Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
ZINC-FREE FARM TRACTOR FLUID
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] [BLANK]
BACKGROUND OF THE INVENTION
[0002] The present invention relates to lubricants useful for farm
tractor
fluids, also referred to as tractor hydraulic fluids or lubricants. The fluids
are
substantially free from zinc salts such as zinc dialkyldithiophosphates.
[0003] Farm tractor lubricants are fluids which are called upon to play
multiple roles in the lubrication of farm tractors and related equipment. In
many
instances the same fluid is used to lubricant the crankcase, clutch,
transmission,
and power take-off components. As a result of exposure to the harsh conditions
of the crankcase, the fluid may become contaminated with water and other
byproducts of combustion.
[0004] For many years, lubricants in general and farm tractor lubricants
in
particular have contained zinc dialkyldithiophosphates ("ZDPs") as important
components, providing antioxidancy, anti-corrosion activity, antiwear activity
and other benefits. However, exposure of such lubricants to water during use
can lead to hydrolysis of the ZDP as well as other interactions with metals
such
as copper and consequent loss of, e.g., corrosion protection for yellow
metals.
[0005] There are many formulations that have been suggested for use as
farm
tractor fluids, also known as tractor hydraulic fluids. For example, U.S.
Patent
5,843,873, Butke et al., December 1, 1998, discloses lubricants and fluids
useful
in pressure transmitting applications such as tractor hydraulic fluids. The
compositions contain a thiocarbamate and a phosphorus acid or ester or an
amine salt thereof, an a surfactant which can be, e.g., glycerol partial
esters.
The phosphorus compound can be a dialkyl hydrogen phosphite. Another
additive which can be present is a dimercaptothiadiazole or a derivative
thereof,
which can be used as a copper corrosion inhibitor. Overbased materials can
also
be present, which can be further treated, if desired with other substances
such as
a boron source.
[0006] European Patent Application Publication EP 0 712 924 A, May 22,
1996, discloses oil based compositions which can serve as a functional fluid,
in
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particular, a tractor hydraulic fluid. Components include a compound of the
structure R1R2N-C(X)S-Q
(an example of which is (C4H9)2N-C(=S)-S-CH2CH2C(=0)-OCH3), and a sulfur-
containing phosphoric acid. A surfactant can also be present. The materials
are
described as providing good antiwear properties even in the absence of typical
zinc compounds such as zinc dialkylthiophosphates. Another additive which can
be present is a dimercaptothiadiazole or a derivative thereof, which can be
used
as a copper corrosion inhibitor. Among the listed surfactants is a borated C16
a-
olefin epoxide.
[0007] U.S. Patent 5,284,591, Bayles et al., February 8, 1994, discloses a
functional fluid (one type of which is a tractor fluid) comprising an
overbased
calcium sulfonate, a ZDP, a borated epoxide, a carboxylic solubilizer in the
form of an ester-salt reaction product of an acylating agent and an alkanol
tertiary monoamine, and a sulfurized composition.
[0008] U.S. patent 5,635,459, Stoffa et al., June 3, 1997, discloses
borated
overbased sulfonates for improved gear performance in functional fluids. The
fluid can also contain a ZDP or other EP/antiwear agent, and a borated
epoxide.
Functional fluids are disclosed to include tractor fluids.
[0009] U.S.
Patent 5,298,177, Stoffa, March 29, 1994, discloses a functional
fluid comprising a triglyceride, a detergent-inhibitor additive, a viscosity
modi-
fying additive, and a synthetic oil. The detergent inhibitor can be free from
phosphorus and zinc and can include, e.g., a metal passivator which can be an
oil-soluble derivative of a dimercaptothiadiazole. The detergent inhibitor may
also be a borated complex of an overbased metal sulfonate, carboxylate, or
phenate.
[0010] The
present invention, therefore, solves the problem of hydrolysis of
ZDP and resulting deterioration in performance by providing a fluid free from
or substantially free from ZDP and other zinc compounds, by including a
dithiophosphate ester or salt (other than zinc), a heterocyclic organic
compound,
and a boron-containing component. The fluid of the invention continues to
exhibit acceptable performance. The absence of ZDP can also provide a fluid
with improved environmental properties.
SUMMARY OF THE INVENTION
[0011] The
present invention therefore provides a lubricating composi-
tion comprising: (a) an oil of lubricating viscosity; (b) at least one amine
salt
of a phosphorus acid ester; (c) at least one thiadiazole compound (which may
be
a copper corrosion inhibitor); (d) at least one overbased metal detergent; (e)
at
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least one boron compound other than an overbased metal detergent; and (f) at
least one friction modifier other than a boron compound; said composition
being
substantially free from zinc dialkyldithiophosphate.
[0012] The invention also provides a method for lubricating a
mechanical device
such as the hydraulic system of a farm tractor, comprising supplying thereto
the
foregoing lubricating composition.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Various preferred features and embodiments will be described
below
by way of non-limiting illustration.
Oil of Lubricating Viscosity.
[0014] One component of the present invention is an oil of lubricating
viscosity, which can be present in a major amount, for a lubricant
composition,
or in a concentrate forming amount, for a concentrate. Suitable oils include
natural and synthetic lubricating oils and mixtures thereof. In a fully
formulated
lubricant, the oil of lubricating viscosity is generally present in a major
amount
(i.e. an amount greater than 50 percent by weight). Typically, the oil of
lubri-
cating viscosity is present in an amount of 75 to 95 percent by weight, and
often
greater than 80 percent by weight of the composition.
[0015] Natural oils useful in making the inventive lubricants and
functional
fluids include animal oils and vegetable oils as well as mineral lubricating
oils
such as liquid petroleum oils and solvent-treated or acid-treated mineral
lubri-
cating oils of the paraffinic, naphthenic or mixed paraffinic/-naphthenic
types
which may be further refined by hydrocracking and hydrofinishing processes.
[0016] Synthetic lubricating oils include hydrocarbon oils and halo-
substituted hydrocarbon oils such as polymerized and interpolymerized olefins,
also known as polyalphaolefins; polyphenyls; alkylated diphenyl ethers; alkyl-
or dialkylbenzenes; and alkylated diphenyl sulfides; and the derivatives,
analogs
and homologues thereof. Also included are alkylene oxide polymers and inter-
polymers and derivatives thereof, in which the terminal hydroxyl groups may
have been modified by esterification or etherification. Also included are
esters
of dicarboxylic acids with a variety of alcohols, or esters made from C5 to
C12
monocarboxylic acids and polyols or polyol ethers. Other synthetic oils
include
silicon-based oils, liquid esters of phosphorus-containing acids, and
polymeric
tetrahydrofurans.
[0017] Unrefined, refined and rerefined oils, either natural or synthetic,
can
be used in the lubricants of the present invention. Unrefined oils are those
obtained directly from a natural or synthetic source without further
purification
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treatment. Refined oils have been further treated in one or more purification
steps to improve one or more properties. They can, for example, be hydrogen-
ated, resulting in oils of improved stability against oxidation.
[0018] In one embodiment, the oil of lubricating viscosity is an API
Group
II, Group III, Group IV, or Group V oil, including a synthetic oil, or
mixtures
thereof. These are classifications established by the API Base Oil Interchange-
ability Guidelines. Both Group II and Group III oils contain < 0.03 percent
sulfur and > 99 percent saturates. Group II oils have a viscosity index of 80
to
120, and Group III oils have a viscosity index > 120. Polyalphaolefins are
categorized as Group IV. The oil can also be an oil derived from hydroisomeri-
zation of wax such as slack wax or a Fischer-Tropsch synthesized wax. Group
V is encompasses "all others" (except for Group I, which contains > 0.03% S
and/or < 90% saturates and has a viscosity index of 80 to 120).
[0019] In one embodiment, at least 50% by weight of the oil of
lubricating
viscosity is a polyalphaolefin (PAO). Typically, the polyalphaolefins are
derived from monomers having from 4 to 30, or from 4 to 20, or from 6 to 16
carbon atoms. Examples of useful PAOs include those derived from 1-decene.
These PAOs may have a viscosity of 1.5 to 150 mm2/s (cSt) at 100 C. PAOs
are typically hydrogenated materials.
[0020] The oils of the present invention can encompass oils of a single
viscosity range or a mixture of high viscosity and low viscosity range oils.
In a
preferred embodiment, the oil exhibits a 100 C kinematic viscosity of 1 or 2
to
8 or 10 mm2/sec (cSt). The overall lubricant composition is preferably formu-
lated using oil and other components such that the viscosity at 100 C is 1 or
1.5
to 10 or 15 or 20 mm2/sec and the Brookfield viscosity (ASTM-D-2983) at
-40 C is less than 20 or 15 Pa-s (20,000 cP or 15,000 cP), or less than 10 Pa-
s,
or even 5 or less.
Amine Salt of Phosphorus Acid Ester
[0021] The invention includes an amine salt of a phosphorus acid ester.
This
material can serve as one or more of an extreme pressure agent, a wear prevent-
ing agent. The amine salt of a phosphorus acid ester includes phosphoric acid
esters and salts thereof; dialkyldithiophosphoric acid esters and salts
thereof;
phosphites; and phosphorus-containing carboxylic esters, ethers, and amides;
and mixtures thereof.
[0022] In one embodiment the phosphorus compound further comprises a
sulfur atom in the molecule. In one embodiment the amine salt of the phospho-
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rus compound is ashless, i.e., metal-free (prior to being mixed with other com-
ponents).
[0023] The amine salt of the phosphorus acid ester may comprise any of
a
variety of chemical structures. In particular, a variety of structures are
possible
when the phosphorus acid ester compound contains one or more sulfur atoms,
that is, when the phosphorus-containing acid is a thiophosphorus acid ester.
The
thiophosphorus acid esters may be mono- or dithiophosphorus acid esters.
Thiophosphorus acid esters are also sometimes referred to as thiophosphoric
acids. A phosphorus acid ester may be prepared by reacting a phosphorus
compound with an alcohol. Suitable phosphorus compound include phosphorus
pentoxide, phosphorus trioxide, phosphorous tetroxide, phosphorus acids,
phosphorus esters, and phosphorus sulfides such as phosphorus pentasulfide.
Suitable alcohols include those containing up to 30 or to 24, or to 12 carbon
atoms, including primary or secondary alcohols such as isopropyl, butyl, amyl,
s-amyl, 2-ethylhexyl, hexyl, cyclohexyl, octyl, decyl and oleyl alcohols, as
well
as any of a variety of commercial alcohol mixtures having, e.g., 8 to 10, 12
to
18, or 18 to 28 carbon atoms. Polyols such as diols may also be used.
[0024] In one embodiment, the phosphorus acid ester is a monothiophos-
phoric acid ester or a monothiophosphate. Monothiophosphates may be pre-
pared by the reaction of a sulfur source with a dihydrocarbyl phosphite. The
sulfur source may, for instance, be elemental sulfur, or an organosufide, such
as
a sulfur coupled olefin or a sulfur coupled dithiophosphate. The preparation
of
monothiophosphates is disclosed in U.S. Patent 4,755,311 and PCT Publication
WO 87/07638, which describe monothiophosphates, sulfur sources, and the
process for making monothiophosphates. Monothiophosphates may also be
formed in the lubricant blend by adding a dihydrocarbyl phosphite to a
lubricat-
ing composition containing a sulfur source, such as a sulfurized olefin. The
phosphite may react with the sulfur source under blending conditions (i.e.,
temperatures from about 30 C to about 100 C or higher) to form the monothio-
phosphate salt with an amine which is present in the blend.
[0025] In certain embodiments, the phosphorus-containing acid is a
dithio-
phosphoric acid or phosphorodithioic acid. The dithiophosphoric acid may be
represented by the formula (R0)2PSSH wherein each R is independently a
hydrocarbyl group containing 3 to 30 carbon atoms. R generally contains up to
18, or to 2, or to 8 carbon atoms. Examples of R include isopropyl, isobutyl,
n-
butyl, sec-butyl, the various amyl, n-hexyl, methylisobutyl carbinyl, heptyl,
2-
ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and tridecyl groups.
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Illustrative lower alkylphenyl R groups include butylphenyl, amylphenyl, and
heptylphenyl. Examples of mixtures of R groups include 1-butyl and 1-octyl; 1-
pentyl and 2-ethyl-l-hexyl; isobutyl and n-hexyl; isobutyl and isoamyl; 2-
propyl
and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl, and isooctyl.
[0026] In certain embodiments, the dithiophosphoric acid may be reacted
with an epoxide or a glycol and this reaction product further reacted with a
phosphorus acid, anhydride, or lower ester. The epoxide is generally an ali-
phatic epoxide or a styrene oxide. Examples of useful epoxides include ethyl-
ene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, and
styrene oxide. The glycols may be aliphatic glycols having from 1 to 12, or 2
to 6, or 2 or 3 carbon atoms. The dithiophosphoric acids, glycols, epoxides,
inorganic phosphorus reagents and methods of reacting the same are described
in U.S. Patents 3,197,405 and 3,544,465.
[0027] The following Examples B-1 and B-2 exemplify the preparation of
useful phosphorus acid esters.
[0028] Example B-1. Phosphorus pentoxide (about 64 grams) is added at
about 58 C over a period of about 45 minutes to about 514 grains of hy-
droxypropyl 0,0-di(4-methy1-2-pentyl)phosphorodithioate (prepared by react-
ing di(4-methyl-2-penty1)-phosphorodithioic acid with about 1.3 moles of
propylene oxide at about 25 C). The mixture is heated at about 75 C for about
2.5 hours, mixed with a diatomaceous earth and filtered at about 70 C. The
filtrate contains about 11.8% by weight phosphorus, about 15.2% by weight
sulfur, and an acid number of 87 (bromophenol blue).
[0029] Example B-2. A mixture of about 667 grams of phosphorus pentox-
ide and the reaction product of about 3514 grams of diisopropyl phosphorodi-
thioic acid with about 986 grams of propylene oxide at about 50 C is heated at
about 85 C for about 3 hours and filtered. The filtrate contains about 15.3%
by
weight phosphorus, about 19.6% by weight sulfur, and an acid number of 126
(bromophenol blue).
[0030] Acidic phosphoric acid esters may be reacted with ammonia or an
amine, including polyamines, to form an ammonium salt. The salts may be
formed separately and then the salt of the phosphorus acid ester may be added
to
the lubricating composition. Alternately, the salts may also be formed in situ
when the acidic phosphorus acid ester is blended with other components to form
a fully formulated lubricating composition.
[0031] The amines which may be suitable for use as the amine salt
include
primary amines, secondary amines, tertiary amines, and mixtures thereof. The
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amines include those with at least one hydrocarbyl group, or, in certain em-
bodiments, two or three hydrocarbyl groups. The hydrocarbyl groups may
typically contain 2 to 30 carbon atoms, or in another embodiments 8 to 26 or
10
to 20 or 13 to 19 carbon atoms.
[0032] Primary amines include ethylamine, propylamine, butylamine, 2-
ethylhexylamine, octylamine, and dodecylamine, as well as such fatty amines as
n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-
hexadecylamine, n-octadecylamine and oleyamine. Other useful fatty amines
include commercially available fatty amines such as "Armeen " amines (prod-
ucts available from Akzo Chemicals, Chicago, Illinois), such as Armeen C,
Armeen 0, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD,
wherein the letter designation relates to the fatty group, such as coco,
oleyl,
tallow, or stearyl groups.
[0033] Examples of suitable secondary amines include dimethylamine, di-
ethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, dihep-
tylamine, methylethylamine, ethylbutylamine and ethylamylamine. The secondary
amines may be cyclic amines such as piperidine, piperazine and morpholine.
[0034] The amine may also be a tertiary-aliphatic primary amine. The
aliphatic group in this case may be an alkyl group containing 2 to 30, or 6 to
26,
or 8 to 24 carbon atoms. Tertiary alkyl amines include monoamines such as
tert-butylamine, tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octyl-
amine, tert-decylamine, tertdodecylamine, tert-tetradecylamine, tert-hexadecyl-
amine, tert-octadecylamine, tert-tetraco s anylamine, and tert-o ctaco
sanylamine.
[0035] Mixtures of amines may also be used in the invention. In one em-
bodiment a useful mixture of amines is "Primenee 81R" and "PrimeneC) JMT."
Primenee 81R and Primene JMT (both produced and sold by Rohm & Haas)
are mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22
tertiary alkyl primary amines respectively.
[0036] Suitable hydrocarbyl amine salts of alkylphosphoric acid of the
invention may be represented by the following formula:
R21-0\ /0_ R2\4 zR25
,N+
Z.P%, \
R22_0
H R23
wherein R21 and R22 are independently hydrogen or hydrocarbyl groups such as
alkyl groups; for the phosphorus acid ester, at least one of R21 and R22 will
be
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hydrocarbyl. R21 and R22 may contain 3 or 4 to 30, or 8 to 25, or 10 to 20, or
13 to 19 carbon atoms. R23, R24 and R25 can be independently hydrogen or
hydrocarbyl groups, such as alkyl branched or linear alkyl chains with 1 to
30,
or 4 to 24, or 6 to 20, or 10 to 16 carbon atoms. These R23, R24 and R25
groups
can be branched or linear groups, and in certain embodiments at least one, or
alternatively two of R23, R24 and R25 are hydrogen. Examples of alkyl groups
suitable for R23, R24 and R25 include butyl, sec-butyl, isobutyl, tert-butyl,
pentyl,
n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonode-
cyl, eicosyl groups and mixtures thereof.
[0037] In one embodiment the hydrocarbyl amine salt of an
alkylphosphoric
acid ester 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 C11
to C14 tertiary alkyl primary amines. Other amines which may be used include
alkyl alkanol amines, dialkanolamines, trialkanolamines such as triethanola-
mines as well as borated amines as described hereinbelow.
[0038] Similarly, hydrocarbyl amine salts of dialkyldithiophosphoric
acid
esters of the invention may be represented by the formula:
S - R24 R25
R27-0\
%/P
\
R26_o S H/ R23
wherein the various R groups are as defined above and R26 and R27 are as
defined for R21 and R22. In some embodiments R26and R27 are both hydrocarbyl
groups, and they may contain 3 carbon atoms. Examples of hydrocarbyl amine
salts of dialkyldithiophosphoric acid esters include the reaction product(s)
of
heptylated or octylated or nonylated dithiophosphoric acids with ethylene
diamine, morpholine, or Primene 81RTm, and mixtures thereof.
[0039] The amine salt of as used as this component in the present
invention
may thus comprise a C8 to C20 alkylamine salt of a mono- or di-alkyl phosphate
ester, or mixtures thereof.
[0040] The amount of the amine salt of the phosphorus acid ester can be
0.04
to 4 percent by weight of the lubricating composition, or 0.1 to 2, or 0.2 to
1, or
0.3 to 0.8, or 0.4 to 0.5 weight percent. The amounts will be proportionally
higher in a concentrate.
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[0041] Another material of the present invention is thiadiazole
compound.
This material may, but need not necessarily, serve as a copper corrosion
inhibi-
tor, and it is sometimes referred to as such herein. Examples of such
materials
include dimercaptothiadozoles ("DMTD") which may typically serve as a metal
passivator and/or an anti-wear agent. DMTDs; their preparation are described
in
greater detail in U.S. Patent 5,298,177, see columns 42 through 47. In sum-
mary, the dimercaptothiadiazoles which can be utilized in the present
invention
typically are soluble forms or derivatives of DMTD. Materials which can be
starting materials for the preparation of oil-soluble derivatives containing
the
dimercaptothiadiazole nucleus can include 2,5-dimercapto-[1,3,4]-thiadiazole,
3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole, and 4,-
5-
dimercapto-[1,2,3]-thiadaizole. Of these the most readily available is 2,5-
dimercapto-[1,3,4]-thiadiazole.
[0042] DMTDs are conveniently prepared by the reaction of one mole of
hydrazine, or a hydrazine salt, with two moles of carbon disulfide in an
alkaline
medium, followed by acidification. For the preparation of oil-soluble
derivatives
of DMTD, it is possible to utilize already prepared DMTD or to prepare the
DMTD in situ and subsequently adding a material to be reacted with DMTD.
[0043] U.S. Patents 2,719,125; 2,719,126; and 3,087,937 describe the
prepa-
ration of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles and 2-
hydrocarbyldithio-5-mercapto-[1,3,4]-thiadiazoles. The hydrocarbon group may
be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and
alkaryl.
Such polysulfides can be represented by the following general formula
N¨N
R¨ (S) xs
)--S¨(S)y ¨R'
wherein R and R' may be the same or different hydrocarbyl groups which may,
generally, be as defined for the R groups of the above hydrocarbyl amine
salts,
and x and y be integers from 0 to 8, and the sum of x and y is at least 1.
Alterna-
tively, in certain embodiments, R' can be H when y is 0. A process for prepar-
ing such derivatives is described in U.S. Pat. No. 2,191,125, comprising
reacting
DMTD with a suitable sulfenyl chloride or by reacting the dimercapto diathia-
zole with chlorine and reacting the resulting disulfenyl chloride with a
primary
or tertiary mercaptan. U.S. Pat. No. 3,087,932 further describes a one-step
process for preparing 2,5-bis (hydrocarbyldithio)-1, 3,4-thiadiazole. As
another
variant, carboxylic esters of DMTD are described in U.S. Pat. No. 2,760,933.
Similarly, condensation products of alpha-halogenated aliphatic monocarboxylic
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acids having at least 10 carbon atoms with DMTD are described in U.S. Pat. No.
2,836,564, while U.S. Pat. No. 2,765,289 describes products obtained by react-
ing DMTD with an aldehyde and a diaryl amine in molar proportions of from
about 1:1:1 to about 1:4:4. The DMTD materials may also be present as salts
such as amine salts. Further derivatives are also described in greater detail
in
the aforementioned US Patent 5,298,177.
[0044] In one embodiment, the thiazole compound may be the reaction
prod-
uct of a phenol with an aldehyde and a dimercaptothiadiazole. The phenol may
be an alkyl phenol wherein the alkyl group contains at least about 6, e.g., 6
to 24,
or 6, or 7, to 12 carbon atoms. The aldehyde may be an aldehyde containing 1
to
7 carbon atoms or an aldehyde synthon, such as formaldehyde. In one embodi-
ment, the aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol
and dimercaptothiadiazole are typically reacted by mixing them at a
temperature
up to about 150 C such as 50 C to 130 C, in molar ratios of 0.5 to 2 moles of
phenol and 0.5 to 2 moles of aldehyde per mole of dimercaptothiadiazole. In
one
embodiment, the three reagents are reacted in equal molar amounts. The product
may be described as an alkylhydroxyphenylmethylthio-substituted [1,3,4]-
thiadiazole; the alkyl moiety may be, among others, hexyl, heptyl, octyl, or
nonyl.
[0045] Useful thiadaizole compounds thus may include 2-alkyldithio-5-
mercapto-[1,3,4]-thiadiazoles, 2,5-bis(alkyldithio){1,3,4]-thiadiazoles, 2-
alkyl-
hydroxyphenylmethylthio-5-mercapto-[1,3,4]-thiadiazoles, and mixtures thereof.
[0046] Another useful DMTD derivative is obtained by reacting DMTD
with an oil-soluble dispersant, such as a substantially neutral or acidic
carbox-
ylic dispersant, e.g., a succinimide dispersant or a succinic ester
dispersant, in a
diluent, by heating the mixture above about 100 C. This procedure and the
derivatives produced thereby are described in U.S. Pat. No. 4,136,043, as are
various types of suitable dispersants.
[0047] The amount of the thiadiazole copper corrosion inhibitor can be
0.01
to 5 percent by weight of the composition, depending in part on the identity
of
the particular compound. For instance, if the thiadiazole compound is as de-
scribed for the structure shown above, the amount may be 0.01 to 1 percent, or
0.02 to 0.4 or 0.03 to 0.1 percent by weight. Alternatively, if the
thiadiazole is
reacted with a nitrogen-containing dispersant, the total weight of the
combined
product may be significantly higher in order to impart the same active thiadia-
zole chemistry; for instance, 0.1 to 5 percent, or 0.2 to 2 or 0.3 to 1 or 0.4
to 0.6
percent by weight. The amounts will be proportionally higher in a concentrate.
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[0048]
Another component of the present invention is a detergent. Deter-
gents as used herein are metal salts of organic acids and are well-known from
such publications as US 2004-0102335 and references cited therein. The or-
ganic acid portion of the detergent is typically a sulfonate, carboxylate,
phenate,
salicylate, or salixarate. The metal portion of the detergent is typically an
alkali
or alkaline earth metal. Suitable metals include sodium, calcium, potassium
and
magnesium.
[0049]
Suitable overbased organic salts include sulfonate salts having a
substantially oleophilic character and which are formed from organic
materials.
Organic sulfonates are well known materials in the lubricant and detergent
arts.
The sulfonate compound can contain on average 10 to 40 carbon atoms, for
instance, 12 to 36 carbon atoms or 14 to 32 carbon atoms. Similarly, the phen-
ates, salicylates, salixarates, and carboxylates have a substantially
oleophilic
character.
[0050] While the present invention allows for the carbon atoms to be either
aromatic or in paraffinic configuration, it is common that alkylated aromatics
be
employed. While naphthalene based materials may be employed, the aromatic
material is typically based on benzene.
[0051]
Suitable compositions thus include overbased monosulfonated alky-
lated benzene, such as monoalkylated benzene. Typically, alkyl benzene frac-
tions are obtained from still bottom sources and are mono- or di-alkylated.
[0052] In
certain embodiments, a mixture of mono-alkylated aromatics
(benzene) are utilized to obtain the mono-alkylated salt (benzene sulfonate).
Mixtures wherein a substantial portion of the composition contains polymers of
propylene as the source of the alkyl groups can also be used to assist in the
solubility of the salt. The use of mono-functional (e.g., mono-sulfonated)
materials can be used to avoid crosslinking of the molecules with less
precipita-
tion of the salt from the lubricant.
[0053] The
detergents are typically "overbased." By overbasing, it is meant
that a stoichiometric excess of the metal is present over that required to
neutral-
ize the anion of the salt, typically facilitated by the addition of carbon
dioxide.
The excess metal from overbasing has the effect of neutralizing acids which
may build up in the lubricant, as well as increasing the dynamic coefficient
of
friction. Typically, the excess metal will be present over that which is
required
to neutralize the anion at in the ratio of up to 30:1, such as 1.5:1 to 20:1
or 5:1
to 18:1 on an equivalent basis.
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[0054] The amount of the overbased metal detergent used in the
composition
is typically 0.05 to 5 or to 6 weight percent on an oil free basis, for
instance, 0.1
to 2 percent or 0.2 to 1.0 percent, or in other embodiments 1 to 5 percent or
2 to
4 percent. The overbased salt as supplied often includes 40% to 50% diluent
oil
and with a total base number (TBN) of 10 to 600 or to 800 on an oil free
basis,
or a proportionally lower TBN when calculated including the diluent oil. The
detergent can be post-treated with such agents as borating agents. Borated and
non-borated overbased detergents are also described in U.S. Patents 5,403,501
and 4,792,410 and references cited therein.
[0055] Another component of the present invention is a boron compound.
The boron compound should be soluble or dispersible in the lubricating compo-
sitions. The boron compound is also to be considered and accounted for sepa-
rately from any borated detergent, described above. The actual chemical iden-
tity of the boron compound can be quite diverse. Suitable materials include
borated fatty epoxides, known from Canadian Patent No. 1,188,704. These oil-
soluble boron- containing compositions can be prepared by reacting boric acid
(in any of its various forms) or boron trioxide with at least a fatty epoxide
of the
general formula
0
/ \
R1R2C¨CR3R4
wherein the R groups are hydrogen or aliphatic radicals or which may together
form cyclic groups. The fatty epoxide generally contains at least 8 carbon
atoms to provide a measure of oil solubility. These materials are often
referred
to as borated epoxides, and they are described in detail in U.S. Pat. No.
4,584,115. These are generally prepared by reacting an epoxide with boric acid
or boron trioxide. Borated epoxides thus are not themselves epoxides but are
the boron-containing reaction products of epoxides. The epoxides can be, for
example, commercial mixtures of C14-16 or C14-18 epoxides, which can be pur-
chased from Elf-Atochem or Union Carbide and which can be prepared, in turn,
from the corresponding olefins by known methods. Purified epoxy compounds
such as 1,2-epoxyhexadecane can be purchased from Aldrich Chemicals. The
borated epoxides are prepared by blending the boron source and the epoxide and
heating until the desired reaction has occurred. One suitable borated epoxide
is
the borated epoxide of a predominantly 16 carbon olefin.
[0056] Other types of organic borate esters can be employed, such as
are
known in the art and described, for instance, in U.S. patent 5,883,057 and
U.S.
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patent application 2005 0014656. Such borate esters may be prepared by
reacting of one or more boron compounds with one or more alcohols. In some
embodiments the alcohols contain 6 to 30, or 8 to 24 carbon atoms. The borate
esters may be of various formulas including
(R0)3B or (R0)2B-0¨B(OR)2
Or
R¨
-R\ B/C)
1 1
O\ B/C)
I
O-R
wherein each R is independently hydrogen or a hydrocarbyl group containing 2
to 24 carbon atoms, provided that at least one R is a hydrocarbyl group. The R
groups may also be aliphatic groups of 4 to 6 carbon atoms and in one embodi-
ment all the R groups are aliphatic groups. Among suitable trihydrocarbyl
borates are triethyl borate, tripropyl borate, triisopropyl borate, tributyl
borate,
tripentyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate,
triisooctyl
borate, tridecyl borate, tri (C8_10) borate, tri (C12_15 borate) and oleyl
borate. The
borate esters can be prepared by reacting 1 to 3 moles of alcohol ROH with 1
mole of orthoboric acid H3B03, typically at a temperature of above 100 C in
order to remove of water of condensation.
[0057] The length of the alkyl groups in any such borate esters can be
varied
to obtain desired performance, e.g., solubility or lubricity. Also, partial
borate
esters can be used. Organic borate salts can also be used.
[0058] Suitable boron compounds also include borated amines, which are
generally known from U.S. Patent 4,622,158. Borated amines (including
borated alkoxylated fatty amines) are conveniently prepared by the reaction of
a
boron compound, as described above, with the corresponding amines. The amine
can be a simple fatty amine or a hydroxy-containing amine. Among the amines
useful in preparing the borated amines are commercial alkoxylated fatty amines
known by the trademark BthomeenTM and available from Akzo Nobel. Represen-
tative examples of these materials is EthomeenTM C/12 (bis[2-hydroxyethyl]-
co co -amine); EthomeenTM C/20 (p olyoxyethylene[10] co co amine); BthomeenTM
S/12 (b is [2-hydroxyethyl] soyamine); EthomeenTM T/12 (b is [2-hydroxyethyl] -
tallow-amine); EthomeenTM T/15 (polyoxyethylene-[5]tallowamine);
BthomeenTM 0/12 (bis[2-hydroxyethyl]oleyl-amine); BthomeenTM 18/12 (bis[2-
13
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hydroxyethyl]octadecylamine); and EthomeenTM 18/25 (polyoxyethyl-ene[15]-
octadecylamine). Fatty amines and ethoxylated fatty amines are also described
in U.S. Patent 4,741,848.
[0059] The
boron compound can also be a borated fatty acid ester, e.g., a
borated fatty ester of glycerol. Such material can be prepared by borating a
fatty acid ester of glycerol with boric acid with removal of the water of
reaction.
[0060] In
one embodiment, the boron compound is a borated dispersant, such
as a borated nitrogen-containing dispersant. Typically, a borated dispersant
contains 0.1% to 5%, or 0.5% to 4%, or 0.7% to 3% by weight boron. In one
embodiment, the borated dispersant is a borated acylated amine, such as a
borated succinimide dispersant. Borated dispersants are described in U.S. Pat.
Nos. 3,000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025;
3,533,945; 3,666,662 and 4,925,983. Borated dispersant are prepared by reac-
tion of one or more dispersant with one or more boron compounds. The dispers-
ants include acylated amines, carboxylic esters, Mannich reaction products,
hydrocarbyl substituted amines, ethoxylated amines, and mixtures thereof.
[0061]
Acylated amines include reaction products of one or more carboxylic
acylating agent and one or more amine. The carboxylic acylating agents include
C8_30 fatty acids, C14-20 isoaliphatic acids, C18-44 dimer acids, addition
dicarbox-
ylic acids, trimer acids, addition tricarboxylic acids, and hydrocarbyl
substituted
carboxylic acylating agents. The hydrocarbyl substituted carboxylic acylating
agents are prepared by a reaction of an olefin or polyalkene with an
unsaturated
carboxylic reagent, such as maleic anhydride. The amines may be any of those
described above or a polyamine, such as an alkylenepolyamine or a condensed
polyamine. Acylated amines, their intermediates and methods for preparing the
same are described in U.S. Pat. Nos. 3,219,666; 4,234,435; 4,952,328;
4,938,881; 4,957,649; 4,904,401; and 5,053,152.
[0062]
Carboxylic ester dispersants are prepared by reacting a carboxylic
acylating agent with an organic hydroxy compound and optionally an amine.
Suitable alcohols include polyhydric alcohols, such pentaerythritol.
Carboxylic ester dispersant is described in U.S. Pat. Nos. 3,522,179 and
4,234,435
[0063] In
another embodiment, the dispersant may be a hydrocarbyl-
substituted amine, such as are disclosed in U.S. Pat. Nos. 3,275,554;
3,438,757;
3,454,555; 3,565,804; 3,755,433; and 3,822,289. Typically, hydrocarbyl substi-
tuted amines are prepared by reacting olefins and olefin polymers, with amines
(mono- or polyamines). The amine may be, for example, an alkylenepolyamine.
14
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[0064] In another embodiment, the dispersant may be a Mannich
dispersant.
Mannich dispersants are generally formed by the reaction of an aldehyde, such
as formaldehyde or paraformaldehyde, an amine such as a polyamine (e.g., a
polyalkylenepolyamine), and a substituted hydroxyaromatic compound. The
amounts of the reagents are typically in a mole ratio of hydroxyaromatic com-
pound to formaldehyde to amine of (1:1:1) to (1:3:3). The hydroxyaromatic
compound is generally an alkyl substituted hydroxyaromatic compound. Man-
nich dispersants are described in the following patents: U.S. Pat. No.
3,980,569;
U.S. Pat. No. 3,877,899; and U.S. Pat. No. 4,454,059.
[0065] The boron compound of the present invention can also be a reaction
product of a dialkanolamine and boric acid, further reacted with a Cg to CH
fatty
acid, that is to say, long chain alkenyl amide borates. Specific examples
include
the reaction product of mixed fatty acids such as tall oil acids with
diethanola-
mine and boric acid. (Tall oil acids are commercially available mixtures of
acids, predominantly oleic and linoleic acids, containing also residual rosin
acids or tallow acids.) In yet another embodiment, the boron compound can be
the reaction product of a borating agent such as boric acid with a
condensation
product of a fatty acid (such as stearic acid or isostearic acid) with a
polyamine
such as tetraethylenepentamine. Such condensation products are described, for
instance, in U.S. Patent Application 2005 0014656, and may be in the form of
an amide, am imidazoline, or mixtures thereof.
[0066] In another embodiment, the boron compound can be an alkali or
mixed alkali metal and alkaline earth metal borate. These metal borates can be
hydrated particulate metal borates, which are available commercially and are
known in the art from U.S. Patents. 3,997,454; 3,819,521; 3,853,772;
3,907,601;
3,997,454; and 4,089,790.
[0067] The amount of the boron compound will typically be 0.05 to 2
weight
percent. The desired amount will, naturally, depend to some extent on the
particular boron compound and the amount of boron present in such compound.
Typical amounts, for borated dispersants or other boron-containing materials,
can also be 0.08 to 1 percent or 0.1 to 0.8 percent or 0.15 to 0.7 percent or
0.2 to
0.5 percent. Alternatively expressed, the amount of the boron compound can be
sufficient to provide 40 to 4000 parts per million by weight boron to the
compo-
sition, or 100 to 1000 or 200 to 800 parts per million.
[0068] The lubricating composition of the present invention will also
contain
at least one friction modifier. Since some of the above-described boron com-
pounds can themselves function as friction modifiers, the present compositions
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will normally contain a friction modifier other than or in addition to a boron
compound, such that any of the boron-containing materials will not be counted
as one of the required friction modifiers. Friction modifiers are well known
to
those skilled in the art. A useful list of friction modifiers is included in
U.S.
Pat. No. 4,792,410. Suitable friction modifiers include: (i) fatty phosphites;
(ii)
fatty acid amides; (iii) fatty epoxides; (iv) fatty amines; (v) fatty esters
(e.g,
glycerol esters, that is, fatty acid glycerides); (vi) alkoxylated fatty
amines; (vii)
metal salts of fatty acids; (viii) sulfurized olefins; (ix) fatty
imidazolines; (x)
condensation products of carboxylic acids and polyalkylene-polyamines; (xi)
metal salts of alkyl salicylates; (xii) amine salts of alkylphosphoric acids;
and
mixtures thereof.
[0069] Representatives of each of these types of friction modifiers are
known
and are commercially available. For instance, (i) fatty phosphites, also
referred
to as fatty alkyl hydrogen phosphites, are generally of the formula (R0)2PHO.
Dialkyl phosphite, as shown in the preceding formula, is typically present
with a
minor amount of monoalkyl phosphite of the formula (R0)(HO)PHO. In these
structures, the term "R" is conventionally referred to as an alkyl group. It
is, of
course, possible that the alkyl is actually alkenyl and thus the terms "alkyl"
and
"alkylated," as used herein, will embrace other than saturated alkyl groups
within the phosphite. The phosphite will normally have sufficient hydrocarbyl
groups of sufficient length to render the phosphite substantially oleophilic,
e.g.,
8 to 24 or 12 to 22 or 16 to 20 carbon atoms in each group. The hydrocarbyl
groups can be substantially unbranched. Many suitable phosphites are available
commercially and may be synthesized as described in U.S. Patent 4,752,416. In
one embodiment the fatty phosphite can be formed from oleyl groups, thus
having 18 carbon atoms in each fatty radical.
[0070] The (vi) alkoxylated fatty amines, and (iv) fatty amines
themselves
(such as oleylamine) are generally useful as friction modifiers in this
invention.
Such amines are commercially available, as described above for borated fatty
amines. Among suitable amines are secondary or tertiary amine represented by
the formula R1R2NR3 where RI and R2 are each independently an alkyl group of
at least 6 carbon atoms and R3 is hydrogen, a hydrocarbyl group, a hydroxyl-
containing alkyl group, or an amine-containing alkyl group. These materials
are
described in U.S.Patent No 7,439,213 filed October 19, 2004
[0071] Fatty acid esters, such as those of glycerol (v) can be used as
friction
modifiers. These materials can be prepared by a variety of methods well known
in the art. Many of these esters, such as glycerol monooleate and glycerol
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tallowate, are manufactured on a commercial scale. The esters useful are oil-
soluble and can be prepared from C8 to C22 fatty acids or mixtures thereof
such
as are found in natural products and as are described in greater detail below.
Fatty acid monoesters of glycerol are suitable, and mixtures of mono- and
diesters may also be used. For example, commercial glycerol monooleate may
contain a mixture of 45% to 55% by weight monoester and 55% to 45% diester.
Other fatty esters, such as pentaerythritol monooleate or other partial esters
of
pentaerythritol or other polyols, are also contemplated.
[0072] Fatty acids can be used in preparing the above glycerol esters;
they
can also be used in preparing their (vii) metal salts, (ii) amides, and (ix)
imida-
zolines, any of which can also be used as friction modifiers. Suitable fatty
acids
include those containing 6 to 24 carbon atoms, e.g., 8 to 18. The acids can be
branched or straight-chain, saturated or unsaturated. Suitable acids include 2-
ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic, myristic,
palmitoleic, linoleic, lauric, and linolenic acids, and the acids from the
natural
products tallow, palm oil, olive oil, peanut oil, corn oil, and Neat's foot
oil. A
particularly preferred acid is oleic acid. Suitable metal salts of such acids
include zinc and calcium salts, although zinc salts may be avoided of a low
zinc
composition is desired. Examples are overbased calcium salts and basic oleic
acid-zinc salt complexes which can be represented by the general formula
Zn4Oleate301. Suitable amides include those prepared by condensation with
ammonia or with primary or secondary amines such as diethylamine and di-
ethanolamine.
[0073] Fatty imidazolines (ix) are the cyclic condensation product of
an acid
with a diamine or polyamine such as a polyethylenepolyamine. The imidazoli-
nes are generally represented by the structure
R'
where R is an alkyl group and 12" is hydrogen or a hydrocarbyl group or a
substituted hydrocarbyl group, including ¨(CH2CH2NH)n¨ groups. In one
embodiment the friction modifier can be the condensation product of a C8 to
C24
fatty acid with a polyalkylene polyamine, and in particular, the product of
isostearic acid with tetraethylenepentamine. The condensation products of
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carboxylic acids and polyalkyleneamines (x) may generally be imidazolines or
amides.
[0074] Sulfurized olefins (vii) are well known commercial materials
used as
friction modifiers. They may be prepared in accordance with the detailed
teachings of U.S. Patents 4,957,651 and 4,959,168. Described therein is a
cosulfurized mixture of 2 or more reactants selected from the group consisting
of (1) at least one fatty acid ester of a polyhydric alcohol, (2) at least one
fatty
acid, (3) at least one olefin, and (4) at least one fatty acid ester of a
monohydric
alcohol. Reactant (3), the olefin component, comprises at least one olefin.
This
olefin can be an aliphatic olefin, which usually will contain 4 to 40 carbon
atoms, or 8 to 36 carbon atoms. Terminal olefins, or alpha-olefins, are
suitable,
especially those having from 12 to 20 carbon atoms. Mixtures of these olefins
are commercially available, and such mixtures may be used.
[0075] Metal salts of alkyl salicylates (xi) include calcium and other
salts of
long chain (e.g. C12 to C16) alkyl-substituted salicylic acids.
[0076] Amine salts of alkylphosphoric acids (xii) include salts of
oleyl and
other long chain esters of phosphoric acid, with amines as described herein.
Useful amines in this regard are tertiary-aliphatic primary amines, some of
which are sold under the tradename PrimeneTM. In certain embodiments the
amines are non-branched, since it is believed that amines with non-branched
hydrocarbyl groups may provide superior friction performance.
[0077] The amount of the friction modifier is generally 0.1 to 10
percent by
weight of the lubricating composition, preferably 0.2 to 4 or 0.3 to 2 or 0.5
to
1.5 percent.
[0078] An optional component of the present invention is a viscosity modi-
fier. Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are
well known. Examples of VMs and DVMs are polymethacrylates, polyacry-
lates, polyolefins, styrene-maleic ester copolymers, and similar polymeric
substances including homopolymers, copolymers and graft copolymers. Exam-
pies of commercially available VMs, DVMs and their chemical types include
polyisobutylenes, olefin copolymers, hydrogenated styrene-diene copolymers,
styrene/maleate copolymers, which are dispersant copolymers, polymethacry-
lates, some of which have dispersant properties, olefin-graft-polymethacrylate
polymers, and hydrogenated polyisoprene star polymers. Recent summaries of
viscosity modifiers can be found in U.S. patents 5,157,088, 5,256,752 and
5,395,539. The VMs and/or DVMs may be incorporated into the fully-
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formulated compositions, if desired, at a level of up to 15% by weight or
greater, such as 1 to 12 % or 3 to 10 %.
[0079] Other materials can optionally be included in the compositions
of the
present invention, provided that they are not incompatible with the afore-
mentioned required components or specifications. Such materials include
antioxidants (that is, oxidation inhibitors), including hindered phenolic
antioxi-
dants (e.g., di-t-butylphenol), secondary aromatic amine antioxidants (e.g.,
mono- and/or dinonyl diphenylamines), sulfurized phenolic antioxidants, oil-
soluble copper compounds, phosphorus-containing antioxidants, organic sul-
fides, disulfides, and polysulfides. Other optional components include seal
swell compositions, such as isodecyl sulfolane or phthalate esters, which are
designed to keep seals pliable. Also permissible are pour point depressants,
such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or
/maleate copolymers, and styrene/maleate copolymers. These optional materi-
als 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,
rust inhibitors such as acids and anhydrides (e.g., polyisobutene succinic
acid or
anhydride), dyes, fluidizing agents, odor masking agents, and antifoam agents.
[0080] The formulations of the present invention permit the successful
lubrication of mechanical devices such as farm tractors without the necessity
of
using such zinc salts as zinc dialkyldithiophosphates (ZDPs). While ZDPs
normally provide antioxidancy, anti-corrosion activity, antiwear activity and
other benefits, the compositions of the present invention are typically
substan-
tially free from ZDPs. By "substantially free from ZDP" it is meant that the
formulation is prepared without the intentional addition of any ZDP, or
alterna-
tively, only a very small amount of ZDP. For example, the formulations may
contain less than 0.5 percent by weight ZDP or 0.005 to 0.3 percent or 0.01 to
0.1 or 0.001 to 0.05 percent or less of ZDPs. In certain embodiments, the
formulations are substantially free from zinc compounds of any type, thus
containing, e.g., less than 0.05 percent by weight Zn or 0.0005 to 0.03
percent
or 0.001 to 0.01 or 0.0001 to 0.005 percent or less of Zn.
[0081] The ZDPs (which are present in only a low amount or are substan-
tially absent) may be represented by the formula
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7R80\ s
\ II
Zn
R 0
In this formula, the R8 and R9 groups are hydrocarbyl groups typically alkyl,
cycloalkyl, aralkyl or alkaryl group having 3 to 20 carbon atoms, such as 3 to
16
carbon atoms or up to 13 carbon atoms, e.g., 3 to 12 carbon atoms. The
alcohols
which are used to provide the R8 and R9 groups can be one or more primary
alcohols, one or more secondary alcohols, or a mixture of secondary alcohol
and
primary alcohol. A mixture of two secondary alcohols such as isopropanol and
4-methyl-2-pentanol are often used in preparing ZDPs.
[0082] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the
art. Specifically, it refers to a group having a carbon atom directly attached
to
the remainder of the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), ali-
cyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-
,
and alicyclic-substituted aromatic substituents, as well as cyclic
substituents
wherein the ring is completed through another portion of the molecule (e.g.,
two
substituents together form a ring);
substituted hydrocarbon substituents, that is, substituents containing non-
hydrocarbon groups which, in the context of this invention, do not alter the
predominantly hydrocarbon nature of the substituent (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso,
and sulfoxy);
hetero substituents, that is, substituents which, while having a predomi-
nantly hydrocarbon character, in the context of this invention, contain other
than
carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms
include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl,
furyl,
thienyl and imidazolyl. In general, no more than two, preferably no more than
one, non-hydrocarbon substituent will be present for every ten carbon atoms in
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the hydrocarbyl group; typically, there will be no non-hydrocarbon
substituents
in the hydrocarbyl group.
[0083] 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 present invention; the present invention
encompasses the composition prepared by admixing the components described
above.
EXAMPLES
[0084] Lubricant compositions are prepared from the components listed
in
the following Tables:
Table 1
Example 1: Component Amount, %
Borated succinimide dispersant, including 33% oil, 1.9% B 0.5
(boron source)
Dispersant/corrosion inhibitor comprising DMTD reacted with an 1.0
ester dispersant, containing about 10% DMTD, 49% oil
C12_14 alkyl amine salt of mono and diesters of phosphoric acid 0.4
(extreme pressure agent)
Glycerol monooleate (commercial grade) (friction modifier) 0.5
Oleamide (friction modifier) 0.35
Tall oil acid, product with diethanolamine and boric acid (antiwear 0.2
agent, boron source)
Dibutyl hydrogen phosphite (anti-wear agent) 0.25
Di-t-butyl phenol (antioxidant) 0.2
Calcium alklbenzenesulfonate detergent, including 42% oil, 400 0.8
TBN (detergent)
Oil of lubricating viscosity balance
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Table 2
Component Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8
Borated succininimide dispers- 0.25 0.25 0.25 0.25 0.25 0.25 0.25
ant as in Ex. 1
Oleylamine friction modifier 0.11 0.11 0.11 0.11 0.11 0.11 0.15
Alkyl amine salt of phosphoric 0.5 0.5 0.5 0.5 0.5 0.5
0.45
ester as in Ex. 1
Glycerol monooleate (f.m.) 0.5 0.5 0.5 0.5 0.5 0.5 0.5
(Bis-t-nonyldithio)thiadiazole 0.02 0.02 0.02 0.02 0.02 0.02 0
Heptylhydroxyphenylthio 0.03 0.03 0.03 0.03 0.03 0.03 0.03
substituted thiadiazole (includ-
ing 20% oil)
Antifoam agent (commercial) 0.02 0.02 0.02 0.02 0.02 0.02 0
Tall oil acid product as in Ex 1 0.25 0.25 0.25 0.25 0.25 0.25 0
Various overbased calcium 0.5 0.5 0.5 0.55 0.46
1.1 1.1
sulfonate and/or phenate
detergents, optionally borated
(including 39 to 52% oil)
Oil of lubricating viscosity ---- balance
[00851
Certain of the above identified formulations are tested according to
John Deere published test procedures JDQ 84, 95, and 96, described in greater
detail below. Results are shown in the following table:
Table 3
Test - JDQ- Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8
-84: % flow decrease 1.4 - - 0 - - - -
Cu, ppm drain 13 - - 9 - -
Fe, ppm drain 7 - - 20
- - - -
Assessment Pass -
- Passa - - - -
-95 : Average rating 9.75 9.33 9.83 9.75 9.08 - - -
Spiral bevel Rating 9 9 8 9 8 -
N Sun gear, 1.1M 5.9 6.1 18.5 3.8 24.1 - -
-
S Sun gear, p.m 5.4 4.6 4.3 3.4 20.5 - - -
Assessment Pass
Pass Pass Pass Pass - - -
22
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-96: 10000 cy/ capacity 323 341 ------------------------------
/ variation 69 54 -------------------------------
20000 cy/ capacity 340 345 -------
/variation 34 28 -----------------
30000 cy/ capacity 330 334 -------
/variation 19 25 -----------------
Assessment Pass Pass ---------------------------------
¨: not determined
a : increase in pressure noted
[0086] The JDQ-84 dynamic corrosion test evaluates whether oils, when
contaminated with limited amounts of water, can still serve as suitable fluids
for
pumps found on agricultural equipment. After running the test oil through an
axial piston pump at 82 C, 34.5 MPa, 1.5 L/sec, for 25 hours, 1% water is
added
to the oil and the test continued for an additional 200 hours. Reduction in
flow,
if any, is reported, as well as the presence of Cu and Fe in the drain fluid.
The
samples tested pass this test.
[0087] The JDQ-95 test measures a fluid's antiwear capability as
measured
in tractor spiral bevel and final drive gear sets. A modified front drive axle
assembly is used as the test device. The test is conducted using new spiral
bevel
ring gear and pinions, final drive sun pinions, and associated planet pinion
gears. After 74 hours total testing with the test fluid, the unit is drained
and the
North and South sun pinion gear teeth are measured for wear, reported in tim
(originally measured as micro-inches) and a visual rating on a scale of 1 ¨ 10
is
assigned. A spiral bevel rating of 7 or higher is considered a passing result.
The "average rating" is determined from a total of 6 distress merit ratings on
both the ring gear and drive pinion. The samples examined pass this test.
[0088] The JDQ-96 test assesses the effect of test oil on brake noise
and
brake capacity compared to that of a reference oil. The test is run at 10,000,
20,000, and 30,000 cycles. Results are presented as torque (arbitrary units,
in
thousands) as well as variation in torque, that is, variability, in the same
units,
which is a measure of "chatter." In this test, a reference material exhibits a
value of 333,913 at 30,000 cycles with a variation of 69,178. The samples
tested provide very strong passing values.
[0089] While the lubricant as described herein may be principally used for
lubricating the hydraulic system of a farm tractor, it may also be used for
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lubricating other mechanical devices such as gears, gear boxes, transmissions
for automobiles and other vehicles, including manual transmissions, automatic
transmissions, continuously variable transmissions, traction drives, dual
clutch
transmissions, and transmissions for hybrid (e.g., gasoline and electric)
vehicles,
as well as other devices such as wind turbines and other machinery. The com-
position may be used as, or as a part of, a grease or a non-grease lubricant.
[0090]
Except in the Examples, or where otherwise explicitly indicated, all
numerical quantities in this description specifying amounts of materials, reac-
tion conditions, molecular weights, and the like, are to
be understood as modified by the word "about." Unless otherwise indicated,
each chemical or composition referred to herein should be interpreted as being
a
commercial grade material which may contain the isomers, by-products, deriva-
tives, and other such materials which are normally understood to be present in
the commercial grade. However, the amount of each chemical component is
presented exclusive of any solvent or diluent oil, which may be customarily
present in the commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits set forth
herein may be independently combined. Similarly, the ranges and amounts for
each element of the invention can be used together with ranges or amounts for
any of the other elements. As used herein, the expression "consisting
essentially
of" permits the inclusion of substances that do not materially affect the
basic
and novel characteristics of the composition under consideration.
24
