Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
BORON CONTAINING AUTOMOTIVE GEAR OIL
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to an automotive gear oil,
which may be
used, for example, in manual transmissions and axles, and includes an oil of
lubricating
viscosity, lwt% or less of a dispersant, and at least one boron containing
compound.
The automotive gear oil is particularly useful as a single lubricant to
lubricate both the
transmission and the axle.
[0002] Deposits of decomposition products such as carbon, varnish and
sludge
cause serious problems in gearboxes. The tendency towards decomposition
products
is particularly strong among synthetic automotive gear oils which have long
drain
intervals. As such, cleanliness is a mandatory requirement in automotive gear
oils,
and particularly modern automotive gear oils based on synthetic base oils.
[0003] Most modern automotive gear oils contain dispersants that help
maintain
.. the cleanliness of the oil. However, dispersants were not always included
in automo-
tive gear oil products. With the tendency towards more synthetics, there is a
need to
provide improved cleanliness to some of the older automotive gear oil
formulations,
without losing the performance that the automotive gear oil provided.
Unfortunately,
it has been found that the addition of dispersant to an automotive gear oil
can have a
detrimental effect on the frictional characteristics of the oil. As frictional
character-
istics are a set parameter for a given oil, a solution is needed to balance
the need for
cleanliness while maintaining proper friction.
SUMMARY OF THE INVENTION
[0004] The present technology solves the problem of balancing
cleanliness with
frictional properties in automotive gear oils by providing an automotive gear
oil for
lubricating an automotive gear having an oil of lubricating viscosity, lwt% or
less of
a dispersant, and at least one boron containing compound in an amount
sufficient to
provide from about 75ppm to about 500 ppm of boron to the automotive gear oil.
[0005] It has been found that the presence of the boron-containing
compound not
only enhances the cleansing ability of any dispersant present, but also
suppresses any
harmful effects to the oil's frictional characteristics from the dispersant.
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[0006] In an embodiment, the dispersant in the automotive gear oil can
be a suc-
cinimide dispersant.
[0007] In an embodiment, the at least one boron-containing compound can
be a
borate ester of formula I,
RO
OR
RI
wherein each R, independently, is a C3 to C12 alkyl,
[0008] In some embodiments, the borate ester can be present from about
0.2 to
2.0 wt % of the automotive gear oil.
[0009] In embodiments, the automotive gear oil can also include at
least one
.. phosphorous containing compound present in an amount to deliver 100 to 1500
ppm
of phosphorus to the automotive gear oil. In embodiments, the phosphorous
contain-
ing compound can be at least one of: (1) a C3-8 hydrocarbyl phosphite, (2) a
phos-
phite ester composition that comprises the reaction product of a monomeric
phos-
phorous acid or an ester thereof with at least two alkylene diols, or (3)
mixtures of
(1) and (2).
[0010] The automotive gear oil can also include 0.01 wt % to 0.5 wt %
of a di-
mercaptothiadiazole or derivative thereof, and/or 0.1 wt % to 5 wt % of a
poly(meth)acrylate ester polymer viscosity modifier.
[0011] In an embodiment, the automotive gear oil can have a kinematic
viscosity
at 100 C of from 8 cSt to 24 cSt.
[0012] The disclosed technology also includes a method of lubricating
an auto-
motive gear by supplying to the automotive gear the automotive gear oil
composi-
tion, and operating the automotive gear. The automotive gear can be, for
example,
in a manual transmission, on an axle, and/or on a differential.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Various preferred features and embodiments will be described
below by way
of non-limiting illustration.
[0014] One aspect of the present technology is an automotive gear oil.
The auto-
motive gear oil can be employed to provide lubrication to the gears of
automotive
vehicles, such as, for example, manual transmissions, axles and differentials.
The
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composition can include, among other things, an oil of lubricating viscosity,
1 wt%
or less of a dispersant, and at least one boron-containing compound.
Oils of Lubricating Viscosity
[0015] Oils of lubricating viscosity may also be defined as specified
in the Amen-
can Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011).
The five
base oil groups are as follows: Group I (sulfur content >0.03 wt %, and/or <90
wt %
saturates, viscosity index 80 to less than 120); Group II (sulfur content
<0.03 wt %,
and >90 wt % saturates, viscosity index 80 to less than 120); Group III
(sulfur content
<0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all
polyalpha-
olefins (PA0s)); and Group V (all others not included in Groups I, II, III, or
IV). The
oil of lubricating viscosity may also be a Group II+ base oil, which is an
unofficial API
category that 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. The oil of lubricating viscosity may also be a
Group
III+ base oil, which, again, is an unofficial API category that refers to a
Group III base
oil having a viscosity index of greater than 130, for example 130 to 133 or
even greater
than 135, such as 135-145. Gas to liquid ("GTL") oils are sometimes considered
Group
III+ base oils.
[0016] 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. The oil of lubricating
viscosity
may also comprise an API Group I, Group II, Group III, Group IV, Group V oil
or
mixtures thereof. Often the oil of lubricating viscosity is an API Group I,
Group II,
Group II+, Group III, Group IV oil or mixtures thereof. Alternatively the oil
of lubri-
cating viscosity is often an API Group II, Group II+, Group III or Group IV
oil or
mixtures thereof. Alternatively the oil of lubricating viscosity is often an
API Group
II, Group II+, Group III oil or mixtures thereof.
[0017] The oil of lubricating viscosity, or base oil, will overall have
a kinematic
viscosity at 100 C of 2 to 10 cSt or, in some embodiments 2.25 to 9 or 2.5 to
6 or 7 or
8 cSt, as measured by ASTM D445. Kinematic viscosities for the base oil at 100
C
of from about 3.5 to 6 or from 6 to 8 cSt are also suitable.
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[0018] 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
performance
additives in the composition. Illustrative amounts may include 50 to 99
percent by
weight, or 60 to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent.
[0019] 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 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.
Dispersant
[0020] The automotive gear oil will contain 1 wt% or less of a
dispersant. Many
types of dispersants are known in the art.
[0021] "Carboxylic dispersants" are reaction products of carboxylic
acylating
agents (acids, anhydrides, esters, etc.) containing at least about 34 and
preferably at
least about 54 carbon atoms with nitrogen containing compounds (such as
amines),
organic hydroxy compounds (such as aliphatic compounds including monohydric
and
polyhydric alcohols, or aromatic compounds including phenols and naphthols),
and/or basic inorganic materials. These reaction products include imide,
amide, and
ester reaction products of carboxylic ester dispersants.
[0022] The carboxylic acylating agents include fatty acides,
isoaliphatic acids
(e.g. 8-methyl-octadecanoic acid), dimer acids, addition dicarboxylic acids
(addition
(4+2) and 2+2) products of an unsaturated fatty acid with an unsaturated
carboxylic
reagent), trimer acids, addition tricarboxylic acids (Empol 1040, Hystrene
5460
and Unidyme 60), and hydrocarbyl substituted carboxylic acylating agents
(from
olefins and/or polyalkenes). In one embodiment, the carboxylic acylating agent
is a
fatty acid. Fatty acids generally contain from about 8 up to about 30, or from
about
12 up to about 24 carbon atoms. Carboxylic acylating agents are taught in U.S.
Pa-
tents No. 2,444,328, 3,219,666 and 4,234,435, the disclosures of which is
hereby
.. incorporated by reference.
[0023] The amine may be a mono- or polyamine. The monoamines generally
have
at least one hydrocarbyl group containing from 1 to about 24 carbon atoms, or
from
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1 to about 12 carbon atoms. Examples of monoamines include fatty (C8-30)
amines
(Armeens), primary ether amines (SURFAMCD amines), tertiary-aliphatic primary
amines ("Primenes"), hydroxyamines (primary, secondary or tertiary alkanol
amines), ether N-(hydroxyhydrocarbyl) amines, and hydroxyhydrocarbyl amines
5 ("Ethomeens" and "Propomeens). The polyamines include alkoxylated
diamines
(Ethoduomeens), fatty diamines ("Duomeens"), alkyl enepolyamines (ethylenepoly-
amines), hydroxy-containing polyamines, polyoxyalkylene polyamines
(Jeffamines),
condensed polyamines (a condensation reaction between at least one hydroxy com-
pound with at least one polyamine reactant containing at least one primary or
sec-
ondary amino group), and heterocyclic polyamines. Useful amines include those
dis-
closed in U.S. Patent 4,234,435 (Meinhart) and U.S. Patent 5,230,714 (Steckel)
which
are incorporated herein by reference.
[0024] An example carboxylic dispersant can include, for example,
"succinimide
dispersants," prepared by the reaction of a hydrocarbyl-substituted succinic
acylating
agent with an amine such as a polyamine.
[0025] The hydrocarbyl-substituted succinic acylating agents include
succinic ac-
ids, halides, esters, and anhydrides, preferably, acids, esters or anhydrides,
more pref-
erably anhydrides. The hydrocarbyl group generally contains an average of at
least
about 8, or about 30, or about 35 up to about 350, or to about 200, or to
about 100
carbon atoms. In one embodiment, the hydrocarbyl group is derived from a
polyal-
kene, such as, for example, polyisobutylene, generally having a number average
mo-
lecular weight of from 100 to 5000, or 500 to 4000 or 1000 to 3000.
[0026] The amine which reacts with the succinic acylating agent may be
a poly-
amine. The polyamine may be aliphatic, cycloaliphatic, heterocyclic or
aromatic.
Examples of the polyamines include alkylene polyamines, hydroxy containing
poly-
amines, arylpolyamines, and heterocyclic polyamines.
[0027] "Amine dispersants" are reaction products of relatively high
molecular
weight aliphatic halides and amines, preferably polyalkylene polyamines.
[0028] "Mannich dispersants" are the reaction products of alkyl phenols
in which
the alkyl group contains at least about 30 carbon atoms with aldehydes
(especially
formaldehyde) and amines (especially polyalkylene polyamines).
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[0029] Post-treated dispersants are obtained by reacting carboxylic,
amine or
Mannich dispersants with reagents such as dimercaptothiadiazoles, urea,
thiourea,
carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-
substituted suc-
cinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or
the
like.
[0030] Polymeric dispersants are interpolymers of oil-solubilizing
monomers
such as decyl methacrylate, vinyl decyl ether and high molecular weight
olefins with
monomers containing polar substituents, e.g., aminoalkyl acrylates or
acrylamides
and poly-(oxyethylene)-substituted acrylates.
[0031] Dispersants and dispersant chemistry is well-known in the art. The
dis-
persants suitable for use in the automotive gear oils described herein are not
particu-
larly limited. Rather, the level of dispersant may be minimized in view of the
use of
the boron-containing compounds, as described below.
[0032] Mixtures of the foregoing dispersants can also be used. The
dispersant can
have a nitrogen content of greater than or equal to about 11,000 ppm by weight
of the
dispersant, or greater than or equal to about 11,500ppm or greater than or
equal to
about 12,000 ppm.
[0033] The total amount of dispersant or dispersants, whether post-
treated or not
(e.g., borated or non-borated) or combinations thereof, in the compositions,
may be,
for instance, 0.01 to 1 percent by weight, or, for example, 0.025 to 0.9
percent or 0.05
to 0.8 weight percent of the final blended fluid formulation, although in a
concentrate,
the amounts will be proportionately higher. In an embodiment, the automotive
gear
oil may be substantially free of the above-described dispersant, or even
completely
free of the above described dispersant.
Boron-Containing Compound
[0034] The automotive gear oil can contain a boron-containing compound
in an
amount sufficient to provide from about 75ppm to about 500 ppm of boron to the
automotive gear oil, or from about 85 to about 450 ppm or about 95 to about
350 ppm
boron, or from about 100 to about 400ppm boron to the automotive gear oil.
[0035] The boron can be delivered by many types of boron-containing com-
pounds. The boron can, for example, come from a borated dispersant.
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[0036] The boron-containing compound can include boron containing
friction
modifiers, such as, for example, borated fatty epoxides, borated glycerol
esters, and
borated alkoxylated fatty amines.
[0037] The boron containing compound can also include borated
detergents. The
borated detergents can include, for example, overbased borated materials,
which are
described in U.S. Patents 5,403,501 and 4,792,410.
[0038] The boron containing compound can also include a borate ester.
The bo-
rate ester may be a compound represented by one or more of the formulae:
RO I, or
\B---"OR
RI
RO OR III, or
ROB-0-BLOR
OR V,
O-=____ -O
RO OR
wherein each R can be, independently a hydrocarbyl group, as that term is
defined
herein, and any two adjacent R groups may together form a cyclic group.
Mixtures
of two or more of the foregoing may be used. The total number of carbon atoms
in
the R groups in each formula should be sufficient to render the compound
soluble in
the oil of lubricating viscosity. Generally, the total number of carbon atoms
in the R
groups is at least about 3, and in one embodiment at least about 5, and in one
embod-
iment at least about 8. There is no limit to the total number of carbon atoms
in the R
groups that is required, but a practical upper limit is about 400 or about 500
carbon
atoms.
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[0039] In embodiments, each R can independently be a hydrocarbyl group
con-
taining 1 to 14, or from 2 to 13 or even 3 to 10 or 12 carbon atoms, provided
the sum
total number of carbon atoms in all R is 3 or more, preferably 4 or more and
even
more preferably 6 or more. In some embodiments, each R, independently, can be
a
C3 to C22, or C3 to C18, or C3 to C12 alkyl. Examples of useful R groups
include
isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, 2-ethyl-1-hexyl,
isooctyl,
decyl, dodecyl, 2-propylheptyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl,
naphthyl,
alkylphenyl, and the like. Others can be found, for example, in W02017/083548.
[0040] Suitable examples of the borate ester include, for example,
tripropyl bo-
rate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate,
trioctyl borate,
trinonyl borate and tridecyl borate. Other borate ester examples can include,
for ex-
ample, the compound of formula I, wherein each R is, independently, a C3 to
C22, or
C3 to C18, or C3 to C12 alkyl, such as, for example, tri-2-ethylhexyl borate,
tris(2-
propylheptyl) borate and mixtures thereof. In an embodiment the borate ester
can be
a C8 borate ester, or a Cio borate ester. In one embodiment the borate ester
can be
tris(2-propylheptyl) borate. In some embodiments the borate ester can be tri-2-
ethylhexyl borate.
[0041] In one embodiment, the borated ester can be represented by the
formula
B(005H11)3 or B(0C4H9)3. In one embodiment, the borated ester can be tri-n-
butyl
borate.
[0042] In one embodiment, the borated ester can be a phenolic compound
repre-
sented by the formula
R1 VII
0
HO
= R5¨ 0¨R6-0¨B-0R4
1R3
R2
wherein in formula VII: R1, R2, R3 and R4 are independently hydrocarbyl groups
of
1 to about 12 carbon atoms; and R5 and R6 are independently alkylene groups of
1 to
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about 6 carbon atoms, and in one embodiment about 2 to about 4 carbon atoms,
and
in one embodiment about 2 or about 3 carbon atoms. In one embodiment, Ri and
R2
independently contain 1 to about 6 carbon atoms, and in one embodiment each is
a t-
butyl group. In one embodiment, R3 and R4 are independently hydrocarbyl groups
of
about 2 to about 12 carbon atoms, and in one embodiment about 8 to about 10
carbon
atoms. In one embodiment, R5 and R6 are independently --CH2CH2 -- or --
CH2CH2CH2
[0043] In one embodiment, the borated ester can be a compound
represented by
the formula:
0
R
-0-/0/(3 \04R
wherein in formula IX, each R is independently hydrogen or a hydrocarbyl
group.
Each of the hydrocarbyl groups may contain from 1 to about 12 carbon atoms,
and in
one embodiment 1 to about 4 carbon atoms. An example is 2,2'-oxy-bis-(4,4,6-
trime-
thy1-1,3,2-dioxaborinane).
[0044] The borate ester may be employed in the automotive gear oil at about
0.2
or 0.3 to about 2.0 wt.% based on the weight of the automotive gear oil, or in
some
cases about 0.35 to 2.0 wt.%, and in one embodiment from about 0.25 to about
1.0
wt.%, and in one embodiment about 0.25 to about 0.75 wt.%.
Other Additives
[0045] The automotive gear oil can contain further additives aside from the
dis-
persant and boron-containing compound.
Phosphorus Containing Compound
[0046] The automotive gear oil can additionally contain a phosphorous
containing
compound. The phosphorus-containing compound may be an acid, salt or ester. In
one embodiment the phosphorus-containing compounds are in the form of a
mixture
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of two or three, or two to four (typically two or three) phosphorus-containing
com-
pounds.
[0047] In some embodiments the phosphorus-containing compound is a phos-
phite. Suitable phosphites include those having at least one hydrocarbyl group
with
5 3 or 4 or more, or 8 or more, or 12 or more, carbon atoms. The phosphite
may be a
mono-hydrocarbyl substituted phosphite, a di-hydrocarbyl substituted
phosphite, or
a tri-hydrocarbyl substituted phosphite.
[0048] In one embodiment the phosphite is sulphur-free i.e., the
phosphite is not
a thiophosphite.
10 [0049] The phosphite may be represented by the formulae:
RO H XI
ROP%
0
R-0
wherein at least one R may be a hydrocarbyl group containing at least 3 carbon
atoms
and the other R groups may be hydrogen. In one embodiment, two of the R groups
are hydrocarbyl groups, and the third is hydrogen. In one embodiment every R
group
is a hydrocarbyl group, i.e., the phosphite is a tri-hydrocarbyl substituted
phosphite.
The hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic or mixtures
thereof.
[0050] The R hydrocarbyl groups may be linear or branched, typically
linear, and
saturated or unsaturated, typically saturated.
[0051] In one embodiment, the phosphorus-containing compound can be a
C3-8
hydrocarbyl phosphite, or mixtures thereof, i.e., wherein each R may
independently
be hydrogen or a hydrocarbyl group having 3 to 8, or 4 to 6 carbon atoms,
typically
4 carbon atoms. Typically the C3-8 hydrocarbyl phosphite comprises dibutyl
phos-
phite. The C3-8 hydrocarbyl phosphite may deliver at least 175 ppm, or at
least 200
ppm of the total amount of phosphorus delivered by the phosphorus-containing
com-
pounds. The C3-8 hydrocarbyl phosphite may deliver at least 45 wt %, or 50 wt
% to
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100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the total amount of
phosphorus from the phosphorus-containing compound.
[0052] In one embodiment, the phosphorus-containing compound can be a
C12-22
hydrocarbyl phosphite, or mixtures thereof, i.e., wherein each R may
independently
be hydrogen or a hydrocarbyl group having 12 to 24, or 14 to 20 carbon atoms,
typi-
cally 16 to 18 carbon atoms. Typically the C12-22 hydrocarbyl phosphite
comprises a
C16-18 hydrocarbyl phosphite. Examples of alkyl groups for R3, R4 and R5
include
octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl,
hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures
thereof. The C12-22 hydrocarbyl phosphite may be present in the automotive
gear oil
at about 0.05 wt.% to about 1.0 wt.% of the automotive gear oil, or from about
0.1
wt.% to about 0.5 wt.% of the automotive gear oil.
[0053] In some embodiments, the phosphorous containing compound can
include
both a C3-8 and a C12 to C24 hydrocarbyl phosphite.
[0054] The lubricant composition optionally further contains an antiwear
agent in
the form of a hydrocarbyl amine salt of an alkyl(thio)phosphate. The
alkyl(thio)phos-
phate may also be an amine alkylthiophoshate, wherein the alkylthiophoshate is
repre-
sented by the formula (R'0)2PSSH, wherein each R' is independently a
hydrocarbyl
group containing from about 3 to about 30, preferably from about 3 up to about
18,
or from about 3 up to about 12, or from up to about 8 carbon atoms. Example R'
groups can include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl,
n-hexyl,
methylisobutyl carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl,
decyl, do-
decyl, and tridecyl groups. Illustrative lower alkylphenyl R' groups include
bu-
tylphenyl, amylphenyl, heptylphenyl, etc. Examples of mixtures of R' groups in-
.. clude: 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-1-hexyl; isobutyl and n-
hexyl; iso-
butyl and isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl;
and iso-
propyl and isooctyl.
[0055] In one embodiment, the alkylthiophoshate of the amine
alkylthiophoshate
may be reacted with an epoxide or a polyhydric alcohol, such as glycerol. This
reac-
tion product may be used alone, or further reacted with a phosphorus acid,
anhydride,
or lower ester. The epoxide is generally an aliphatic epoxide or a styrene
oxide. Ex-
amples of useful epoxides include ethylene oxide, propylene oxide, butene
oxide,
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octene oxide, dodecene oxide, styrene oxide, etc. Ethylene oxide and propylene
oxide
are preferred. The polyhydric alcohols are described above. The glycols may be
ali-
phatic glycols having from 1 to about 12, or from about 2 to about 6, or from
2 or 3
carbon atoms. Glycols include ethylene glycol, propylene glycol, and the like.
The
alkylthiophoshate, glycols, epoxides, inorganic phosphorus reagents and
methods of
reacting the same are described in U.S. Pat. Nos. 3,197,405 and 3,544,465
which are
incorporated herein by reference for their disclosure to these.
[0056]
[0057] In one embodiment the hydrocarbyl amine salt of an
alkyl(thio)phosphate is
the reaction product of a C14 to C18 alkylated phosphoric acid with Primene
81RTM
(produced and sold by Rohm & Haas) which is a mixture of CH to C14 tertiary
alkyl
primary amines. Other amines which may be used include alkyl alkanol amines,
dial-
kanolamines, trialkanolamines such as triethanolamines as well as borated
amines as
described hereinb el ow.
[0058] The amine salt as used as this component may thus comprise a C8 to
C20
alkylamine salt of a mono- or di-alkyl phosphate ester, or mixtures thereof.
[0059] The amount of the hydrocarbyl amine salt of an alkylphosphoric
acid ester
in the lubricant can be 0.3 to 2 weight percent, or 0.4 to 1.9, or 0.5 to 1.8,
or 0.7 to 1.7
weight percent. The amounts will be proportionally higher in a concentrate.
The
amount of said amine salt may also be an amount to contribute 0.03 to 0.2
weight
percent phosphorus to the lubricant composition, or alternatively 0.08 to
0.17, or 0.11
to 0.17 weight percent.
[0060] The automotive gear oil can also include a substantially sulfur-
free alkyl
phosphate amine salt having at least 30 mole percent of the phosphorus atoms
in an
alkyl pyrophosphate structure, as opposed to an orthophosphate (or monomeric
phos-
phate) structure. The percentage of phosphorus atoms in the pyrophosphate
structure
may be 30 to 100 mole %, or 40 to 90% or 50 to 80% or 55 to 70 % or 55 to 65%.
The
remaining amount of the phosphorus atoms may be in an orthophosphate structure
or
may consist, in part, in unreacted phosphorus acid or other phosphorus
species. In one
embodiment, up to 60 or up to 50 mole percent of the phosphorus atoms are in
mono-
or di-alkyl-orthophosphate salt structure.
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[0061]
The substantially sulfur-free alkyl phosphate amine salt, as present in the
pyrophosphate form (sometimes referred to as the POP structure), may be
represented
in part by the following formulas (I) and/or (II):
O 0
0 0
pl
(3¨R1
O 0 0
R23NH R23NI-1 R23NI-1
or
(I) (II)
or variants thereof, such as:
O 0 0 0
g=-=1
R1¨ o1 1 o1 OH
O 0
R1
R23NH R23NH R23NH+
0 0 0
0 0
R23NH+ R23NH+
where, each le is independently an alkyl group of 3 to 12 carbon atoms, such
as, for
example, 2-butyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-hexyl,
cyclohexyl,
4-methyl-2-pentyl, and other such secondary groups and isomers thereof having
6, 7,
8, 9, 10, 11, or 12 carbon atoms. In some embodiments the alkyl group can have
a
methyl branch at the a-position of the group, an example being the 4-methyl-2-
pentyl
(also referred to as 4-methylpent-2-y1) group.
[0062]
While the pyrophosphate ester may be isolated, if desired, from the ortho-
esters, it is also possible, and may be commercially preferable, to use the
reaction mix-
ture without separation of the components.
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14
[0063] The structures of formulas (I) and (II) are shown as entirely
sulfur-free spe-
cies, in that the phosphorus atoms are bonded to oxygen, rather than sulfur
atoms.
However, it is possible that a small molar fraction of the 0 atoms could be
replaced by
S atoms, such as 0 to 5 percent or 0.1 to 4 percent or 0.2 to 3 percent or 0.5
to 2 percent.
[0064] The pyrophosphate phosphate ester or mixture of phosphate esters
with be
reacted with an amine to form an amine salt. The extent of neutralization in
practice,
that is, the degree of salting of the ¨OH groups of the phosphorus esters, may
be 50%
to 100%, or 80% to 99%, or 90% to 98%, or 93% to 97%, or about 95%, which may
be determined or calculated on the basis of the amount of amine charged to the
phos-
phate ester mixture.
[0065] The amine may be represented by R23N, where each R2 is
independently
hydrogen or a hydrocarbyl group or an ester-containing group, or an ether-
containing
group, provided that at least one R2 group is a hydrocarbyl group or an ester-
containing
group or an ether-containing group (that is, not NH3). Suitable hydrocarbyl
amines
include primary, secondary or tertiary amines having 1 to 18 carbon atoms, or
3 to 12,
or 4 to 10 carbon atoms. Ester containing amines, such as an N-hydrocarbyl-
sub stituted y- or 6-amino(thio)ester. The amine, of whatever type, will be
reacted to
neutralize the acidic group(s) on the phosphorus ester component, which will
comprise
the pyrophosphate ester as described above as well as any orthophosphate
esters that
may be present.
[0066] The amount of the substantially sulfur-free alkyl phosphate
amine salt in the
lubricant composition may be 0.1 to 5 percent by weight. This amount refers to
the
total amount of the phosphate amine salt or salts, of whatever structure, both
ortho-
phosphate and pyrophosphate (with the understanding that at least 30 mole
percent of
.. the phosphorus atoms are in an alkyl pyrophosphate salt structure). The
amounts of the
phosphate amine salts in the pyrophosphate structure may be readily calculated
there-
from. Alternative amounts of the alkyl phosphate amine salt may be 0.2 to 3
percent,
or 0.2 to 1.2 percent, or 0.5 to 2 percent, or or 0.6 to 1.7 percent, or 0.6
to 1.5 percent,
or 0.7 to 1.2 percent by weight. The amount may be suitable to provide
phosphorus to
the lubricant formulation in an amount of 200 to 3000 parts per million by
weight
(ppm), or 400 to 2000 ppm, or 600 to 1500 ppm, or 700 to 1100 ppm, or 1100 to
1800
ppm.
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[0067] The automotive gear oil can also include a material represented
by the for-
mula
0
0
R1O__SO R4
0 ______________________________________________ [1
(!)R2 R3 ((!)R5) _
'2 n FORMULA X
¨n
wherein It' and R2 are each independently hydrocarbyl groups of 3 to 12 carbon
at-
5 oms, or 6 to 8 carbon atoms, or are groups represented by
0
1CIR2 R3
or wherein le and R2 together with the adjacent 0 and P atoms form a ring
contain-
ing 2 to 6 carbon atoms; R3 is hydrogen or a methyl group, R4 is an alkylene
group of
2 to 6 carbon atoms, R5 is hydrogen or a hydrocarbyl group of 1 to about 12
carbon
10 atoms, and n is 1 or 2. The material represented by the above formula is
typically a
neutral compound (or mixture of compounds) as the hydrogen atom shown attached
to the phosphorus is not considered to be particularly acidic.
[0068] In certain embodiments the material of Formula X may be
represented by
the formula
0 0
(!)R2 2 FORMULA XI
that is, Formula X in which R3 is hydrogen, R4 is an ethylene group, and n is
2. As in
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the case of Formula X, one or both of the R1 or R2 groups may groups
represented by
0
(1R2
In either Formula X or Formula XI, in certain embodiments le and R2 may each
inde-
pendently be C6 or C8 alkyl groups, or mixtures thereof, such as 2-ethylhexyl
groups or
4-methyl-2-pentyl groups or mixtures thereof.
[0069] The amount of any the phosphorous ester product described above
used in
the automotive gear oil may be an amount sufficient to provide 0.01 to 0.3 or
to 0.1
weight percent phosphorus to the composition or, in other embodiments, 0.02 to
0.07
weight percent or 0.025 to 0.05 weight percent. The actual amount of the
product
which corresponds to these amounts of phosphorus will, of course, depend upon
its
phosphorus content. Suitable amounts of the ester product in the automotive
gear oil
may be 0.01 to 1.0 weight percent, or 0.02 to 0.5 weight percent, or 0.03 to
0.30 weight
percent, or even 0.05 to 0.25 weight percent.
[0070] While each of the phosphorus containing compounds described above
may
be present in the automotive gear oil on its own, the automotive gear oil may
also
include a mixture of two or more. In some embodiments, the phosphorous
containing
compound can include a C3-8 hydrocarbyl phosphite and a phosphite ester
product. In
some embodiments, the phosphorous containing compound can include each of a C3-
8
.. hydrocarbyl phosphite, a C12 to C24 hydrocarbyl phosphite, and a phosphite
ester prod-
uct. In either event, the phosphorus containing compound should be present in
an
amount to deliver 100 to 1500 ppm of phosphorus to the automotive gear oil. In
some
embodiments, the at least one phosphorus containing compound can be present in
an
amount to deliver 250 to 1250 ppm of phosphorus, or from 500 to 1000 ppm
phospho-
rus to the automotive gear oil.
[0071] Another component of the automotive gear oil can be a metal
deactivator.
Examples of such materials include 2,5-dimercapto-1,3,4-thiadiazole and/or
deriva-
tives thereof. Such materials are described in European Patent Publication
0761805,
incorporated herein by reference. Further examples of the metal deactivator
include
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the thiadiazole compounds, such as those described in US9,816,044, and
represented
by the formula:
N-----N
N-N
SH SR
R = t-nonyl, n-octyl
or n-dodecyl or t-dodecyl
[0072]
The metal deactivators that are useful herein reduce the corrosion of met-
als, such as copper. Metal deactivators are also referred to as metal
passivators. These
metal deactivators are typically nitrogen and/or sulfur containing
heterocyclic com-
pounds, such as dimercaptothiadiazoles, triazoles, aminomercaptothiadiazoles,
imid-
azoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines,
thio-
phenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles,
oxatriazoles,
pyridines, piperazines, triazines, and derivatives of any one or more thereof.
The
metal deactivator preferably comprises at least one triazole, which may be
substituted
or unsubstituted. Examples of suitable compounds are benzotriazole, alkyl-
substi-
tuted benzotriazole (e.g., tolyltriazole, ethylbenzotriazole,
hexylbenzotriazole, oc-
tylbenzotriazole, etc.), aryl-substituted benzotriazole (e.g., phenol
benzotriazol es,
etc.), and alkylaryl- or arylalkyl-substituted benzotriazole and substituted
benzotria-
zoles where the substituent may be hydroxy, alkoxy, halo (especially chloro),
nitro,
carboxy and carboxyalkoxy. Preferably, the triazole is a benzotriazole or an
alkylben-
zotriazole in which the alkyl group contains 1 to about 20 carbon atoms,
preferably
1 to about 8 carbon atoms. Benzotriazole and tolyltriazole are useful.
[0073] In one embodiment, the metal deactivator is the reaction product of
a dis-
persant with a dimercaptothiadiazole. The dispersants may be generally
characterized
as the reaction products of carboxylic acids with amines and/or alcohols.
These reac-
tion products are commonly used in the lubricant arts as dispersants and are
some-
times referred to generically as dispersants despite the fact that they may
have other
uses in addition to or instead of that as dispersants. The carboxylic
dispersants in-
clude succinimide dispersants, ester type dispersants and the like.
Succinimide dis-
persants are generally the reaction of a polyamine with an alkenyl succinic
anhydride
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or acid. Ester type dispersants are the reaction product of an alkenyl
succinic anhy-
dride or acid with a polyol compound. The reaction product may then be further
treated with an amine such as a polyamine. Examples of useful dispersants are
dis-
closed in U.S. Pat. Nos. 3,219,666 and 4,234,435, incorporated herein by
reference.
Useful dispersants also include the ashless dispersants discussed below.
Generally
the reaction occurs between the dispersant and the dimercaptothiadiazole by
mixing
the two and heating to a temperature above about 100 C. U.S. Pat. Nos.
4,140,643
and 4,136,043 describe compounds made by the reaction of such dispersants with
a
dimercaptothiadiazole. These patents are incorporated herein by reference for
their
disclosure of dispersants, dimercaptothiadiazole, the method for reacting the
two and
the products obtained from such reaction.
[0074] In one embodiment, the metal deactivator is the reaction product
of a phe-
nol with an aldehyde and a dimercaptothiadiazole. The phenol is preferably an
alkyl
phenol wherein the alkyl group contains at least about 6, preferably from 6 to
about
24, more preferably about 6, or about 7, to about 12 carbon atoms. The
aldehyde is
preferably an aldehyde containing from 1 to about 7 carbon atoms or an
aldehyde
synthon, such as formaldehyde. Preferably, the aldehyde is formaldehyde or
para-
formaldehyde. The aldehyde, phenol and dimercaptothiadiazole are typically
reacted
by mixing them at a temperature up to about 150 C, preferably about 50 C to
about
130 C, in molar ratios of about 0.5 to about 2 moles of phenol and about 0.5
to about
2 moles of aldehyde per mole of dimercaptothiadiazole. Preferably, the three
reagents
are reacted in equal molar amounts.
[0075] In one embodiment, the metal deactivator is a
bis(hydrocarbyldithio)thia-
diazole. Preferably each hydrocarbyl group is independently an alkyl, aryl or
aralkyl
group, having from 6 to about 24 carbon atoms. Each hydrocarbyl can be inde-
pendently t-octyl, nonyl, decyl, dodecyl or ethylhexyl. The metal deactivator
can be
bis-2,5-tert-octyl-dithio-1,3,4-thiadiazole or a mixture thereof with 2-tert-
octylthio-
5-mercapto-1,3,4-thiadiazole. These materials are available commercially under
the
trade name of Amoco 150, which is available from Amoco Chemical Company. These
dithiothiadiazole compounds are disclosed as Component (d) in PCT Publication
WO
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88/03551, incorporated by reference for its disclosure of dithiothiadiazole
com-
pounds. In the preferred embodiments the metal deactivator is a
dimercaptothiadia-
zole derivative. Example D-1 is a specific example.
[0076] Example D-1
[0077] 2,5-dimercapto-1,3,4-thiadiazole oxidatively coupled with t-nonyl
mer-
captan; 100% chemical, 36% S, 6.4% N.
[0078] When used, the amount of metal deactivator in the automotive
gear oil is
generally in the range of about 0.01 to about 0.5 wt.% by weight of the
automotive
gear oil. In some embodiments, the amount of the metal deactivator is in the
range of
about 0.02 to about 0.42 wt.% or about 0.03 to about 0.33 wt,% or about 0.04
to about
0.24 wt.% by weight of the automotive gear oil.
[0079] Another material which may optionally be present is a viscosity
modifier.
Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are well
known.
Examples of VMs and DVMs may include polymethacrylates, polyacrylates, polyole-
fins, hydrogenated vinyl aromatic-diene copolymers (e.g., styrene-butadiene,
styrene-
isoprene), styrene-maleic ester copolymers, and similar polymeric substances
includ-
ing homopolymers, copolymers, and graft copolymers, including polymers having
lin-
ear, branched, or star-like structures. The DVM may comprise a nitrogen-
containing
methacrylate polymer or nitrogen-containing olefin polymer, for example, a
nitrogen-
containing methacrylate polymer derived from methyl methacrylate and dimethyla-
minopropyl amine. The DVM may alternatively comprise a copolymer with units de-
rived from an a-olefin and units derived from a carboxylic acid or anhydride,
such as
maleic anhydride, in part esterified with a branched primary alcohol and in
part reacted
with an amine-containing compound.
[0080] 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 Lubrizol 7060, 7065,
and
7067, and Lucant HC-2000, HC-1100, and HC-600 from Lubrizol); hydrogenated
sty-
rene-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
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HitecTM series of viscosity index improvers from Afton, and LZ 7702, LZ
7727, LZ
7725 and LZ 7720C from Lubrizol); olefin-graft-polymethacrylate polymers
(such as
ViscoplexTM 2-500 and 2-600 from RohMax); and hydrogenated polyisoprene star
pol-
ymers (such as ShellvisTM 200 and 260, from Shell). Viscosity modifiers that
may be
5 used are described in U.S. patents 5,157,088, 5,256,752 and 5,395,539.
The VMs
and/or DVMs may be used in the functional fluid at a concentration of up to
50% or to
20% by weight, depending on the application. Concentrations of 1 to 20%, or 1
to 12%,
or 3 to 10%, or alternatively 20 to 40%, or 20 to 30% by weight may be used.
[0081] Other optional materials may include antioxidants, e.g.,
aromatic amine an-
10 .. tioxidants, hindered phenolic antioxidants including ester-containing
hindered phe-
nolic antioxidants, and sulfurized olefin antioxidants. In an embodiment, the
automo-
tive gear oil may contain a mixture of at least two anti-oxidants. These
antioxidants
may optionally be present in amounts of 0.01 to 5, or 0.15 to 4.5 or 0.2 to 4,
or 0.2 to
2 percent by weight.
15 [0082] In one embodiment, the automotive gear oil can include an
aryl amine an-
tioxidant. The aryl amine antioxidant may be a phenyl-a-naphthylamine (PANA)
or a
hydrocarbyl substituted diphenylamine, or mixtures thereof. The hydrocarbyl
sub-
stituted diphenylamine may include mono- or di- C4 to C16-, or C6 to C12-, or
C9-
alkyl diphenylamine. For example the hydrocarbyl substituted diphenylamine may
20 be octyl diphenylamine, or di-octyl diphenylamine, dinonyl
diphenylamine, typically
dinonyl diphenylamine.
[0083] When present the aryl amine antioxidant may be present at 0.2 wt
% to 1.2
wt %, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt % or 0.5 wt % to 0.8 wt
%, of
the automotive gear oil.
[0084] The hindered phenol antioxidant often contains a secondary butyl
and/or a
tertiary butyl group as a sterically hindering group. The phenol group is
often further
substituted with a hydrocarbyl group and/or a bridging group linking to a
second
aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-
di-
tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-
butylphenol,
4-propy1-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-
dodecy1-
2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant may
be
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21
an ester and may include, e.g., IrganoxTM L-135 from Ciba, or butyl 3-(3,5-di-
tert-
buty1-4-hydroxyphenyl)propanoate.
[0085] If present, the hindered phenol antioxidant may be present at
0.1 wt % to
1 wt %, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt % to 1.0 wt
%, of
the automotive gear oil.
[0086] Antioxidants also include sulfurized olefins such as mono-, or
disulfides
or mixtures thereof. These materials generally have sulfide linkages having 1
to 10
sulfur atoms, for instance, 1 to 4, or 1 or 2. Materials which can be
sulfurized to
employ as sulfurized antioxidants in the automotive gear oil can include oils,
fatty
.. acids and esters, olefins and polyolefins made thereof, terpenes, or Diels-
Alder ad-
ducts. Details of methods of preparing some such sulfurized materials can be
found
in U.S. Pat. Nos. 3,471,404 and 4,191,659.
[0087] The automotive gear oil may also include a calcium-containing
detergent.
While the calcium-containing detergent is preferably not present, it can be
included
.. in an amount to deliver up to 150 ppm or 180 ppm of calcium to the
composition, or
from 30 ppm to 180 ppm, or 30 ppm to 150 ppm of calcium, or from 60 ppm to 180
ppm, or even from 60 ppm to 150 ppm of calcium.
[0088] In some embodiments, the calcium-containing detergent may be
present at
90 ppm or less, or from 1 to 90 ppm, or even from 5 to 80 ppm or 10 to 75 ppm.
[0089] The calcium-containing detergent may be an overbased detergent, a
non-
overbased detergent, or mixtures thereof. Typically the detergent is
overbased.
[0090] The preparation of the calcium-containing detergent is known in
the art.
Patents describing the preparation of overbased calcium-containing detergents
in-
clude U.S. patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874;
3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and
3,629,109.
[0091] The calcium-containing detergent may be a non-overbased
detergent (may
also be referred to as a neutral detergent). The TBN of a non-overbased may be
20
to less than 200, or 30 to 100, or 35 to 50 mg KOH/g. The TBN of a non-
overbased
calcium-containing detergent may also be 20 to 175, or 30 to 100 mg KOH/g.
When
.. a non-overbased calcium-containing detergent is prepared from a strong acid
such as
a hydrocarbyl-substituted sulphonic acid, the TBN may be lower (for example 0
to
50 mg KOH/g, or 10 to 20 mg KOH/g).
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[0092] As used herein the TBN values quoted and associated range of TBN
is on "an
as is basis," i.e., containing conventional amounts of diluent oil.
Conventional amounts
of diluent oil typically range from 30 wt % to 60 wt % (often 40 wt % to 55 wt
%) of the
detergent component.
[0093] The calcium-containing detergent may be an overbased detergent,
having,
for example, a TBN of greater than 200 mg KOH/g (typically 250 to 600, or 300
to
500 mg KOH/g).
[0094] The overbased calcium-containing detergent may be formed by the
reaction
of a basic calcium compound and an acidic detergent substrate. The acidic
detergent
substrate may include an alkyl aromatic sulphonic acid (such as, alkyl
naphthalene sul-
phonic acid, alkyl toluene sulphonic acid or alkyl benzene sulphonic acid), an
alkyl sali-
cylic acid, or mixtures thereof.
[0095] The basic calcium compound is used to supply basicity to the
detergent.
The basic calcium compound is a compound of a hydroxide or oxide of the
calcium.
[0096] The oxides and/or hydroxides may be used alone or in combination.
The
oxides or hydroxides may be hydrated or dehydrated, although hydrated is
typical.
In one embodiment the basic calcium compound may be calcium hydroxide, which
may be used alone or mixtures thereof with other metal basic compounds.
Calcium
hydroxide is often referred to as lime. In one embodiment the calcium basic
com-
pound may be calcium oxide which may be used alone or mixtures thereof with
other
metal basic compounds.
[0097] In one embodiment the calcium-containing detergent may be a
sulphonate,
or mixtures thereof. The sulphonate may be prepared from a mono- or di- hydro-
carbyl-sub stituted benzene (or naphthalene, indenyl, indanyl, or
bicyclopentadienyl)
sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35
or 9 to
carbon atoms.
[0098] The hydrocarbyl group may be derived from polypropylene or a
linear or
branched alkyl group containing at least 10 carbon atoms. Examples of a
suitable
alkyl group include branched and/or linear decyl, undecyl, dodecyl, tridecyl,
30 tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl,
nonodecyl,
eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl,
hexa-eicosyl
or mixtures thereof.
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[0099] In one embodiment the hydrocarbyl-substituted sulphonic acid may
in-
clude polypropene benzenesulphonic acid and/or C16-C24 alkyl benzenesulphonic
acid, or mixtures thereof.
[0100] In one embodiment a calcium sulphonate detergent may be a
predominantly
linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 as
is described
in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and
granted as US
7,407,919). In some embodiments the linear alkyl group may be attached to the
benzene
ring anywhere along the linear chain of the alkyl group, but often in the 2, 3
or 4 position
of the linear chain, and in some instances predominantly in the 2 position.
[0101] When neutral or slightly basic, a calcium sulphonate detergent may
have
TBN of less than 100, or less than 75, typically 20 to 50 mg KOH/g, or 0 to 20
mg
KOH/g.
[0102] When overbased, a calcium sulphonate detergent may have a TBN
greater
than 200, or 300 to 550, or 350 to 450 mg KOH/g.
[0103] Phenate detergents are typically derived from p-hydrocarbyl phenols
or,
generally, alkylpheols. Alkylphenols of this type may be coupled with sulfur
and
overbased, coupled with aldehyde and overbased, or carboxylated to form
salicylate
detergents. Suitable alkylsalicylates include those alkylated with oligomers
of pro-
pylene, oligomers of butene, especially tetramers and pentamers of n-butenes,
as
well as those alkylated with alpha-olefins, isomerized alpha-olefins, and
polyolefins
like polyisobutylene. In one embodiment, the automotive gear oil comprises
less
than 0.2 wt %, or less than 0.1 wt %, or even less than 0.05 wt % of a
salicylate de-
tergent derived from para-dodecylphenol (PDDP). In one embodiment, the automo-
tive gear oil comprises a salicylate detergent that is not derived from PDDP.
In one
embodiment, the automotive gear oil can comprise a salicylate detergent
prepared
from PDDP, such detergent contains less than 1.0 weight percent unreacted
PDDP,
or less than 0.5 weight percent unreacted PDDP, or is substantially free of
PDDP.
[0104] The detergent may be borated or non-borated.
[0105] Chemical structures for sulphonates, and salicylate detergents
are known to
a person skilled in the art. The standard textbook entitled "Chemistry and
Technology
of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik,
Copyright
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2010, pages 220 to 223 under the sub-heading 7.2.6 provide general disclosures
of
said detergents and their structures.
[0106] In one embodiment the calcium-containing detergent may be an
overbased
calcium sulphonate, an overbased calcium salicylate, or mixtures thereof.
Typically
the detergent may be an overbased calcium sulphonate.
[0107] In one embodiment the calcium-containing detergent may be in a
mixture
with a zinc-, barium-, sodium-, or magnesium- containing detergent. The zinc-,
bar-
ium-, sodium-, or magnesium- containing detergent is also well known in the
art and
described in the same references describing a calcium-containing detergent.
The
.. TBN and metal ratios may however, differ slightly. The zinc-, barium-,
sodium-, or
magnesium- containing detergent may be a phenate, a sulphur-containing
phenate,
sulphonate, salixarate or salicylate. Typically a zinc-, barium-, sodium-, or
magne-
sium- containing detergent may be a magnesium phenate, a magnesium sulphur-con-
taining phenate, or a magnesium sulphonate.
[0108] A more detailed description of the expressions "metal ratio", TBN
and
"soap content" are known to a person skilled in the art and explained in
standard
textbooks, such as, for example, "Chemistry and Technology of Lubricants",
Third
Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219
to
220 under the sub-heading 7.2.5. Detergent Classification.
[0109] The automotive gear may also include a friction modifier. In one
embod-
iment the friction modifier may be, for example, long chain fatty acid
derivatives of
amines, long chain fatty esters, or derivatives of a long chain fatty
epoxides; fatty
imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates;
fatty alkyl
tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty
glycolamides, or com-
binations thereof. The friction modifier may be present at 0 wt % to 6 or to 5
wt %,
or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the
lubricating composition. The amount of friction modifier, if present, also may
be 0.05
to 5 percent by weight, or 0.1 to 2 percent, or 0.1 to 1.5 percent by weight,
or 0.15 to
1 percent, or 0.15 to 0.6 percent.
[0110] As used herein the term "fatty alkyl" or "fatty" in relation to
friction mod-
ifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight
carbon
chain. Alternatively, the fatty alkyl may be a mono branched alkyl group, with
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branching typically at the 3-position. Examples of mono branched alkyl groups
in-
clude 2-ethylhexyl, 2-propylheptyl or 2-octyldodecyl.
[0111] Examples of suitable friction modifiers include long chain fatty
acid de-
rivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such
as conden-
5 sation products of carboxylic acids and polyalkylene-polyamines; amine
salts of al-
kylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty
alkyl tar-
tramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated
fatty
epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated
fatty
amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty
amines
10 including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal
salts of fatty
acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated
alcohols;
condensation products of carboxylic acids and polyalkylene polyamines; or
reaction
products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or
thiou-
rea and salts thereof.
15 [0112] Friction modifiers may also encompass materials such as
sulphurised fatty
compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithio-
carbamates, sunflower oil or soybean oil monoester of a polyol and an
aliphatic car-
boxylic acid.
[0113] In one embodiment the friction modifier may be a long chain
fatty acid
20 ester. In another embodiment the long chain fatty acid ester may be a
mono-ester and
in another embodiment the long chain fatty acid ester may be a triglyceride
[0114] In an embodiment, the automotive gear oil is substantially free
of friction
modifiers. In some embodiments, the automotive gear oil is completely free of
fric-
tion modifiers.
25 [0115] The automotive gear oil may have a kinematic viscosity at
100 C of from
8 cSt to 24 cSt, or for example, from 9 cSt to 21 cSt, or even 10 cSt to 20
cSt.
[0116] One aspect is therefore a method of lubricating an automotive
gear by sup-
plying to the automotive gear the automotive gear oil as disclosed herein, and
oper-
ating the automotive gear. The automotive gear oil will be suitable for
lubricating
automotive gears, including gears in transmissions, such as manual or dual
clutch
transmission, gears on axles, and gears on differentials.
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[0117] The automotive gear oil may, in particular, be employed in a
manual gear-
box of a manual transmission, which may be unsynchronized, or may contain a
syn-
chronizer mechanism. The gearbox may be self-contained, or may additionally
con-
tain any of a transfer gearbox, planetary gear system, differential, limited
slip differ-
ential or torque vectoring device, which may be lubricated by a manual
transmission
fluid.
[0118] The automotive gear oil may be used in planetary hub reduction
axles,
mechanical steering and transfer gear boxes in utility vehicles, synchromesh
gear
boxes, power take-off gears, limited slip axles, and planetary hub reduction
gear
boxes.
[0119] In an embodiment, the automotive gear oil can be employed as a
single lub-
ricant to lubricate the entire driveline system of an automobile having a
manual trans-
mission. That is, in an embodiment, the automotive gear oil may be employed as
a
"total driveline lubricant," suitable to lubricate all the gears in the
automobile, in-
cluding in the transmission and in the axles and differentials.
[0120] As used herein, the term "condensation product" is intended to
encompass
esters, amides, imides and other such materials that may be prepared by a
condensation
reaction 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
actually 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
reaction. The resulting product is still considered a condensation product.
[0121] The amount of each chemical component described is presented
exclusive
of any solvent or diluent oil, which may be customarily present in the
commercial ma-
terial, that is, on an active chemical basis, unless otherwise indicated.
However, unless
otherwise indicated, each chemical or composition referred to herein should be
inter-
preted as being a commercial grade material which may contain the isomers, by-
prod-
ucts, derivatives, and other such materials which are normally understood to
be present
in the commercial grade.
[0122] 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. Specifi-
cally, it refers to a group having a carbon atom directly attached to the
remainder of
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27
the molecule and having predominantly hydrocarbon character. Examples of hydro-
carbyl groups include:
[0123] hydrocarbon substituents, that is, aliphatic (e.g., alkyl or
alkenyl), alicyclic
(e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and
alicyclic-
substituted aromatic substituents, as well as cyclic substituents wherein the
ring is com-
pleted through another portion of the molecule (e.g., two substituents
together form a
ring);
[0124] substituted hydrocarbon substituents, that is, substituents
containing non-
hydrocarbon groups which, in the context of this invention, do not alter the
predomi-
nantly hydrocarbon nature of the substituent (e.g., halo (especially chloro
and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
[0125] hetero substituents, that is, substituents which, while having a
predomi-
nantly hydrocarbon character, in the context of this invention, contain other
than car-
bon in a ring or chain otherwise composed of carbon atoms and encompass
substituents
as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen,
and ni-
trogen. In general, no more than two, or no more than one, non-hydrocarbon
substitu-
ent will be present for every ten carbon atoms in the hydrocarbyl group;
alternatively,
there may be no non-hydrocarbon substituents in the hydrocarbyl group.
[0126] It is known that some of the materials described above may
interact in the
final formulation, so that the components of the final formulation may be
different
from those that are initially added. For instance, metal ions (of, e.g., a
detergent) can
migrate to other acidic or anionic sites of other molecules. The products
formed
thereby, including 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 modifications and reaction products are included within the scope of
the pre-
sent invention; the present invention encompasses the composition prepared by
admix-
ing the components described above.
[0127] As used herein, the term "about" means that a value of a given
quantity is
within 20% of the stated value. In other embodiments, the value is within
15% of
the stated value. In other embodiments, the value is within 10% of the stated
value. In other embodiments, the value is within 5% of the stated value. In
other
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embodiments, the value is within 2.5% of the stated value. In other
embodiments,
the value is within 1% of the stated value.
[0128] Additionally, as used herein, the term "substantially" means
that a value
of a given quantity is within 10% of the stated value. In other embodiments,
the
value is within 5% of the stated value. In other embodiments, the value is
within
2.5% of the stated value. In other embodiments, the value is within 1% of the
stated value.
[0129] The invention herein is useful for lubricating an automotive
gear, which may
be better understood with reference to the following examples.
[0130] EXAMPLES
[0131] Automotive gear oils were prepared and tested for dynamic
friction, 1,i-V
gradient, and thermal stability (to test cleanliness). The fluids can be seen
in table 1
below.
Baseline Baseline Experimental
Fluid 1 Fluid 2 Fluid 1
4 cSt Oil of Lubricating 70.49 71.99 70.99
Viscosity
Viscosity Modifier 21 21 21
Extreme Pressure Agent 3.80 3.80 3.80
Corrosion Inhibitor 0.10 0.10 0.10
Berated Dispersant' 0.43 0.31 0.31
Non-Borated Dispersant 0.71 0.18 0.18
Antiwear Agent2 1.32 1.00 1.00
Antifo am 0.01 0.01 0.01
Friction Modifier 0.35 0.3 0.3
Boron Containing Com-
1.0
pound3
Total 100 100 100
'Delivers 133, 95 and 95 ppm Boron to the fluids, respectively
'Delivers 1115, 845 and 845 ppm Phosphorus to the fluids, respectively
'Delivers 270ppm Boron to the fluid
[0132] The formulations were tested in a synchronizer test rig in a
"durability test."
This is a screening test that is customarily used to evaluate friction and
durability charac-
teristic of a clutch synchronizer. The test rig typically does not simulate a
ful I engagement
of the synchronizer components, but does measure the friction between the
synchronizer
ring and the gear cone. The rig comprises a test rig bath in which the
components are
assembled.
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[0133] An Automax rig comprises a test rig bath in which the
components are as-
sembled. The synchronizer is attached to the test rig key on one side of the
chamber and
the cone assembled onto a test rig jig on the other side. The test conditions
used are shown
in the Table below. The fluids are maintained at 80 C. with the synchronizer
typically
rotating at 1000 rpm. In each test, there is an initial break-in phase of 100
cycles of en-
gagement. Thereafter, multiple cycles of engagement consist of 0.2 seconds of
contact
followed by 5 seconds of separation, running at 1000 r.p.m. at 80 C. and a
load during
contact of 981 N (100 kg).
Oil Temperature ( C.) 80
Speed (rpm) 1000
Load (kg) 100
(N) 980.6
On Time (sec) 0,2
Off Time (sec) 5.0
Inertia (kg cm sec2) 2.67
Calculated Torque (NM) 41
[0134] The key features of the synchronizer used in this experiment are
summarized
in the table below. All other parts are original equipment manufacturer
production parts
used in standard vehicles:
Phenolic Resin Synchronizer
Gear Cone Angle (degrees) 7,0
Effective radius (mm) 62
Composition Phenolic Resin
[0135] The data from the test provides several key parameters that
allow a comparison
of the friction performance of the candidates. Comparisons of the relative
durability and
shift quality of the different candidates are made based upon a number of
parameters in-
cluding dynamic friction level assessed by the friction value during
durability testing, fric-
tion durability assessed by the stability, and trends in average friction
values during the
durability phase.
[0136] Shift quality is assessed by examining the performance test
profiles which
show the variation of friction with rotational speed. It is desirable to have
a flat frictional
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101351 The data from the teat provides several key parameters that
allow a comparison
of the fiction perfomiance of the candidates, Comparisons of the relative
durability and
shift quality of the different candidates are made based upon a number of
parameters in
-
eluding dynamic fiction level assessed by the fiction value during durability
testing, frit:-
tion durability assessed by the stability, and trends in average friction
values during the
durability phase. ..
[01361 Shift quality is assessed by examining the performance test
profiles which
show the variation of friction with rotational speed. it is desirable to have
a fat frictional
profile, with 3 level or slight decrease in friction at low speed providing
improved syn-
cbronizer engagement and improved shift quality.
[01371 The dynamic coefficient of friction may be presented as a
function of cycle
number. A quantitative representation of the performance may be obtained by
calculating
the number of cycles to stability. Ideally, a fluid should show stable
friction throughout
the duration of the test. Some fluids may vary in friction at the start of the
test, before
stabilizing to a final value after a number of cycles. Other fluids may not
stabilize at all
and the friction may be still increasing or decreasing after 10,000 cycles.
One method of
assessing dynamic fiction is to evaluate the mean and standard deviation of
the friction
values &nine the 10,000 cycle teat.
Dynamic Friction õ
Baseline = --1'.== Baseline 1 Experimental =:,
Fluid 1 Fluid 2 1 Finial .
= - ==,. ¨
Cycle pV-AVG .. . ly-AvG r pv-ANG ,
-1,-- ,-
1 t 0.116 ii 0112 ' 0 113 '
f--Too- 0.119 ii 0.116 I 0.115
i.I.
500 0.12 0.114 i 0.115
., t ........ f i ....
1000 j 0118 i 0 0116 . ¨
108 : -
+:
= 2000 I. 0.114 . ; ..... 0.105 _4
0.116 '
_
'= ..................... 3000 :1. 0.113 . . Ø104 , 0.115
....................... 4000 i 0112 - 0.103 0115
- ¨ . .
5000 1 0.112 0.102 !
: 0.115
:. ....
= 6000 1! . _0.111 0.102
0.114... .. ..... :
. 7000 =õ.,,. 0111 ' 0.102 _____ = = 0.114
8000 ' 0,111
9001: p,i11 . .
, 0.102 _ . _ . _0.114 .
0.102 , . .. 0.113 = =
-
' 10000 0 11
4 0.102 0 113
:--- , ..
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õ õ ,... ..
.
, . . PCT/US 2019/012 031 -
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Case No. 4573 31
[0138] In order to assess the shift-quality of an individual
engagement it is necessary
to evaluate the friction versus speed relationship. One parameter that is
useful is to assess
the curvature of the speed-friction relationship. In order to do this a chord
is drawn between
the p values between 50 to 1000 rpm. The area of the difference between the
actual !Id and
the chord gives a value that we will refer to as the curvature of the line. A
large negative
curvature value represents a poor result and a value that is close to zero or
positive, indi-
cates a better performance.
, .. ..... -
.. i
pre lest Friction , ' Post Test Friction
Baseline Baseline I Experimental I
: I Baseline :3 Baseline Experimental(,1
; .......... Fittid 1 Fluid 2 i Fluid 1
= I Fluid 1 ii, 'Fluid 2 õFluid 1 .1
r-----: 1--
I Initial i : Final Final Final
Bridal Meas- Initial Meas- i
Was- 1 I
flrpm Measure- 1 uremen, rpm Meas- Meas.
urement 1
i = L ment .. I ... - $ 1 . urement . ,.urement
...,.uremeint t I
= r
t- = i
50 0.119 I 0.112 t 0.116 __ 11 50. '
i_ 0.131 ' ' 0.125 , 0.22
75I .
.'= 75 0.121 - A 0.114 i - DITir ' ' 0.129 ' :
0.122 .. : .. 0.121
100 !. :
..Q.123 _ 4 0.115 ..1 Ø118 . . ......
1,00 I 0.126 .0,118
0i23 .'3 _. 0115s i . 0.118
125 = 0.126 1 0.1.16 ' 0.123 -
_13.123 . .
i ---/-
' 200 0121 ,. 0114 1 0.117 1 200 . 0.121
I 0 0 .112 .
.122
. .,
......... 300 i Ø12 ..... ',: 0.113 .. i .. 0 117 : I 300
0.119 I 0.11 ' 0,121 - =
..... ..,,: I. ..,
,....... ' ..,
500 1 0118 "4' - 0.111 1 " ails i 500
0.116 ....1 0.107 0.119
,-,.........._ . ..f. - I
: 750 .'1, 0.117 0.111 0.114 L 750 ..
0.11.3. ...1. 0.105 . 0.116 .
...4, .....: -
. , .... 1000 0.117 1 0.112 0113 = L_Ipiti2:21.2._'
j_91o3 : - '''' 6414
, .. 6 . - ...,
., -.
101391 As can be seen in the tables, Experimental Fluid 1 shows a
stabilized friction
over the test cycles.
101401 The wear performance provided by the lubricant was also be
tested. Wear
may be determined from the test rig profile described above, by measuring mg
weight
loss from the synchronizer ring at the end of the testing. The wear readings
for the
fluids are provided belowõ
.... ...... ..........::
i .... .
- Baseline 1 Basethre Experinientii .
1 Fluid 1 Fluid 2 Fluid 1
..................................... J.''' ... WO I . Amid OW
' Wear read- 1
879 1 41.4 36.4
, ing . .
(01411 500 ml samples of the fluids were tested for thermal
stability by the JIS
IC2514-1 Indiana Stirring Oxidation Test at 150 C, heated for 96 hours at
1,300 rpm.
The results are shown in the table below. The laquer rating scale is as
follows: 0 - no
deposit, I = light deposit, 2 - medium deposit and 3 = heavy deposit.
31
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Baseline I¨Baseline Expe.rimental
Fluid I ' Fluid 2 Fluid 1
Heating Time/hours Lacquer Rating
___________________ 0 0
24 1 1 1 1
48 ________________________________________ 1 ........ 1
96 3 .. I .. 3 T
2
________________________________ ¨ -
[0142] Each of the
documents referred to above is incorporated herein by reference,
including any prior applications, whether or not specifically listed above,
from which
priority is claimed. The mention of any document is not an admission that such
docu-
ment qualifies as prior art or constitutes the general knowledge of the
skilled person in
any jurisdiction. Except in the Examples, or where otherwise explicitly
indicated, all
numerical quantities in this description specifying amounts of materials,
reaction con-
ditions, molecular weights, number of carbon atoms, and the like, are to be
understood
as 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. Sim-
ilarly, the ranges and amounts for each element of the invention can be used
together
with ranges or amounts for any of the other elements.
(01431 As used
herein, the transitional term "comprising," which is synonymous
with "including," "containing," or "characterized by," is inclusive or open-
ended and
5 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 alter-
native embodiments, the phrases "consisting essentially of" and "consisting
of," where
"consisting of' excludes any element or step not specified and "consisting
essentially
of' permits the inclusion of additional un-recited elements or steps that do
not materi-
ally affect the essential or basic and novel characteristics of the
composition or method
under consideration.
101441 While
certain representative embodiments and details have been shown for
the purpose of illustrating the subject invention, it will he apparent to
those skilled
in this art that various changes and modifications can be made therein without
de-
parting from the scope of the subject invention. In this regard, the scope of
the in-
vention is to be limited only by the following
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