such as an acid, acid halide, or ester) with an amine, as described
above. The hy-
drocarbyl substituent group generally contains an average of at least 8, or
20, or 30, or 35
up to 350, or to 200, or to 100 carbon atoms. In one embodiment, the
hydrocarbyl group is
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derived from a polyalkene. Such a polyalkene can be characterized by an M.
(number av-
erage molecular weight, which may also be written as MO of at least 500.
Generally, the
polyalkene is characterized by an M. of 500 or 700 or 800 or 900, up to 5000
or to 2500
or to 2000 or to 1500. In another embodiment M. varies from 500 or 700 or 800,
to 1200
or 1300. In one embodiment the polydispersity /M.) is at least 1.5.
[0040] The polyalkenes include homopolymers and inter-polymers of
polymerizable
olefin monomers of 2 to 16 or to 6, or to 4 carbon atoms. The olefins may be
monoole-
fins such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a
polyolefinic
monomer, such as diolefinic monomer, such 1,3-butadiene and isoprene. In one
embodi-
ment, the polymer is a homo-polymer. An example of a polymer is a polybutene.
In one
instance about 50% of the polybutene is derived from isobutylene. The
polyalkenes can
be prepared by conventional procedures.
[0041] In one embodiment, the succinic acylating agents are prepared by
reacting a
polyalkene with an excess of maleic anhydride to provide substituted succinic
acylating
agents wherein the number of succinic groups for each equivalent weight of
substituent
group is at least 1.3, e.g., 1.5, or 1.7, or 1.8. The maximum number of
succinic groups
per substituent group generally will not exceed 4.5, or 2.5, or 2.1, or 2Ø
The prepara-
tion and use of substituted succinic acylating agents wherein the substituent
is derived
from such polyolefins are described in U.S. Patent 4,234,435. The succinic
acylating
agents may be prepared either by a chlorine-assisted route or by a thermal
("ene") reac-
tion. These synthetic routes are more fully described in U.S. Patent
7,615,521, see col-
umns 3-5.
[0042] The substituted succinic acylating agent can be reacted with an
amine, includ-
ing those amines described above and heavy amine products known as amine still
bot-
toms. The amount of amine reacted with the acylating agent is typically an
amount to
provide a mole ratio of CO:N of 1:2 to 1:0.25, or 1:2 to 1:0.75 or 1:1.4 to
1:0.95. In an-
other embodiment the CO:N ratio may be 1:0.2 to 1:0.3, and for this or any of
the other
ratios the resulting dispersant may be further treated with, e.g.,
dimercaptothiadiazole. If
the amine is a primary amine, complete condensation to the imide can occur.
Varying
amounts of amide product, such as the amidic acid, may also be present. If the
reaction
is, rather, with an alcohol, the resulting dispersant will be an ester
dispersant. If both
amine and alcohol functionality are present, whether in separate molecules or
in the
same molecule (as in the above-described condensed amines), mixtures of amide,
ester,
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13
and possibly imide functionality can be present. These are the so-called ester-
amide dis-
persants.
[0043] "Amine dispersants" are reaction products of relatively high
molecular
weight aliphatic or alicyclic halides and amines, such as polyalkylene
polyamines. Ex-
amples thereof are described in the following U.S. Patents: 3,275,554,
3,438,757,
3,454,555, and 3,565,804.
[0044] "Mannich dispersants" are the reaction products of alkyl phenols
in which the
alkyl group contains at least 30 carbon atoms with aldehydes (especially
formaldehyde)
and amines (especially polyalkylene polyamines). The materials described in
the follow-
ing U.S. Patents are illustrative: 3,036,003, 3,236,770, 3,414,347, 3,448,047,
3,461,172,
3,539,633, 3,586,629, 3,591,598, 3,634,515, 3,725,480, 3,726,882, and
3,980,569.
[0045] Post-treated dispersants may also be a part of the disclosed
technology. They
are generally obtained by reacting carboxylic, amine or Mannich dispersants
with rea-
gents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic
acids, hy-
drocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds
such as
boric acid (to give "borated dispersants"), phosphorus compounds such as
phosphorus
acids or anhydrides, or 2,5-dimercaptothiadiazole (DMTD). In certain
embodiments one
or more of the individual dispersants may be post-treated with boron or DMTD
or with
both boron and DMTD. Exemplary materials of these kinds are described in the
follow-
ing U.S. Patents: 3,200,107, 3,282,955, 3,367,943, 3,513,093, 3,639,242,
3,649,659,
3,442,808, 3,455,832, 3,579,450, 3,600,372, 3,702,757, and 3,708,422.
[0046] In one embodiment, the dispersant component will be present in an
amount of
1 to 6 percent by weight of the lubricant formulation, or alternatively 2 to
5.5 or 3 to 5
percent. These amounts represent the total of the individual dispersants that
may be pre-
sent, if more than one species is present. In one embodiment, the dispersant
component
comprises one or more succinimide dispersants. In one embodiment, the
succinimide
dispersant or dispersants will be borated, that is, boron-containing or
reacted with a bo-
ron species or borating agent, such that the dispersant component as a whole
will con-
tain 0.05 to 1 percent by weight boron, or alternatively, 0.1 to 0.7 percent
or 0.2 to 0.6
percent. If multiple succinimide dispersants are present, the boron may be
contained on
or associated with one or more of the dispersants while one or more of the
other disper-
sants will not be borated. (The form of the reaction or association of the
boron with the
dispersant species is not intended to be limiting.) The TBN of the overall
dispersant
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14
component, may be 40 to 100, or 40 to 95, or 40 to 90, or 45 to 70, or 50 to
68, as ex-
pressed on an oil-free basis. (TBN, or total base number, is the quantity of
acid, ex-
pressed in milligrams of KOH per gram of sample, that is required to titrate a
sample to
the specified end point, and is defined in ASTM D-794.)
[0047] In one embodiment the dispersant component comprises a first borated
suc-
cinimide dispersant component (that is, one more individual species) having a
boron
content of about 0.1 to about 1 percent by weight, or 0.3 to 0.8, or 0.5 to
0.7 percent by
weight and a TBN, in certain embodiments, of 4 to 90 or 50 to 70. In this
embodiment
the dispersant component will also comprise a second dispersant component (one
or
more individual species) that is not borated or is borated to a lesser extent
than that of
the first dispersant component. The second succinimide dispersant component
may thus
have a boron content of less than 0.1 percent by weight, or less than 0.05 or
0.01 percent
by weight, or may be free of boron. The TBN of the second succinimide
dispersant com-
ponent may be, in certain embodiments, 40 to 80 or 40 to 70 or 50 to 60.
[0048] In certain embodiments the dispersant component comprises more than
one
individual dispersant species, e.g., more than one individual succinimide
dispersant spe-
cies. One or more of these may be a succinimide dispersant that is reacted (or
post-
treated) with at least one of terephthalic acid, or an inorganic phosphorus
compound, or
a dimercaptothiadiazole compound. For example, in one embodiment there may be
three
individual succinimide dispersant species present: one may be treated with
boron and
terephthalic acid; a second may be treated with boron, terephthalic acid, and
dimercap-
tothiadiazole, and the third may be treated with none of the post-treatment
agents. Many
such combinations of individual dispersants will be apparent to the person of
skill in the
art; such combinations may be selected such that the specified amounts of
boron are met
for the overall dispersant component.
[0049] Other additives may be present in the lubricants of the disclosed
technology.
One component frequently used is a viscosity modifier, also referred to as a
viscosity
improver. Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM)
are well
known. Examples of VMs and DVMs may include polymethacrylates, polyacrylates,
polyolefins, styrene-maleic ester copolymers, and similar polymeric substances
includ-
ing homopolymers, copolymers, and graft copolymers. The DVM may comprise a
nitro-
gen-containing methacrylate polymer, for example, a nitrogen-containing
methacrylate
polymer derived from methyl methacrylate and dimethylaminopropylamine.
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[0050] Examples of commercially available VMs, DVMs and their chemical
types
may include the following: polyisobutylenes (such as IndopolTM from BP Amoco
or
ParapolTM from ExxonMobil); olefin copolymers (such as LubrizolTM 7060, 7065,
and
7067 from Lubrizol and LucantTM HC-2000L and HC-600 from Mitsui); hydrogenated
5 styrene-diene copolymers (such as ShellvisTM 40 and 50, from Shell and LZ
7308, and
7318 from Lubrizol); styrene/maleate copolymers, which are dispersant
copolymers
(such as LZ 3702 and 3715 from Lubrizol); polymethacrylates, some of which
have
dispersant properties (such as those in the ViscoplexTm series from RohMax,
the HitecTM
series from Afton, and LZ 7702TM, LZ 7727TM, LZ 7725TM and LZ 7720CTM from
Lubri-
10 zol); olefin-graft-polymethacrylate polymers (such as ViscoplexTM 2-500
and 2-600
from RohMax); and hydrogenated polyisoprene star polymers (such as ShellvisTM
200
and 260, from Shell). Also included are AstericTM polymers from Lubrizol
(methacrylate
polymers with radial or star architecture). Viscosity modifiers that may be
used are de-
scribed in U.S. patents 5,157,088, 5,256,752 and 5,395,539. The VMs and/or
DVMs
15 may be used in the functional fluid at a concentration of up to 20% by
weight. Concen-
trations of 1 to 12%, or 3 to 10% by weight may be used.
[0051] Another component that may be used in the composition used in the
present
technology is a supplemental friction modifier. These friction modifiers arc
well known
to those skilled in the art. A list of friction modifiers that may be used is
included in
U.S. Patents 4,792,410, 5,395,539, 5,484,543 and 6,660,695. U.S. Patent
5,110,488 dis-
closes metal salts of fatty acids and especially zinc salts, useful as
friction modifiers. A
list of supplemental friction modifiers that may be used may include:
fatty phosphites borated alkoxylated fatty amines
fatty acid amides metal salts of fatty acids
fatty epoxides sulfurized olefins
borated fatty epoxides fatty imidazolines
fatty amines other than the fatty condensation products of carboxylic
amines discussed above acids and polyalkylene-polyamines
glycerol esters metal salts of alkyl salicylates
borated glycerol esters amine salts of alkylphosphoric acids
alkoxylated fatty amines ethoxylated alcohols
oxazolines imidazolines
hydroxyalkyl amides polyhydroxy tertiary amines
-- and mixtures of two or more thereof.
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[0052] Representatives of each of these types of friction modifiers are
known and are
commercially available. For instance, fatty phosphites may be generally of the
formula
(R0)2PHO or (R0)(HO)PHO where R may be an alkyl or alkenyl group of sufficient
length to impart oil solubility. Suitable phosphites are available
commercially and may
be synthesized as described in U.S. Patent 4,752,416.
[0053] Borated fatty epoxides that may be used are disclosed in Canadian
Patent No.
1,188,704. These oil-soluble boron- containing compositions may be prepared by
react-
ing a boron source such as boric acid or boron trioxide with a fatty epoxide
which may
contain at least 8 carbon atoms. Non-borated fatty epoxides may also be useful
as sup-
plemental friction modifiers.
[0054] Borated amines that may be used are disclosed in U.S. Patent
4,622,158. Bo-
rated amine friction modifiers (including borated alkoxylated fatty amines)
may be pre-
pared by the reaction of a boron compounds, as described above, with the
corresponding
amines, including simple fatty amines and hydroxy containing tertiary amines.
The
amines useful for preparing the borated amines may include commercial
alkoxylated fatty
amines known by the trademark "ETHOMEEN" and available from Akzo Nobel, such
as
bis[2-hydroxyethy1]-cocoamine, polyoxyethylenc[10]cocoamine, bis[2-
hydroxyethy1]-
soyamine, bis[2-hydroxyethy1]-tallowamine, polyoxyethylenc-[5]tallowamine,
bis[2-hy-
droxyethyl]oleylamine, bis[2¨hydroxyethyl]octadecylamine, and
polyoxyethylene[15]-
octadecylamine. Such amines are described in U.S. Patent 4,741,848.
[0055] Alkoxylated fatty amines and fatty amines themselves (such as
oleylamine)
may be useful as friction modifiers. These amines are commercially available.
[0056] Both borated and unborated fatty acid esters of glycerol may be
used as fric-
tion modifiers. Borated fatty acid esters of glycerol may be prepared by
borating a fatty
acid ester of glycerol with a boron source such as boric acid. Fatty acid
esters of glyc-
erol themselves may be prepared by a variety of methods well known in the art.
Many of
these esters, such as glycerol monooleate and glycerol tallowate, are
manufactured on a
commercial scale. Commercial glycerol monooleates may contain a mixture of 45%
to
55% by weight monoester and 55% to 45% by weight diester.
[0057] Fatty acids may be used in preparing the above glycerol esters; they
may also
be used in preparing their metal salts, amides, and imidazolines, any of which
may also
be used as friction modifiers. The fatty acids may contain 6 to 24 carbon
atoms, or 8 to
18 carbon atoms. A useful acid may be oleic acid.
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[0058] The amides of fatty acids may be those prepared by condensation
with ammo-
nia or with primary or secondary amines such as diethylamine and
diethanolamine. Fatty
imidazolines may include the cyclic condensation product of an acid with a
diamine or
polyamine such as a polyethylenepolyamine. In one embodiment, the friction
modifier
may be the condensation product of a C8 to C24 fatty acid with a polyalkylene
polyamine,
for example, the product of isostearic acid with tetraethylenepentamine. The
condensation
products of carboxylic acids and polyalkyleneamines may be imidazolines or
amides.
[0059] The fatty acid may also be present as its metal salt, e.g., a
zinc salt. These
zinc salts may be acidic, neutral, or basic (overbased). These salts may be
prepared from
the reaction of a zinc containing reagent with a carboxylic acid or salt
thereof. A useful
method of preparation of these salts is to react zinc oxide with a carboxylic
acid. Useful
carboxylic acids are those described hereinabove. Suitable carboxylic acids
include
those of the formula RCOOH where R is an aliphatic or alicyclic hydrocarbon
radical.
Among these are those wherein R is a fatty group, e.g., stearyl, oleyl,
linoleyl, or pal-
mityl. Also suitable are the zinc salts wherein zinc is present in a
stoichiometric excess
over the amount needed to prepare a neutral salt. Salts wherein the zinc is
present from
1.1 to 1.8 times the stoichiometric amount, e.g., 1.3 to 1.6 times the
stoichiometric
amount of zinc, may be used. These zinc carboxylates arc known in the art and
are de-
scribed in U.S. Pat. 3,367,869. Metal salts may also include calcium salts.
Examples
may include overbased calcium salts.
[0060] Sulfurized olefins are also well known commercial materials used
as friction
modifiers. A suitable sulfurized olefin is one which is prepared in accordance
with the
detailed teachings of U.S. Patents 4,957,651 and 4,959,168. Described therein
is a cosul-
furized mixture of 2 or more reactants selected from the group consisting of
at least one
fatty acid ester of a polyhydric alcohol, at least one fatty acid, at least
one olefin, and at
least one fatty acid ester of a monohydric alcohol. The olefin component may
be an ali-
phatic olefin, which usually will contain 4 to 40 carbon atoms. Mixtures of
these olefins
are commercially available. The sulfurizing agents useful in the process of
the present
invention include elemental sulfur, hydrogen sulfide, sulfur halide plus
sodium sulfide,
and a mixture of hydrogen sulfide and sulfur or sulfur dioxide.
[0061] Metal salts of alkyl salicylates include calcium and other salts
of long chain
(e.g. C12 to C16) alkyl-substituted salicylic acids.
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[0062] Amine salts of alkylphosphoric acids include salts of oleyl and
other long
chain esters of phosphoric acid, with amines such as tertiary-aliphatic
primary amines,
sold under the trade name PrimeneTM.
[0063] The amount of the supplemental friction modifier, if it is
present, may be 0.1
to 1.5 percent by weight of the lubricating composition, such as 0.2 to 1.0 or
0.25 to
0.75 percent. In some embodiments, however, the amount of the supplemental
friction
modifier is present at less than 0.2 percent or less than 0.1 percent by
weight, for exam-
ple, 0.01 to 0.1 percent.
[0064] The compositions of the present technology can also include a
detergent. De-
tergents as used herein are metal salts of organic acids. The organic acid
portion of the
detergent may be a sulfonate, carboxylate, phenate, or salicylate. The metal
portion of
the detergent may be an alkali or alkaline earth metal. Suitable metals
include sodium,
calcium, potassium, and magnesium. Typically, the detergents are overbased,
meaning
that there is a stoichiometric excess of metal base over that needed to form
the neutral
metal salt.
[0065] Suitable ovcrbased organic salts include the sulfonate salts
having a substan-
tially oleophilic character and which are formed from organic materials.
Organic sul-
fonates arc well known materials in the lubricant and detergent arts. The
sulfonate com-
pound should contain on average 10 to 40 carbon atoms, such as 12 to 36 carbon
atoms
or 14 to 32 carbon atoms on average. Similarly, the phenates, salicylates, and
carbox-
ylates have a substantially oleophilic character.
[0066] While the present invention allows for the carbon atoms to be
either aromatic
or in paraffinic configuration, in certain embodiments alkylated aromatics are
employed.
While naphthalene based materials may be employed, the aromatic of choice is
the ben-
zene moiety.
[0067] Suitable compositions thus include an overbased monosulfonated
alkylated
benzene such as a monoalkylated benzene. Typically, alkyl benzene fractions
are ob-
tained from still bottom sources and are mono- or di-alkylated. It is
believed, in the pre-
sent invention, that the mono-alkylated aromatics are superior to the
dialkylated aromat-
ics in overall properties.
[0068] It is sometimes desired that a mixture of mono-alkylated
aromatics (benzene)
be utilized to obtain the mono-alkylated salt (benzene sulfonate) in the
present inven-
tion. The mixtures wherein a substantial portion of the composition contains
polymers
of propylene as the source of the alkyl groups may assist in the solubility of
the salt. The
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use of mono-functional (e.g., mono-sulfonated) materials avoids crosslinking
of the
molecules with less precipitation of the salt from the lubricant. It is also
frequently de-
sired to use an alkylated benzene prepared by alkylation with an a-olefin.
[0069] The salt may be "overbased." By overbasing, it is meant that a
stoichiometric
excess of the metal base be present over that required for the anion of the
neutral salt.
The excess metal from overbasing has the effect of neutralizing acids which
may build
up in the lubricant. Typically, the excess metal will be present over that
which is re-
quired to neutralize the anion at in the ratio of up to 30:1, such as 5:1 to
18:1 on an
equivalent basis. Overbased materials arc often carbonated, that is, reacted
with carbon
dioxide, to aid in the acceptance of an equivalent excess of metal.
[0070] The amount of the overbased salt utilized in the composition is
typically
0.025 to 3 weight percent on an oil free basis, such as 0.1 to 1.0 percent. In
other em-
bodiments, the final lubricating composition may contain no detergent or
substantially
no detergent or only a low amount of detergent. That is, for a calcium
overbased deter-
gent for instance, the amount may be such as to provide less than 250 parts
per million
calcium, e.g., 0 to 250 or 1 to 200 or 10 to 150 or 20 to 100 or 30 to 50
parts per million
calcium, or less than any of the foregoing non-zero amounts. This is in
contrast with
more conventional formulations which may contain sufficient calcium detergent
to pro-
vide 300 to 600 ppm calcium. The overbased salt usually has up to about 50%
oil and
has a TBN range of 10-800 or 10-600 on an oil free basis. Borated and non-
borated
overbased detergents are described in U.S. Patents 5,403,501 and 4,792,410.
[0071] The compositions of the present invention can also include at
least one phos-
phorus acid, phosphorus acid salt, phosphorus acid ester or derivative thereof
including
sulfur-containing analogs in the amount of 0.002-1.0 weight percent. The
phosphorus
acids, salts, esters or derivatives thereof include phosphoric acid,
phosphorous acid,
phosphorus acid esters or salts thereof, phosphites, phosphorus-containing
amides, phos-
phorus-containing carboxylic acids or esters, phosphorus-containing ethers,
and mix-
tures thereof.
[0072] In one embodiment, the phosphorus acid, ester or derivative can
be an or-
ganic or inorganic phosphorus acid, phosphorus acid ester, phosphorus acid
salt, or de-
rivative thereof. The phosphorus acids include the phosphoric, phosphonic,
phosphinic,
and thiophosphoric acids including dithiophosphoric acid as well as the
monothiophos-
phoric, thiophosphinic and thiophosphonic acids. One group of phosphorus
compounds
are alkylphosphoric acid mono alkyl primary amine salts as represented by the
formula
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0
R'0¨ P ¨ Cr +NH3R3
5 R20
where R1, R2, R3 are alkyl or hydrocarbyl groups or one of R1 and R2 can be H.
The ma-
terials can be a 1:1 mixture of dialkyl and monoalkyl phosphoric acid esters.
Com-
pounds of this type are described in U.S. Patent 5,354,484.
[0073] Eighty-five percent phosphoric acid is a suitable material for
addition to the
10 fully-formulated compositions and can be included at a level of 0.01-0.3
weight percent
based on the weight of the composition, such as 0.03 to 0.2 or to 0.1 percent.
[0074] Other phosphorus-containing materials that may be present include
dial-
kylphosphites (sometimes referred to as dialkyl hydrogen phosphonates) such as
dibutyl
phosphite. Yet other phosphorus materials include phosphorylated hydroxy-
substituted
15 triesters of phosphorothioic acids and amine salts thereof, as well as
sulfur-free hy-
droxy-substituted di-esters of phosphoric acid, sulfur-free phosphorylated
hydroxy-sub-
stituted di- or tri-esters of phosphoric acid, and amine salts thereof. These
materials are
further described in U.S. patent application US 2008-0182770.
[0075] Other materials can optionally be included in the compositions of
the present
20 technology, provided that they are not incompatible with the afore-
mentioned required
components or specifications. Such materials include antioxidants (that is,
oxidation in-
hibitors), including hindered phenolic antioxidants, secondary aromatic amine
antioxi-
dants such as dinonyldiphenylamine as well as such well-known variants as
monononyldiphenylamine and diphenylamines with other alkyl substituents such
as
mono- or di-octyl, sulfurized phenolic antioxidants, oil-soluble copper
compounds,
phosphorus-containing antioxidants, and organic sulfides, disulfides, and
polysulfides
such as 2-hydroxyalkyl, alkyl thioethers or 1-t-dodecylthio-2-propanol or
sulfurized 4-
carbobutoxycyclohexene or other sulfurized olefins. Also included may be
corrosion in-
hibitors such as tolyl triazole and dimercaptothiadiazole and oil-soluble
derivatives of
such materials. Other optional components include seal swell compositions,
such as iso-
decyl sulfolane or phthalate esters, which are designed to keep seals pliable.
Also per-
missible are pour point depressants, such as alkylnaphthalenes,
polymethacrylates, vinyl
acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers. Other
materi-
als are anti-wear agents such as zinc dialkyldithiophosphates, tridecyl
adipate, and vari-
ous long-chain derivatives of hydroxy carboxylic acids, such as tartrates,
tartramides,
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tartrimides, and citrates as described in US Application 2006-0183647. These
optional
materials are known to those skilled in the art, are generally commercially
available, and
are described in greater detail in published European Patent Application
761,805. Also
included can be known materials such as corrosion inhibitors (e.g.,
tolyltriazole, dimer-
captothiadiazoles), dyes, fluidizing agents, odor masking agents, and antifoam
agents.
Organic borate esters and organic borate salts can also be included.
[0076] The above components can be in the form of a fully-formulated
lubricant or
in the form of a concentrate within a smaller amount of lubricating oil. If
they are pre-
sent in a concentrate, their concentrations will generally be directly
proportional to their
concentrations in the more dilute form in the final blend.
[0077] 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 mole-
cule and having predominantly hydrocarbon character. Examples of hydrocarbyl
groups
.. include:
¨ hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cyclo-
alkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-
substituted aro-
matic substituents, as well as cyclic substituents wherein the ring is
completed through an-
other portion of the molecule (e.g., two substituents together form a ring);
¨ substituted hydrocarbon substituents, that is, substituents containing non-
hydrocarbon
groups which, in the context of this invention, do not alter the predominantly
hydrocar-
bon nature of the substituent (e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy,
mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
¨ hetero substituents, that is, substituents which, while having a
predominantly hydro-
.. carbon character, in the context of this invention, contain other than
carbon in a ring or
chain otherwise composed of carbon atoms and encompass substituents as
pyridyl, furyl,
thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. In
general, no
more than two, or no more than one, heteroatom will be present for every ten
carbon at-
oms in the hydrocarbyl group; typically, there will be no heteroatoms in the
hydrocarbyl
group.
[0078] It is known that some of the materials described above may
interact in the fi-
nal formulation, so that the components of the final formulation may be
different from
those that are initially added. For instance, metal ions (of, e.g., a
detergent) can migrate
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22
to other acidic or anionic sites of other molecules. The products formed
thereby, includ-
ing the products formed upon employing the composition of the present
invention in its
intended use, may not be susceptible of easy description. Nevertheless, all
such modifi-
cations and reaction products are included within the scope of the present
invention; the
present invention encompasses the composition prepared by admixing the
components
described above.
[0079] The amount of the phosphorus-containing compound or compounds in
the
compositions of the present invention may, in certain embodiments, be 0.01 to
2 percent
by weight, alternatively, 0.02 to 1 or 0.05 to 0.5 percent by weight.
Correspondingly, the
total phosphorus content of the compositions may be, for instance 0.01 to 0.3
percent by
weight or 0.003 or 0.03 to 0.20 percent by weight or 0.05 to 0.15 percent by
weight, de-
pending, of course, on the phosphorus content of the particular compounds that
are se-
lected. In certain embodiments, the formulations of the disclosed technology
may con-
tain, or may not contain, phosphorus in the form of a zinc
dialkyldithiophosphate. In
some embodiments there is less than 0.1 percent or 0.01 percent by weight of a
zinc di-
alkyldithiophosphate. Such materials may be represented by the formula
[(R80)(R90)P(=S)-S-]2¨Zn
where R8 and R9 are independently hydrocarbyl groups such as alkyl,
cycloalkyl, aralkyl
or alkaryl groups having 3 to 20 carbon atoms, or 3 to 16 or 3 to 12 carbon
atoms. They
are typically prepared by the reaction of one or a mixture of alcohols R8OH
and R9OH,
which can be a mixture of a secondary alcohol and a primary alcohol, for
instance, iso-
propanol and 4-methyl-2-pentanol, with phosphorus pentasulfide to give the
acid, fol-
lowed by neutralization with zinc oxide.
[0080] When the composition is in the form of a concentrate, the
relative amounts of
the various components will be proportionately increased, for instance, by a
factor such as
10 (except for the oil of lubricating viscosity, which will be correspondingly
decreased).
[0081] As used herein, the term "condensation product" is intended to
encompass es-
ters, amides, imides and other such materials that may be prepared by a
condensation re-
action of an acid or a reactive equivalent of an acid (e.g., an acid halide,
anhydride, or
ester) with an alcohol or amine, irrespective of whether a condensation
reaction is actu-
ally performed to lead directly to the product. Thus, for example, a
particular ester may
be prepared by a transesterification reaction rather than directly by a
condensation reac-
tion. The resulting product is still considered a condensation product.
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[0082] The amount of each chemical component described is presented
exclusive of
any solvent or diluent oil, which may be customarily present in the commercial
material,
that is, on an active chemical basis, unless otherwise indicated. However,
unless other-
wise indicated, each chemical or composition referred to herein should be
interpreted as
being a commercial grade material which may contain the isomers, by-products,
deriva-
tives, and other such materials which are normally understood to be present in
the com-
mercial grade.
[0083] 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 mole-
cule and having predominantly hydrocarbon character. Examples of hydrocarbyl
groups
include: hydrocarbon substituents, including aliphatic, alicyclic, and
aromatic substitu-
ents; substituted hydrocarbon substituents, that is, substituents containing
non-hydrocar-
bon groups which, in the context of this invention, do not alter the
predominantly hydro-
carbon nature of the substituent; and hetero substituents, that is,
substituents which simi-
larly have a predominantly hydrocarbon character but contain other than carbon
in a ring
or chain. A more detailed definition of the term "hydrocarbyl substituent" or
"hydro-
carbyl group" is found in paragraphs [0137] to [0141] of published application
US 2010-
0197536 .
[0084] It is known that some of the materials described above may interact
in the fi-
nal formulation, so that the components of the final formulation may be
different from
those that are initially added. For instance, metal ions (of, e.g., a
detergent) can migrate
to other acidic or anionic sites of other molecules. The products formed
thereby, includ-
ing the products formed upon employing the composition of the present
invention in its
intended use, may not be susceptible of easy description. Nevertheless, all
such modifi-
cations and reaction products are included within the scope of the present
invention; the
present invention encompasses the composition prepared by admixing the
components
described above.
[0085] The invention herein is useful for providing good friction
performance to
transmission fluids, which may be better understood with reference to the
following ex-
amples.
EXAMPLES
[0086] The following formulations are prepared for testing:
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[0087] A Starting Lubricant, representing a typical or conventional
lubricant for an
automatic transmission, is prepared containing the following (each of the
components
other than oil being presented on an oil-free basis, and all percentages being
by weight):
Oil(s) of lubricating viscosity (in an amount to total 100%);
Polymethacrylate viscosity modifier, 3.4%
Pour point depressant, 0.2%
Antiwear agents: 0.28%, including dibutyl phosphite and di(long chain alkyl)
phosphite
Succinimide dispersants: 4.28%, including borated succinimide dispersant(s)
and dimer-
captothiadiazole-treated dispersant(s)
Seal swell agent: 0.5%
Corrosion inhibitors: 0.06%
Antioxidants: 1.1%, including a hindered phenolic ester antioxidant and an
aromatic
amine antioxidant
Detergents: 0.18% overbased calcium sulfonate detergents (low and high TBN
materials)
Conventional friction modifier package: 0.61%, including phosphoric acid
(85%), bo-
rate ester, polyoxyethylene tallowalkylaminc, hydroxyethyl hcptadecenyl
imidazolinc, and a long chain hydroxyalkylamine
Small amounts of other conventional additives (including antifoam agents, dye
and fra-
grance additive(s))
[0088] Example 1 also contains, within the Starting Lubricant, 0.70 percent
by
weight of the condensation product (amide) of dicocoamine and glycolic acid
and 0.70
percent by weight of the bisamide formed by reaction of dimethyl oxalate with
and N,N-
di(C18 alkyl) propylene-1,3-diamine. (The C18 alkyl groups are characteristic
of the
structure of isostearic acid.)
[0089] Example 2. The same Starting Lubricant is used as for Example 1,
except
that the amount of the long chain hydroxyalkylamine is less by an amount of
0.01%, the
antioxidant component further comprises 0.4% of a substituted hydrocarbyl
sulfide, and
the specific small amounts of the other conventional additives are slightly
different.
The formulation of Example 2 contains, within the modified Starting Lubricant,
0.70
percent by weight of the bisamide formed by reaction of dimethyl oxalate with
and N,N-
di(C18 alkyl) propylene-1,3-diamine. (The C18 alkyl groups are characteristic
of the
structure of isostearic acid.)
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[0090] For Reference Examples B (138), C (129), and D (123), similar
starting lubri-
cants are used, which, however, differ in amounts and compositions of certain
of the
specific components and amounts, generally indicated as follows:
[0091] Reference Example B (138): amount of antiwear component: 0.28%
5 amount of dispersant component: 3.71%
amount of antioxidant component: 1.5%
amount of detergent component: 0.29%
amount of conventional friction modifier component: 0.51%
Reference Example B (138) also contains 0.60 percent by weight of the bisamide
formed
10 by reaction of dimethyl oxalate with and N,N-di(C18 alkyl) propylene-1,3-
diamine.
[0092] Reference Example C (129): amount of antiwear component: 0.2%
amount of dispersant component: 3.77%
amount of corrosion inhibitor component: 0.11%
amount of antioxidant component: 1.5%
15 amount of detergent component: 0.23%
amount of conventional friction modifier component: 0.62%
Reference Example C (129) also contains 0.75% by weight of the condensation
product
(amide) of dicocoaminc and glycolic acid.
[0093] Reference Example D (123): amount of antiwear component: 0.2%
20 amount of dispersant component: 3.99%
amount of corrosion inhibitor component: 0.12%
amount of antioxidant component: 1.5%
amount of detergent component: 0.10%
amount of conventional friction modifier component: 0.57%
25 Reference Example D (123) also contains 0.66 percent by weight of the
condensation
product (amide) of dicocoamine and glycolic acid.
[0094] The formulations thus prepared are subjected to a friction test
involving re-
peated engagement and disengagement of lubricated steel clutch plates with
paper-based
friction disks. The testing is conducted on an SAE No. 2 Universal Wet
Friction Material
Test Machine or on an equivalent machine according to GK or DKA
specifications. The
values of measurements are reported at 500, 2500, and 10,000 disengagement
cycles.
[0095] All measurements are made with a lubricant formulation maintained
at 100 C.
A first measurement is the "quasi-static" coefficient of friction. For this
measurement, at a
hot condition, the clutch is broken away immediately after the shift with 10
r.p.m to reach
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270 C steel plate temperature. The quasi-static friction coefficient is
measured 0.5 sec-
onds after breakaway has started and the slip speed has stabilized. A second
measurement
is for "static" coefficient of friction, which condition is defined as the
coefficient of fric-
tion immediately after disengagement of the clutch plates, the plates moving
at a relative
rate of 10 r.p.m. Similarly, dynamic coefficients of friction are reported at
90%, 50%, and
10% slip speeds as the clutch engages.
[0096] Results from the testing is shown in the Table below. For each
entry, the rele-
vant coefficients of friction are reported, in turn, at 500 cycles (start of
test), 2500 cycles
(middle of test), and 10,000 cycles (end of test):
rt- quasi-static u- static -90% u-50% u-10%
Ex. 1-both f.m.s 0.106 0.128 0.136 0.135 0.136
(start) 0.103 0.131 0.129 0.127 0.131
(oxalic bisamide (mid- 0.108 0.123 0.130 0.129 0.134
die)
and amide (c))
(end)
Ex. 2 - both f.m.s 0.109 0.136 0.139 0.137 0.143
(start) 0.102 0.134 0.135 0.128 0.132
(oxalic bisamide (mid- 0.107 0.128 0.132 0.132 0.135
die)
and amide (c))
(end)
Ref. Ex. B(138) - 0.108 0.160 0.129 0.127 0.133
(start) 0.102 0.157 0.126 0.120 0.126
(with oxalic (mid- 0.099 0.161 0.125 0.115 0.120
die)
bisamide)
(end)
Ref. Ex. C(129) - 0.105 0.154 0.131 0.126 0.130
(start) 0.098 0.158 0.129 0.120 0.125
(with amide (c)) (mid- 0.097 0.158 0.129 0.119 0.122
die)
27
(end)
Ref. Ex. D(123) ¨ 0.103 0.133 0.130 0.132 0.131
(start) 0.100 0.134 0.128 0.127 0.129
(with amide (c)) (mid- 0.094 0.107 0.110 0.125 0.125
die)
(end)
[0097] The results show that the inventive examples, containing both the
oxalic bis-
amide and the amide of component (c), exhibit superior friction performance
properties
that remain relatively stable from 500 to 10,000 cycles in the test. The quasi-
static coef-
ficient of friction is a high, stable value of 1.02-1.09. The static
coefficient of friction is
a stable value that does not substantially exceed 0.135.
[0098] The mention of any document herein is not an admission that such
document
qualifies as prior art or constitutes the general knowledge of the skilled
person in any ju-
risdiction. Except in the Examples, or where otherwise explicitly indicated,
all numeri-
cal quantities in this description specifying amounts of materials, reaction
conditions,
molecular weights, number of carbon atoms, and the like, are to be understood
as op-
tionally modified by the word "about." It is to be understood that the upper
and lower
amount, range, and ratio limits set forth herein may be independently
combined. Simi-
larly, the ranges and amounts for each element of the invention can be used
together
with ranges or amounts for any of the other elements.
[0099] 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 embodi-
ments, the phrases "consisting essentially of' and "consisting of," where
"consisting of'
excludes any element or step not specified and "consisting essentially of'
permits the in-
clusion of additional un-recited elements or steps that do not materially
affect the essential
or basic and novel characteristics of the composition or method under
consideration. The
expression "consisting of' or "consisting essentially of," when applied to one
element of a
Date recue / Date received 2021-12-02
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claim, is intended to restrict all species of the type represented by that
element, notwith-
standing the presence of "comprising" elsewhere in the claim.
[0100] While certain representative embodiments and details have been
shown for the
purpose of illustrating the subject invention, it will be apparent to those
skilled in this art
that various changes and modifications can be made therein without departing
from the
scope of the subject invention. In this regard, the scope of the invention is
to be limited
only by the following claims. In certain jurisdictions, recitation of one or
more of nar-
rower values for a numerical range or recitation of a narrower selection of
elements from
a broader list means that such recitations represent preferred embodiments.
