U.S. patent application number 12/016968 was filed with the patent office on 2009-01-29 for amine tungstates and lubricant compositions.
Invention is credited to Farouk Abi-Karam, Edward T. Hessell, Michel Hourani, Ramanathan Ravichandran, Ingo Roehrs, Alena Yermolenka.
Application Number | 20090029888 12/016968 |
Document ID | / |
Family ID | 40295919 |
Filed Date | 2009-01-29 |
United States Patent
Application |
20090029888 |
Kind Code |
A1 |
Ravichandran; Ramanathan ;
et al. |
January 29, 2009 |
AMINE TUNGSTATES AND LUBRICANT COMPOSITIONS
Abstract
This invention relates to lubricating oil additives, and to
lubricating oil compositions, their method of preparation, and use.
More specifically, this invention relates to several novel
lubricating oil additives and compositions which contain a tungsten
compound and an antioxidant, namely aminic antioxidants such as a
secondary diarylamine or an alkylated phenothiazine. The use of the
tungsten compound with the secondary diarylamine and/or the
alkylated phenothiazine provides improved oxidation and deposit
control to lubricating oil compositions. The lubricating oil
compositions of this invention are particularly useful as crankcase
and transmission lubricants, gear oils and other high performance
lubricant applications.
Inventors: |
Ravichandran; Ramanathan;
(Suffern, NY) ; Abi-Karam; Farouk; (Wilton,
CT) ; Yermolenka; Alena; (Norwalk, CT) ;
Hourani; Michel; (Brookfield, CT) ; Roehrs; Ingo;
(Sandy Hook, CT) ; Hessell; Edward T.; (Fairfield,
CT) |
Correspondence
Address: |
MORGAN & FINNEGAN, L.L.P.
3 WORLD FINANCIAL CENTER
NEW YORK
NY
10281-2101
US
|
Family ID: |
40295919 |
Appl. No.: |
12/016968 |
Filed: |
January 18, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11457144 |
Jul 12, 2006 |
|
|
|
12016968 |
|
|
|
|
60698750 |
Jul 12, 2005 |
|
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|
Current U.S.
Class: |
508/362 |
Current CPC
Class: |
C10M 2215/064 20130101;
C10M 2203/065 20130101; C10M 2207/40 20130101; C10M 2223/045
20130101; C10M 2223/063 20130101; C10M 2219/108 20130101; C10N
2040/04 20130101; C10M 2207/16 20130101; C10M 2219/068 20130101;
C10M 2215/04 20130101; C10N 2010/12 20130101; C10M 2215/042
20130101; C10M 2207/289 20130101; C10N 2030/06 20130101; C10M
2223/047 20130101; C10M 141/08 20130101; C10M 2205/0285 20130101;
C10M 2215/223 20130101; C10N 2030/10 20130101; C10M 2219/044
20130101; C10M 2215/224 20130101; C10M 2215/082 20130101; C10M
2215/086 20130101; C10M 141/06 20130101; C10M 2223/041 20130101;
C07F 11/005 20130101; C10M 141/10 20130101; C10M 2207/026 20130101;
C10M 2205/223 20130101; C10M 2219/068 20130101; C10N 2010/12
20130101; C10M 2223/045 20130101; C10N 2010/04 20130101; C10M
2219/068 20130101; C10N 2010/12 20130101; C10M 2223/045 20130101;
C10N 2010/04 20130101 |
Class at
Publication: |
508/362 |
International
Class: |
C10M 159/18 20060101
C10M159/18 |
Claims
1. A lubricating oil composition providing improved performance
properties, comprising: 1) a lubricating oil; 2) at least one
oil-soluble or oil-dispersible organo amine tungstate; and 3) an
oil-soluble secondary diaryl amine and/or an oil-soluble alkylated
phenothiazine; 4) an ashless friction modifier, a metal-containing
antiwear additive, an ashless antiwear additive, an extreme
pressure agent, a corrosion inhibitor/detergent, a yellow metal
deactivator/copper passivating agent, a pour point depressant or
mixtures thereof, and optionally one or more antioxidant,
dispersant, detergent, friction modifier, antiwear additive,
corrosion inhibitor, metal deactivator, fuel economy agent,
viscosity index improver, or mixtures thereof.
2. The lubricating oil composition of claim 1, wherein said
composition has a performance property that is better than the same
performance property of both a) an analogous composition without
2); and b) an analogous composition without 4).
3. The lubricating oil composition of claim 2, wherein said
performance property is oxidative stability.
4. The lubricating oil composition of claim 2, wherein said
performance property is anti-friction performance.
Description
[0001] This application is a continuation-in-part of U.S. patent
application Ser. No. 11/457,144, filed on Jul. 12, 2006, which
claims the benefit of priority to U.S. Provisional Application
60/698,750, filed on Jul. 12, 2005. The contents of both U.S.
patent application Ser. No. 11/457,144 and U.S. Provisional
Application 60/698,750 are incorporated herein by reference in
their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to lubricating oil additives, and to
lubricating oil compositions, their method of preparation, and use.
More specifically, this invention relates to several novel
lubricating oil additives and compositions which contain a tungsten
compound and an antioxidant, namely aminic antioxidants such as a
secondary diarylamine or an alkylated phenothiazine. The use of the
tungsten compound with the secondary diarylamine and/or the
alkylated phenothiazine provides improved oxidation and deposit
control to lubricating oil compositions. The lubricating oil
compositions of this invention are particularly useful as crankcase
and transmission lubricants, gear oils and other high performance
lubricant applications.
BACKGROUND OF THE INVENTION
[0003] Lubricating oils as used in, for example, the internal
combustion engines of automobiles or trucks are subjected to a
demanding environment during use. This environment results in the
oxidation of the oil catalyzed by the presence of impurities in the
oil, such as iron compounds, and is also promoted by the elevated
temperatures experienced by the oil during use. This catalyzed
oxidation of the oil not only contributes to the formation of
corrosive oxidation products and sludge in the oil but can also
cause the viscosity of the oil to increase or even cause the oil to
solidify. This oxidation of lubricating oils during use is usually
controlled to some extent by the use of antioxidant additives which
may extend the useful life of the oil, for example, by reducing or
preventing unacceptable viscosity increases.
[0004] Aminic antioxidants are antioxidants that contain one or
more nitrogen atoms, such as alkylated diphenyl amines and
phenothiazines. Phenolic antioxidants contain one or more
sterically hindered phenol functionalities, and can be either used
alone or in synergistic combinations with alkylated aminic
antioxidants. The synthesis and uses of phenolic antioxidants,
phenothiazines and aromatic amines have been reported.
Phenothiazine antioxidants have been used as a stand alone
additive, chemically modified or grafted onto the backbone of
polymers.
[0005] There is, however, a continuing need for new antioxidants
and antioxidant systems which offer improved performance and which
are effective at low levels. There are a number of factors which
have contributed to this continuing need. One such factor is that
in recent years internal combustion engines are often operated at
even higher temperatures, which tend to increase the rate of
oxidation and shorten the useful life of the oil. In addition,
there is a strong desire to use cheaper base stocks for lubricating
oil compositions which have inferior resistance to oxidation and
require more efficient and effective antioxidants. There is also a
need for lubricating oils to have a longer in service life span to
support the longer service intervals for motor vehicles. There is
also a desire to find antioxidants and antioxidant systems which
meet the above requirements and at the same time are not
detrimental to other aspects of motor vehicle performance. In this
respect there is a desire for antioxidants which do not contribute
to the phosphorus content of motor vehicle exhausts, as phosphorus
is detrimental to the performance of catalyst based exhaust
purification systems. The trend to reduce phosphorus levels in the
final formulation has led to use of lower levels of zinc
dialkyldithiophosphates, (ZDDP). This has led to an overall
reduction in the levels of antioxidants used in the final
formulation because ZDDP also serves as an antioxidant, in addition
to an extreme-pressure/antiwear additive. The trend to reduce the
total levels of sulfur in lubricants will also lead to lower use
levels of sulfur containing multifunctional antioxidant
extreme-pressure additives such as sulfurized olefins, and other
sulfur containing detergents. In addition some antioxidants, such
as for example diphenylamines, cannot be used at relatively high
concentrations as this may result in sedimentation or deposits in
hot engine areas such as the diesel ring areas in diesel engines.
The invention is concerned with the problem of providing an
improved antioxidant for use in lubricating oils.
SUMMARY OF THE INVENTION
[0006] This invention relates to new tungsten containing
lubricating oil additives, compositions, their method of
preparation, and use. More specifically, this invention relates to
lubricating oil compositions which contain a tungsten compound and
an aminic antioxidant such as alkylated diphenyl amines and/or
alkylated phenothiazines. In addition the composition may
additionally include a sulfur-containing additive such as
sulfurized olefins, sulfurized vegetable oils, sulfurized animal
fats and oils, sulfurized fatty acids, sulfurized synthetic esters,
sulfurized acrylates and sulfurized methacrylates, and sulfurized
succinic acid derivatives, thiadiazole, dithiocarbamate,
dithiophosphate and mixtures thereof. The use of both the tungsten
containing additive and the alkylated secondary diarylamine, and
alternatively further with phenothiazine, provides improved
oxidation and deposit control to lubricating oil compositions. The
lubricating oil compositions of this invention are particularly
useful as crankcase and transmission lubricants, gear oils and
other high performance lubricant applications.
[0007] The antioxidant additive compositions of this invention
result in low levels of deposits and display improved corrosion
inhibition and friction properties.
[0008] This invention provides compositions comprising certain
tungsten containing compounds and antioxidants, namely certain
aromatic amines, either alone or in combination with phenolic
antioxidants, that provide a highly effective regenerative
antioxidant system for use in lubricating oils, especially in
lubricating oils for gasoline and diesel engines. Lubricating oils
as used in the internal combustion engines and transmissions of
automobiles or trucks, gear oils and other high temperature
lubricant applications are subjected to a demanding environment
during use. This environment results in the oxidation of oil which
is catalyzed by the presence of impurities in the oil (such as iron
compounds) and promoted by the elevated temperatures of the oil
during use.
[0009] This invention also provides lubricating oil compositions
with enhanced performance properties that result from suprising
synergistic interactions between the amine tungstates and various
lubricant additives, such as ashless friction modifiers,
metal-containing antiwear additives, ashless antiwear additives,
extreme pressure agents, corrosion inhibitors/detergents, yellow
metal deactivators/copper passivating agents, or mixtures
thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0010] This invention provides compositions containing various
amine tungstate compounds and various amine additives which display
synergistically enhanced friction reducing properties compared to
previously reported amine tungstate-based compositions that include
sulfur or phosphorus compounds and additional metallic
additives.
[0011] It has been found that the combination of (1) an oil soluble
or dispersible tungsten compound and (2) a secondary diarylamine,
such as an alkylated diphenylamine, either alone or in combination
with also preferably an alkylated, phenothiazine, is highly
effective at controlling crankcase lubricant oxidation and deposit
formation. Examples of the types of compounds that may be used in
this invention are described in the following. The tungsten
compound may be used between 20 and 4000 ppm, preferably between 20
to 1000 ppm, based on the amount of tungsten delivered to the
finished lubricating oil. Alkylated phenothiazines, secondary
diarylamines, and other suitable aminic antioxidants may be used at
concentrations ranging from 0.05 to 2.5 wt. % in the finished
lubricant, preferably between 0.1 to 1.0 wt. %. In some embodiments
of the invention, an oil soluble or dispersible molybdenum compound
may be substituted for the tungsten compound. In addition to the
antioxidants of this invention, the lubricating composition may
also contain dispersants, detergents, anti-wear additives including
for example ZDDP, ashless dithiophosphates, ashless
phosphorothioates and thiophosphates, ashless dithiocarbamates,
additional antioxidants if required, friction modifiers, corrosion
inhibitors, anti-foaming additives, pour point depressants and
viscosity index improvers. The lubricant may be prepared from any
paraffinic, naphthenic, aromatic, or synthetic base oil, or
mixtures thereof. In an embodiment, the lubricant may contain
between 250 and 1000 ppm of phosphorus derived from ZDDP and
between 500 and 3000 ppm of calcium from calcium containing
sulfonate detergents or calcium containing phenate detergents. In
this manner, both crankcase and automatic transmission fluid (ATF)
lubricants, gear oils and other high temperature lubricants are
readily prepared.
[0012] Thus, one embodiment of the present invention provides
crankcase and transmission fluid lubricants, gear oils and other
high temperature industrial lubricants and additive package
concentrates, which contain very low levels of phosphorus. More
preferred are lubricant compositions containing zero or essentially
zero phosphorus. By "essentially zero phosphorus" herein is meant
phosphorus levels of less than or equal to about 100 ppm.
[0013] In another embodiment, the lubricant does not contain ZDDP,
but may contain other sources of phosphorus, including ashless
dithiophosphates,
I. Tungsten Compounds of the Current Invention and their
Preparation
1.0 Sulfur- and Phosphorus-Free or Organotungsten Compounds
[0014] Sulfur- and phosphorus-free organotungsten compounds that
are a component of the present invention may be prepared by
reacting a sulfur and phosphorus-free tungsten source with an
organic compound containing an amino group. Examples of sulfur- and
phosphorus-free tungsten sources include tungstic acid, tungsten
trioxide, ammonium ortho tungstate, ammonium para tungstate,
ammonium meta tungstate, sodium tungstate and potassium tungstate.
The amino groups may be monoamines, diamines, or polyamines,
containing primary, secondary or tertiary amine functionalities.
The primary amine structure may be
##STR00001##
which R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen,
C.sub.1-C.sub.25 alkyl, C.sub.2-C.sub.25 alkyl interrupted by
oxygen or sulfur; C.sub.2-C.sub.24 alkenyl, C.sub.4-C.sub.15
cycloalkyl which is unsubstituted or substituted by C.sub.1-C.sub.4
allyl and/or carboxyl; C.sub.5-C.sub.15 cycloalkenyl which is
unsubstituted or substituted by C.sub.1-C.sub.4 alkyl and/or
carboxyl; C.sub.13-C.sub.26 polycycloalkyl, C.sub.7-C.sub.9
phenylalkyl which is unsubstituted or substituted on the phenyl
ring by C.sub.1-C.sub.4 alkyl; --COR.sub.6, a 5- or 6-membered
heterocyclic ring which is unsubstituted or substituted by
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, halogen or carboxyl;
a 5- or 6-membered heterocyclic ring which is benzo-fused and is
unsubstituted or substituted by C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, halogen or carboxyl.
[0015] For example, the secondary amine is of the following
structure
##STR00002##
[0016] wherein R.sup.4 and R.sup.5 are independently hydrogen,
linear, branched, saturated or unsaturated alkyl of 1 to 40 carbon
atoms, cycloalkyl of 5 to 40 carbon atoms, aryl of 6 to 40 carbon
atoms, aralkyl of 7 to 9 carbon atoms, where the aralkyl may be
substituted by alkyl of 1 to 36 carbon atoms.
[0017] The tertiary amine is preferably represented by general
formula
##STR00003##
[0018] wherein R.sub.1, R.sub.2, and R.sub.3 are independently each
a C.sub.1 to C.sub.36 residue that may optionally contain at least
one --O--, --S--, --SO--, --CO.sub.2--, --CO--, or --CON-- moiety,
cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms,
where the aralkyl may be substituted by alkyl of 1 to 36 carbon
atoms.
[0019] Specific examples of the amine tungstates are those derived
from Primene JM-T, tert-octadecylamine, tert-eicosylamine,
1-methyl-1-ethyl octadecyl amine, 1,1-dimethyl octadecylamine,
1-methyl-1-butyl hexadecylamine, 1-triacontylamine, oleyl amine,
lauryl amine, and tall oil amine.
[0020] Polyamines are preferably represented by general formula
##STR00004##
[0021] wherein R.sub.7, R.sub.8 and R.sub.9 are each independently
hydrogen; C.sub.1 to C.sub.25 straight or branched chain alkyl
radicals; C.sub.1 to C.sub.12 alkoxy-(C.sub.6 alkylene) radicals;
C.sub.2 to C.sub.12 alkylamino-C.sub.2 to C.sub.6 alkylene)
radicals; each s can be the same or a different number of from 1 to
6, preferably 2 to 4; and t is a number from 0 to 10, preferably 2
to 7. At least one of R.sub.7, R.sub.8 and R.sub.9 must be
hydrogen.
[0022] Suitable amines include: 1,2-diaminoethane;
1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane;
polyethylene amines such as diethylene triamine; triethylene
tetramine; tetraethylene pentamine; polypropylene amines such as
1,2-propylene diamine; di-(1,2-propylene)triamine;
di(1,3-propylene)-triamine; N,N-dimethyl-1,3-diaminopropane;
N,N-di-(2-aminoethyl) ethylene diamine;
N,N-di(2-hydroxyethyl)-1,3-propylene diamine;
3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris
hydroxymethylaminomethane (THAM); diisopropanol amine; diethanol
amine; triethanol amine; amino morpholines such as
N-(3-amino-propyl) morpholine; etc.
[0023] In order to improve solubility of the organotungsten product
in base oils and finished oils, it is useful for the
mono-substituted diamine to have a high hydrocarbon character. For
example, the diamine can be represented by the following general
structure:
##STR00005##
where x is 1 or 2, and R is a hydrocarbon-containing group
containing a minimum of about 6 carbon atoms, and up to 24 carbon
atoms. R can be aliphatic or aromatic. R, in addition to the
minimum of about 6 carbon atoms, may also contain oxygen, but
preferably R does not include sulfur or additional nitrogen. It is
preferred that R contains a minimum of 10 carbon atoms in order to
further improve the organotungsten product solubility in base oil.
The most preferred R contains oxygen in addition to the carbons,
such as where R is an alkyloxyalkylene group. Where R represents an
alkyloxyalkylene group, R can be represented by the structure
--X.sub.1--O--X.sub.2, where X.sub.1 is an alkylene of 2, 3 or 4
carbons and preferably is propylene or ethylene, and X.sub.2 is an
alkyl moiety having 3 to 30 carbon atoms, more preferably an alkyl
moiety having 7 to 20 carbon atoms, and where X.sub.2 can be a
straight or branched, saturated or partially unsaturated
hydrocarbon chain.
[0024] Examples of some mono-substituted diamines that may be used
include phenylaminopropylamine, hexylaminopropylamine,
benzylaminopropylamine, octylaminopropylamine,
octylaminoethylamine, dodecylaminopropylamine,
dodecylaminoethylamine, hexadecylaminopropylamine,
hexadecylaminoethylamine, octadecylaminopropylamine,
octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,
octyloxypropyl-1,3-diaminopropane,
decyloxypropyl-1,3-diaminopropane,
isodecyloxypropyl-1,3-diaminopropane,
dodecyloxypropyl-1,3-diaminopropane,
tetradecyloxypropyl-1,3-diaminopropane,
isodecyloxypropyl-1,3-diaminopropane,
isododecyloxypropyl-1,3-diaminopropane, isotridecyloxypropyl-1,3-di
a-minopropane. Mono-substituted diamines derived from fatty acids
may also be used. Examples include N-coco alkyl-1,3-propanediamine
(Duomeen C), N-tallow alkyl-1,3-propanediamine (Duomeen T), and
N-oleyl-1,3-propanediamine (Duomeen OL), all obtained from Akzo
Nobel.
[0025] Other useful amine compounds include alicyclic diamines such
as 1,4-di-(aminomethyl) cyclohexane, and heterocyclic nitrogen
compounds such as imidazolines, and N-aminoalkyl piperazines of the
general formula:
##STR00006##
[0026] wherein p.sub.1 and p.sub.2 are the same or different and
each is an integer from 1 to 4, and e, f and o are the same or
different and each is an integer from 1 to 3.
##STR00007##
in which n=2 or 3, m=1 or 2, R.sup.a, R.sup.b and R.sup.c are
identical or different, and represent hydrogen, alkyl, or
substituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,
heterocyclics, ether, thioether, halogen, --N(R).sub.2,
polyethylene polyamines, nitro groups, keto groups, ester groups,
or carbonamide groups, alkyl substituted with the various
functional groups described above, and T represents alkyl,
alkylene, aryl, aralkyl, cycloalkyl or heterocyclic radical,
substituted if desired with halogen, nitro groups, alkyl groups,
alkoxy groups or amino groups, and, when m=1, T represents
hydrogen. Salts of the above structures include carboxylic
including aliphatic, aromatic and poly carboxylic, carbonic,
sulfonic and phosphoric acid salts.
[0027] R.sup.a, R.sup.b, R.sup.c are independently hydrogen, alkyl,
alkenyl, or alkoxy of 1 to 36 carbons, cycloalkyl of 6 to 32
carbons, alkylamino of 1 to 36 carbon atoms, cycloalkyl of 5 to 12
carbon atoms, phenyl, hydroxyalkyl, or hydroxycycloalkyl of 1 to 20
carbon atoms, methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to
9 carbon atoms, where the aryl group of the aralkyl is further
substituted by alkyl of 1 to 36 carbon atoms. When m=2, T is
alkylene of 1 to 12 carbons or arylene of 6 to 10 carbons, or a
plurality of radicals being able to be joined, containing hetero
atoms also by hetero atoms such as O, N or S, if desired.
[0028] Preferred imidazoline structures are where R is a long chain
alkyl up to 18 carbon atoms, m=1 and R.sup.c is one of
2-hydroxyethyl, or 2-aminoethyl or 2-amido ethyl substituents.
[0029] Examples of such amines include 2-pentadecyl imidazoline,
aminoethyl oleyl imidazoline and N-(2-aminoethyl) piperazine.
2.0 Sulfur-Containing Organotungsten Compounds
[0030] The sulfur-containing organotungsten compounds of the
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an amino group and one or more sulfur sources. Non-limiting
examples of sulfur sources include carbon disulfide, hydrogen
sulfide, sodium sulfide and elemental sulfur. Alternatively, the
sulfur-containing tungsten compounds may be prepared by the
reaction of a sulfur-free tungsten source with an amino group or
thiuram group and optionally a second sulfur source. Examples of
sulfur- and phosphorus-free tungsten sources include tungstic acid,
tungsten trioxide, ammonium ortho tungstate, ammonium meta
tungstate, ammonium paratungstate, sodium tungstate, potassium
tungstate and tungsten halides. The amino groups may be monoamines,
diamines, or polyamines. As an example, the reaction of tungsten
trioxide with a secondary amine and carbon disulfide produces
tungsten dithiocarbamates.
[0031] An alternate approach includes the reaction of sulfur- and
phosphorus-free tungsten sources including tungstic acid, tungsten
trioxide, ammonium ortho tungstate, ammonium meta tungstate,
ammonium paratungstate, sodium tungstate, and potassium tungstate
with a sulfurated amine precursor.
[0032] Examples of sulfur containing organotungsten compounds
appearing in patents and patent applications include the following
all of which are hereby incorporation by reference in their
entirety:
[0033] Compounds prepared by the reaction of divalent metal
tungstates with dithiocarbamates in an alkaline sodium sulfide
and/or sodium hydrogen sulfide solution as described in WO
2004/043910 A2.
[0034] Compounds prepared by the reaction of a primary amine with a
CS.sub.2 or COS, and subsequent reaction of the dithiocarbamic acid
produced with a tungsten containing compound, as described in U.S.
Pat. No. 4,846,983.
[0035] Sulfurized oxymetalorganophosphorodithioates, and sulfurized
oxymetal dithiocarbamates as described in U.S. Pat. No. 4,529,526
wherein the metal is tungsten.
[0036] Tungsten dithiocarbamates are illustrated with the following
structure,
##STR00008##
where R.sup.6 and R.sup.7 are independently the same or different
and are selected from H and C.sub.1 to C.sub.30 and are an alkyl
group, a cycloalkyl group, an aryl group or an alkaryl group, with
the proviso that at least one of R.sup.6 or R.sup.7 is H for at
least one of the thiocarbamate groups, and at least one of R.sup.6
or R.sup.7 is hydrocarbyl for each of the thiocarbamate groups, M
is W, X is O or S, b.sub.1 is at least 1, a.sub.1 is at least 1
depending on the oxidation state of M, c.sub.1 is at least 1
depending on the oxidation state of M and d.sub.1 is 0 or at least
1 depending on the oxidation state of M. Generally, a.sub.1 and
b.sub.1 will range from 1 to about 5, c.sub.1 will range from 1 to
about 6 and d.sub.1 will be 0 or range from 2 to about 10. In a
preferred embodiment, a.sub.1 will be 1 or 2, b.sub.1 will be 1 or
2, c.sub.1 will be 1 or 2, and d.sub.1 will be 0 or 2.
[0037] Sulfurized oxymetal organophosphorodithioates are
illustrated with the following structure.
##STR00009##
wherein M is tungsten, R.sup.8 and R.sup.9 may be the same or
different, each of R.sup.8 and R.sup.9 contains from 1 to 30 carbon
atoms and are selected from the group consisting of an alkyl group,
a cycloalkyl group, an aryl group, and a alkylaryl group; and
x.sub.1 and y.sub.1 are positive real numbers satisfying the
equation: x.sub.1+y.sub.1=4.
3. Silicon Containing Organotungsten Compounds
[0038] The silicon containing organotungsten compound of this
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an amino silane. Examples of sulfur- and phosphorus-free tungsten
sources include tungstic acid, tungsten trioxide, ammonium ortho
tungstate, ammonium meta tungstate, ammonium paratungstate, sodium
tungstate and potassium tungstate.
[0039] Particularly useful are aminosilanes of the formula
##STR00010##
in which R.sub.17 and R.sub.18 are independently hydrogen,
C.sub.1-C.sub.25 alkyl, 2-hydroxyethyl, C.sub.3-C.sub.25 alkyl
which is interrupted by oxygen or sulfur; C.sub.2-C.sub.24 alkenyl
or
##STR00011##
[0040] R.sub.19 is C.sub.1-C.sub.25 alkyl, C.sub.2-C.sub.25 alkyl
which is interrupted by oxygen or sulfur; hydroxyl,
C.sub.1-C.sub.18 alkoxy or C.sub.2-C.sub.24 alkenyl, R.sub.20 is
hydroxyl, C.sub.1-C.sub.18 alkoxy or C.sub.2-C.sub.18 alkoxy which
is interrupted by oxygen or sulfur; and, if a and b together are 1,
three radicals R.sub.20 together are N(CH.sub.2CH.sub.2O--).sub.3,
X.sub.3 is C.sub.1-C.sub.18 alkylene, C.sub.2-C.sub.20 alkylidene,
C.sub.7-C.sub.20 phenylalkylidene, C.sub.5-C.sub.8 cycloalkylene,
phenylene or naphthylene which is unsubstituted or substituted by
C.sub.1-C.sub.4 alkyl; or is C.sub.4-C.sub.18 alkylene which is
interrupted by oxygen, sulfur or
##STR00012##
[0041] R.sub.21 is hydrogen or C.sub.1-C.sub.8 alkyl with the
proviso that two nitrogen atoms are not attached to the same carbon
atom, a is 1 or 2, and b is 0, 1 or 2.
[0042] Examples of amino silanes useful in this invention include,
aminopropyl triethoxysilane, aminopropyl trimethoxy silane,
aminopropyl diethoxysilane, aminopropyl methyldimethoxysilane,
aminoethyl aminopropyltrimethoxysilane, aminoethyl
aminopropylmethyldimethoxysilane, aminoethyl
aminopropylmethyldiethoxysilane, aminoethyl
aminomethyltriethoxysilane, aminoethyl
aminomethylmethyldiethoxysilane,
diethylenetriaminopropyltrimethoxysilane,
diethylenetriaminopropyltriethoxysilane,
diethylenetriaminopropylmethyldimethoxysilane,
diethylenetriaminopropylmethyldiethoxysilane,
diethylenetriaminomethyldimethoxysilane,
cyclohexylaminopropyltrimethoxysilane,
cyclohexylaminopropyltriethoxysilane,
cyclohexylaminopropylmethyldimethoxysilane,
cyclohexylaminopropylmethyldiethoxysilane,
cyclohexylaminomethyltriethoxysilane,
cyclohexylaminomethylmethyldiethoxysilane,
hexanediaminomethyltriethoxysilane,
phenylaminomethyltrimethoxysilane,
phenylaminopropyltrimethoxysilane,
phenylaminopropyltriethoxysilane, phenylaminopropyl
methyldimethoxysilane, phenylaminopropyl methyldiethoxysilane,
phenylaminomethylmethyldimethoxysilane,
phenylaminomethylmethyldiethoxysilane,
phenylaminomethyltriethoxysilane,
diethylaminomethyltriethoxysilane,
diethylaminomethyltrimethoxysilane,
diethylaminopropyltrimethoxysilane, diethylaminopropyl
methyldimethoxysilane, diethylaminopropyl methyldiethoxysilane,
dimethylaminopropyl methyldiethoxysilane,
(diethylaminomethyl)methyldiethoxysilane,
methylaminopropyltrimethoxysilane, bis((3-triethoxysilyl)propyl)
amine, piperazinylpropylmethyldimethoxysilane,
piperazinylpropylmethyldiethoxysilane,
piperazinylmethylmethyldiethoxysilane,
morpholinylpropyltrimethoxysilane,
morpholinylpropyltriethoxysilane,
morpholinylpropylmethyldimethoxysilane,
morpholinylpropylmethyldiethoxysilane,
morpholinylmethyltriethoxysilane,
morpholinylmethylmethyldiethoxysilane,
diaminomethylmethyldiethoxysilane,
dimethyldiaminopropylmethyldiethoxysilane,
dimethyldiaminomethylmethyldiethoxysilane,
aminohexylaminomethyltrimethoxysilane,
aminohexylaminopropyltrimethoxysilane,
octanoylaminopropyltriethoxysilane,
methylaminopropyltrimethoxysilane,
methylaminopropylmethyldiethoxysilane,
methylaminomethylmethyldiethoxysilane,
ethylaminopropylmethyldiethoxysilane,
ethylaminomethylmethyldiethoxysilane.
[0043] Also useful are silicone amines commercially available from
Siltech under the Silamine tradename. The structures mentioned in
the U.S. Pat. No. 5,378,787, which is hereby incorporation by
reference in its entirety, are also useful and are as follows:
##STR00013##
[0044] where a and b are integers ranging from 0 to 2000.
4.0 Organoamine Tungstates with Ethoxylated Amines
[0045] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an ethoxylated amine. Examples of sulfur- and phosphorus-free
tungsten sources include tungstic acid, tungsten trioxide, ammonium
ortho tungstate, ammonium meta tungstate, ammonium paratungstate,
sodium tungstate and potassium tungstate.
[0046] Particularly useful ethoxylated fatty amines are
##STR00014##
[0047] where Z is straight or branched chain alkyl of from about 8
to 26 carbon atoms, alkoxy alkyl of 4 to 22 carbon atoms, n=2 to
about 50, and x.sub.1=from about 1 to about 49.
[0048] Specific embodiments include, isopropyloxypropyl amine,
isohexyloxypropyl amine, 2-ethylhexyloxypropyl amine,
octyl/decyloxy propyl amine, isodecyloxypropyl amine,
isododecyloxypropyl amine, dodecyl/tetradecyloxypropyl amine,
isotridecyloxypropyl amine, tetradecyloxypropyl amine, linear
alkoxypropyl amine, octadecyl/hexadecyloxypropyl amine,
octyl/decyloxy propyl-1,3-diaminopropane, isodecyloxypropyl
1,3-diaminopropane, isododecyloxypropyl 1,3-diaminopropane,
dodecyl/tetradecyloxypropyl 1,3-diaminopropane,
isotridecyloxypropyl 1,3-diaminopropane, tetradecyloxypropyl
1,3-diaminopropane, bis-(2-hydroxyethyl) isodecyloxypropyl amine,
bis-(2-hydroxyethyl) isotridecyloxypropyl amine,
bis-(2-hydroxyethyl) linear alkoxypropyl amine,
bis-(2-hydroxyethyl) soya amine, bis-(2-hydroxyethyl) tallow amine,
poly (5) oxyethylene isodecyloxypropyl amine, poly (5) oxyethylene
isotridecyloxypropyl amine, N-tallow-poly (3)
oxyethlene-1,3-diaminopropane, isodecyloxypropyl
bis-(2-hydroxyethyl)methyl ammonium chloride, isotridecyloxypropyl
bis-(2-hydroxyethyl)methyl ammonium chloride, octadecyl
bis-(2-hydroxyethyl)methyl ammonium chloride, isotridecyloxypropyl
poly (5) oxyethylene methyl ammonium chloride, monosoya methyl
ammonium chloride, tallow diamine diquaternary coco poly (15)
oxyethylene methyl ammonium chloride and trimethyl stearyl ammonium
chloride.
5. Organoamine Tungstates with Alkylated Phenothiazine
[0049] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an alkylated phenothiazine. Examples of sulfur- and phosphorus-free
tungsten sources include tungstic acid, tungsten trioxide, ammonium
ortho tungstate, ammonium meta tungstate, ammonium paratungstate,
sodium tungstate and potassium tungstate.
[0050] An alkylated phenothiazine suitable for this invention must
be oil soluble or dispersible and correspond to the general formula
below where the substituents R.sub.11-R.sub.14 could contain
heteroatoms,
##STR00015##
[0051] R.sub.11 and R.sub.12 are hydrogen or together can form a
fused six-member aromatic ring.
[0052] One of R.sub.13 and R.sub.14 is hydrogen and the other is
C.sub.2-C.sub.30 alkyl, cyclo-C.sub.5-C.sub.12 alkyl,
--C.sub.2-C.sub.4 alkyl, .alpha.-C.sub.1-C.sub.2 alkylbenzyl or
.alpha.,.alpha.-dimethylbenzyl; or both R.sub.13 and R.sub.14 are
C.sub.2-C.sub.30 alkyl, cyclo-C.sub.5-C.sub.12
alkyl-C.sub.2-C.sub.4 alkyl, .alpha.-C.sub.1-C.sub.2 alkylbenzyl or
.alpha.,.alpha.-dimethylbenzyl, if R.sub.11 and R.sub.12 hydrogen;
or R.sub.13 is hydrogen and R.sub.14 is C.sub.2-C.sub.30 alkyl,
cyclo-C.sub.5-C.sub.12 alkyl-C.sub.2-C.sub.4 alkyl,
.alpha.-C.sub.1-C.sub.2 alkylbenzyl or
.alpha.,.alpha.-dimethylbenzyl, if R.sub.11 and R.sub.12 together
form a fused six-member aromatic ring.
[0053] R.sub.15 is hydrogen, C.sub.1-C.sub.12 alkyl, benzyl, allyl,
methallyl, phenyl or a group --CH.sub.2SR.sub.4, where R.sub.4 is
C.sub.4-C.sub.18 alkyl, --CH.sub.2CH.sub.2COO(C.sub.4-C.sub.18
alkyl), or an alkylene, aralkylene bridging two phenothiazine
moieties.
[0054] Typical examples of alkylphenothiazine include but are not
limited to monotetradecylphenothiazine, ditetradecylphenothiazine,
monodecylphenothiazine, didecylphenothiazine
monononylphenothiazine, dinonylphenothiazine, monoctylphenothiazine
and dioctylphenothiazine.
6. Organoamine Tungstates with Alkylated Diarylamine
[0055] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an alkylated diarylamine. Examples of sulfur- and phosphorus-free
tungsten sources include tungstic acid, tungsten trioxide, ammonium
ortho tungstate, ammonium meta tungstate, ammonium paratungstate,
sodium tungstate and potassium tungstate.
[0056] The diarylamines that may optionally be used and that have
been found to be useful in this invention are well known
antioxidants and there is no known restriction on the type of
diarylamine that can be used. Preferably, the diarylamine has the
formula:
##STR00016##
[0057] Wherein R.sub.22 and R.sub.23 each independently represents
a substituted or unsubstituted aryl group having from 6 to 30
carbon atoms. Illustrative of substituents for the aryl group
include aliphatic hydrocarbon groups such as alkyls having from 1
to 30 carbon atoms, hydroxy groups, halogen radicals, carboxylic
acid or ester groups, or nitro groups. The aryl is preferably
substituted or unsubstituted phenyl or naphthyl, particularly
wherein one or both of the aryl groups are substituted with at
least one alkyl having from 4 to 30 carbon atoms, preferably from 4
to 18 carbon atoms, most preferably from 4 to 12 carbon atoms. It
is preferred that one or both aryl groups be substituted, e.g.
mono-alkylated diphenylamine, di-alkylated diphenylamine, or
mixtures of mono- and di-alkylated diphenylamines.
[0058] R.sub.24 is hydrogen, C.sub.1-C.sub.12 alkyl, benzyl, allyl,
methallyl, phenyl or a group --CH.sub.2SR.sub.5, where R.sub.5 is
C.sub.4-C.sub.18 alkyl, --CH.sub.2CH.sub.2COO(C.sub.4-C.sub.18
alkyl), or an alkylene, aralkylene bridging two amine moieties.
[0059] The diarylamines used in this invention can be of a
structure other than that shown in the above formula that shows but
one nitrogen atom in the molecule. Thus the diarylamine can be of a
different structure provided that at least one nitrogen has 2 aryl
groups attached thereto, e.g. as in the case of various diamines
having a secondary nitrogen atom as well as two aryl groups bonded
to one of the nitrogen atoms.
[0060] The diarylamines used in this invention should be soluble in
the formulated crankcase oil package. Examples of some diarylamines
that may be used in this invention include diphenylamine; alkylated
diphenylamines; 3-hydroxydiphenylamine;
N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine;
monobutyldiphenylamine; dibutyldiphenylamine;
monooctyldiphenylamine; dioctyldiphenylamine;
monononyldiphenylamine; dinonyldiphenylamine;
monotetradecyldiphenylamine; ditetradecyldiphenylamine;
phenyl-alpha-naphthylamine; monooctyl phenyl-alpha-naphthylamine;
phenyl-beta-naphthylamine; monoheptyldiphenylamine;
diheptyldiphenylamine; p-oriented styrenated diphenylamine; mixed
butyloctyldiphenylamine; and mixed octylstryryldiphenylamine, and
mixtures thereof. Examples of commercial diarylamines include, for
example, IRGANOX.TM. L06, IRGANOX.TM. L57 (mixed butyloctyl
diphenyl amine) and I IRGANOX.TM. L67 from Ciba Specialty
Chemicals; NAUGALUBE.TM. AMS, NAUGALUBE.TM. 438, NAUGALUBE.TM.
438R, NAUGALUBE.TM. 438L, NAUGALUBE.TM. 500, NAUGALUBE.TM. 640,
NAUGALUBE.TM. 680, and NAUGARD PANA.TM. from Crompton Corporation;
GOODRITE.TM. 3123, GOODRITE.TM. 3190X36, GOODRITE.TM. 3127,
GOODRITE.TM. 3128, GOODRITE.TM. 3185X1, GOODRITE.TM. 3190.times.29,
GOODRITE.TM. 3190.times.40, GOODRITE.TM. 3191 and GOODRITE.TM. 3192
from Noveon Specialty Chemicals; VANLUBE.TM. DND, VANLUBE.TM. NA,
VANLUBE.TM. PNA, VANLUBE.TM. SL (mixed octylstyryl diphenylamine),
VANLUBE.TM. SLHP, VANLUBE.TM. SS, VANLUBE.TM. 81, VANLUBE.TM. 848,
and VANLUBE.TM. 849, VANLUBE.TM. 961 (mixed butyloctyl diphenyl
amine) from R. T. Vanderbilt Company Inc, LUBRIZOL.TM. 5150A &
C from LUBRIZOL.TM., and NA-LUBE.TM. AO-140 (mixed butyloctyl
diphenyl amine), NA-LUBE.TM. AO-150 (mixed octylstyryl
diphenylamine), from King Industries.
7. Organoamine Tungstates with Amines Containing Other Stabilizing
Moieties
[0061] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an alkylated triazole, or a phenolic antioxidant. Examples of
sulfur- and phosphorus-free tungsten sources include tungstic acid,
tungsten trioxide, ammonium ortho tungstate, ammonium meta
tungstate, ammonium paratungstate, sodium tungstate and potassium
tungstate.
[0062] A triazole having the formula
##STR00017##
[0063] wherein R.sub.25 is hydrogen or a C.sub.1-C.sub.20 alkyl
residue; R.sub.26 and R.sub.27 are the same or different and each
is H, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 alkenyl,
C.sub.5-C.sub.12 cycloalkyl, C.sub.7-C.sub.13 aralkyl,
C.sub.6-C.sub.10 aryl or R.sub.26 and R.sub.27, together with the
nitrogen atom to which they are attached, form a 5-, 6- or
7-membered heterocyclic residue or R.sub.26 and R.sub.27 is each a
residue of formula:
R.sub.28X.sub.3[(alkylene)O]n.sub.1(alkylene)-
wherein X.sub.3 is O, S or N(R.sub.28), R.sub.28 is hydrogen or
C.sub.1-C.sub.20 alkyl, "alkylene" is a C.sub.1-C.sub.12 alkylene
residue and n.sub.1 is an integer from 0 to 6;
[0064] R.sub.30 is hydrogen, C.sub.1-C.sub.20 alkyl or
C.sub.6-C.sub.10 aryl or C.sub.7-C.sub.18 alkyl phenyl; and
R.sub.31 is hydrogen, C.sub.1-C.sub.20 alkyl or a residue
--CH.sub.2NR.sub.26R.sub.27 wherein R.sub.26 and R.sub.27 have
their previous significance or
[0065] R.sub.26 has its previous significance and R.sub.27 is a
residue of formula
##STR00018##
[0066] or R.sub.27 is a residue of formula as defined above and
R.sub.26 is a residue of formula
-[alkylene]n.sub.1-N(R.sub.32)-A-[N(R.sub.32).sub.2]m.sub.1)
in which m.sub.1 is 0 or 1, and when m.sub.1 is 0, A is a residue
of formula (I,) and when m.sub.1 is 1, A is alkylene or
C.sub.6-C.sub.10 arylene, and alkylene and n.sub.1 have their
previous significance and R.sub.32 is a residue of formula I, as
defined above.
[0067] A substituted phenol of the formula
##STR00019##
wherein, R.sub.42, are independently alkyl of 1 to 18 carbon atoms,
cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by
alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 9 carbon atoms or
said aralkyl substituted by alkyl of 1 to 18 carbon atoms. R.sub.26
and R.sub.27 are the same or different and each is H,
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 alkenyl, C.sub.5-C.sub.12
cycloalkyl, C.sub.7-C.sub.13 aralkyl, C.sub.6-C.sub.10 aryl or
R.sub.26 and R.sub.27, together with the nitrogen atom to which
they are attached, form a 5-, 6- or 7-membered heterocyclic residue
or R.sub.26 and R.sub.27 is each a residue of formula:
R.sub.28X.sub.3[(alkylene)O]n.sub.1(alkylene)-)
wherein X.sub.3 is O, S or N(R.sub.28), R.sub.28 is hydrogen or
C.sub.1-C.sub.20 alkyl, "alkylene" is a C.sub.1-C.sub.12 alkylene
residue and n.sub.1 is 0 or an integer from 1 to 6. 8.0 Organoamine
Tungstates from Polyamine Salts
[0068] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
an amine, carboxylate, sulfonate, dithiophosphate, naphthenates,
phosphonates, phenoxy alkanoates, and N-acyl sarcosinates. Examples
of sulfur- and phosphorus-free tungsten sources include tungstic
acid, tungsten trioxide, ammonium ortho tungstate, ammonium meta
tungstate, ammonium paratungstate, sodium tungstate and potassium
tungstate.
[0069] A soluble acid salt of a carboxylic acid, a mono or
disulfonic acid, naphthenic acid, dithiophosphoric acid or alkyl
phosphonic acid with a polyamine is prepared in the first step and
subsequently reacted with various tungsten sources as outlined
above to the desired tungstate, which are oil soluble
[0070] In certain embodiments, long-chain monocarboxylic acids
suitable for use in the present invention preferably contain at
least 8, and more preferably at least 12, and up to 100 carbon
atoms. In preferred embodiments, examples of suitable acids for use
in the present invention include fatty acids such as coconut acid,
hydrogenated coconut acid, menhaden acid, hydrogenated menhaden
acid, tallow acid, hydrogenated tallow acid, and soya acid.
Additional long-chain carboxylic acids that may be used include
lauric acid, myristic acid, palmitic acid, stearic acid, isostearic
acid, arachidic acid, behenic acid, erucic acid, oleic acid,
linoleic acid, and linolenic acid. Mixtures of acids may also be
used and are sometimes preferred. For example, commercial oleic
acid is actually a mixture of many fatty acids ranging in carbon
chain length from 14 to 20.
[0071] The sulfonic acid of the current invention could be one of
the following:
[0072] 1) An alkylated aryl sulfonic acid selected from the group
consisting of
##STR00020##
wherein R.sup.10 is H or an alkyl group containing up to 20 carbon
atoms, and x is an integer from 0 to 2.
[0073] An alkylated aryl sulfonic acid selected from the group
consisting of
##STR00021##
wherein R.sub.51, R.sub.52, R.sub.53 and R.sub.54 are individually
selected from the group consisting of hydrogen or essentially
linear hydrocarbyl groups having about 9 to about 22 carbon atoms;
and wherein l, m, n and p are integers from 0 to 4 and the sum of
l+m+n+p is at least 1; and wherein R.sub.51, R.sub.52, R.sub.53,
and R.sub.54 is a hydrogen where either l, m, n, or p is 0.
[0074] 2) An alkylated aryl disulfonic acid selected from the group
consisting of
##STR00022##
and structure II
##STR00023##
wherein each of R.sup.11 and R.sup.12 is the same or different and
is a linear or branched alkyl group with 6 to 16 carbons, y is 0 to
3, z is 0 to 3 with the proviso that y+z is 1 to 4, n is 0 to 3, B
is a divalent moiety selected from the group consisting of
--C(R.sup.13)(R.sup.14)--, wherein each of R.sup.13 and R.sup.14 is
H or independently a linear or branched alkyl group of 1-4 carbons
and n is 1; --C(.dbd.O)--, wherein n is 1; --O-- wherein n is 1;
--S--, wherein n is 1 to 3; and --SO.sub.2--, wherein n is 1;
[0075] Suitable sulfonic acids include alkane sulfonic acid,
aralkyl sulfonic acid, including dodecyl benzene sulfonic acid,
didodecyl benzenesulfonic acid, and sulfonic acids derived from
various hydrocarbon feedstock. Examples of other suitable sulfonic
acids include mono-, di-, and poly-alkylated naphthalenesulfonic
acids, e.g., dinonyl napthalene sulfonic acid, didodecyl
naphthalene sulfonic acids, diphenyl ether sulfonic acid,
napthalene disulfide sulfonic acid, dicetyl thianthrene sulfonic
acid, dialauryl betanaphthol sulfonic acid, dicapryl
nitronaphthalene sulfonic acid, unsaturated paraffin wax sulfonic
acid, hydroxy substituted paraffin wax sulfonic acid, tetraamylene
sulfonic acid, mono- and poly-chlorosubstituted paraffin wax
sulfonic acid, nitrosoparaffin wax sulfonic acid, cycloaliphatic
sulfonic acid such as lauryl-cyclohexyl sulfonic acid, mono- and
poly-wax-substituted cyclohexyl sulfonic acid, and the like.
Suitable acid components include naphthenic acid, which encompasses
a mixture of monobasic acids of cycloparaffins which are derived
from either cyclopentane or cyclohexane and cyclopentane and a
great variety of homologs and higher molecular weight analogs.
Conventionally, the acids of commercial mixtures of naphthenic
acids have molecular weights in the range of from about 180 to 350.
Suitable acid components include dihydrocarbylphosphoric acids,
dihydrocarbyldithiophosphoric acids, and
dihydrocarbylmonothiophosphoric acids, from the following
##STR00024##
wherein Y.sub.1 and Y.sub.2 are each independently of the other S
or O R.sup.15 and R.sup.16 are each independently of the other H,
C.sub.3-C.sub.18 alkyl, C.sub.5-C.sub.12 cycloalkyl,
C.sub.5-C.sub.6 cycloalkylmethyl, C.sub.9-C.sub.10
bicycloalkylmethyl, C.sub.9-C.sub.10 tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.24-alkylphenyl, or R.sup.15 and R.sup.16 together are
the group of the partial formula:
##STR00025##
R.sup.15 and R.sup.16 defined as C.sub.9-C.sub.10
bicycloalkylmethyl are typically decalinylmethyl. R.sup.15 and
R.sup.16 defined as C.sub.9-C.sub.10 tricycloalkylmethyl are
preferably a group of formula:
##STR00026##
R.sup.15 and R.sup.16 are preferably i-propyl, i-butyl,
2-ethylhexyl, octyl phenyl or oleyl. Suitable acid components also
include an alkyl phenoxyalkanoic acid of the formula
##STR00027##
wherein R.sup.q, R.sup.r, R.sup.s, R.sup.t and R.sup.u are, each
independently of the other, hydrogen or C.sub.1-C.sub.20 alkyl and
Q is a divalent C.sub.1-C.sub.20 hydrocarbon radical, saturated or
unsaturated, selected from the group consisting of
##STR00028##
Suitable acid components also include an N-acyl sarcosine
derivative of the formula
##STR00029##
wherein the acyl group R.sup.t--C(.dbd.O)-- is the residue of a
fatty acid having 10 to 20 carbon atoms.
[0076] The polyamine compounds which may be employed in the
production of the oil-soluble tungstate can be any suitable
polyamine compound. In order to improve solubility of the organo
tungstate product in base oils and finished oils, it is important
for the mono-substituted diamine to have a high hydrocarbon
character. For example, the diamine can be represented by the
following general structure:
##STR00030##
where x is 1 or 2, and R is a hydrocarbon-containing group
containing a minimum of about 6 carbon atoms and up to 24 carbon
atoms. R can be aliphatic or aromatic. R, in addition to the
minimum of about 6 carbon atoms, may also contain oxygen, but
preferably R does not include sulfur or additional nitrogen. It is
preferred that R contains a minimum of 10 carbon atoms in order to
further improve the organotungsten product solubility in base oil.
The most preferred R contains oxygen in addition to the carbons,
such as where R is an alkyloxyalkylene group. Where R represents an
alkyloxyalkylene group, R can be represented by the structure
--X.sub.1--O--X.sub.2, where X.sub.1 is an alkylene of 2, 3 or 4
carbons and preferably is propylene or ethylene, and X.sub.2 is an
alkyl moiety having 3 to 30 carbon atoms, more preferably an alkyl
moiety having 7 to 20 carbon atoms, and where X.sub.2 can be a
straight or branched, saturated or partially unsaturated
hydrocarbon chain. The use of a diamine including an R group
represented by --X.sub.1--O--X.sub.2 as defined herein in the
reaction process makes it possible to maximize the level of
tungsten incorporation levels in the oil soluble reaction product
while performing the process without the use of volatile organic
processing solvents.
[0077] Examples of some mono-substituted diamines that may be used
include phenylaminopropylamine, hexylaminopropylamine,
benzylaminopropylamine, octylaminopropylamine,
octylaminoethylamine, dodecylaminopropylamine,
dodecylaminoethylamine, hexadecylaminopropylamine,
hexadecylaminoethylamine, octadecylaminopropylamine,
octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,
octyloxypropyl-1,3-diaminopropane,
decyloxypropyl-1,3-diaminopropane,
isodecyloxypropyl-1,3-diaminopropane,
dodecyloxypropyl-1,3-diaminopropane,
tetradecyloxypropyl-1,3-diaminopropane,
isodecyloxypropyl-1,3-diaminopropane,
isododecyloxypropyl-1,3-diaminopropane,
isotridecyloxypropyl-1,3-dia-minopropane. Mono-substituted diamines
derived from fatty acids may also be used. Examples include N-coco
alkyl-1,3-propanediamine (Duomeen C), N-tallow
alkyl-1,3-propanediamine (Duomeen T), and
N-oleyl-1,3-propanediamine (Duomeen OL), all obtained from Akzo
Nobel.
[0078] Especially preferred polyamine compounds include diamine
1,3-diaminopropane having an alkyl moiety selected from the group
consisting of N-coco, N-tallow, N-soya and N-oleyl. The compound
1,3-diaminopropane can be represented by the general formula
R--NH(C.sub.3H.sub.6NH.sub.2) wherein R is an alkyl group
representing the coco, tallow, soya or oleyl moiety.
[0079] Other suitable polyamines include tetraethylene pentamine
and similar polyamine types containing primary and/or secondary
amine groups. Further suitable polyamines can be represented by the
general formulas R(NH.sub.2).sub.2 and R
NH--(C.sub.3H.sub.6NH.sub.2).sub.2 wherein R is an alkyl radical
derived from the dimerization of a C.sub.18 unsaturated fatty acid.
Another group of suitable polyamine compounds can be represented by
the general formula R--N--(C.sub.3H.sub.6NH.sub.2).sub.2 wherein R
is an alkyl radical derived from tallow, oleyl and lauryl fatty
acids.
Other useful amine compounds include alicyclic diamines such as
1,4-di-(aminomethyl)cyclohexane, and heterocyclic nitrogen
compounds such as imidazolines, and N-aminoalkyl piperazines of the
general formula:
##STR00031##
wherein p.sub.1 and p.sub.2 are the same or different and each is
an integer from 1 to 4, and e, f and o are the same or different
and each is an integer from 1 to 3.
##STR00032##
in which n=2 or 3, m=1 or 2, R.sup.a, R.sup.b and R.sup.c are
identical or different, and represent hydrogen, alkyl, or
substituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,
heterocyclics, ether, thioether, halogen, --N(R).sub.2,
polyethylene polyamines, nitro groups, keto groups, ester groups,
or carbonamide groups, alkyl substituted with the various
functional groups described above, and T represents alkyl,
alkylene, aryl, aralkyl, cycloalkyl or heterocyclic radical,
substituted if desired with halogen, nitro groups, alkyl groups,
alkoxy groups or amino groups, and, when m=1, represents also
hydrogen. Salts of the above structures include carboxylic
including aliphatic, aromatic and poly carboxylic, carbonic,
sulfonic and phosphoric acid salts. R.sup.a, R.sup.b, R.sup.c are
independently hydrogen, alkyl, alkenyl or alkoxy of 1 to 36
carbons, cycloalkyl of 6 to 32 carbons or alkylamino of 1 to 36
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl,
hydroxyalkyl or hydroxycycloalkyl of 1 to 20 carbon atoms,
methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbon
atoms, where the aryl group of the aralkyl group is further
substituted by alkyl of 1 to 36 carbon atoms. When m=2, T is
alkylene of 1 to 12 carbons or arylene of 6 to 10 carbons, or a
plurality of radicals being able to be joined, containing hetero
atoms also by hetero atoms such as O, N or S, if desired. Preferred
imidazoline structures are where R is a long chain alkyl up to 18
carbon atoms, m=1 and R.sup.c is one of 2-hydroxyethyl, or
2-aminoethyl or 2-amido ethyl substituents. Examples of such amines
include 2-pentadecyl imidazoline, aminoethyl oleyl imidazoline and
N-(2-aminoethyl) piperazine.
[0080] Ammonium molybdates derived from these precursor salts that
are a component of the present invention may also be prepared from
a molybdenum source. The process for preparing the organoammonium
molybdates of the invention involves the use of one of several
molybdenum sources including molybdenum trioxide, ammonium
paramolybdate or ammonium heptamolybdate. A preferred molybdenum
source is molybdenum trioxide. The use of molybdenum trioxide
results in effective molybdenum incorporation into the organic
ligand made by the aforementioned first process step, and it
produces a reaction mass by the completion of the second step that
does not require filtration.
9.0 Organoammonium Tungstates from the Reaction Product of Mono
Carboxylic Acid with Diamines, Fatty Oil with Diamines and
Naphthenyl, Alkylphenoxyalkanoyl and N-Sarcosoyl Polyamines.
[0081] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
the reaction product of a mono carboxylic acid, fatty oil,
vegetable oil, triglyceride or glycerol esters of fatty acids,
naphthenic acid, alkylphenoxy alkanoic acid or N-acyl sarcosine
with a mono substituted alkylene diamine. Examples of sulfur- and
phosphorus-free tungsten sources include tungstic acid, tungsten
trioxide, ammonium ortho tungstate, ammonium meta tungstate,
ammonium paratungstate, sodium tungstate and potassium
tungstate.
[0082] In certain embodiments, examples of long-chain
monocarboxylic acids suitable for use in the present invention
preferably contain at least 8, and more preferably at least 12, and
up to 100 carbon atoms. In preferred embodiments, examples of
suitable acids for use in the present invention include fatty acids
such as coconut acid, hydrogenated coconut acid, menhaden acid,
hydrogenated menhaden acid, tallow acid, hydrogenated tallow acid,
and soya acid. Additional long-chain carboxylic acids that may be
used include lauric acid, myristic acid, palmitic acid, stearic
acid, isostearic acid, arachidic acid, behenic acid, erucic acid,
oleic acid, linoleic acid, and linolenic acid. Mixtures of acids
may also be used and are sometimes preferred. For example,
commercial oleic acid is actually a mixture of many fatty acids
ranging in carbon chain length from 14 to 20.
[0083] Examples of preferred fatty or vegetable oils that may be
used in the process of the present invention include groundnut oil,
coconut oil, linseed oil, palm kernel oil, olive oil, cottonseed
oil, grapeseed oil, corn oil, canola oil, palm oil, peanut oil,
safflower seed oil, sesame seed oil, caster oil, rapeseed oil (low
or high erucic acids), soyabean oil, sunflower oil, herring oil,
sardine oil, lard, menhaden oil, hazel nut oil, walnut oil, and
tallow, and mixtures thereof. These fatty or vegetable oils can
include those compounds generally known as triglycerides, which
have the general structure as shown below
##STR00033##
where R', R'', or R''' independently represent saturated or
unsaturated aliphatic hydrocarbon groups having from about 8 to
about 22 carbon atoms, and preferably are hydrocarbon chains having
about 12 to about 22 carbon atoms. Mono- and diglycerides, either
separately or in mixtures with one or more triglycerides, are also
useful as fatty or vegetable oils in the present invention, in
which the R', R'', or R''' groups present have the same above
meaning.
[0084] Suitable acid components include naphthenic acid, which
encompasses a mixture of monobasic acids of cycloparaffins which
are derived from either cyclopentane or cyclohexane and
cyclopentane and a great variety of homologs and higher molecular
weight analogs. Conventionally, the acids of commercial mixtures of
naphthenic acids have molecular weights in the range of from about
180 to 350.
[0085] Suitable acid components also include an alkyl
phenoxyalkanoic acid of the formula
##STR00034##
wherein R.sup.q, R.sup.r, R.sup.s, R.sup.t and R.sup.u are, each
independently of the other, hydrogen or C.sub.1-C.sub.20 alkyl and
Q is a divalent C.sub.1-C.sub.20 hydrocarbon radical, saturated or
unsaturated, selected from the group consisting of
##STR00035##
Suitable acid components also include an N-acyl sarcosine
derivative of the formula
##STR00036##
wherein the acyl group R.sup.t--C(.dbd.O)-- is the residue of a
fatty acid having 10 to 20 carbon atoms.
[0086] The polyamine compounds which may be employed in the
production of the oil-soluble sulfonate tungstate can be any
suitable polyamine compound. In order to improve solubility of the
organo tungstate product in base oils and finished oils, it is
important for the mono-substituted diamine to have a high
hydrocarbon character. For example, the diamine can be represented
by the following general structure:
##STR00037##
where x is 1 or 2, and R is a hydrocarbon-containing group
containing a minimum of about 6 carbon atoms and up to 24 carbon
atoms. R can be aliphatic or aromatic. R, in addition to the
minimum of about 6 carbon atoms, may also contain oxygen, but
preferably R does not include sulfur or additional nitrogen. It is
preferred that R contains a minimum of 10 carbon atoms in order to
further improve the organotungsten product solubility in base oil.
The most preferred R contains oxygen in addition to the carbons,
such as where R is an alkyloxyalkylene group. Where R represents an
alkyloxyalkylene group, R can be represented by the structure
--X.sub.1--O--X.sub.2, where X.sub.1 is an alkylene of 2, 3 or 4
carbons and preferably is propylene or ethylene, and X.sub.2 is an
alkyl moiety having 3 to 30 carbon atoms, more preferably an alkyl
moiety having 7 to 20 carbon atoms, and where X.sub.2 can be a
straight or branched, saturated or partially unsaturated
hydrocarbon chain. The use of a diamine including an R group
represented by --X.sub.1--O--X.sub.2 as defined herein in the
reaction process makes it possible to maximize the level of
tungsten incorporation levels in the oil soluble reaction product
while performing the process without the use of volatile organic
processing solvents.
[0087] Examples of some mono-substituted diamines that may be used
include phenylaminopropylamine, hexylaminopropylamine,
benzylaminopropylamine, octylaminopropylamine,
octylaminoethylamine, dodecylaminopropylamine,
dodecylaminoethylamine, hexadecylaminopropylamine,
hexadecylaminoethylamine, octadecylaminopropylamine,
octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,
octyloxypropyl-1,3-diaminopropane,
decyloxypropyl-1,3-diaminopropane,
isodecyloxypropyl-1,3-diaminopropane,
dodecyloxypropyl-1,3-diaminopropane,
tetradecyloxypropyl-1,3-diaminopropane,
isodecyloxypropyl-1,3-diaminopropane,
isododecyloxypropyl-1,3-diaminopropane,
isotridecyloxypropyl-1,3-diaminopropane. Mono-substituted diamines
derived from fatty acids may also be used. Examples include N-coco
alkyl-1,3-propanediamine (Duomeen C), N-tallow
alkyl-1,3-propanediamine (Duomeen T), and
N-oleyl-1,3-propanediamine (Duomeen OL), all obtained from Akzo
Nobel. Especially preferred are polyamine compounds including
diamine 1,3-diaminopropane having an alkyl moiety selected from the
group consisting of N-coco, N-tallow, N-soya and N-oleyl. The
compound 1,3-diaminopropane can be represented by the general
formula R--NH(C.sub.3H.sub.6NH.sub.2) wherein R is an alkyl group
representing the coco, tallow, soya or oleyl moiety.
[0088] Other suitable polyamines include tetraethylene pentamine
and similar polyamine types containing primary and/or secondary
amine groups. Further suitable polyamines can be represented by the
general formulas R(NH.sub.2).sub.2 and R
NH--(C.sub.3H.sub.6NH.sub.2).sub.2 wherein R is an alkyl radical
derived from the dimerization of a C.sub.18 unsaturated fatty acid.
Another group of suitable polyamine compounds can be represented by
the general formula R--N--(C.sub.3H.sub.6NH.sub.2).sub.2 wherein R
is an alkyl radical derived from tallow, oleyl and lauryl fatty
acids.
10.0 Organoammonium Tungstates from the Reaction Product of
Substituted Succinic Anhydrides with Polyamines
[0089] The organoamine tungstate compounds useful in the present
invention may be prepared by a variety of methods. One method
involves reacting a sulfur and phosphorus-free tungsten source with
the reaction product of substituted succinic anhydrides with
polyamines. Examples of sulfur- and phosphorus-free tungsten
sources include tungstic acid, tungsten trioxide, ammonium ortho
tungstate, ammonium meta tungstate, ammonium paratungstate, sodium
tungstate and potassium tungstate.
[0090] Succinimides of the current invention may be represented by
the following general formula.
##STR00038##
where R.sup.18 is a C6 to C30 isomerized alkenyl group, represented
by:
##STR00039##
(where g and h are integers whose sum is from 1 to 25), or its
fully saturated alkyl analog, R.sup.17 is an alkyl group, aryl
group, containing one or more nitrogen atom and other heteroatoms.
The succinimides of the present invention are those produced from
succinic anhydrides substituted with isomerized alkenyl groups or
their fully saturated alkyl analogs. Preparation of isomerized
alkenyl succinic anhydrides is described in, for example, U.S. Pat.
No. 3,382,172, hereby incorporated by reference in its entirety.
Often these materials are prepared by heating alpha-olefins with
acidic catalysts to migrate the double bond to form an internal
olefin. This mixture of olefins (2-enes, 3-enes, etc.) is then
thermally reacted with maleic anhydride.
[0091] Typically olefins from C.sub.6 (e.g. 1-hexene) to C.sub.30
(e.g. 1-tricosane) are used. Suitable isomerized alkenyl succinic
anhydrides of structure (1)
##STR00040##
include isodecylsuccinic anhydride (x+y=5), iso-dodecylsuccinic
anhydride (x+y=7), iso-tetradecylsuccinic anhydride (x+y=9),
iso-hexadecylsuccinic anhydride (x+y=11), iso-octadecylsuccinic
anhydride (x+y=13) and isoeicosylsuccinic anhydride (x+y=15).
Preferred materials are isohexadecylsuccinic anhydride and
iso-octadecylsuccinic anhydride.
[0092] The materials produced by this process contain one double
bond (alkenyl group) in the alkyl chain. The alkenyl substituted
succinic anhydrides may be easily converted to their saturated
alkyl analogs by hydrogenation.
[0093] Suitable primary and secondary amines useful to produce the
succinimides are represented by structure
##STR00041##
where R.sup.25, R.sup.26, and R.sup.27 are independently selected
from the group consisting of H, C.sub.1 to C.sub.25 straight or
branched chain alkyl radicals, C.sub.1 to C.sub.12 alkoxy radicals;
C.sub.2 to C.sub.6 alkylene radicals; u is an integer from 1 to 6,
preferably 2 to 4; and v is an integer from 0 to 10, preferably
from 1 to 4.
[0094] Bis succinimides of the current invention may be represented
by the following general formula
##STR00042##
wherein, R.sup.21 and R.sup.22 may be identical or different from
each other and are each hydrocarbon groups having 5 or more
carbons; R.sup.23 is a divalent hydrocarbon group having 1 to 5
carbons; R.sup.24 is a hydrogen atom or a hydrocarbon group having
1 to 20 carbons; and n is an integer in the range of 0 to 10. In
the above general formula, R.sup.21 and R.sup.22 may be the same as
each other or different from each other, and are each saturated or
unsaturated hydrocarbon groups having 5 or more carbons, preferably
5 to 40 carbons. Examples of hydrocarbon groups include pentyl
groups, hexyl groups, heptyl groups, octyl groups, nonyl groups,
decyl groups, dodecyl groups, tridecyl groups, tetradecyl groups,
pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl
groups, nonadecyl groups, oleyl groups and other hydrocarbon groups
having up to 40 carbons. Preferred hydrocarbon groups include
straight chain hydrocarbon groups having between 8 and 25 carbons.
In the above general formula, R.sup.23 is a divalent hydrocarbon
group having 1 to 5 carbons, preferably an alkylene group having 2
or 3 carbons.
[0095] In the above general formula, R.sup.24 is a hydrogen atom or
a hydrocarbon group having 1 to 20 carbons. Examples of hydrocarbon
groups include alkyl groups having 1 to 20 carbons; alkenyl groups
having 2 to 20 carbons; cycloalkyl groups having 6 to 20 carbons;
and aryl groups having 6 to 20 carbons. The aryl groups may have an
alkyl group having 1 to 12 carbons. Hydrogen atoms and alkyl groups
having 1 to 10 carbons are particularly preferred as R.sup.24.
Groups having a number of (i.e. 1 to 5 of each) amino groups and/or
amide bonds in their structure can be used as the above-described
hydrocarbon groups.
[0096] The amino groups are represented by --NH-- or --NH.sub.2;
and the amide bonds are represented by
##STR00043##
They may be bonded with the carbons of the hydrocarbon group at an
arbitrary position.
[0097] The bis succinimides of the present invention are those
produced from succinic anhydrides substituted with isomerized
alkenyl groups or their fully saturated alkyl analogs, and
polyamines. Suitable polyamines are saturated amines of the general
formula:
##STR00044##
where R.sup.25, R.sup.26, and R.sup.27 are independently selected
from the group consisting of H, C.sub.1 to C.sub.25 straight or
branched chain alkyl radicals, C.sub.1 to C.sub.12 alkoxy radicals;
C.sub.2 to C.sub.6 alkylene radicals; u is an integer from 1 to 6,
preferably 2 to 4; and v is an integer from 0 to 10, preferably
from 1 to 4.
[0098] Non-limiting examples of suitable polyamine compounds
include: 1,6-diaminohexane, diethylene triamine, triethylene
tetramine, tetraethylene pentamine, and pentaethylene hexamine.
Useful mixtures of polyamines having from 5 to 7 nitrogen atoms per
molecule are available from Dow Chemical Co. as Polyamine H,
Polyamine 400 and Polyamine E-300.
[0099] Polyoxyalkylene amines are also useful in this invention and
are shown as structure
H.sub.2N-alkylene-(--O-alkylene-)u.sub.1-NH.sub.2
where u.sub.1 is an integer of from 1 to 10. The polyamines have
molecular weights from about 100 to 500. The preferred
polyoxyalkylene polyamines include polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines.
Commercial polyoxyalkylene amines are available from Jefferson
Chemical Co. sold under the trade name "Jeffamines D-230, D-400,
D-1000, T-430," etc.
[0100] Organo ammonium molybdates derived from these precursor
succinimides according to the invention may also be prepared from
one of various molybdenum sources. The process for preparing the
organoammonium molybdates of the invention involves the use of one
of several molybdenum sources including molybdenum trioxide,
ammonium paramolybdate or ammonium heptamolybdate. A preferred
molybdenum source is molybdenum trioxide. The use of molybdenum
trioxide results in effective molybdenum incorporation into the
organic ligand made by the aforementioned first process step, and
it produces a reaction mass by the completion of the second step
that does not require filtration. There is no particular
restriction on the type of secondary diarylamine used in the
invention as an antioxidant. Preferably, the secondary diarylamine
antioxidant has the general formula:
##STR00045##
wherein R.sub.22 and R.sub.23 each independently represents a
substituted or unsubstituted aryl group having from 6 to 30 carbon
atoms. Illustrative of substituents for the aryl include aliphatic
hydrocarbon groups such as alkyl having from about 1 to 20 carbon
atoms, hydroxy, carboxyl or nitro, e.g., an alkaryl group having
from 7 to 20 carbon atoms in the alkyl group. The aryl is
preferably substituted or unsubstituted phenyl or naphthyl,
particularly wherein one or both of the aryl groups are substituted
with an alkyl such as one having from 4 to 30 carbon atoms,
preferably from 4 to 18 carbon atoms, most preferably from 4 to 9
carbon atoms. It is further preferred that one or both aryl groups
be substituted, e.g. mono alkylated diphenylamine, dialkylated
diphenylamine, or mixtures of mono- and di-alkylated
diphenylamines.
[0101] The secondary diarylamines used in this invention can be of
a structure other than that shown in the above formula which shows
but one nitrogen atom in the molecule. Thus, the secondary
diarylamine can be of a different structure provided that at least
one nitrogen has 2 aryl groups attached thereto, e.g., as in the
case of various diamines having a secondary nitrogen atom as well
as two aryls on one of the nitrogens. The secondary diarylamines
used in this invention preferably have antioxidant properties in
lubricating oils, even in the absence of the tungsten compound.
[0102] It is preferred that the oil-soluble secondary aromatic
amines are diphenylamines of general formula:
##STR00046##
wherein D.sub.1 and D.sub.2 may be the same or different and each
independently represents a hydrocarbyl radical as hereinbefore
defined. It is preferred that D.sub.1 and D.sub.2 are C.sub.1 to
C.sub.28 aliphatic hydrocarbyl radicals. E and F may be the same or
different and may equal 0, 1, 2 or 3. It is preferred that E and F
are the same and that they equal 1. It is also preferred that the
diphenylamines have a nitrogen content of between 2.5 and 5% by
weight. It is preferred that D.sub.1 and D.sub.2 are located in the
meta or para positions relative to the amino substitution in the
aromatic rings of the diphenylamines. Examples of suitable
diphenylamines include di-octyldiphenylamine,
t-pentyldiphenylamine, diisobornyldiphenylamine,
didecyldiphenylamine, didodecyldiphenylamine, dihexyldiphenylamine,
di-t-butyldiphenylamine, di-t-octyldiphenylamine, dinonylamine,
dibutyldiphenylamine, distyryldiphenylamine. Other suitable
diphenylamines include di-substituted derivatives wherein the
D.sub.1 and D.sub.2 are different and independently represent
hydrocarbyl radicals, such as t-butyl, t-octyl, styryl, n-butyl or
n-octyl for example. Some of these diphenylamines are commercially
available and are sold under the trademarks, VANLUBE.TM. DND,
NAUGALUBE.TM. 438L, PEARSALL.TM. OA502, LUBRIZOL.TM. 5150A,
VANLUBE.TM. SL, NAUGALUBE.TM. 680, INGANOX.TM. L-57 and VANLUBE.TM.
848. VANLUBE.TM. DND, NAUGALUBE.TM. 438L, PEARSALL.TM. OA502 and
LUBRIZOL.TM. 5150A nominally have structures as represented by the
above formula wherein D.sub.1 and D.sub.2 are C.sub.9 hydrocarbyl
groups and E=F=1. VANLUBE.TM. SL and NAUGALUBE.TM. 680 nominally
have structures as represented by above formula wherein D.sub.1 and
D.sub.2 are either one of C.sub.4, C.sub.8 or styryl hydrocarbyl
groups and E=F=1; these are mixed diphenyl amines. IRGANOX.TM. L-57
and VANLUBE.TM. 848 nominally have structures as represented by
above formula wherein D.sub.1 and D.sub.2 are either one of t-butyl
or t-octyl groups and E=F=1.
[0103] Other secondary diarylamines used in this invention soluble
in the formulated crankcase oil package include: diphenylamine;
various alkylated diphenylamines; 3-hydroxydiphenylamine;
N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine;
monobutyldiphenylamine; dibutyldiphenylamine;
monooctyldiphenylamine; monononyldiphenylamine;
dinonyldiphenylamine; monotetradecyldiphenylamine;
ditetradecyldiphenylamine; phenyl-alpha-naphthylamine; monooctyl
phenyl-alpha-naphthylamine; phenyl-beta-naphthylamine;
monoheptyldiphenylamine; diheptyldiphenylamine; p-oriented
styrenated diphenylamine; mixed butyloctyldiphenylamine; and mixed
octylstryryldiphenylamine, and mixtures thereof. Other examples of
commercial diarylamines include, for example, IRGANOX.TM. L06,
IRGANOX.TM. L57 (mixed butyloctyl diphenyl amine) and IRGANOX.TM.
L67 from Ciba Specialty Chemicals; NAUGALUBE.TM. AMS, NAUGALUBE.TM.
438, NAUGALUBE.TM. 438R, NAUGALUBE.TM. 438L, NAUGALUBE.TM. 500,
NAUGALUBE.TM. 640, NAUGALUBE.TM. 680, and NAUGARD.TM. PANA from
Crompton Corporation; GOODRITE.TM. 3123, GOODRITE.TM.
3190.times.36, GOODRITE.TM. 3127, GOODRITE.TM. 3128, GOODRITE.TM.
3185X1, GOODRITE.TM. 3190.times.29, GOODRITE.TM. 3190.times.40,
GOODRITE.TM. 3191 and GOODRITE.TM. 3192 from Noveon Specialty
Chemicals; VANLUBE.TM. DND, VANLUBE.TM. NA, VANLUBE.TM. PNA,
VANLUBE.TM. SL (mixed octylstyryl diphenylamine), VANLUBE.TM. SLHP,
VANLUBE.TM. SS, VANLUBE.TM. 81, VANLUBE.TM. 848, and VANLUBE.TM.
849, VANLUBE.TM. 961 (mixed butyloctyl diphenyl amine) from R. T.
Vanderbilt Company Inc, LUBRIZOL.TM. 5150A & C from
LUBRIZOL.TM., and NA-LUBE.TM. AO-140 (mixed butyloctyl diphenyl
amine), NA-LUBE.TM. AO-150 (mixed octylstyryl diphenylamine), from
King Industries.
[0104] The concentration of the secondary diarylamine in the
lubricating composition can vary from about 0.075 to 2.5 wt %,
depending upon the application. A practical diarylamine use range
in the lubricating composition is from about 750 parts per million
to 5,000 parts per million (i.e. 0.075 to 0.5 wt %), preferably
from 1,000 to 4,000 parts per million (ppm) and even more
preferably from about 1,200 to 3,000 ppm
[0105] Preferably, the quantity of tungsten is relation to the
quantity of the secondary amine should be within a certain ratio.
The quantity of tungsten should be about 0.020 to 0.6 parts by
weight for each part by weight of the amine in the lubricating oil
composition. Preferably, this ratio will be from about 0.040 to
0.40 parts of the tungsten per part of the amine and particularly
about 0.05 to 0.3 parts of the tungsten per part of the amine. The
total quantity of tungsten and amine can be provided by one or more
than one tungsten or amine compound.
[0106] An alkylated phenothiazine suitable for this invention is
preferably oil soluble or dispersible and preferably corresponds to
the general formula below where the substituents R.sub.11-R.sub.14
could contain heteroatoms,
##STR00047##
R.sub.11 and R.sub.12 are hydrogen or together form a fused
six-membered aromatic ring; one of R.sub.13 and R.sub.14 is
hydrogen and the other is C.sub.2-C.sub.30 alkyl,
cyclo-C.sub.5-C.sub.12 alkyl, --C.sub.2-C.sub.4 alkyl,
.alpha.-C.sub.1-C.sub.2 alkylbenzyl or
.alpha.,.alpha.-dimethylbenzyl; or both R.sub.13 and R.sub.14 are
C.sub.2-C.sub.30 alkyl, cyclo-C.sub.5-C.sub.12
alkyl-C.sub.2-C.sub.4 alkyl, .alpha.-C.sub.1-C.sub.2 alkylbenzyl or
.alpha.,.alpha.-dimethylbenzyl, if R.sub.11 and R.sub.12 hydrogen;
or R.sub.13 is hydrogen and R.sub.14 is C.sub.2-C.sub.30 alkyl,
cyclo-C.sub.5-C.sub.12 alkyl C.sub.2-C.sub.4 alkyl,
.alpha.-C.sub.1-C.sub.2 alkylbenzyl or
.alpha.,.alpha.-dimethylbenzyl, if R.sub.11 and R.sub.12 together
form a fused six-membered aromatic ring, R.sub.15 is hydrogen,
C.sub.1-C.sub.12 alkyl, benzyl, allyl, methallyl, phenyl or a group
--CH.sub.2SR.sub.4, where R.sub.4 is C.sub.4-C.sub.18 alkyl,
--CH.sub.2CH.sub.2COO(C.sub.4-C.sub.18 alkyl), or an alkylene,
aralkylene bridging two phenothiazine moieties.
[0107] Typical examples of alkylphenothiazine include but are not
limited to monotetradecylphenothiazine, ditetradecylphenothiazine,
monodecylphenothiazine, didecylphenothiazine
monononylphenothiazine, dinonylphenothiazine, monoctylphenothiazine
and dioctylphenothiazine.
[0108] The antioxidant lubrication compositions of the present
invention may optionally contain additional friction modifiers,
antioxidants and/or copper corrosion inhibitors. Embodiments of
friction modifiers which may optionally be added can be found for
example in U.S. Pat. Nos. 4,792,410 and 5,110,488, which are
incorporated herein by reference in their entirety and include
fatty phosphites, fatty acid amides, fatty epoxides, borated fatty
epoxides, fatty amines, glycerol esters, borated glycerol esters,
alkoxylated fatty amines, borated alkoxylated fatty amines, metal
salts of fatty acids, sulfurized olefins, fatty imidazolines and
mixtures thereof.
[0109] Embodiments of antioxidants which may optionally be added
include hindered phenolic antioxidants, secondary aromatic amine
antioxidants, sulfurized phenolic antioxidants, oil-soluble copper
compounds, phosphorus-containing antioxidants, organic sulfides,
disulfides and polysulfides.
[0110] Embodiments of copper corrosion inhibitors which may
optionally be added include thiazoles, triazoles and thiadiazoles.
Example embodiments of such compounds include benzotriazole,
tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole,
2-mercapto benzothiazole, 2,5-dimercapto-1,3,4-thiadiazole,
2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles,
2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles,
2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and
2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles.
[0111] The organotungsten compound, alkylated diphenylamine and
sulfur containing compound can either be added individually to a
base oil to form the lubricating composition of the invention or
they can be premixed to form a composition which can then be added
to the base oil. The resulting lubricating composition preferably
comprises a major amount (i.e. at least 90% by weight) of base oil
and a minor amount (i.e. less than 10% by weight) of the additive
composition.
[0112] In another aspect the invention provides for a lubricating
oil composition which comprises lubricating oil and a lubricating
oil additive comprising the combination of an oil-soluble tungsten
compound and at least one oil-soluble aromatic amine. The
concentration of the lubricating oil additive is typically in the
range of 0.01 to about 15% by weight based on the total weight of
the composition and is preferably from about 0.1 to about 7% by
weight.
[0113] Suitable lubricating oils for use in preparing the
lubricating composition include those oils which are conventionally
employed as crankcase lubricating oils for internal combustion
engines and those which may be employed as power transmitting
fluids such as automatic transmission fluids, hydraulic fluids, or
gear lubricants.
[0114] The lubricating oil may be a synthetic oil such as for
example alkylesters of dicarboxylic acids, polyglycols and
alcohols, polyalphaolefins, alkylbenzenes, alkyl naphthalenes,
organic esters of phosphoric acids, or polysilicone oils. The
lubricating oil may be a natural oil including mineral oils which
may vary widely as to their crude source e.g. whether paraffinic,
naphthenic or mixed paraffinic-naphthenic; as well as to their
formation, e.g. distillation range, straight run or cracked,
hydrorefined, or solvent extracted.
[0115] The invention further provides a lubricating oil
concentrate. In the preparation of lubricating oil compositions it
is a convenient practice to introduce additives in the form of a
concentrate; which introduction may be made by methods known in the
art. The lubricating oil concentrate may contain between 2.5 to 90
weight percent more preferably 5 to 75 weight percent of the
additive composition in a suitable solvent. Suitable solvents may
include hydrocarbon oils (e.g. mineral lubricating oil or synthetic
oil).
[0116] The ratio of tungsten compound to the oil-soluble aromatic
amine may be selected so as to provide an antioxidant effect of
sufficient magnitude to meet the end use requirements of the
lubricating oil--for example, to achieve adequate performance in
the Sequence III E engine test for crankcase lubricating oils
(according to the procedure of ASTM STP315). Preferably the
tungsten compound and the oil-soluble aromatic amine are employed
in a ratio of from 1:10 to 10:1 (by wt), more preferably from 3:1
to 1:3 (by wt).
[0117] The lubricating oil additive may be used as the sole
additive for the composition or concentrate or may be used in
combination with several different types of additives which may be
required to fulfill other requirements of the composition or
concentrate during use. The composition may be used as a crankcase
lubricating oil, a cylinder lubricant for applications such as
marine diesel, industrial oil, functional fluid such as power
transmission fluid, tractor oil, gear oil or hydraulic fluid.
Accordingly the compositions or concentrates of the invention may
in addition to the lubricating oil additive contain one or more of
the following:
[0118] (a) a dispersant, preferably an ashless dispersant;
[0119] (b) a metal containing detergent, preferably having a high
total base number;
[0120] (c) an antiwear and/or extreme pressure additive;
[0121] (d) a viscosity index improver, which may also have
dispersant properties;
[0122] (e) a pour point depressant;
[0123] (f) a corrosion inhibitor and/or metal deactivator; and
[0124] (g) a friction modifier or fuel economy agent,
[0125] as well as other additives such as demulsifiers, seal swell
agents, or even supplementary antioxidants.
[0126] Where such compositions are for use as crankcase lubricants
they preferably contain at least an ashless dispersant and/or a
viscosity index improver dispersant, a detergent, and an antiwear
additive in amounts effective to provide their respective
functions.
Dispersants
[0127] The preferred ashless dispersant in the compositions and
concentrates of this invention is a long chain hydrocarbyl
substituted mono- or di-carboxylic acid material, (i.e. acid,
anhydride, or ester) and includes a long chain hydrocarbon,
generally a polyolefin, substituted with an alpha or beta
unsaturated C4 to C10 carboxylic acid material, such as itaconic
acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl
fumarate, chloromaleic anhydride, acrylic acid, methacrylic acid,
crotonic acid, or cinnamic acid. Preferably, the dispersant
contains at least about 1 mole (e.g. 1.05 to 1.2 moles, or higher)
of the acid material per mole of polyolefin. The proportion of the
dispersant is preferably from 1 to 10, and even more preferably 3
to 7 weight percent of the lubricating oil.
[0128] Preferred olefin polymers for the reaction with carboxylic
acids are polymers derived from a C2 to C5 monoolefin. Such olefins
include ethylene, propylene, butylene, isobutylene, pentene,
oct-1-ene or styrene. The polymers may be homopolymers such as
polyisobutylene or copolymers of two or more of such olefins. These
include copolymers of ethylene and propylene; butylene and
isobutylene; propylene and isobutylene; etc. Other copolymers
include those in which a minor molar amount of the copolymer
monomers (e.g. 1 to 10 mole percent), is a C4 to C18 diolefin,
(e.g., a copolymer of isobutylene and butadiene; or a copolymer of
ethylene, propylene and 1,4-hexadiene; etc).
[0129] In some cases, the olefin polymer may be completely
saturated, for example an ethylene-propylene copolymer made by a
Ziegler-Natta synthesis using hydrogen as a moderator to control
molecular weight.
[0130] The olefin polymers usually have number average molecular
weights above about 700, including number average molecular weights
within the range of from 1,500 to 5,000 with approximately one
double bond per polymer chain. An especially suitable starting
material for a dispersant additive is polyisobutylene. The number
average molecular weight for such polymers can be determined by
several known techniques. A convenient method for such
determination is by gel permeation chromatography (GPC) which
additionally provides molecular weight distribution information.
(see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size
Exclusion Liquid Chromatography," John Wiley and Sons, New York,
1979).
[0131] Processes for the reaction of the olefin polymer with the
unsaturated carboxylic acid, anhydride, or ester are known in the
art. For example, the olefin polymer and the carboxylic acid
material may be simply heated together as disclosed in U.S. Pat.
Nos. 3,361,673 and 3,401,118 (hereby incorporated by reference in
their entirety) to cause a thermal "ene" reaction to take place.
Alternatively, the olefin polymer can be first halogenated, for
example chlorinated or brominated, to about 1 to 8, preferably 3 to
7, weight percent chlorine or bromine, based on the weight of
polymer, by passing chlorine or bromine through the polyolefin at a
temperature of 100.degree. C. to 250.degree. C., e.g. 120.degree.
C. to 160.degree. C., for about 0.5 to 10 hours, more preferably 1
to 7 hours. The halogenated polymer may then be reacted with
sufficient unsaturated acid or anhydride at 100.degree. to
250.degree. C., usually 180.degree. C. to 220.degree. C., for 0.5
to 10 hours, more preferably 3 to 8 hours. Processes of this
general type are taught in U.S. Pat. Nos. 3,087,436; 3,172,892;
3,272,746, hereby incorporated by reference in their entirety.
[0132] Alternatively, the olefin polymer and the unsaturated acid
or anhydride are mixed and heated while chlorine is added to the
hot material. Processes of this type are disclosed in U.S. Pat.
Nos. 3,215,707; 3,231,587; 3,912,764; 4,110,349; 4,234,435; and
GB-A-1 440 219, all of which are incorporated by reference in their
entirety.
[0133] When a halogen is used, from 65 to 95 weight percent of the
polyolefin normally reacts with the carboxylic acid or anhydride.
Thermal reactions, carried out without the use of halogen or a
catalyst, cause only from 50 to 75 weight percent of the
polyisobutylene to react. Chlorination increases reactivity.
[0134] The carboxylic acid or anhydride can then be further reacted
with amines, alcohols, including polyols, amino-alcohols, etc., to
form other useful dispersant additives. Thus if the acid or
anhydride is to be further reacted, (e.g. neutralized) then
generally a major proportion of at least 50 percent of the acid
units up to all the acid units will be reacted.
[0135] The ashless dispersants useful in this invention are
polyisobutenyl succinimides formed from polyisobutenyl succinic
anhydride and an alkylene polyamine such as triethylene tetramine
or tetraethylene pentamine, wherein the polyisobutenyl substituent
is derived from polyisobutene having a number average molecular
weight preferably in the range of 700 to 1200 more preferably from
900 to 1100. It has been found that selecting certain dispersants
within the broad range of alkenyl succinimides produces fluids with
improved frictional characteristics. The most preferred dispersants
of this invention are those wherein the polyisobutene substituent
group has a molecular weight of approximately 950 atomic mass
units, the basic nitrogen containing moiety is polyamine (PAM) and
the dispersant has been post treated with a boronating agent.
[0136] The ashless dispersants of the invention can be used in any
effective amount. However, they are typically used from about 0.1
to 10.0 mass percent in the finished lubricant, preferably from
about 0.5 to 7.0 percent, and most preferably from about 2.0 to
about 5.0 percent.
[0137] Useful amine compounds for reaction with the hydrocarbyl
substituted carboxylic acid or anhydride include mono- and
polyamines with preferably 2 to 60, and more preferably 3 to 20,
total carbon atoms and from 1 to 12, and more preferably 2 to 8
nitrogen atoms in a molecule. These amines may be hydrocarbyl
amines or may be hydrocarbyl amines including other groups, e.g.
hydroxy groups, alkoxy groups, amide groups, nitriles, or
imidazoline groups. Hydroxy amines with 1 to 6 hydroxy groups,
preferably 1 to 3 hydroxy groups, are particularly useful.
Preferred amines are aliphatic saturated amines, including those of
the general formulae:
##STR00048##
wherein R.sup.28, R.sup.29 and R.sup.30 are each independently
hydrogen; C.sub.1 to C.sub.25 straight or branched chain alkyl
radicals; C.sub.1 to C.sub.12 alkoxy-(C.sub.6 alkylene) radicals;
or C.sub.2 to C.sub.12 alkylamino-C.sub.2 to C.sub.6 alkylene)
radicals; each s.sub.1 can be the same or a different number of
from 2 to 6, preferably 2 to 4; and w is a number from 0 to 10,
preferably 2 to 7. Preferably at least one of R.sup.28, R.sup.29
and R.sup.30 is hydrogen.
[0138] Suitable amines include 1,2-diaminoethane;
1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane;
polyethylene amines such as diethylene triamine; triethylene
tetramine; tetraethylene pentamine; polypropylene amines such as
1,2-propylene diamine; di-(1,2-propylene)triamine;
di(1,3-propylene)-triamine; N,N-dimethyl-1,3-diaminopropane;
N,N-di-(2-aminoethyl) ethylene diamine;
N,N-di(2-hydroxyethyl)-1,3-propylene diamine;
3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris
hydroxymethylaminomethane (THAM); diisopropanol amine; diethanol
amine; triethanol amine; amino morpholines such as
N-(3-amino-propyl) morpholine; etc.
[0139] Other useful amine compounds include alicyclic diamines such
as 1,4-di-(aminomethyl) cyclohexane, and heterocyclic nitrogen
compounds such as imidazolines, and N-aminoalkyl piperazines of the
general formula:
##STR00049##
wherein p.sub.1 and p.sub.2 are the same or different and each is
an integer from 1 to 4, and e, f and o are the same or different
and each is an integer from 1 to 3. Examples of such amines include
2-pentadecyl imidazoline and N-(2-aminoethyl) piperazine.
[0140] Hydroxyamines which can be reacted with the long chain
hydrocarbon substituted dicarboxylic acid material mentioned above
to form dispersants include 2-amino-1-butanol,
2-amine-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline,
2-amino-1-propanol, 3-amino-1-propanol,
2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,
N-(beta-hydroxy propyl)N'-(beta-aminoethyl)-piperazine,
ethanolamine and beta-(beta-hydroxyethoxy)-ethylamine. Mixtures of
these or similar amines can also be employed. Commercial mixtures
of amine compounds may advantageously be used. For example, one
process for preparing alkylene amines involves the reaction of an
alkylene dihalide (such as ethylene dichloride or propylene
dichloride) with ammonia, which results in a complex mixture of
alkylene amines wherein pairs of nitrogens are joined by alkylene
groups, forming such compounds as diethylene triamine, triethylene
tetramine, tetraethylene pentamine and corresponding piperazines.
Useful poly(ethyleneamine) compounds averaging about 5 to 7
nitrogen atoms per molecule are available commercially under trade
names such as "Polyamine H", "Polyamine 400", "Dow Polyamine
E-100", etc.
[0141] Useful amines also include polyoxyalkylene polyamines such
as those of the formulae:
[0142] (i) NH.sub.2-alkylene(O-alkylene)m NH.sub.2 where m has a
value of from 3 to 70, preferably 10 to 35; and
[0143] (ii) R-(alkylene(O-alkylene)n NH2)3-6 where each n has a
value of about 1 to 40, with the proviso that the sum of all the
n's is from 3 to 70 and preferably from 6 to 35, and R is a
saturated hydrocarbon radical of up to ten carbon atoms, wherein
the number of substituents on the R group is from 3 to 6. The
alkylene groups in either formula (I) or (ii) may be straight or
branched chains containing about 2 to 7, and preferably about 2 to
4, carbon atoms.
[0144] The polyoxyalkylene polyamines above, preferably
polyoxyalkylene diamines and polyoxyalkylene triamines, may have
average molecular weights ranging from 200 to 4,000 and preferably
from 400 to 2,000. The preferred polyoxyalkylene polyamines include
the polyoxyethylene and polyoxypropylene diamines and the
polyoxypropylene triamines having average molecular weights ranging
from 200 to 2,000. The polyoxyalkylene polyamines are commercially
available and may be obtained, for example, from the Jefferson
Chemical Company, Inc. under the trade name "Jeffamines D-230,
D400, D-1000, D-2000, T-403," etc.
[0145] The amine is readily reacted with the carboxylic acid
material, e.g. alkenyl succinic anhydride, by heating an oil
solution containing 5 to 95 weight percent of carboxylic acid
material to from 100 to 250.degree. C., preferably 125 to
175.degree. C., generally for 1 to 10 hours, more preferably from 2
to 6 hours, until the desired amount of water has been removed. The
heating is preferably carried out to favor formation of imides, or
mixtures of imides and amides, rather than amides and salts.
Reaction ratios can vary considerably, depending upon the
reactants, amounts of excess amine, type of bonds formed, etc.
Generally from 0.3 to 2 moles of amine, more preferably from 0.3 to
1.0 moles of amine, and even more preferably 0.4 to 0.8 mole of
amine (e.g. bis-primary amine) is used per mole of the carboxylic
acid moiety content (e.g. grafted maleic anhydride content). For
example, one mole of olefin reacted with sufficient maleic
anhydride to add 1.0 mole of maleic anhydride groups or mole of
olefin when converted to a mixture of amides and imides, about 0.55
moles of amine with two primary groups would preferably be used,
i.e. 0.50 mole of amine per mole of dicarboxylic acid moiety.
[0146] The nitrogen-containing dispersant can be further treated by
boration as generally taught in U.S. Pat. Nos. 3,087,936 and
3,254,025, hereby incorporated by reference in their entirety.
[0147] Tris (hydroxymethyl) amino methane (THAM) can be reacted
with the aforesaid acid material to form amides, imides or ester
type additives as taught by GB-A-984 409, or to form oxazoline
compounds and borated oxazoline compounds as described, for
example, in U.S. Pat. Nos. 4,102,798, 4,116,876 and 4,113,639,
hereby incorporated by reference in their entirety.
[0148] The ashless dispersants may also be esters derived from the
long chain hydrocarbyl substituted carboxylic acid material and
from hydroxy compounds such as monohydric and polyhydric alcohols
or aromatic compounds such as phenols and naphthols, etc. The
polyhydric alcohols are the most preferred hydroxy compound and
preferably contain from 2 to 10 hydroxy radicals, for example,
ethylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol, dipropylene glycol, and other alkylene
glycols in which the alkylene radical contains from 2 to 8 carbon
atoms. Other useful polyhydric alcohols include glycerol,
mono-oleate of glycerol, monostearate of glycerol, monomethyl ether
of glycerol, pentaerythritol, dipentaerythritol, etc.
[0149] The ester dispersant may also be derived from unsaturated
alcohols such as allyl alcohol, cinnamyl alcohol, propargyl
alcohol, 1-cyclohexane-3-ol, and oleyl alcohol. Still other classes
of alcohols capable of yielding the esters comprise the
ether-alcohols and amino-alcohols including, for example the
oxy-alkylene-, oxy-arylene-, amino-alkylene-, and
amino-arylene-substituted alcohols having one or more oxy-alkylene,
amino-alkylene or amino-arylene or amino-arylene oxy-arylene
radicals. They are exemplified by Cellosolve, carbitol,
N,N,N',N'-tetrahydroxy-tri-methylene di-amine, and ether-alcohols
having up to about 150 oxyalkylene radicals in which each alkylene
radical contains from 1 to 8 carbon atoms.
[0150] The ester dispersant may be a di-ester of succinic acid or
an acidic ester (i.e. a partially esterified succinic acid), or a
partially esterified polyhydric alcohol or phenol, (i.e. an ester
having free alcoholic or phenolic hydroxyl radicals). Mixtures of
the above illustrated esters are likewise contemplated.
[0151] The ester dispersant may be prepared by one of several known
methods as illustrated for example in U.S. Pat. No. 3,381,022,
hereby incorporated by reference in their entirety.
[0152] Mannich base type dispersants such as those described in
U.S. Pat. Nos. 3,649,229 and 3,798,165 (hereby incorporated by
reference in their entirety) may also be used in these
compositions. Such Mannich base dispersants can be formed by
reacting a high molecular weight, hydrocarbyl-substituted mono- or
polyhydroxyl benzene (e.g. having a number average molecular weight
of 1,000 or greater) with amines (e.g. polyalkyl polyamines,
polyalkenyl polyamines, aromatic amines, carboxylic
acid-substituted polyamines and the succinimide formed from any one
of these with an olefinic succinic acid or anhydride) and carbonyl
compounds (e.g. formaldehyde or para formaldehyde).
[0153] A particularly suitable dispersant is one derived from
polyisobutylene substituted with succinic anhydride groups and
reacted with polyethylene amines, e.g. tetraethylene pentamine,
pentaethylene hexamine, polyoxyethylene and polyoxypropylene
amines, e.g. polyoxypropylene diamine, trismethylolaminomethane and
pentaerythritol, and combinations thereof.
Detergents
[0154] Metal-containing rust inhibitors and/or detergents are
frequently used with ashless dispersants. Such detergents and rust
inhibitors include oil-soluble mono- and dicarboxylic acids, the
metal salts of sulfonic acids, alkyl phenols, sulfurized alkyl
phenols, alkyl salicylates and naphthenates in neutral or basic
form. Highly basic (or "over-based") metal salts, which are
frequently used as detergents, appear particularly prone to promote
oxidation of hydrocarbon oils containing them. Usually these
metal-containing rust inhibitors and detergents are used in
lubricating oil in amounts of from 0.01 to 10 weight percent, more
preferably from 0.1 to 5 weight percent, based on the weight of the
total lubricating composition.
[0155] Highly basic alkali metal and alkaline earth metal
sulfonates are frequently used as detergents. They are usually
produced by heating a mixture comprising an oil-soluble sulfonate
or alkaryl sulfonic acid, with an excess of alkali metal or
alkaline earth metal compound above that required for complete
neutralization of any sulfonic acid present and thereafter forming
a dispersed carbonate complex by reacting the excess metal with
carbon dioxide to provide the desired overbasing. The sulfonic
acids are typically obtained by the sulfonation of alkyl
substituted aromatic hydrocarbons such as those obtained from the
fractionation of petroleum by distillation and/or extraction or by
the alkylation of aromatic hydrocarbons as for example those
obtained by alkylating benzene, toluene, xylene, naphthalene,
diphenyl and the halogen derivatives such as chlorobenzene,
chlorotoluene and chloronaphthalene. The alkylation may be carried
out in the presence of a catalyst with alkylating agents having
from about 3 to more than 30 carbon atoms. For example,
haloparaffins, olefins obtained by dehydrogenation of paraffins,
polyolefin polymers produced from ethylene, propylene, etc. are all
suitable. The alkaryl sulfonates usually contain from 9 to 70 or
more carbon atoms, preferably from 16 to 50 carbon atoms per alkyl
substituted aromatic moiety.
[0156] The alkali metal or alkaline earth metal compounds which may
be used in neutralizing these alkaryl sulfonic acids to provide the
sulfonates include the oxides and hydroxides, alkoxides,
carbonates, carboxylates, sulfides, hydrosulfides, nitrates,
borates and ethers of sodium, magnesium, calcium, strontium and
barium. Non-limiting examples include calcium oxide, calcium
hydroxide, magnesium oxide, magnesium acetate, and magnesium
borate. As noted, the alkaline earth metal compound is used in
excess of that required to complete neutralization of the alkaryl
sulfonic acids. Generally, the amount ranges from 100 to 220
percent, although it is preferred to use at least 125 percent of
the stoichiometric amount of metal required for complete
neutralization.
[0157] Various other preparations of basic alkali metal and
alkaline earth metal alkaryl sulfonates are known, such as those
described in U.S. Pat. Nos. 3,150,088 and 3,150,089 (hereby
incorporated by reference in their entirety) wherein overbasing is
accomplished by hydrolysis of an alkoxide-carbonate complex with
the alkaryl sulfonate in a hydrocarbon solvent-diluent oil.
[0158] Preferred alkaline earth sulfonate additives are magnesium
alkyl aromatic sulfonate additives having a high total base number
(TBN) as measured by ASTM 02896 of at least 250, more preferably
ranging from 300 to 400, and calcium alkyl aromatic sulfonates
having a TBN of at least 250, preferably from 300-400.
[0159] Neutral metal sulfonates are frequently used as rust
inhibitors. Polyvalent metal alkyl salicylate and naphthenate
materials are known additives for lubricating oil compositions to
improve their high temperature performance and to counteract
deposition of carbonaceous matter on pistons (e.g. U.S. Pat. No.
2,744,069, hereby incorporated by reference in their entirety). An
increase in reserve basicity of the polyvalent metal alkyl
salicylates and naphthenates can be realized by utilizing alkaline
earth metal, e.g. calcium, salts of mixtures of C.sub.8-C.sub.26
alkyl salicylates and phenates (e.g. U.S. Pat. No. 2,744,069,
hereby incorporated by reference in their entirety) or polyvalent
metal salts of alkyl salicylic acids, said acids obtained from the
alkylation of phenols followed by phenation, carboxylation and
hydrolysis (e.g. U.S. Pat. No. 3,704,315, hereby incorporated by
reference in their entirety) which could then be converted into
highly basic salts by techniques generally known and used for such
conversion. The reserve basicity of these metal-containing rust
inhibitors is useful at TBN levels of between 60 and 150.
Non-limiting examples of useful polyvalent metal salicylate and
naphthenate materials are the methylene and sulfur bridged
materials which are readily derived from alkyl substituted
salicylic or naphthenic acids or mixtures of either or both with
alkyl substituted phenols. Basic sulfurized salicylates and a
method for their preparation are disclosed in U.S. Pat. No.
3,595,791, hereby incorporated by reference in their entirety. Such
materials include alkaline earth metal, particularly magnesium,
calcium, strontium and barium, salts of aromatic acids having the
general formula:
HOOC--ArR.sup.31OH-Q.sub.k(ArR.sup.31OH)r
where Ar is an aryl radical of 1 to 6 rings, R31 is an alkyl group
having from 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms
(optimally about 12), Q is a sulfur (--S--) or methylene
(--CH.sub.2--) bridge, k is a number from 0 to 4 and r is a number
from 0 to 4.
[0160] Preparation of the overbased Methylene Bridged
Salicylate-Phenate Salt is readily carried out by conventional
techniques such as by alkylation of a phenol followed by phenation,
carboxylation, hydrolysis, methylene bridging a coupling agent such
as an alkylene dihalide followed by salt formation concurrent with
carbonation. An overbased calcium salt of a methylene bridged
phenol-salicylic acid with a TBN of 60 to 150 is also useful.
[0161] Another type of basic metal detergent, the sulfurized metal
phenates, can be considered a metal salt whether neutral or basic,
of a compound typified by the general formula:
##STR00050##
where j=1 or 2, q=0, 1 or 2 or a polymeric form of such a compound,
where Rp is an alkyl radical, j and q are each integers from 1 to
4, and the average number of carbon atoms in all of the R groups is
at least about 9 in order to ensure adequate solubility in oil. The
individual R p groups may each contain from 5 to 40, preferably 8
to 20, carbon atoms. The metal salt is prepared by reacting an
alkyl phenol sulfide with a sufficient quantity of metal containing
material to impart the desired alkalinity to the sulfurized metal
phenate.
[0162] Regardless of the manner in which they are prepared, the
sulfurized alkyl phenols which are useful generally contain from 2
to 14 percent by weight, preferably 4 to 12 weight percent sulfur
based on the weight of sulfurized alkyl phenol. The sulfurized
alkyl phenol may be converted by reaction with a metal-containing
material including oxides, hydroxides and complexes in an amount
sufficient to neutralize said phenol and, if desired, to overbase
the product to a desired alkalinity by procedures well known in the
art. Preferred is a process of neutralization utilizing a solution
of metal in glycol ether.
[0163] The neutral or normal sulfurized metal phenates are those in
which the ratio of metal to phenol nucleus is about 1:2. The
"overbased" or "basic" sulfurized metal phenates are sulfurized
metal phenates wherein the ratio of metal to phenol is greater than
the stoichiometric ratio, e.g. basic sulfurized metal dodecyl
phenate has a metal content up to (or greater) than 100 percent in
excess of the metal present in the corresponding normal sulfurized
metal phenate. The excess metal is produced in oil-soluble or
dispersible form (as by reaction with CO.sub.2).
[0164] The detergents which may be included in the compositions of
the present invention may optionally be borated in a known manner.
Such boration provides the detergent with a measure of anti-wear
activity.
[0165] It is preferred to use a combination of metal-containing
detergents comprising calcium and magnesium salts or calcium,
magnesium and sodium salts, as described above.
Antiwear Additives (Including Extreme Pressure Agents)
[0166] A wide variety of anti-wear additives may be included in the
compositions or concentrates of the invention. For example, organic
sulfides and polysulfides including especially dialkyl sulfides and
polysulfides (e.g. dibutyl polysulfides, and dibenzyl sulfides and
polysulfides) which may be substituted (e.g. with halogen, may be
incorporated in the compositions or concentrates). Sulfurized
esters, (e.g. sulfurized methyl or isopropyl oleate) and other
sulfurized compounds, (e.g. sulfurized olefins such as sulfurized
diisobutylene, sulfurized tripropylene or sulfurized dipentene) may
also be added to the compositions. More complex sulfurized
compounds such as sulfurized alkyl phenols and sulfurized terpenes
and Diels-Alder adducts and sulfurized polymers, e.g.
butadiene/butyl acrylate copolymers, may also be used, as may
sulfurized tall oil fatty acid esters. Esters of
beta-thiodipropionic acid, e.g. butyl, nonyl, tridecyl or eicosyl
esters may also be used.
[0167] Anti-wear additives in the form of phosphorus esters, (e.g.
di- and tri-alkyl, cycloalkyl or aryl phosphites) may also be used.
Examples of such phosphites include dibutyl phosphite, dihexyl
phosphite, dicyclohexyl phosphite, alkyl phenyl phosphites such as
dimethylphenyl phosphite and mixed higher alkyl, (e.g. oleyl, alkyl
phenyl phosphate, an example of which includes 4-pentyl phenyl
phosphite). Phosphites based on polymers such as low molecular
weight, polyethylenes and polypropylenes may also be used.
[0168] Preferred anti-wear additives for addition to the
compositions and concentrates of the present invention are the
dihydrocarbyl dithiophosphate metal salts. They also provide some
antioxidant activity. The zinc salts are most commonly used in
lubricating oils in amounts of 0.1 to 10, preferably 0.2 to 2,
weight percent, based upon the total weight of the lubricating oil
composition. Salts of other metals, e.g. barium and cadmium, can
also be used. They may be prepared in accordance by first forming a
dithiophosphoric acid, usually by reaction of an alcohol or a
phenol with P2 S5 and then neutralizing the dithiophosphoric acid
with a suitable zinc compound.
[0169] Alcohols may be used including mixtures of primary and
secondary alcohols, with secondary alcohols generally for imparting
improved antiwear properties, and primary alcohols forgiving
improved thermal stability properties. Mixtures of the two are
particularly useful. In general, any basic or neutral zinc compound
could be used but the oxides, hydroxides and carbonates are most
generally employed. Commercial additives frequently contain an
excess of zinc due to use of an excess of the basic zinc compound
in the neutralization reaction.
[0170] The zinc dihydrocarbyl dithiophosphates useful in the
present invention are oil-soluble salts of dihydrocarbyl esters of
dithiphosphoric acids and may be represented by the following
formula
##STR00051##
wherein A.sup.12 and A.sup.13 may be the same or different
hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12,
carbon atoms and including radicals such as alkyl, alkenyl, aryl,
aralkyl, alkaryl and cycloaliphatic radicals. Particularly
preferred as A.sup.12 and A.sup.13 groups are alkyl groups of 2 to
8 carbon atoms. Thus, the radicals may, for example be ethyl,
n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, s-hexyl,
i-hexyl, i-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl,
nonyl-phenyl, dodecyl-cyclohexyl, methylcyclopentyl, propenyl,
butenyl, etc. In order to obtain oil solubility, the total number
of carbon atoms in the dithiophosphoric acid (i.e. A.sup.12 and
A.sup.13) generally should be about 5 or greater and preferably 8
or greater.
[0171] Borated derivatives of the aforesaid antiwear agents may
also be included in the compositions or concentrates of the
invention.
Thiadiazole
[0172] The 1,3,4-thiadiazoles of formula I may be prepared by the
method disclosed in U.S. Pat. Nos. 4,761,482 and 4,880,437,
incorporated herein by reference in their entirety:
##STR00052##
wherein T.sup.1 and T.sup.2 are independently selected from the
group consisting of hydrogen, alkyl, hydroxyalkyl, alkylthio,
phenylalkyl, alkylated phenylalkyl, terpene residue and maleic acid
residue of the formula
##STR00053##
wherein R.sup.32 and R.sup.33 are independently selected from the
group consisting of hydrogen, branched or straight chain alkyl
groups and cyclic aliphatic groups, wherein at least one of
R.sup.32 and R.sup.33 is not hydrogen.
[0173] An embodiment for the present invention includes alkyls
which have from 1 to 50 carbon atoms which may be branched or
straight chain and may be substituted with a hydroxyl group and an
aryl group. Another embodiment for the present invention are
T.sup.1 and T.sup.2 which are alkyl and alkylthio groups which
contain 1 to 22 carbon atoms and may be branched or straight chain.
Additional embodiments for the present invention include compounds
wherein T.sup.1 and T.sup.2 together contain a total of at least 22
carbon atoms in their alkyl and/or alkylthio groups.
[0174] Embodiments of terpene residues for the present invention
include terpenes which are derived from pinene and limonene.
[0175] An embodiment of maleic acid residues for the present
invention include maleic acid residues where R.sup.32 and R.sup.33
independently represents an alkyl group with 1 to 22 carbon atoms
or C5-C7 cycloalkyl group. A further embodiment includes the total
number of carbon atoms for R.sup.32 and R.sup.33 combined being
from 8 to 44 carbon atoms.
[0176] Commercially available thiadiazoles derivatives are
VANLUBE.RTM. 871 (butanedioic acid
((4,5-dihydro-5-thioxo-1,3,4-thiadiazol-2-yl)
thio-bis(2-ethylhexyl) ester) CUVAN.RTM. 826
(2,5-dimercapto-1,3,4-thiadiazole) and CUVAN.RTM. 484
(alkylthiadiazole) manufactured by R. T. Vanderbilt Company,
Hitec.TM. 4313, 4312, RC 8210, and RC 8213.
Dithiocarbamates
(i) Bisdithiocarbamates
[0177] The bisdithiocarbamates of formula are known compounds
described in U.S. Pat. No. 4,648,985, incorporated herein by
reference in its entirety.
##STR00054##
[0178] The compounds are characterized by R.sup.34, R.sup.35,
R.sup.36 and R.sup.37 which are the same or different and are
hydrocarbyl groups having 1 to 13 carbon atoms.
[0179] Embodiments for the present invention include
bisdithiocarbamates wherein R.sup.34, R.sup.35, R.sup.36 and
R.sup.37 are the same or different and are branched or straight
chain alkyl groups having 1 to 8 carbon atoms.
[0180] R.sup.38 is an aliphatic group such as straight and branched
alkylene groups containing 1 to 8 carbons. An embodiment for
R.sup.38 is methylenebis (dibutyldithiocarbamate) available
commercially from R. T. Vanderbilt Company, Inc. under the
tradename VANLUBE.RTM. 7723, and from King Industries under the
tradename NA-LUBE.RTM. ADTC.
(ii) Ashless Dithiocarbamate Esters
##STR00055##
[0182] The compounds of the above formula are characterized by
groups R.sup.39, R.sup.40, R.sup.41 and R.sup.42 which are the same
or different and are hydrocarbyl groups having 1 to 13 carbon
atoms. VANLUBE.RTM. 732 and VANLUBE..RTM. 981 are commercially
available from R. T. Vanderbilt Company, Inc.
(iii) Metal Dithiocarbamates
##STR00056##
[0183] The dithiocarbamates of the above formula are known
compounds. One of the processes of preparation is disclosed in U.S.
Pat. No. 2,492,314, which is hereby incorporated by reference in
its entirety. R.sup.d and R.sup.e represent branched or straight
chain alkyl groups having 1 to 8 carbon atoms, M is a metal cation
and n is an integer based upon the valency of the metal cation
(e.g. n=1 for sodium (Na.sup.+); n=2 for zinc (Zn.sup.++); etc.).
Molybdenum dithiocarbamate processes are described in U.S. Pat.
Nos. 3,356,702; 4,098,705; and 5,627,146, each of which is hereby
incorporated by reference. Substitution is described as branched or
straight chain ranging from 8 to 13 carbon atoms in each alkyl
group.
[0184] Embodiments for the present invention include metal
dithiocarbamates which are antimony, zinc and tungsten
dithiocarbamates.
[0185] Additionally the lubricant composition may also include
phosphorous dithiophosphate compounds. Embodiments of
dithiophosphates for the present invention include:
(i) Metal Phosphorodithioates
##STR00057##
[0187] The metal phosphorodithioates are known, commercially
available materials. One of the processes of preparation is taught
by U.S. Pat. No. 4,215,067, which is hereby incorporated by
reference in its entirety. (M and n are as defined above for the
metal dithiocarbamates) R.sup.f and R.sup.g represent branched and
straight chain alkyl groups having 1-22 groups and may be derived
from fatty acids. In one embodiment the metal phosphorodithioates
are zinc phosphorodithioates. The metal ion in formula V may be
selected from the following groups of the Periodic Table: IIA,
IIIA, VA, VIA, IB, IIB, VIB and VIII. Amine salts of the compounds
are also useful synergists of the invention. Embodiments of such
amine salts include those prepared from alkyl amines and mixed
alkyl amines. An additional embodiment includes amine salts based
on fatty acid amines.
(ii) Phosphorodithioate Esters
##STR00058##
[0189] The phosphorodithioate esters are known compounds. One of
the processes of manufacture is disclosed in U.S. Pat. No.
3,567,638, which is hereby incorporated by reference in its
entirety. R.sup.j, R.sup.k, R.sup.l and R.sup.m may be the same or
different and may be branched and straight chain alkyl groups.
Embodiments for the present invention include branched or straight
chain alkyl groups containing 1 to 8 carbon atoms.
[0190] Embodiments for the ranges of phosphorodithioate (also known
as dithiophosphate) compound, or mixture of dithiophosphate
compounds, are 0.05-2.00%; 0.5-1.50%; and 0.5-0.8% (each percentage
being percent by weight based upon the total weight of the
composition).
Additional Antioxidants
[0191] Additional antioxidants which are especially useful in
lubricating oil compositions or concentrates are based on
oil-soluble copper compounds, e.g. in the form of a synthetic or
natural carboxylic acid salt. By "oil-soluble" is meant that the
compound is oil-soluble or solubilized under normal blending
conditions in the oil or concentrate. Examples of oil-soluble
copper compounds include salts of C.sub.10 to C.sub.18 fatty acids
such as stearic or palmitic acid; but unsaturated acids (such as
oleic acid), branched carboxylic acids (such as naphthenic acids)
of molecular weight from 200 to 500, dicarboxylic acids such as
polyisobutenyl succinic acids, and synthetic carboxylic acids can
all be used because of the acceptable handling and solubility
properties of the resulting copper carboxylates.
[0192] Suitable oil-soluble copper dithiocarbamates have the
general formula
##STR00059##
where p is 1 or 2 and R44 and R45 may be the same or different
hydrocarbyl radicals containing from 1 to 18 carbon atoms each and
including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl
and cycloaliphatic radicals. Particularly preferred as R.sup.44 and
R.sup.45 groups are alkyl groups of 2 to 8 carbon atoms. Thus, the
radicals may be, for example, ethyl, n-propyl, n-butyl, i-butyl,
sec-butyl, amyl, sec-hexyl, i-hexyl, i-octyl, decyl, dodecyl,
octadecyl, 2-ethylhexyl, nonyl-phenyl, dodecyl-phenyl, cyclohexyl,
methylcyclopentyl, propenyl, butenyl, etc. In order to obtain oil
solubility, the total number of carbon atoms (i.e. R.sup.44 and
R.sup.45) generally should be about 5 or greater.
[0193] Copper salts of dithiophosphonic acids (the acid as
described hereinbefore in relation to antiwear additives
specifically as zinc salts), copper sulfonates, phenates, copper
polyisobutylene succinic anhydride ("Copper PIBSA") carboxylates
such as oleates, stearates and mixtures thereof, and acetyl
acetonates can also be used.
[0194] These antioxidants can be used in amounts such that, in the
final lubricating composition, a copper concentration of from 5 to
500 ppm is present.
[0195] Other known oil-soluble or oil-ispersible, and preferably
liquid, antioxidants may also be used in the compositions of the
invention. Examples of such antioxidants include hindered phenols,
which may contain sulphur, e.g. 4,4'-methylene
bis(2,6-di(t-butyl)phenol), 4,4'-thio bis(2,6-di(t-butyl)phenol)
and p-alkylated hindered phenols; unhindered phenols which again
may contain sulphur such as 2,2'-thio bis-(4-nonyl phenol) and
2,2'-methylene bis(4-nonylphenol); phenothiazine derivatives, e.g.
those containing higher alkyl substituents such as dioctyl and
dinonyl phenothiazines; substituted alpha and betanaphthyl amines
such as phenyl beta-naphthylamine and its alkylated derivatives;
other amino aryl compounds such as for example 4,
4'-bis(secbutylamino) diphenylmethane; dithiocarbamates such as
zinc, nickel, copper, or molybdenum dithiocarbamates; and
phosphosulfurized olefins, e.g. phosphosulfurized pinene or
styrene.
Corrosion Inhibitors and Metal Deactivators
[0196] Corrosion inhibitors which act by deactivating metal parts
with which they come in contact and/or as sulfur scavengers can
also be used in the compositions or concentrates of the invention.
Examples of such agents include benzotriazole derivatives;
thiadiazole compounds, e.g. 2,5-dimercapto 1,3,4-thiadiazole;
mercaptobenzothiazole compounds in the form of amine salts,
sulphonamides, thiosulphonamides, and condensates of
mercaptobenzothiazole with amines and formaldehyde;
salicylaldehyde/diamine condensation products; dialkylphosphites,
e.g. dioleyl or di-2-ethylhexyl phosphite; trialkyl and
triarylphosphites, e.g. tris-(2-ethyl-hexyl), triphenyl or
tri(4-nonylphenol) phosphites; and thiophosphonates such as
triphenyl or trilauryl thiophosphonate or trilauryl
tetrathiophosphonate.
[0197] Also useful are corrosion inhibitors based on aromatic
sulfonic acid derivatives, for example derivative of a mono-, di-,
or poly-alkylated naphthalenesulfonic acid selected from the group
consisting of:
[0198] (i) neutral metal salts of said mono-, di-, and
poly-alkylated naphthalenesulfonic acids;
[0199] (ii) basic metal salts of said mono-, di-, and
poly-alkylated naphthalenesulfonic acids;
[0200] (iii) amine salts of said mono-, di-, and poly-alkylated
naphthalenesulfonic acids; and
[0201] (iv) esters of said mono-, di-, and poly-alkylated
naphthalenesulfonic acids; wherein the mono-, di-, and
poly-alkylated naphthalenesulfonic acids are represented by
formula
##STR00060##
[0202] wherein R.sub.51, R.sub.52, R.sub.53 and R.sub.54 are
individually selected from the group consisting of hydrogen or
essentially linear hydrocarbyl groups having about 9 to about 22
carbon atoms; and wherein l, m, n and p are integers from 0 to 4
and the sum of l+m+n+p is at least 1; and wherein R.sub.51,
R.sub.52, R.sub.53 and R.sub.54 is a hydrogen where either l, m, n,
or p is 0.
[0203] One derivative of the alkylated naphthalenesulfonic acid
composition is the neutral metal salt component and is represented
by the formula (II):
##STR00061##
wherein R.sub.51, R.sub.52, R.sub.53 and R.sub.54, l, m, n and p
are as defined above; M is a metal selected from the group
consisting of alkali metals, alkaline earth metals, transition
metals, Group IVb metals, and Group Vb metals; and x is the valence
of M. M in formula (II) is an alkali metal selected from the group
consisting of lithium, sodium, potassium, and mixtures thereof. M
may also be an alkaline earth metal selected from the group
consisting of magnesium, calcium, strontium, barium and mixtures
thereof. In other embodiments, M is a transition metal selected
from the group consisting of zinc, copper, cerium, molybdenum, and
mixtures thereof. In still other embodiments M may be a Group IVb
metal and selected from the group consisting of tin, lead, and
mixtures thereof M may be a Group Vb metal selected from the group
consisting of bismuth, antimony, and mixtures thereof.
[0204] The functional fluid composition may also contain at least
one derivative of the alkylated naphthalenesulfonic acid
composition that is the overbased metal salt component described
above and represented by formulae
##STR00062##
and mixtures thereof wherein R.sub.51, R.sub.52, R.sub.53 and
R.sub.54, l, m, n and p are as defined earlier; M is a metal
selected from the group consisting of alkali metals, alkaline earth
metals, transition metals, Group IVb metals, and Group Vb metals; x
is the valence of M; and z is 0.1 to 50.
[0205] The functional fluid composition contains one ammonium or
organic amine salt of formulae
##STR00063##
wherein R.sub.51, R.sub.52, R.sub.53 and R.sub.54, l, m, n and p
are as defined earlier and each R.sub.55 is individually selected
from a hydrogen atom or a hydrocarbyl group consisting of from 1 to
25 carbon atoms; and x is from 2 to 5.
[0206] The functional fluid composition contains at least one
compound represented by formula
##STR00064##
wherein R.sub.51, R.sub.52, R.sub.53 and R.sub.54, l, m, n and p
are as defined earlier and R.sub.56 is a hydrocarbyl group
consisting of from 2 to 18 carbon atoms.
[0207] Also useful are corrosion inhibitors based on
N-acyl-N-hydrocarbonoxyalkyl aspartic acid compounds having the
formula
##STR00065##
wherein R.sup.61 is a hydrocarbonoxyalkyl group of from about 6 to
about 30 carbon atoms, R.sup.62 is a carboxyl substituted acyl
group containing from about 2 to about 30 carbon atoms, or such a
group at least partially neutralized with an alkali metal base, an
alkaline earth metal base, an amine or a mixture of any of the
foregoing, and R.sup.64, R.sup.61, R.sup.66, and R.sup.67 are each,
independently, selected from hydrogen or a hydrocarbon group of
from about 1 to about 30 carbon atoms.
Friction Modifiers and Fuel Economy Agents
[0208] Friction modifiers and fuel economy agents, compatible with
the other ingredients of the new compositions or concentrates may
also be included. Examples of such materials are glyceryl
monoesters and/or diesters of higher fatty acids, e.g. glyceryl
mono-oleate and esters of long-chain polycarboxylic acids with
diols, e.g. the butane diol ester of a dimerized unsaturated fatty
acid, and oxazoline compounds.
Succinimides
[0209] Succinimides friction modifiers of the current invention may
be represented by the following general formula.
##STR00066##
where R18 is a C6 to C30 isomerized alkenyl group, represented
by:
##STR00067##
(where g and h are integers whose sum is from 1 to 25), or its
fully saturated alkyl analog, R17 is an alkyl group, aryl group,
and their heteroatom containing derivatives.
[0210] The succinimides of the present invention are those produced
from succinic anhydrides substituted with isomerized alkenyl groups
or their fully saturated alkyl analogs. Preparation of the
Isomerized Alkenyl Succinic Anhydrides is Described in, for
Example, U.S. Pat. No. 3,382,172 hereby incorporated by reference
in its entirety.
[0211] Often these materials are prepared by heating alpha-olefins
with acidic catalysts to migrate the double bond to form an
internalolefin. This mixture of olefins (2-enes, 3-enes, etc.) is
then thermally reacted with maleic anhydride. Typically olefins
from C.sub.6 (e.g. 1-hexene) to C.sub.30 (e.g. 1-tricosane) are
used. Suitable isomerized alkenyl succinic anhydrides of structure
(1)
##STR00068##
include isodecylsuccinic anhydride (x+y=5), iso-dodecylsuccinic
anhydride (x+y=7), iso-tetradecylsuccinic anhydride (x+y=9),
iso-hexadecylsuccinic anhydride (x+y=11), iso-octadecylsuccinic
anhydride (x+y=13) and isoeicosylsuccinic anhydride (x+y=15).
Preferred materials are isohexadecylsuccinic anhydride and
iso-octadecylsuccinic anhydride.
[0212] The materials produced by this process contain one double
bond (alkenyl group) in the alkyl chain. The alkenyl substituted
succinic anhydrides may be easily converted to their saturated
alkyl analogs by hydrogenation.
[0213] Suitable primary and secondary amines useful to produce the
succinimides are represented by structure
##STR00069##
[0214] where: R.sup.19 and R.sup.20 are independently alkyl, aryl,
their heteroatom containing derivatives, or H with the proviso that
R.sup.19 and R.sup.20 are not both H. Preferred amines are
n-hexylamine, di-n-hexylamine, dimethylamine, n-butylamine,
diethanol amine and di-methyiaminopropylamine.
[0215] Bis succinimides of the current invention may be represented
by the following general formula
##STR00070##
wherein R.sup.21 and R.sup.22 may be identical or different from
each other and are each hydrocarbon groups having 5 or more
carbons; R.sup.23 is a divalent hydrocarbon group having 1 to 5
carbons; R.sup.24 is a hydrogen atom or a hydrocarbon group having
1 to 20 carbons; and n is an integer in the range of 0 to 10
[0216] In the above general formula, R.sup.21 and R.sup.22 may be
the same as each other or different from each other, and are each
saturated or unsaturated hydrocarbon groups having 5 or more
carbons, preferably 5 to 40 carbons. Examples of hydrocarbon groups
include pentyl groups, hexyl groups, heptyl groups, octyl groups,
nonyl groups, decyl groups, dodecyl groups, tridecyl groups,
tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl
groups, octadecyl groups, nonadecyl groups, oleyl groups and other
hydrocarbon groups having up to 40 carbons. Preferred hydrocarbon
groups include straight chain hydrocarbon groups having between 8
and 25 carbons. In the above general formula, R.sup.23 is a
divalent hydrocarbon group having 1 to 5 carbons, preferably an
alkylene group having 2 or 3 carbons.
[0217] In the above general formula, R.sup.24 is a hydrogen atom or
a hydrocarbon group having 1 to 20 carbons. Examples of hydrocarbon
groups include alkyl groups having 1 to 20 carbons; alkenyl groups
having 2 to 20 carbons; cycloalkyl groups having 6 to 20 carbons;
and aryl groups having 6 to 20 carbons. The aryl groups may have an
alkyl group having 1 to 12 carbons. Hydrogen atoms and alkyl groups
having 1 to 10 carbons are particularly preferred as R.sup.24.
Groups having a number of amino groups and/or amide bonds in their
structure (e.g. 1 to 5 of each) can be used as the above-described
hydrocarbon groups.
[0218] The amino groups are represented by --NH-- or --NH.sub.2;
and the amide bonds are represented by
##STR00071##
They may be bonded with the carbons of the hydrocarbon group at an
arbitrary position.
[0219] The bis succinimides of the present invention are those
produced from succinic anhydrides substituted with isomerized
alkenyl groups or their fully saturated alkyl analogs, and
polyamines. Suitable polyamines are saturated amines of the general
formula
##STR00072##
where R.sup.25, R.sup.26, and R.sup.27 are independently selected
from the group consisting of H, C.sub.1 to C.sub.25 straight or
branched chain alkyl radicals, C.sub.1 to C.sub.12 alkoxy radicals;
C.sub.2 to C.sub.6 alkylene radicals; u is an integer from 1 to 6,
preferably 2 to 4; and v is an integer from 0 to 10, preferably
from 1 to 4.
[0220] Non-limiting examples of suitable polyamine compounds
include: 1,6-diaminohexane, diethylene triamine, triethylene
tetramine, tetraethylene pentamine, and pentaethylene hexamine.
Useful mixtures of polyamines having from 5 to 7 nitrogen atoms per
molecule are available from Dow Chemical Co. as Polyamine H,
Polyamine 400 and Polyamine E-300.
[0221] Polyoxyalkylene amines are also useful in this invention and
are shown as structure
H.sub.2N-alkylene-(--O-alkylene-)u.sub.1-NH.sub.2
where u.sub.1 is an integer of from 1 to 10. The polyamines have
molecular weights from about 100 to 500. The preferred
polyoxyalkylene polyamines include polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines.
Commercial polyoxyalkylene amines are available from Jefferson
Chemical Co. sold under the trade name "Jeffamines.RTM. D-230,
D-400, D-1 000, T-430," etc.
[0222] In preferred embodiments, the alkenyl succinic anhydride
starting materials for forming the friction modifiers of above
structure can be either of two types. The two types differ in the
linkage of the alkyl side chain to the succinic acid moiety. In the
first type, the alkyl group is joined through a primary carbon atom
in the starting olefin, and therefore the carbon atom adjacent to
the succinic acid moiety is a secondary carbon atom. In the second
type, the linkage is made through a secondary carbon atom in the
starting olefin and these materials accordingly have a branched or
isomerized side chain. The carbon atom adjacent to the succinic
acid moiety therefore is necessarily a tertiary carbon atom.
[0223] The alkenyl succinic anhydrides of the first type, shown
below, with linkages through secondary carbon atoms, are prepared
simply by heating .alpha.-olefins, that is, terminally unsaturated
olefins, with maleic anhydride. Non-limiting examples of these
materials include n-decenyl succinic anhydride, tetradecenyl
succinic anhydride, n-octadecenyl succinic anhydride, tetrapropenyl
succinic anhydride, poly butenyl succinic anhydrides, etc.
##STR00073##
wherein R.sup.78 is C.sub.2 to C.sub.37 alkyl.
[0224] A second type of alkenyl succinic anhydrides, with linkage
through tertiary carbon atoms, is produced from internally
unsaturated olefins and maleic anhydride. Internal olefins are
olefins which are not terminally unsaturated, and therefore do not
contain the
##STR00074##
moiety. These internal olefins can be introduced into the reaction
mixture as such, or they can be produced in situ by exposing
.alpha.-olefins to isomerization catalysts at high temperatures. A
process for producing such materials is described in U.S. Pat. No.
3,382,172 hereby incorporated by reference in its entirety. The
isomerized alkenyl substituted succinic anhydrides are compounds
having structure
##STR00075##
where x and y are independent integers whose sum is from 1 to
35.
[0225] The preferred succinic anhydrides are produced from
isomerization of linear .alpha.-olefins with an acidic catalyst
followed by reaction with maleic anhydride. The preferred
.alpha.-olefins are 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosane, or mixtures of these
materials. The products described can also be produced from
internal olefins of the same carbon numbers, 8 to 20. The preferred
materials for this invention are those made from 1-tetradecene
(x+y=9), 1-hexadecene (x+y=11), 1-octadecene (x+y=13), 1-didodecene
(x+y=15), and 1-tetradidodecene (x+y=19) or mixtures thereof.
[0226] The preferred succinimide friction modifiers of this
invention are products produced by the reaction of isomerized
alkenyl succinic anhydride with diethylene triamine, triethylene
tetramine, tetraethylene pentamine or mixtures thereof. The most
preferred products are prepared using diethylene triamine,
triethylene tetramine, and tetraethylene pentamine. The alkenyl
succinic anhydrides are typically reacted with the amines in a 2:1
molar ratio so that both primary amines are converted to
succinimides. Sometimes a slight excess of isomerized alkenyl
succinic anhydride is used to insure that all primary amines have
reacted.
[0227] The two types of succinimide friction modifiers can be used
individually or in combination.
[0228] The disuccinimides may be post-treated or further processed
by any number of techniques known in the art. These techniques
would include, but are not limited to, boration, maleation, and
acid treating with inorganic acids such as phosphoric acid,
phosphorous acid, and sulfuric acid. Descriptions of these
processes can be found in, for example, U.S. Pat. Nos. 3,254,025;
3,502,677; 4,686,054; and 4,857,214 hereby incorporated by
reference in their entirety.
[0229] Other useful derivatives of the succinimide modifiers are
where the alkenyl groups of above structures have been hydrogenated
to form their saturated alkyl analogs. Saturation of the
condensation products of olefins and maleic anhydride may be
accomplished before or after reaction with the amine. These
saturated versions of above structures may likewise be post-treated
as previously described.
[0230] While any effective amount of the compounds of above
structure and its derivatives may be used to achieve the benefits
of this invention, typically these effective amounts will range
from 0.01 to 10 weight percent of the finished fluid, preferably
from 0.05 to 7 weight percent, most preferably from 0.1 to 5 weight
percent.
Viscosity Index Improvers
[0231] Viscosity index improvers or viscosity modifiers are
typically polymers of number average molecular weight 103 to
106--for example ethylene copolymers or polybutenes. Viscosity
index improvers may be modified to have dispersant properties and
suitable viscosity index improver dispersants for use in
compositions of the invention are described in, for example, EP 24
146 A and are as follows:
[0232] (a) polymers comprising monomer units derived from a C.sub.4
to C.sub.24 unsaturated ester of vinyl alcohol or a C.sub.3 to
C.sub.10 unsaturated mono- or dicarboxylic acid and an unsaturated
nitrogen-containing monomer having 4 to 20 carbon atoms;
[0233] (b) polymers comprising monomer units derived from a C.sub.4
to C.sub.20 olefin and an unsaturated C.sub.3 to C.sub.10 mono- or
dicarboxylic acid neutralized with an amine, a hydroxyamine or an
alcohol; and
[0234] (c) polymers of ethylene with a C.sub.3 to C.sub.20 olefin
further reacted by grafting a C.sub.4 to C.sub.20
nitrogen-containing monomer thereon or by grafting an unsaturated
acid onto the polymer backbone and then reacting the carboxylic
acid groups with an amine, hydroxy amine, or alcohol. (Other
additives which may be used in accordance with the present
invention are described in EP24146A). These viscosity index
improvers also have dispersant properties, as is preferred in
accordance with the invention, although viscosity index improvers
without dispersant properties may be used if desired.
[0235] Preferred viscosity index improvers with dispersant
properties for use in the compositions of the present invention
comprise a polyolefin moiety to which is grafted an unsaturated
carboxylic acid moiety, the carboxylic acid groups being reacted
with an amine, hydroxyamine or alcohol.
[0236] Antioxidants may be evaluated using the sequence III E test
(ASTM STP 315) which is a standard test used for assessing the
oxidation resistance of lubricants and which is a more stringent
version of the sequence III D test (ASTM STP 315M and ASTM STP
315). The sequence III method produces a result after 64 hrs of
testing with an acceptable performance being a 375% or less
increase in kinematic viscosity as measured at 40.degree. C. after
this period. The principle of this method is to observe oil
thickening as a result of oxidation. When evaluating antioxidants
for lubricants it is desirable to be able to use screening test
methods which are quicker and easier to use than the Sequence III
test. One such method which is commonly used is a thin film high
temperature catalytic oxidation test performed using a DSC.
Synergistic Relationships Between Amine Tungstates and Lubricant
Additives
[0237] Applicants have found a surprising synergistic interaction
of the amine tungstates of the invention with various lubricant
additives, described herein. The synergistic interaction is
evidenced by enhanced performance properties of a lubricating oil
composition of the invention compared to the analogous lubricating
oil composition both without the amine tungstates and without the
lubricant additive.
[0238] The enhanced properties that demonstrate the synergistic
interaction of the invention include but are not limited to
oxidative stability, antiwear, extreme pressure, and anti-friction
performance.
[0239] A first embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
ashless friction modifier. Ashless friction modifiers of this first
embodiment include, but are not limited to succinimide dispersants,
borates succinimide dispersants, glycerol monooleate, cocoamide
DEA, long chain fatty amines, and long chain fatty esters. The
synergistic interaction of the first embodiment may be demonstrated
by any analytical test including, but not limited to Optimol SRV
(ASTM D 5707 Method).
[0240] A second embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
metal-containing antiwear additive. Metal-containing antiwear
additives of this second embodiment include, but are not limited
to, molybdenum dialkyldithiocarbamates, molybdenum
dialkyldithiophosphates, and zinc dialkyldithiophosphates. The
synergistic interaction of the first embodiment may be demonstrated
by any analytical test including, but not limited to ASTM D 2272
Rotory Pressure Vessel Oxidation Test and ASTM D 4172 4-Ball Wear
Test.
[0241] A third embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
ashless antiwear additive. Ashless antiwear additives of this third
embodiment include, but are not limited to, amine dithiocarbamates,
ashless dithiophosphates, ashless phosphates, ashless phosphites,
ashless trialkylthiophosphates, and ashless triarylthiophosphates.
The synergistic interaction of the third embodiment may be
demonstrated by any analytical test including, but not limited to
ASTM D 4172 4-Ball Wear Test.
[0242] A fourth embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
extreme pressure agent. Extreme pressure agents of this fourth
embodiment include, but are not limited to, sulfurized olefins and
sulfurized esters. The synergistic interaction of the fourth
embodiment may be demonstrated by any analytical test including,
but not limited to ASTM D 2783 4-Ball Weld Extreme Pressure
Test.
[0243] A fifth embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
corrosion inhibitor/detergent. Corrosion inhibitors/detergents of
this fifth embodiment include, but are not limited to, metallic
sulfonates (including "overbased" metal sulfonates containing high
total base number), ashless sulfonates, metallic salicylates,
organic amine carboxylates. The synergistic interaction of the
fifth embodiment may be demonstrated by any analytical test
including, but not limited to, ASTM D-665B Rust Test, ASTM D 2783
4-Ball Weld Extreme Pressure Test, and Optimol SRV (ASTM D 5705
Method).
[0244] A sixth embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
yellow metal deactivator/copper passivating agent. Yellow metal
deactivators/copper passivating agents of this sixth embodiment
include, but are not limited tobenzotriazole, tolyltriazole and
dimercaptothiadiazole derivatives. The synergistic interaction of
the sixth embodiment may be demonstrated by any analytical test
including, but not limited to, Optimol SRV (ASTM D 5707 Method) and
ASTM D 130 Copper Strip Corrosion Test.
[0245] A seventh embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
viscosity index improvers. Viscosity index improvers of this
seventh embodiment include, but are not limited to, olefin
copolymers (OCPs), olefin/diene copolymers such as styrene
divinylbenzene copolymers, polyacrylates and graft olefin
copolymers containing amine and/or carboxylic acid functional
groups. The synergistic interaction of the seventh embodiment may
be demonstrated by any analytical test including, but not limited
to, Optimol SRV (ASTM D 5707 Method), ASTM D 7342 Shear Stability
Test and viscosity index measurement.
[0246] An eighth embodiment of the invention that demonstrates the
synergistic effect is a lubricating oil composition comprising a
lubricating oil, an organo amine tungstate, a secondary diarylamine
and/or alkylated phenothiazine, and further comprising one or more
pour point depressants. Pour point depressants of this eighth
embodiment include, but are not limited to, polyacrylates and
poly(alkylaromatics). The synergistic interaction of the eighth
embodiment may be demonstrated by any analytical test including,
but not limited to, Optimol SRV (ASTM D 5707 Method), ASTM D 4172
4-Ball Wear Test and ASTM D 97 Pour Point Test.
[0247] Other examples of friction modifiers suitable for use in the
present invention include substituted succinimides such as
glycolated or borated succinimide friction modifiers. Also useful
are such compounds as aliphatic fatty amines or alkoxylated
aliphatic fatty amines, alkoxylated aliphatic ether amines,
aliphatic carboxylic acids, aliphatic fatty acid amides,
alkoxylated aliphatic fatty acid amides, aliphatic fatty
imidazolines, and aliphatic fatty tertiary amines, wherein the
aliphatic group usually contains above about eight carbon atoms so
as to render the compound suitably oil soluble. Also useful are
aliphatic substituted succinimides formed by reacting one or more
aliphatic succinic acids or anhydrides with ammonia or other
primary amines such as those taught in EP-A-0389237, as well as
mixtures of two or more friction modifiers. Friction modifiers
suitable for use in the present invention are described in the
following U.S. patents, incorporated herein by reference for their
disclosures relating to friction modifiers: U.S. Pat. Nos.
5,344,579; 5,372,735 and 5,441,656.
[0248] In addition, other types of ashless friction modifiers can
include
(i) fatty phosphites (ii) fatty acid amides (iii) fatty epoxides
(iv) borated fatty epoxides (v) fatty amines other than component
(b) above (vi) glycerol esters (vii) borated glycerol esters (viii)
alkoxylated fatty amines (ix) borated alkoxylated fatty amines (x)
metal salts of fatty acids (xi) sulfurized olefins (xii) fatty
imidazolines (xiii) condensation products of carboxylic acids and
polyalkylene-polyamines (xv) amine salts of alkylphosphoric acids
and mixtures thereof.
[0249] Representatives of each of these types of friction modifiers
are known and are commercially available. For instance, (i) fatty
phosphites are generally of the formula (RO).sub.2PHO. The
preferred dialkyl phosphite, as shown in the preceding formula, is
typically present with a minor amount of monoalkyl phosphite of the
formula (RO)(HO)PHO. In these structures, the term "R" is
conventionally referred to as an alkyl group. The terms "alkyl" and
"alkylated," as used herein, will embrace both saturated and
unsaturated alkyl groups within the phosphite. The phosphite should
have sufficient hydrocarbyl groups to render the phosphite
substantially oleophilic. Preferably the hydrocarbyl groups are
substantially unbranched. Many suitable phosphites are available
commercially and may be synthesized as described in U.S. Pat. No.
4,752,416. It is preferred that the phosphite contain 8 to 24
carbon atoms in each of R groups. Preferably, the fatty phosphite
contains 12 to 22 carbon atoms in each of the fatty radicals, most
preferably 16 to 20 carbon atoms. In one embodiment the fatty
phosphite can be formed from oleyl groups, thus having 18 carbon
atoms in each fatty radical.
[0250] (iv) Borated fatty epoxides are known from Canadian Patent
No. 1,188,704. These oil-soluble boron-containing compositions are
prepared by reacting, at a temperature from 80.degree. C. to
250.degree. C., boric acid or boron trioxide with at least one
fatty epoxide having the formula wherein each of R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 is hydrogen or an aliphatic radical, or any two
thereof together with the epoxy carbon atom or atoms to which they
are attached, form a cyclic radical. The fatty epoxide preferably
contains at least 8 carbon atoms.
[0251] The borated fatty epoxides can be characterized by the
method for their preparation which involves the reaction of two
materials. Reagent A can be boron trioxide or any of the various
forms of boric acid including metaboric acid (HBO.sub.2),
orthoboric acid (H.sub.3BO.sub.3) and tetraboric acid
(H.sub.2B.sub.4O.sub.7). Boric acid, and especially orthoboric
acid, is preferred. Reagent B can be at least one fatty epoxide
having the above formula. In the formula, each of the R groups is
most often hydrogen or an aliphatic radical with at least one being
a hydrocarbyl or aliphatic radical containing at least 6 carbon
atoms. The molar ratio of reagent A to reagent B is generally
1:0.25 to 1:4. Ratios of 1:1 to 1:3 are preferred, with about 1:2
being an especially preferred ratio. The borated fatty epoxides can
be prepared by merely blending the two reagents and heating them at
temperature of 80.degree. to 250.degree. C., preferably 100.degree.
to 200.degree. C., for a period of time sufficient for reaction to
take place. If desired, the reaction may be effected in the
presence of a substantially inert, normally liquid organic diluent.
During the reaction, water is evolved and may be removed by
distillation.
[0252] (iii) Non-borated fatty epoxides, corresponding to "Reagent
B" above, are also useful as friction modifiers.
[0253] Borated amines are generally known from U.S. Pat. No.
4,622,158. Borated amine friction modifiers (including (ix) borated
alkoxylated fatty amines) are conveniently prepared by the reaction
of a boron compounds, as described above, with the corresponding
amines. The amine can be a simple fatty amine or hydroxy containing
tertiary amines. The borated amines can be prepared by adding the
boron reactant, as described above, to an amine reactant and
heating the resulting mixture at a 500 to 300.degree. C.,
preferably 100.degree. C. to 250.degree. C. or 150. .degree. C. to
230.degree. C., with stirring. The reaction is continued until
by-product water ceases to evolve from the reaction mixture
indicating completion of the reaction.
[0254] Among the amines useful in preparing the borated amines are
commercial alkoxylated fatty amines known by the trademark
"ETHOMEEN" and available from Akzo Nobel. Representative examples
of these ETHOMEEN..TM.. materials is ETHOMEEN..TM.. C/12
(bis[2-hydroxyethyl]-coco-amine); ETHOMEEN..TM.. C/20
(polyoxyethylene[10]cocoamine); ETHOMEEN..TM.. S/12
(bis[2-hydroxyethyl]soyamine); ETHOMEEN..TM.. T/12
(bis[2-hydroxyethyl]-tallow-amine); ETHOMEEN..TM.. T/15
(polyoxyethylene-[5]tallowamine); ETHOMEEN..TM.. 0/12
(bis[2-hydroxyethyl]oleyl-amine); ETHOMEEN..TM.. 18/12
(bis[2-hydroxyethyl]octadecylamine); and ETHOMEEN..TM.. 18/25
(poly-oxyethyl-ene[15]octadecylamine). Fatty amines and ethoxylated
fatty amines are also described in U.S. Pat. No. 4,741,848.
[0255] The (viii) alkoxylated fatty amines, and (v) fatty amines
themselves (such as oleylamine) are useful as friction modifiers in
this invention. Such amines are commercially available.
[0256] Both borated and unborated fatty acid esters of glycerol can
be used as friction modifiers. The (vii) borated fatty acid esters
of glycerol are prepared by borating a fatty acid ester of glycerol
with boric acid with removal of the water of reaction. Preferably,
there is sufficient boron present such that each boron will react
with from 1.5 to 2.5 hydroxyl groups present in the reaction
mixture. The reaction may be carried out at a temperature in the
range of 60.degree. C. to 135.degree. C., in the absence or
presence of any suitable organic solvent such as methanol, benzene,
xylenes, toluene, or oil.
[0257] (vi) Fatty acid esters of glycerol themselves can be
prepared by a variety of methods well known in the art. Many of
these esters, such as glycerol monooleate and glycerol tallowate,
are manufactured on a commercial scale. The esters useful are
oil-soluble and are preferably 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 preferred, although, mixtures of mono- and diesters
may be used. For example, commercial glycerol monooleate may
contain a mixture of 45% to 55% by weight monoester and 55% to 45%
diester.
[0258] Fatty acids can be used in preparing the above glycerol
esters; they can also be used in preparing their (x) metal salts,
(ii) amides, and (xii) imidazolines, any of which can also be used
as friction modifiers. Preferred fatty acids are those containing 6
to 24 carbon atoms, preferably 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. Preferred metal salts include zinc and calcium
salts. Examples are overbased calcium salts and basic oleic
acid-zinc salt complexes which can be represented by the general
formula Zn4Oleate.sub.3O.sub.1. Preferred amides are those prepared
by condensation with ammonia or with primary or secondary amines
such as diethylamine and diethanolamine. Fatty imidazolines are the
cyclic condensation product of an acid with a diamine or polyamine
such as a polyethylenepolyamine.
[0259] Sulfurized olefins (xi) are well known commercial materials
used as friction modifiers. A particularly preferred sulfurized
olefin is one which is prepared in accordance with the detailed
teachings of U.S. Pat. Nos. 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.
[0260] Reactant (3), the olefin component, comprises at least one
olefin. This olefin is preferably an aliphatic olefin, which
usually will contain 4 to 40 carbon atoms, preferably from 8 to 36
carbon atoms. Terminal olefins, or alpha-olefins, are preferred,
especially those having from 12 to 20 carbon atoms. Mixtures of
these olefins are commercially available, and such mixtures are
contemplated for use in this invention.
[0261] The cosulfurized mixture of two or more of the reactants, is
prepared by reacting the mixture of appropriate reactants with a
source of sulfur. The mixture to be sulfurized can contain 10 to 90
parts of Reactant (1), or 0.1 15 parts by weight of Reactant (2);
or 10 to 90 parts, often 15 to 60 parts, more often 25 to 35 parts
by weight of Reactant (3), or 10 to 90 parts by weight of reactant
(4). The mixture, in the present invention, includes Reactant (3)
and at least one other member of the group of reactants identified
as reactants (1), (2) and (4). The sulfurization reaction generally
is effected at an elevated temperature with agitation and
optionally in an inert atmosphere and in the presence of an inert
solvent. The sulfurizing agents useful in the process of the
present invention include elemental sulfur, which is preferred,
hydrogen sulfide, sulfur halide plus sodium sulfide, and a mixture
of hydrogen sulfide and sulfur or sulfur dioxide. Typically often
0.5 to 3 moles of sulfur are employed per mole of olefinic
bonds.
[0262] Amine salts of alkylphosphoric acids (xv) include salts of
oleyl and other long chain esters of phosphoric acid, with amines
as described below. Useful amines in this regard are
tertiary-aliphatic primary amines, sold under the tradename
Primene..TM.. The supplemental friction modifier can be used in
addition to component (a). The amount of the supplemental friction
modifier is generally 0.1 to 1.5 percent by weight of the
lubricating composition, preferably 0.2 to 1.0 or 0.25 to 0.75
percent. In some embodiments, however, the amount of the
supplemental friction modifier is present at less than 0.2 percent
or less than 0.1 percent by weight, for example, 0.01 to 0.1
percent. In one embodiment the amount of dihydroxyethyl tallowamine
(commercially sold as ENT-12..TM..) in particular is restricted to
these low amounts or less.
[0263] A wide variety of sulfur-containing extreme pressure or
antiwear agents are available for use in the practice of this
invention. Among suitable compositions for this use are included
sulfurized animal or vegetable fats or oils, sulfurized animal or
vegetable fatty acid esters, fully or partially esterified esters
of trivalent or pentavalent acids of phosphorus, sulfurized olefins
(see for example U.S. Pat. Nos. 2,995,569; 3,673,090; 3,703,504;
3,703,505; 3,796,661; 3,873,545; 4,119,549; 4,119,550; 4,147,640;
4,191,659; 4,240,958; 4,344,854; 4,472,306; and 4,711,736),
dihydrocarbyl polysulfides (see for example U.S. Pat. Nos.
2,237,625; 2,237,627; 2,527,948; 2,695,316; 3,022,351; 3,308,166;
3,392,201; 4,564,709; and British 1,162,334), sulfurized
Diels-Alder adducts (see for example U.S. Pat. Nos. 3,632,566;
3,498,915; and Re No. 27,331), sulfurized dicyclopentadiene (see
for example U.S. Pat. Nos. 3,882,031 and 4,188,297), sulfurized or
co-sulfurized mixtures of fatty acid esters and monounsaturated
olefin (see for example U.S. Pat. Nos. 4,149,982; 4,166,796;
4,166,797; 4,321,153; 4,481,140), co-sulfurized blends of fatty
acid, fatty acid ester and .alpha.-olefin (see for example U.S.
Pat. No. 3,953,347), functionally-substituted dihydrocarbyl
polysulfides (see for example U.S. Pat. No. 4,218,332),
thia-aldehydes, thia-ketones and derivatives thereof (e.g., acids,
esters, imines, or lactones) (see for example, U.S. Pat. No.
4,800,031; and International Application Publication No. WO
88/03552), epithio compounds (see for example, U.S. Pat. No.
4,217,233), sulfur-containing acetal derivatives (see for example
U.S. Pat. No. 4,248,723), co-sulfurized blends of terpene and
acyclic olefins (see for example U.S. Pat. No. 4,584,113), and
polysulfide olefin products (see for example U.S. Pat. No.
4,795,576).
[0264] Preferred sulfur-containing extreme pressure or antiwear
agents sulfur-containing organic compounds in which the
sulfur-containing species are bound directly to carbon or to more
sulfur.
[0265] A particularly preferred class of such agents is made by
reacting an olefin, such as isobutene, with sulfur. The product,
e.g., sulfurized isobutene, preferably sulfurized polyisobutylene,
typically has a sulfur content of 10 to 55%, preferably 30 to 50%
by weight. A wide variety of other olefins or unsaturated
hydrocarbons, e.g., isobutene dimer or trimer, may be used to form
such agents.
[0266] Another particularly preferred class of such agents is that
of polysulfides composed of one or more compounds represented by
the formula: R6-S.sub.x--R7 where R6 and R7 are hydrocarbyl groups
each of which preferably contains 3 to 18 carbon atoms and x is
preferably in the range of from 2 to 8, and more preferably in the
range of from 2 to 5, especially 3. The hydrocarbyl groups can be
of widely varying types such as alkyl, cycloalkyl, alkenyl, aryl,
or aralkyl. Tertiary alkyl polysulfides such as di-tert-butyl
trisulfide, and mixtures comprising di-tert-butyl trisulfide (e.g.,
a mixture composed principally or entirely of the tri, tetra-, and
pentasulfides) are preferred. Examples of other useful
dihydrocarbyl polysulfides include the diamyl polysulfides, the
dinonyl polysulfides, the didodecyl polysulfides, and the dibenzyl
polysulfides.
[0267] The invention will be further illustrated by means of the
following examples. The following examples illustrate the invention
and are not to be used to limit the scope of the invention.
Preparation of Amine Tungstates from Tungstic Acid (Method A)
[0268] A mixture of the starting amine (2 eq.), tungstic acid (1
eq.), dissolved in aqueous ammonia was stirred at 95-1100 C for 2-3
hrs, and water and excess ammonia were then removed by distillation
followed by the isolation of the product as viscous liquid.
Preparation of Amine Tungstates from Ammonium Para Tungstate
(Method B)
[0269] A mixture of the starting amine (26 eq.) and aqueous
ammonium paratungstate (1 eq.) was heated with vigorous mixing.
Water and excess ammonia were then removed by distillation followed
by the isolation of the product as viscous liquid.
Preparation of Amine Tungstates from Metal Tungstates (Method
C)
[0270] Tungstic acid can also be prepared from an appropriate metal
tungstate and sulfuric acid. The reaction of tungstic acid (1 eq.)
with the appropriate amine (2 eq.) can be conducted in a
hydrocarbon solvent at elevated temperatures, to yield the desired
amine tungstate product.
Preparation of Amine Tungstates from Metal Tungstates and
Quaternary Ammonium Halides or Sulfates (Method D)
[0271] The amine tungstates can also be prepared by the reaction of
quaternary ammonium halides or sulfates, in heptane with sodium or
potassium tungstate in water.
TABLE-US-00001 Method Physical Example Starting amine Used Form % W
1 Primene JMT(C.sub.16-C.sub.22 tert-alkyl primary A Yellow 18.7
aliphatic amine) Liquid 2 Primene JMT(C.sub.16-C.sub.22 tert-alkyl
primary B Yellow 19.5 aliphatic amine) Liquid 3 Primene
JMT(C.sub.16-C.sub.22 tert-alkyl primary C Yellow 11 aliphatic
amine) Liquid 4 Primene JMT(C.sub.16-C.sub.22 tert-alkyl primary C
Yellow 32.6 aliphatic amine) (tungstic Liquid acid:amine 1:1) 5
Primene JMT(C.sub.16-C.sub.22 tert-alkyl primary D Yellow 34
aliphatic amine) viscous Liquid 6 Primene 81R(C12-C14 tert-alkyl
primary A White waxy 18 aliphatic amine amine) solid 7 Di(tridecyl)
amine A Yellow 9.1 liquid 8 Di(tridecyl) amine B Yellow 15.0 liquid
9 Di(tridecyl) amine C Yellow 28.4 liquid 10 Salt of
N-oleyl-1,3-propanediamine B Blue-Green 8.9 (Duomeen OL), with
Dinonyl naphthalene Liquid sulfonic acid 11 Salt of
N-oleyl-1,3-propanediamine B Blue-Green 8.3 (Duomeen OL), with
Didodecyl naphthalene Liquid sulfonic acid 12 Salt of
N-oleyl-1,3-propanediamine B Yellow 13.8 (Duomeen OL), with
Naphthenic acid liquid 13 Reaction product of Canola Oil with N- B
Yellow 9.6 oleyl-1,3-propanediamine (Duomeen OL) Liquid 14 Reaction
product of aminoethyl imidazoline C Yellow 8.0 with Didodecyl
naphthalene sulfonic acid Liquid 15 Bis succinimide from alkenyl
succinic B Yellow 2.5 anhydride and diethylene triamine Liquid 16
Bis(2-hydroxyethyl)cocoalkylamine B Yellow 17.4 Liquid 17 Alkyl
(C14-C18) bis(2-hydroxyethyl) B Yellow 5.7 amine Liquid 18 Alkyl
(C14-C18) bis(2-hydroxyethyl) B Yellow 7.9 amine Liquid 19 Salt of
N-oleyl-1,3- B Yellow 7.4 propanediamine(Duomeen OL), with Di(2-
Liquid ethylhexyl) phosphonic acid 20 Salt of N-oleyl-1,3- B Brown
10.9 propanediamine(Duomeen OL), with Di(2- Liquid ethylhexyl)
dithiophosphoric acid 21 Bis succinimide from alkenyl succinic C
Yellow 8.3 anhydride and diethylene triamine Liquid 22 Salt of
N-oleyl-1,3- B Yellow propanediamine(Duomeen OL), with Liquid
dioleyl phosphonic acid
Preparation of New Amine Molybdates
[0272] A solution of starting amine (2 eq.), in heptane was
combined with Molybdenum trioxide (1 eq.) in water and the
resulting mixture was heated under reflux for 4-6 hrs. Water was
removed by azeotropic distillation, under reduced pressure,
resulting in the desired amine molybdates as a viscous oily
product.
[0273] Another method involved the reaction of sodium molybdate (1
eq.) in water with amine (2 eq.) at 60-70.degree. C., for 1 hr.,
followed by the addition of 1 eq., of aqueous sulfuric acid. The
aqueous layer was separated and the organic residue was dehydrated
under reduced pressure tresulting in the desired molybdate as a
viscous oily product.
[0274] Yet another method involved the reaction of ammonium
molybdate (1 eq.), with amine (2 eq.) in refluxing toluene, and
removing water continuously. The molybdate was isolated as a
viscous liquid.
TABLE-US-00002 Moly source Physical Example Starting amine Used
Form % Mo 23 Salt of N-oleyl-1,3-propanediamine (Duomeen MoO.sub.3
Brown 5.37 OL), with Dinonyl naphthalene sulfonic acid Liquid 24
Salt of N-oleyl-1,3-propanediamine (Duomeen MoO.sub.3 Viscous 4.1
OL), with Naphthenic acid Yellow Liquid 25 Salt of
N-oleyl-1,3-propanediamine(Duomeen MoO.sub.3 Yellow 4.2 OL), with
Di(2-ethylhexyl) phosphoric acid Liquid 26 Bis succinimide from
alkenyl succinic MoO.sub.3 Viscous 2.6 anhydride and diethylene
triamine Green Liquid 27 Salt of N-oleyl-1,3-propanediamine(Duomeen
MoO.sub.3 Brown 6.3 OL), with Di(2-ethylhexyl) dithiophosphoric
Liquid acid
Test for Oxidation Induction Time by Pressure Differential Scanning
Calorimetry (PDSC)
[0275] The Pressure Differential Scanning Calorimetry (PDSC) test
method is a thin film high temperature catalytic oxidation test,
for determination of oxidation induction time (OIT). The procedure
used for this analysis was ASTM 6186-03. In the test, the compounds
to be evaluated for antioxidancy performance were added at the
required treat rate to a sample of Chevron Group II ISOVG 46 base
oil containing no other additive. This test sample (6-9 mg) was
placed in the center of an aluminum DSC pan and inserted into a
DuPont 910 High Pressure DSC, equipped with a pressure cell and
interfaced to a TA Instruments 2000 thermal analysis controller.
The pressure cell of the DSC was closed, purged with O.sub.2,
equilibrated at 70.degree. C., and heated to 210.degree. C. at a
rate of 40.degree. C./min. When the temperature had reached
209.degree. C. the cell was pressurized with oxygen to a pressure
of 500 psi and the cell held at 210.degree. C. After a period of
time the test sample underwent an exothermic oxidative reaction;
this event and magnitude of the associated heat effects compared to
the inert reference were monitored and recorded. The data obtained
was analyzed using TA Instruments Universal Analysis program V4.1D.
The oxidation induction time (OIT; time to auto-oxidation) is the
time at which the baseline intersects with a line tangent to the
curve of the exothermal heat flow versus time scan. The OIT is
reported in minutes. The magnitude of the OIT is an indication of
the effectiveness of the compounds or compound mixtures under test
as antioxidants; the larger the OIT the greater the antioxidant
effect.
TABLE-US-00003 Oxidation induction time Sample (minutes) 0.5% amine
tungstate of Ex. 1 0 0.5% NA-LUBE AO142(Octyl/butyldiphenyl amine)
2.8 0.5% NA-LUBE AO142(Octyl/butyldiphenyl amine) + 12.0 900 ppm
amine tungstate of Ex. 1
Clearly the amine tungstates of the current invention provided
synergistic antioxidant activity, in combination with aminic
antioxidants. Synergistic antioxidant effects of combining amine
tungstate compounds of the current invention with an aminic
antioxidant were noted with a larger OIT for these
combinations.
Oxidative Stability by Rotating Pressure Vessell Oxidation Test
(RPVOT)
[0276] Also thermo-oxidative stability of these synergistic
mixtures in combination with Group II base oil at various
concentrations were determined using the ASTM D 2272 Rotating
Pressure Vessell Oxidation Test (RPVOT) method.
[0277] The RPVOT test utilizes an oxygen-pressure bomb to evaluate
the oxidation stability of oils in the presence of water and a
copper catalyst coil at 150.degree. C. The test oil, water and a
copper catalyst coil, contained in a covered glass container, were
placed in a vessel equipped with a pressure gauge. The bomb was
charged with oxygen to a pressure of 90 psi, placed in a constant
temperature oil bath at 150.degree. C., and rotated axially at 100
rpm at an angle of 30.degree. from the horizontal. The time period
required for the pressure to drop to 25 psi is the measure of the
oxidation stability of the test sample: the longer the time, the
better the oxidative stability of the material.
TABLE-US-00004 Sample in Chevron ISO VG 46 base Oil W (ppm) RPVOT
minutes No additive 38 0.5% NA-LUBE .RTM. AO142(Octyl/butyldiphenyl
amine) -- 313 0.5% NA-LUBE .RTM. AO142(Octyl/butyldiphenyl amine) +
142 1359 amine tungstate of Ex. 10 0.5% NA-LUBE .RTM.
AO142(Octyl/butyldiphenyl amine) + 133 1274 amine tungstate of Ex.
11 0.5% NA-LUBE .RTM. AO142(Octyl/butyldiphenyl amine) + 139 918
amine tungstate of Ex. 16 0.5% NA-LUBE .RTM.
AO142(Octyl/butyldiphenyl amine) + 143 1202 amine tungstate of Ex.
17 0.5% NA-LUBE .RTM. AO142(Octyl/butyldiphenyl amine) + 145 1163
amine tungstate of Ex. 15 0.5% NA-LUBE .RTM.
AO142(Octyl/butyldiphenyl amine) + 142 1170 amine tungstate of Ex.
18 0.5% NA-LUBE .RTM. AO142(Octyl/butyldiphenyl amine) + 142 828
amine tungstate of Ex. 8 0.5% NA-LUBE .RTM.
AO142(Octyl/butyldiphenyl amine) + 142 532 amine tungstate of Ex. 9
0.5% NA-LUBE .RTM. AO142(Octyl/butyldiphenyl amine) + 142 801 amine
tungstate of Ex. 5 0.5% NA-LUBE AO142(Octyl/butyldiphenyl amine) +
140 1023 amine tungstate of Ex. 12 0.5% NA-LUBE
AO142(Octyl/butyldiphenyl amine) + 140 1790 amine tungstate of Ex.
14 0.5% NA-LUBE AO142(Octyl/butyldiphenyl amine) + 140 636 amine
tungstate of Ex. 13
[0278] Synergistic antioxidant effects of combining amine tungstate
compounds of the current invention with an aminic antioxidant were
once again noted with a larger induction time for these
combinations.
TABLE-US-00005 RPVOT Sample in Chevron ISO VG 46 base Oil W (ppm)
minutes No additive 38 Amine tungstate of Ex. 1 144 32 0.5% NA-LUBE
.RTM. AO142(Octyl/butyldiphenyl -- 313 amine) 0.5% NA-LUBE .RTM.
AO142(Octyl/butyldiphenyl 144 865 amine) + amine tungstate of Ex. 1
0.7% ZDDP(Zinc dialkyldithiophosphate) -- 130 0.7% ZDDP(Zinc
dialkyldithiophosphate) + 144 488 amine tungstate of Ex. 1
[0279] Synergistic antioxidant effects of combining amine tungstate
compounds of the current invention with an aminic antioxidant, and
a dialkyl dithiophosphate were once again noted with a larger
induction time for these combinations.
Friction Performance
[0280] The friction coefficients of compounds of current invention
were evaluated in prototype motor oil using a modified ASTM D5707
SRV Ball on Plate protocol; 400N, 50 Hz; 1.00 mm stroke 120.degree.
C.; 120 min. The data showed an improvement in friction coefficient
for compounds of current invention compared to the base oil with no
friction modifier additive.
TABLE-US-00006 Sample in Chevron ISO VG 46 base Oil, containing
ashless dithiophosphate, ZDDP, Final friction triphenylphosphate
ester, and alkylated coefficient) naphthalene sulfonate rust
inhibitor W (ppm) after 120 min.) No additive -- 0.103 Ex. 8 142
0.069 Ex. 5 142 0.065 Ex. 9 142 0.085 Ex. 1 144 0.061 Ex. 2 142
0.062 Ex. 10 142 0.076 Ex. 18 142 0.070 Ex. 11 142 0.079 Ex. 12 142
0.079 Ex. 13 451 0.071 Ex. 14 448 0.078 Ex. 17 143 0.080 Ex. 19 500
0.061 Sample in Exxon Superflo 10w-30 Final friction coefficient)
oil Mo (ppm) after 120 min.) No additive -- 0.135 Molyvan 855 800
0.054 Ex. 23 537 0.053 Ex. 24 520 0.057 Ex. 25 521 0.063 Ex. 26 520
0.054
[0281] I. Synergy of Amine Tungstates with Metal-Containing
Antiwear Additives
[0282] a) Oxidative Stability by Rotating Pressure Vessel Oxidation
Test
[0283] The synergistic thermo-oxidative stability of combinations
of the amine tungstates of the invention and metal-containing
antiwear additives in an ISO VG 46 Group II oil containing an amine
antioxidant is demonstrated using the ASTM D 2272 Rotating Pressure
Vessel Oxidation Test (RPVOT) method.
[0284] The RPVOT test utilizes an oxygen-pressure bomb to evaluate
the oxidation stability of oils in the presence of water and a
copper catalyst coil at 150.degree. C. The test oil, water and a
copper catalyst coil, contained in a covered glass container, were
placed in a vessel equipped with a pressure gauge. The bomb was
charged with oxygen to a pressure of 90 psi, placed in a constant
temperature oil bath at 150.degree. C. and rotated axially at 100
rpm at an angle of 30.degree. from the horizontal. The time period
(in minutes) required for the pressure to drop to 25 psi is the
measure of the oxidation stability of the test sample: the longer
the time, the better the oxidative stability of the material.
EXAMPLE 28
[0285] NALUBE AO-142, an alkylated diphenylamine antioxidant
available from King Industries, Inc., Norwalk, Conn., the product
of Example 2 and an ISO VG 46 Group II base oil from Chevron were
blended in the amounts shown in Table 1 for 30 minutes at
50.degree. C. The resulting formulated oil was evaluated for
oxidative stability by the ASTM D 2272 Rotating Pressure Vessel
Oxidation Test (RPVOT) as described above.
EXAMPLES 29-30
[0286] The formulated oils of Examples 29 and 30 were prepared
using the procedure of Example 28 except that Molyvan 822, a
molybdenum dialkyldithiocarbamate available from R. T. Vanderbilt
was substituted completely or partially for the product of Example
2 in the amounts designated in Table 1.
[0287] The RPVOT results show that the formulation of Example 30,
containing a combination of the amine tungstate and
organomolybdenum compound (Molyvan 855) gave an improved oxidation
stability compared to formulations containing only the amine
tungstate or organomolybdate at equivalent total metal content.
TABLE-US-00007 TABLE 1 Example Components, wt % 28 29 30 NA-LUBE
AO-142 0.25 0.25 0.25 Molyvan 822 (4.9% Mo) -- 0.59 0.295 Amine
Tungstate of Example 2 (18% W) 0.16 -- 0.08 Chevron ISO 46 Grp II
Base Oil 99.59 99.16 99.38 Molybdenum Content (ppm) 288 0 144
Tungsten Content (ppm) 0 288 144 Total Metal Content (ppm) 288 288
288
[0288] b) Wear Performance by ASTM D 4172 Four Ball Wear
Testing
[0289] The synergistic wear performance of combinations of the
amine tungstates of the invention and metal-containing antiwear
additives in a formulated ISO VG Group II oil containing both and
amine antioxidant and a phenolic antioxidant is demonstrated using
the Four Ball Wear Test. The wear tests were conducted on a four
ball friction and wear machine manufactured by Falex Corporation
using the conditions specified in ASTM D 4172 test method. Tests
were conducted at a temperature of 75.degree. C., load of 40 Kg,
rotation speed of 1200 rpm and test duration of 1 hour.
EXAMPLE 31
[0290] The base model formulated oil used for this test is shown in
Table 1 to which a fixed amount of metal-containing antiwear
additive was added. Metal-containing antiwear additives evaluated
were Molyvan 822, a molybdenum dialkyldithiocarbamate available
from R. T. Vanderbilt; Molyvan L, a molybdenum dialkylthiophosphate
available from R. T. Vanderbilt; and Rhein Chemie RC 8210, a zinc
dialkyldithiophosphate available from Rhein Chemie. To the
formulation containing the fixed concentration of metal-containing
antiwear additive was added increasing amounts of the amine
tungstates of the invention (Example 2). Each resulting formulation
was tested by the ASTM D 4172 Four Ball Wear Test. In all cases,
the wear scar of formulations with the metal-containing antiwear
additive decreased with increasing concentration of the amine
tungstate of the invention (Example 2). It was also demonstrated
that the amine tungstate at the highest concentration of Table 3
(0.32 wt percent) did not provide any improvement in wear scar over
the base formulation of Table 2.
[0291] The results show that the amine tungstates of the invention
impart little to no wear performance to formulated oils when used
alone, however; the amine tungstates of the invention improve the
wear performance of formulations already containing
metal-containing antiwear additives as demonstrated by the
improvement in wear performance with increasing amine tungstate
concentration at a fixed concentration of the metal-containing
antiwear additive.
TABLE-US-00008 TABLE 2 Base Formulation ASTM D 4172 Four-ball Wear
Tests Additive Percent of Composition NA-LUBE AO-130 0.1 NA-LUBE
AO-210 0.1 K-CORR NF-200 0.05 ISO VG 46 Gr II balance
TABLE-US-00009 TABLE 3 Amount of Amine Tungstate (Example 2) added
to formulations containing the Metal-Containing Antiwear Additives
at a Fixed Concentration Concentration of Amine Tungsten Tungstate,
(Percent) Concentration (ppm) 0.04 72 0.08 144 0.16 288 0.32 576 a)
Available from R. T. Vanderbilt as Molyvan 822 b) Available from R.
T. Vanderbilt as Molybvan L c) Available from Rein Chemie as RC
3180.
[0292] II. Synergy of Amine Tungstates with Ashless Friction
Modifiers
[0293] a) Anti-Friction Performance
[0294] The synergistic anti-friction performance of the amine
tungstates of the invention in combination with ashless friction
modifiers in a model formulated oil is demonstrated using an SRV4
friction and wear instrument manufactured by Optimol Instruments.
The specific conditions for the all tests were according to ASTM D
5707 test method. All tests were conducted at 120.degree. C. using
a ball on plate configuration, a load of 400N, frequency of 50 Hz,
a stroke of 1.00 mm stroke and test duration of 120 minutes. The
coefficient of friction is measured as a function of time and an
average coefficient of friction is calculated for the entire run at
the completion of the test. A lower value for the average
coefficient of friction is indicative of an oil with better
anti-friction performance.
EXAMPLE 32
[0295] The amine tungstate of Example 2 and a bis(succinimide)
ashless friction modifier derived from the reaction of C20-C24
alkenyl succinic anyhdride (available as ASA2024 from Dixie
Chemical Company) and tetratethylenepentamine (available from Akzo
Nobel Functional Chemicals, AB) are blended at 50.degree. C. for 30
minutes with CP Chem PAO 40, CP Chem PAO 8, NALUBE KR-015, K-CORR
NF 200, and a zinc dialkyldithiophosphate (RC 8210, available from
Rhein Chemie) at the weight percentage composition according Table
4, Example 32. The formulated gear oil thus prepared contains 0.5
wt % of the amine tungstate and 0.5 wt % of the bis(succinimide)
ashless friction modifier. The formulated oil is evaluated in the
SRV friction and wear test according to the ASTM D 5707 general
method using the specific conditions outlined above. The average
coefficient of friction for the test was 0.044.
EXAMPLES 33-34
[0296] Formulated gear oils were prepared and tested according to
the procedure of Example 32 using the amounts of each component
listed in Table 4. The average coefficient of friction for Examples
33 and 34 were 0.083 and 0.10, respectively. The results of
Examples 32-34 demonstrate that the anti-friction performance for
the combination of the amine tungstate with a succinimide ashless
friction modifier is significantly improved over the anti-friction
performance of the amine tungstate and ashless friction modifier
alone at equivalent total concentration.
EXAMPLES 35-37
[0297] Formulated gear oils were prepared and tested according to
the procedure of Example 32 using the amounts of each component
listed in Table 4. The average coefficient of friction for Examples
35-39 were 0.058, 0.10 and 0.105, respectively. The results of
Examples 35-37 demonstrate that the anti-friction performance for
the combination of the amine tungstate with a succinimide ashless
friction modifier is significantly improved over the anti-friction
performance of the amine tungstate and ashless friction modifier
alone at equivalent total concentration.
EXAMPLES 38-39
[0298] Formulated gear oils were prepared and tested according to
the procedure of Example 32 using the amounts of each component
listed in Table 4. In this case the succinimide ashless friction
modifier was replaced with glycerol monooleate. The average
coefficient of friction for Examples 38 (containing the combination
of amine tungstate of Example 2 and glycerol monooleate) was
significantly lower than that of Example 33 (containing only the
amine tungstate of Example 2) and Example 39 (containing only
glycerol monooleate). The results of Examples 33, 38 and 39
demonstrate that the anti-friction performance for the combination
of the amine tungstate with an ashless glycerol ester friction
modifier is significantly improved over the anti-friction
performance of the amine tungstate and ashless friction modifier
alone at equivalent total concentration.
EXAMPLES 40-41
[0299] Formulated gear oils were prepared and tested according to
the procedure of Example 32 using the amounts of each component
listed in Table 4. In this case the succinimide ashless friction
modifier was replaced with cocoamide diethanolamine ashless
friction modifier. The results of Examples 33, 40 and 41
demonstrate that the anti-friction performance for the combination
of the amine tungstate with an ashless hydroxyalkylamide friction
modifier is significantly improved over the anti-friction
performance of the amine tungstate and ashless friction modifier
alone at equivalent total concentration.
TABLE-US-00010 TABLE 4 Example 32 33 34 35 36 37 38 39 40 41
Components PAO 40.sup.a 70.10 70.10 70.10 70.60 70.6 70.6 70.10
70.10 70.10 70.10 PAO 8.sup.b 17.78 17.78 17.78 17.78 17.78 17.78
17.78 17.78 17.78 17.78 Alkylated Aromatic.sup.c 9.87 9.87 9.87
9.87 9.87 9.87 9.87 9.87 9.87 9.87 Zinc 1.2 1.2 1.2 1.2 1.2 1.2 1.2
1.2 1.2 1.2 Dialkyldithiophosphate Benzotriazole derivative 0.05
0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 yellow metal
deactivator.sup.e Amine Tungstate of 0.50 1.0 0 0.25 0.50 0 0.50 0
0.50 0 Example 2 Bis(succinimide) Ashless 0.50 0 1.0 0.25 0 0.50 --
-- -- -- Friction Modifier Glycerol Monooleate -- -- -- -- -- --
0.50 1.0 -- -- Ashless Friction Modifier Cocamide DEA Ashless -- --
-- -- -- -- -- -- 0.50 1.0 Friction Modifier.sup.f Average
Coefficient of 0.044 0.083 0.10 0.058 0.10 0.105 Friction
.sup.aAvailable from CP Chem .sup.bAvailable from CP Chem
.sup.cKR-015 from King Industries, Inc. .sup.dRC-8210 from Rhein
Chemie .sup.eK-CORR NF 200 from King Industries, Inc. .sup.fAMIDEX
DEA from Noveon/Lubrizol
[0300] III. Synergy of Amine Tungstates with Ash Less Antiwear
Additives
EXAMPLE 42
[0301] The amine tungstate of Example 2 is blended at 50.degree. C.
for 30 minutes with an ISO VG 46 Group II base oil, a nonylated
diphenylamine antioxidant (NA-LUBE AO-130), a phenolic antioxidant
(NALUBE AO-210, and a triazole yellow metal deactivator (K-CORR NF
200) at the weight percentage composition according Table 5,
Example 42. The formulated oil thus prepared contains 0.32 wt % of
the amine tungstate of Example 2 and 576 ppm of tungsten. The oil
was evaluated by the ASTM D 4172 Four Ball Wear Test and gave a
wear scar of 0.80 mm.
EXAMPLE 43
[0302] The procedure of Example 42 was repeated except that the
amine tungstate of Example 2 component was omitted. The resulting
wear scar was 0.78.
[0303] The results of Examples 42 and 43 demonstrate that the amine
tungstates of the invention do not provide antiwear performance
when used alone.
EXAMPLES 44-47
[0304] The procedure of Example 42 was repeated for Examples 44-47
using the amounts of each component specified in Table 5. Each of
these examples contained 0.25 percent of an ashless
dialkyldithiocarbamate antiwear additive (NALUBE ADTC, available
from King Industries, Inc.). The wear scar for each formulation is
reported in Table 5. The results demonstrate the synergistic
performance derived from the combination of the amine tungstates of
the invention with ashless antiwear additives in that the wear
performance of the formulation improves with increasing
concentration of tungsten in the presence of a constant
concentration of ashless antiwear additive.
TABLE-US-00011 TABLE 5 Example 42 43 44 45 46 47 48 Composition (%)
NA-LUBE AO-130 0.1 0.1 0.1 0.1 0.1 0.1 0.1 NA-LUBE AO-210 0.1 0.1
0.1 0.1 0.1 0.1 0.1 K-CORR NF-200 0.05 0.05 0.05 0.05 0.05 0.05
0.05 Amine Tungstate of 0.32 -- 0 0.04 0.08 0.16 0.32 Example 2
Ashless -- -- 0.25 0.25 0.25 0.25 0.25 dialkyldithiocarbamate
(NALUBE ADTC) ISO VG 46 Group II balance balance balance balance
balance balance balance base oil Tungsten 576 0 0 72 144 288 576
Concentration (ppm) ASTM D 2172 Wear 0.80 0.78 0.72 0.72 0.65 0.58
0.50 Scar (mm) *All NALUBE .TM. products are available from King
Industries, Inc.
[0305] IV. Synergy of Amine Tungstates with Extreme Pressure
Additives
[0306] It has been demonstrated that the addition of amine
tungstates to lubricant formulations containing extreme pressure
additives results in improved performance in the ASTM D 2783 Four
Ball Weld Test. The Four Ball Extreme Pressure Test measures a
lubricant's extreme pressure properties under high Hertzian contact
under pure sliding, or pure rolling, motion. In the test, a 1/2
inch steel ball is rotated while under load contact with 3 similar
steel balls held stationary in test cup while immersed in the test
lubricant. A timed test is performed. The test is repeated with new
steel balls and test lubricant under increasing load increments
until the top rotating ball welds to the lower stationary balls.
The point at which the balls weld together is the "weld load". A
higher weld load is associated with a lubricant with better extreme
pressure performance.
EXAMPLE 49
[0307] A semi-synthetic gear oil formulation was prepared by
blending the amine tungstate of Example 2 with a ISO VG 46 base
oil, a synthetic ester (Emery 2970), a viscosity index improver
(Viscoplex 0-030) for 30 minutes at 50.degree. C. in the amounts
reported in Table 6. This formulation contains HiTEC 350, a
commercial automotive and industrial gear oil additive package from
Afton Chemical. HiTEC 350 is a blend of various antioxidants,
antiwear additives such as alkyl phosphates and extreme pressure
additives such as sulfurized olefins and esters. The major
constituents of the package are sulfurized hydrocarbon extreme
pressure additives. When used at a treat level of 5.25 wt %, HiTEC
350 delivers 1.6% of sulfur to the final formulated oil.
Formulations prepared using HiTEC 350 at 5.25 wt % in suitable base
stocks meet the performance requirements of API GL-5 and
MIL-L-2105D specifications for automotive gear lubricants. The
formulated gear oil thus prepared was evaluated in the ASTM D 2783
test. The weld load is reported in Table 6.
EXAMPLE 50
[0308] The procedure of Example 49 was repeated except that the
amine tungstate of Example 2 was omitted from the formulation.
TABLE-US-00012 TABLE 6 Example Composition (all values in percent)
49 50 Amine Tungstate of Example 2 0 0.36 Rohm and Haas Viscoplex
0-030 VI Improver 20 20 Emery 2970 Synthetic Ester 9.75 9.75 HiTEC
350 Gear Oil Package 5.25 5.25 Chevron 220 R ISO VG 46 Tungsten
Content of Formulation 700 0 Weld Load (Kg) 260 240
[0309] The results of the four ball extreme pressure tests
demonstrate the improved performance of the formulations containing
a combination of the amine tungstates of the invention with extreme
pressure additives.
* * * * *