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BACKGROUND OF THE INVENTION
The present invention relates to alkanol solutions of hydrocarbon-soluble
molybdenum complexes of thio-bis-phenols, their method of preparation and
their utility as an additive for hydrocarbon compositions such as
gasoline, fuel oil and lubricating oils including greases, industrial
oils, gear oils and lubricants for engines and other equipment having
moving parts operating under boundary lubricating conditions.
There are many instances, as is well known, particularly under "Boundary
Lubrication" conditions where two rubbing surfaces must be lubricated, or
otherwise protected, so as to prevent wear and to insure continued
movement. Moreover, where, as in most cases, friction between the two
surfaces will increase the power required to effect movement and where the
movement is an integral part of an energy conversion system, it is most
desirable to effect the lubrication in a manner which will minimize this
friction. As is also well known, both wear and friction can be reduced,
with various degrees of success, through the addition of a suitable
additive or combination thereof, to a natural or synthetic lubricant.
Similarly, continued movement can be insured, again with varying degrees
of success, through the addition of one or more appropriate additives.
While there are many known additives which may be classified as antiwear,
antifriction and extreme pressure agents and some may in fact satisfy more
than one of these functions as well as provide other useful functions, it
is also known that many of these additives act in a different physical or
chemical manner and often compete with one another, e.g. they may compete
for the surface of the moving metal parts which are subjected to
lubrication. Accordingly, extreme care must be exercised in the selection
of these additives to insure compatibility and effectiveness.
The metal dihydrocarbyl dithiophosphates are one of the additives which are
known to exhibit antioxidant and antiwear properties. The most commonly
used additives of this class are the zinc dialkyl dithiophosphates which
are conventionally used in lubricant compositions. While such zinc
compounds afford excellent oxidation resistances and exhibit superior
antiwear properties, it has heretofore been believed that the same
increases or significantly limits the ability to decrease friction between
moving surfaces. As a result, compositions containing zinc dialkyl
dithiophosphates were not believed to provide the most desirable lubricity
and, in turn, it was believed that use of compositions containing the same
would lead to significant energy losses in overcoming friction even when
antifriction agents are included in the composition.
Known ways to solve the problem of energy losses due to high friction, e.g.
in crankcase motor oils include the use of synthetic ester base oils which
are expensive and the use of insoluble molybdenum sulfides which have the
disadvantage of giving the oil composition a black or hazy appearance.
Other types of molybdenum compounds taught to be useful in lubricating oils
include the alkyl esters of molybdic acid as corrosion inhibitors (see
U.S. Pat. No. 2,805,997) and nitrogenous thiomolybdates as metal antiwear
additives which are said to function by providing a coating of reduced
coefficient of friction (see U.S. Pat. No. 2,938,869).
Similarly, antifriction agents or oiliness or lubricity agents as the same
are often referred to in the prior art, function by forming a coating on
the surface of the moving metal parts. As in the case of antiwear agents,
however, the coating bonds are, generally, effected physically, rather
than chemically, and, indeed, the bonding between an antifriction agent
and the surface is, generally weaker than the bond formed between an
antiwear agent and the metal surface.
In light of the foregoing, the need for improved lubricating compositions,
particularly for engine lubricating oils, that will permit operation of
moving parts under boundary conditions with reduced friction is believed
to be readily apparent. Similarly, the need for such a composition that
can include conventional base oils and other conventional additives such
as ashless dispersants, detergents, antioxidants (e.g. hindered phenols),
demulsifiers (e.g. up to about 0.01 wt.% alkanols--see U.S. Pat. No.
3,591,497, col. 1, lines 50-58), seal swellants (e.g. C.sub.8 -C.sub.13
alkanols--see U.S. Pat. No. 3,389,088), V.I. improvers, etc., and can be
used without the loss of other desirable lubricant properties,
particularly those provided by zinc dialkyl dithiophosphates, is also
readily apparent.
SUMMARY OF THE INVENTION
In U.S. patent application Ser. No. 843,964 filed Oct. 20, 1977, and of
common assignee, there is a teaching of a class of organo molybdenum
complexes believed to be represented by the following formula I:
##STR1##
where n is 1-3, Y is 1-2, X is selected from sulphur or oxygen and R is a
substantially hydrocarbyl group containing from 1 to 50, preferably 12 to
28, carbon atoms and X is selected from sulphur or oxygen. These complexes
are produced by the solution reaction of a thio-bis-phenol, a source of
molybdenum and an amine in a mineral oil solvent which are reported as
therein useful friction-reducing additives for lubricants and fuels. It
has now been discovered that said complexes containing from about 0.5 to
about 5, preferably 1 to 2.5, optimally 1.4, wt.% of nitrogen are more
readily produced in quantitative yields at lower temperatures and with a
broader spectrum of amines (all with respect to said teaching) when their
preparative reaction is carried out in an alkanol solvent wherein said
alkanol is a C.sub.5 to C.sub.50, preferably C.sub.8 to C.sub.18,
optimally C.sub.13 Oxo alkanol.
The amine reactants include ammonia, simple amines such as C.sub.6
-C.sub.30 alkyl amines, alkylene polyamines such as ethylene diamine
(preferred) and diethylene triamine, akanolamines such as ethanolamine,
ethoxylated derivatives of alkylene diamines such as hydroxyethyl ethylene
diamine, urea and ureides. When said complex is introduced into the
lubricating oil in combination with said phenol, e.g. as the solution of
said reaction, the modified lubricating oil exhibits of dynamic
coefficient of friction markedly reduced relative to that obtained with
the addition of only a common amount of organo molybdenum complex.
In accordance with the present invention, the foregoing and other objects
and advantages are accomplished with a hydrocarbon composition comprising
a major portion of a hydrocarbon, e.g. a lubricating oil and at least a
friction reducing amount of a solution of said organo molybdenum complex
in a C.sub.5 -C.sub.50 alkanol solvent and preferably a lubricity
enhancing combination of: (a) said organo molybdenum complex; (b) said
C.sub.5 to C.sub.50 alkanol; and, (c) an oil-soluble sulfur donor,
preferably zinc dialkyl dithiophosphate, and if desired, at least a
sludge-dispersing amount of an oil-soluble dispersant, e.g. an ashless
dispersant and at least a rust-inhibiting amount of a rust inhibitor. In
practice, the lubricity enhancing combination is present in an amount
sufficient to provide from about 0.005 to 0.2, preferably 0.03 to 0.15,
optimally about 0.1, wt.% molybdenum, at least about 0.25, e.g. 0.25 to 1,
wt.% sulfur donor and from 0.25 to 5 wt.% C.sub.5 -C.sub.50 alkanol, all
weight percent being based on the total weight of the hydrocarbon
composition such as lubricating oil or fuel.
DETAILED DESCRIPTION OF THE INVENTION
OIL-SOLUBLE ORGANO MOLYBDENUM COMPOUND
The hydrocarbon-soluble molybdenum complexes are believed to be derived
from a thio-bis-phenol as shown in Formula I. The R group of said Formula
I as defined is substantially hydrocarbyl and thus is alkyl; aryl,
aralkyl, cycloalkyl, or alkaryl; however, the hydrocarbyl group may
contain prior substituents such as amino, aminoalkyl, hydroxy,
hydroxyalkyl, halo, mercapto, keto, phosphinyl, phosphoryl, thiophosphoryl
and dithiophosphoryl radicals.
Specific examples of the R group include methyl, ethyl, propyl, isopropyl,
isobutyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, heptyl, octyl,
nonyl-decyl, dodecyl, tridecyl, heptadecyl, octadecyl, polyisobutyl,
polypropyl, etc.
The organic molybdenum complexes are the reaction product of a
thio-bis-phenol, an amine and molybdenum. The aforesaid thio-bis-phenols
can be characterized by Formula II.
##STR2##
wherein R and n are each the same as previously described with R
preferably para to the hydroxyl substituent. These thio-bis-phenols are
readily produced from the reaction of alkyl phenols and a source of
sulfur, e.g. chemical sulfur or sulfur halides. The alkyl phenols are
readily produced by alkylation of a phenol with an olefin, e.g. nonene, in
presence of an alkylation catalyst.
A particularly useful reactant for the preparation of the molybdenum
complex can be characterized by Formula III.
##STR3##
The source of molybdenum is a molybdenum containing compound capable of
reacting with the thio-bis-phenol to provide a molybdenum complex
containing from about 0.5 to 20, preferably 2 to 10, optimally about 5
wt.% molybdenum based on the total weight of said complex. The sources of
molybdenum include molybdic trioxide (preferred) also known as molybdic
anhydride, ammonium thiomolybdate, ammonium bismolybdate, molybdenum
halides, and ammonium heptamolybdate tetrahydrate.
The organo molybdenum complex is substantially the product of a solution
reaction between 1-2 moles thio-bis-phenol, 1 mole of molybdenum and 1-2
moles of an amine. The reaction is readily carried out by reaction at an
elevated temperature of from 135.degree. C. to 225.degree. C., preferably
160.degree. C. to 190.degree. C. optimally 175.degree. C. to accelerate
said reaction and remove the water of reaction. The reaction is carried
out in a C.sub.8 to C.sub.50 alkanol, preferably C.sub.8 -C.sub.18
alkanol, optimally tridecyl alcohol. The reaction is carried out over a
period of from about 4 to 20, preferably 6 to 12, hours in order to
suitably stabilize the complex and for removal of the water of reaction as
by nitrogen sparging or distillation at atmospheric or reduced pressure.
AMINES
The amine reactants broadly contain from 1 to 5, preferably 2, nitrogens
and from 0 to 60, preferably 2 to 20 carbons. The preferred amines are of
the class consisting of: C.sub.6 -C.sub.30 alkyl amines such as n-octyl
amine and dodecyl amine; alkylene polyamines which can be represented by
the general formula NH.sub.2 (CH.sub.2).sub.n --[NH(CH.sub.2).sub.n
].sub.m --NH.sub.2 wherein n is 2 to 3 and m is a number from 0 to 3
including ethylene diamine, diethylene triamine, tetraethylene pentamine
and mixtures of such polyamines formed from the reaction of ethylene
dichloride and ammonia; alkanolamines such as ethanolamine and
diethanolamine; ethoxylated derivatives of alkylene polyamine such as
hydroxyethyl ethylenediamine and the reaction product of alkylene oxides
such as an ethylene oxide or propylene oxide with polyamines e.g.
dinitrilo tetraethanol; urea and ureides such as ethylurea.
Carrying out the organo molybdenum complexing reaction in a C.sub.5
-C.sub.50, preferably C.sub.8 -C.sub.18, optimally C.sub.13, alkanol
solvent in an amount ranging from about 0.25 to 5, preferably 1, parts by
weight of alkanol per part by weight of organo molybdenum complex product
provides a number of benefits over a reaction without solvent or in a
light aromatic solvent such as toluene or a ligh hydrocarbon oil, e.g.
mineral oil including: a faster reaction time; completion of reaction to a
stabilized molybdenum complex at a lower temperature; faster and simpler
filtration of the reaction product solution; and, an additive product
solution which when added to lubricating oil provides enhanced friction
reduction (as seen from the subsequent Table I.).
ALKANOLS
The C.sub.5 to C.sub.50, preferably C.sub.8 to C.sub.18, optimally
C.sub.13, alkanols useful as solvents for the organo molybdenum complexing
reaction are in generally commercially available aliphatic alcohols which
can be straight or branched chain. Among these alcohols useful in
preparing said complexes are amyl alcohol, hexanol, heptanol, etc.,
through pentacontanol with the preferred alcohols being octanol through
octadecanol. A highly suitable source of alcohols are the Oxo alcohols
which are prepared in a two-stage reaction as has been described in U.S.
Pat. No. 2,327,066. The first stage of the Oxo process involves reacting
olefins, such as polymers and copolymers of C.sub.3 and C.sub.4
monoolefins, with carbon monoxide and hydrogen at temperatures about
150.degree. to 200.degree. C. and pressures of about 30 to 400 atmospheres
in the presence of a suitable catalyst to form a mixture of aldehydes
having one carbon atom more than the olefin. In the second stage, the
aldehyde mixture is hydrogenated, to form an isomeric mixture of highly
branched chain primary alcohols which is recovered by distillation.
Particularly, suitable as a reaction solvent for this invention is
tridecyl Oxo alcohol.
The C.sub.5 to C.sub.50 alkanols are usefully present in the hydrocarbon
composition in an amount of from about 0.25 to 5, preferably 1, parts by
weight per part by weight of said organo molybdenum complex.
SULFUR DONORS
The C.sub.5 -C.sub.50 alkyl phenol solutions of the hydrocarbon-soluble
organo molybdenum complexes provide enhanced lubricity in lubricating oils
when used in combination with an active sulfur donor which can be defined
as a compound which when used in admixture with the organo molybdenum
complex reduces the coefficient of friction at least about 10% relative to
that provided by the complex alone. The active sulfur donor is present in
an amount of from about 0.1 to 10, preferably 0.2 to 2, parts by weight
per part by weight of molybdenum complex.
Illustrative of active sulfur donors are metal dihydrocarbyl
dithiophosphates and the corresponding precursor esters, phosphosulfurized
pinenes, sulfurized olefins and hydrocarbons, sulfurized fatty esters and
sulfurized alkyl phenols.
Preferred are the zinc dihydrocarbyl dithiophosphates which are salts of
dihydrocarbyl esters of dithiophosphoric acids and may be represented by
the following formula:
##STR4##
wherein R and R' may be the same or different hydrocarbyl radicals
containing from 1 to 18 and preferably 2 to 12 carbon atoms and including
radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic
radicals. Particularly preferred as R and R' 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, tert-butyl, amyl n-hexyl,
i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl,
phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl,
etc. In order to obtan oil solubility, the total number of carbon atoms in
the dithiophosphoric acid will average about 5 or greater.
The zinc dihydrocarbyl dithiophosphates which are useful as the coadditive,
i.e. sulfur donor of the present invention may be prepared in accordance
with known techniques by first esterifying a dithiophosphoric acid usually
by reaction of an alcohol or phenol with P.sub.2 S.sub.5 and then
neutralizing the dithiophosphoric acid ester with a suitable zinc compound
such as zinc oxide.
In general, the zinc dihydrocarbyl dithiophosphate will be used in the
lubricating composition at a concentration within the range of about 0.01
to about 5 parts by weight per 100 parts of lubricating oil and preferably
from about 0.5 to about 1.5. This is adequate for sulfur donation whereby
the lubricity enhancement of the lubricating oil composition by the
coadditive combination is realized.
As noted earlier, an equally suitable active sulfur donor is the
dihydrocarbyl esters of dithiophosphoric acid which may be represented by
the formula:
##STR5##
where R and R" are as previously defined. Particularly useful is the
dibutylphenyl dithiophosphate.
The phosphorosulfurized terpenes as represented by pinene, dipenene,
allo-ocimene, etc., are another group of dithiophosphate diesters which
are active sulfur donors. Of the terpenes, the bicyclic pinene is
preferred. The phosphosulfurized terpene is readily obtained by reaction
of about one mole of diester of thiophosphoric acid and one mole of pinene
at a temperature of at least 100.degree. C., e.g. 100.degree. C. to
200.degree. C. The preferred active sulfur donor can be characterized as
the bornyl ester of dihydrocarbyl (C.sub.2 -C.sub.20) dithiophosphoric
acids (as shown in U.S. Pat. No. 2,689,258).
The sulfurized olefins and hydrocarbons are further esters of
thiophosphoric acids which are useful sulfur donors. These esters are
achieved by reaction with olefins such as ethylene, propylene,
isobutylene, decene, dodecene, octadecene, etc., olefin polymers of
molecular weight ranging from 100 to 50,000 such as ethylene, propylene,
isobutylene, etc., aromatics such as benzene, naphthylene, toluene,
xylene, etc., petroleum fractions and condensation products of halogenated
aliphatic hydrocarbons with aromatic compounds, e.g. wax naphthalene (see
U.S. Pat. No. 2,804,431).
The sulfurized fatty esters are another subclass of esters which are active
sulfur donors. These products are readily obtained from the reaction of
P.sub.2 S.sub.5 and aliphatic alcohols usefully having from about 8 to 22
carbons obtained from natural sources including linoleic, palmolitic,
behenic, stearic, palmitic, lauric, capric, etc., as well as mixtures
obtained from vegetable and animal oils such as tall oil.
The sulfurized alkyl phenols are generally C.sub.4 to C.sub.20 alkyl phenol
sulfides. These sulfurized alkyl phenols are readily produced by
sulfurizing an alkyl phenol with a sulfur halide or elemental sulfur.
OTHER ADDITIVES FOR LUBRICATING COMPOSITIONS
In addition to the organo molybdenum complex, alkanol and active sulfur
donor, the lubricating oil composition may contain other well-known
lubricating oil additives to provide trouble-free operation of the
lubricated equipment, such as ashless dispersants, metallic detergents,
supplemental oxidation and corrosion inhibitors, extreme pressure agents,
rust inhibitors, pour point depressants, viscosity index improvers, etc.
1. ASHLESS DISPERSANTS
As used herein, the terminology "ashless dispersant" is intended to
describe the now well-known class of non-metal-containing oil-soluble
polymeric additives or the acyl derivatives of relatively high molecular
weight carboxylic acids which are capable of dispersing contaminants and
the like in hydrocarbons such as lubricating oils. The carboxylic acids
may be mono- or polycarboxylic acids and they are generally characterized
by substantially hydrocarbon constituents containing an average of 50 to
250 aliphatic carbon atoms.
A preferred class of ashless dispersants are the nitrogen-containing
dispersant additives which are generally known in the art as sludge
dispersants for crankcase motor oils. These dispersants include mineral
oil-soluble salts, amides, imides and esters made from high molecular
weight mono- and dicarboxylic acids (and where they exist the
corresponding acid anhydrides) and various amines of nitrogen-containing
materials having amino nitrogen or heterocyclic nitrogen and at least one
amido or hydroxy group capable of salt, amide, imide or ester formation.
Usually, these dispersants are made by condensing a monocarboxylic acid or
a dicarboxylic acid or anhydride, preferably a succinic acid producing
material such as alkenyl succinic anhydride, with an amine or alkylene
polyamine. Usually, the molar ratio of acid or anhydride to amine is
between 1:1 to 5:1, e.g. 1 mole of C.sub.10 -C.sub.100 polyisobutenyl
succinic anhydride to 2 moles of tetraethylene pentamine.
Primarily because of its ready availability and low cost, the hydrocarbon
portion of the mono-, or dicarboxylic acid or anhydride is preferably
derived from a polymer of a C.sub.2 to C.sub.5 monoolefin, said polymer
generally having between 50 and 250 carbon atoms. A particularly preferred
polymer is polyisobutylene.
Polyalkyleneamines are usually used to make the non-metal-containing
dispersant. These polyalkyleneamines include those represented by the
general formula:
NH.sub.2 (CH.sub.2).sub.n --[NH(CH.sub.2).sub.n ].sub.m --NH.sub.2
wherein n is 2 to 3 and m is a number from 0 to 10. Specific compounds
coming within the formula include diethylenetriamine,
tetraethylenepentamine, dipropylenetriamine, octaethylenenonamine, and
tetrapropylenepentamine; N,N-di-(2-aminoethyl) ethylenediamine may also be
used. Other aliphatic polyamino compounds that may be used are
N-amino-alkylpiperazines, e.g. N-(2-aminoethyl) piperazine. Mixtures of
alkylene polyamines approximating tetraethylene pentamine are commercially
available, e.g. Dow E-100 sold by Dow Chemical Company of Midland,
Michigan.
Representative dispersants are formed by reacting about one molar amount of
polyisobutenyl succinic anhydride with from about one to about two molar
amounts of tetraethylene pentamine or with from about 0.5 to 1 moles of a
polyol, e.g. pentaerythritol.
It is possible to modify the ashless dispersants generally by the addition
of metals such as boron in order to enhance the dispersancy of the
additive. This is readily accomplished by adding boric acid to the
reaction mixture after the imidation or esterification is substantially
complete and heating the mixture at temperatures of 100.degree. to
150.degree. C. for a few hours.
2. OTHER ADDITIVES
Detergents useful in conjunction with dispersants, preferably the ashless
type, include normal, basic or overbased metal, e.g. calcium, magnesium,
etc., salts of petroleum naphthenic acids, petroleum sulfonic acids, alkyl
benzene sulfonic acids, oil-soluble fatty acids, alkyl salicyclic acids,
alkylene-bis-phenols, and hydrolyzed phosphorosulfurized polyolefins.
Oxidation inhibitors include hindered phenols, e.g. 2,6-ditert. butyl
para-cresol, amines, sulfurized phenols and alkyl phenothiazines.
Pour point depressants include wax alkylated aromatic hydrocarbons, olefin
polymers and copolymers, acrylate and methacrylate polymers and
copolymers.
Viscosity Index Improvers include olefin polymers such as polybutene,
ethylene-propylene copolymers, hydrogenated polymers and copolymers and
terpolymers of styrene with isoprene and/or butadiene, polymers of alkyl
acrylates or alkyl methacrylates, copolymers of alkyl methacrylates with
N-vinyl pyrollidone or dimethylaminoalkyl methacrylate, post-grafted
polymers of ethylenepropylene with an active monomer such as maleic
anhydride which may be further reacted with an alcohol or an alkylene
polyamine, styrene/maleic anhydride polymers post-reacted with alcohols
and amines, etc.
The hydrocarbons in which the additive combination of the invention is most
effective are mineral oils having a viscosity as measured by ASTM D-445 of
from about 2 to 40, preferably 5 to 20 centistokes at 99.degree. C.
If the additive combination of oil-soluble organo molybdenum complex
C.sub.5 -C.sub.20 alkanol and active sulfur donor are used as an additive
concentrate, the concentrate may consist essentially of from about 5 to
95% of the additive combination, the remainder being an additional
hydrocarbon solvent such as kerosene, mineral oil, a naphtha and the like
or a C.sub.5 -C.sub.50 alkyl phenol as disclosed in my copending
application Ser. No. 898,769 filed on Apr. 21, 1978. The preferred
concentrate contains about 40 to 90% of the additive combination in a
second solvent of mineral oil.
Whether the organo molybdenum complex-alkanol solution is used alone or in
combination with an active sulfur donor, its concentration may vary
appreciably with the particular hydrocarbon. For example, when said
molybdenum complex-alkanol solution is used alone in a fuel such as
gasoline, the concentration of the complex ranges from 10 to 1,000,
preferably 20 to 50 weight parts per million based on the total weight of
the fuel composition, whereas in a lubricant, it is used in combination
with the active sulfur donor, which three-component combination then
ranges from about 0.5 to 5, preferably 1 to 3 wt.% based on the total
weight of the lubricating oil.
The invention will be further understood by reference to the following
Examples which illustrate a preferred form of the invention and compares
the same with different, though similar compositions.
The following Examples illustrate more clearly the compositions of the
present invention. However, these illustrations are not to be interpreted
as specific limitations on this invention.
EXAMPLE 1
Nonyl phenol sulfide (183 g) as ECA 9001, Solvent Neutral 150 mineral oil
(183 g) and molybdic trioxide (28.1 g) as an undensified grade obtained
from Climax Molybdenum Company, Fort Madison, Wisconsin were stirred
together and then raised in temperature to 94.degree. C. at which time
ethylene diamine (23.4 g) was thereafter slowly added over a 20-minute
period. The temperature was raised with stirring to 121.degree. C. over
0.6 hour. While stirring at this temperature, the volatiles including
water and ammonia were removed by gentle nitrogen sparging for 18 hours.
After filtration, the resulting product solution, useful as a lubricating
oil additive, had a viscosity of 177 S.U.S. @ 100.degree. C. and was black
in color and contained about 4.3 wt.% molybdenum and 1.9 wt.% nitrogen.
ECA 9001, a 70 wt.% active mineral solution of di-(C.sub.9 average) nonyl
phenol sulfide is commercially available from Exxon Chemical Company,
Houston, Texas.
This was an organo metallic complex prepared according to the teachings of
said copending application Ser. No. 843,964 using a mineral oil solvent
for the reaction medium. Filtration through a steam-heated Buchner funnel
holding a 1/4" precoat of Celite 535 took in excess of 1 hr. Exposure of
the product solution to about 150.degree. C. for 3 hours reduced its
nitrogen content to 1.43 wt.% and appeared to evolve ammonia during said 3
hours.
EXAMPLE 2
The procedure of Example 1 was followed except that the mineral oil was
replaced by: 183 g of tridecyl Oxo alcohol; use of densified MoO.sub.3 ;
going to 149.degree. C. over a 2-hour period while adding the ethylene
diamine; and reacting by raising the temperature to 177.degree. C. after 1
hour followed by a temperature decrease to 149.degree. C. where it was
held for 2 hours. The resulting filtered product solution (the filtration
of which took less than 10 minutes to fully filter) analyzed for 4.72 wt.%
molybdenum.
EXAMPLE 3
The filtered product solution of Example 2 was thereafter heated under
nitrogen sparging at 177.degree. C. for 3 hours.
EXAMPLE 4
As earlier noted before, a preferred process provides for from 6 to 12
hours exposure of the reaction medium to a temperature about 175.degree.
C., usefully 160.degree. C. to 190.degree. C. This is shown in a procedure
in which 183 weight parts of nonylphenol sulfide (e.g. ECA 9001) are
admixed with 183 weight parts of tridecyl Oxo alcohol and heated toward
105.degree. C. during which time 28.1 weight parts of molybdic trioxide
are added. When 105.degree. C. is reached 23.4 weight parts of ethylene
diamine is slowly added over a 30-minute period. Thereafter raise the
temperature to about 150.degree. C. and initiate inert gas (e.g. nitrogen)
sparge. Raise to about 175.degree. C. during the next 2-hour period and
heat soak at 175.degree. C. for about 4 to 6 hours after which it can be
readily filtered as shown in Example 2.
EXAMPLE 5
A lubricating oil composition was prepared for comparative testing of
additives by blending together the individual components, noted below,
usually at a slightly elevated temperature, i.e. from about 45.degree. C.
to above 65.degree. C. to insure complete mixing. The final composition of
Blend 5 formulated into a 10 W/30 SE quality automotive engine oil was as
follows:
______________________________________
Blend 5
Wt. % Active Ingredient
______________________________________
Mineral Oil 94.9
Ashless Dispersant 2.9
Magnesium Sulfonate 0.2
ZDDP.sup.(1) 0.9
Rust-Inhibitor 0.1
Viscosity Index Improvers
1.0
Silicone Defoamer 0.01
Ashless Antioxidant --
Metal Detergent-Inhibitor
--
______________________________________
.sup.(1) Zinc dihydrocarbyl dithiophosphate such as zinc dinonyl phenol
dithiophosphate
This formulated blend was itself and in modified forms according to the
teaching of this invention and the teaching of said Ser. No. 843,964
subjected to testing as hereinafter set forth:
1. Testing Procedure A
The Roxana Four-ball wear tester with the Brown/GE modification from Roxana
Machine Works, St. Louis, MO was used to measure friction properties by
the following procedure. The tester was assembled in the normal wear
procedure as described in ASTM D2266-67 using four 1/2" bearing steel
balls. The tester was brought to 110.degree. C. and run at 1200 rpm and 15
kg for a minimum of 45 minutes. If the frictional force as seen on the
strip chart recorder is constant for the last 10 minutes, the speed is
reduced to 25 rpm. Otherwise, the test is carried on until frictional
force has stabilized. The test at 25 rpm is carried out at 110.degree. C.
and 15 kg for 15 minutes or until frictional force has stabilized.
The compounds of the invention were then evaluated by subjecting the
products to a study of their utility as a lubricity enhancing and/or
antiwear additive for lubricating oils by using the Testing Procedure A.
The weight percentage of amounts of molybdenum complex added is given in
amount of complex added.
The results of tests under Procedure A are set forth in Table I.
From Table I, it is shown that the additive combination of the invention
provides improved lubricity enhancement to lubricating oils when an active
sulfur donor is present and that these three-component combinations of
this invention have utility as additives for lubricating oils.
While the additive combination of this invention provides frictional
performance to a fully formulated lubricating oil superior to that
provided by the additive according to the teaching of said application
Ser. No. 843,964, it is also much easier to filter and thereby remove
unwanted and deleterious reaction byproducts than the products prepared
according to the teachings of said Ser. No. 843,964, e.g. where a quantity
of the former as shown by Example 2 filters through in less than 10
minutes a similar quantity of the latter would take from 0.5 to several
hours (see Example 1 where it took in excess of 1 hour). In this regard, a
solvent mixture of up to an equal amount of mineral oil with said alkanol
solvent provides useful filtering ease of the solution reaction products.
Another advantage of said alkylphenol as a solvent for the reaction of the
hydrocarbyl phenol sulfide and molybdenum compound, preferably molybdic
oxide (MoO.sub.3) resides in the enhanced reactivity of the components,
i.e. shorter reaction times and/or more heat stable complexes when such a
solvent is used as compared with mineral oil solvent. The heat stability
of said complexes is enhanced by heating at from 160.degree. to
190.degree. C. for at least 4 hours, preferably 6 to 12 hours which in
turn appears to impart increased antifriction activity to said
complex-alkanol solution.
It is to be understood that the Examples present in the foregoing
specification are merely illustrative of this invention and are not
intended to limit it in any manner; nor is the invention to be limited by
any theory regarding its operability. The scope of the invention is to be
determined by the appended claims.
TABLE I
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Added Mo Coefficient Friction
Complex of Friction Reduction (%)
Example Wt 46 46
Test # (%) cm/sec 1 cm/sec
cm/sec 1 cm/sec
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1 -- -- 0.0835 0.1006 -- --
2 1 2.2 0.0436 0.0563 47.6 44.6
3 2 2.2 0.0478 0.0712 52.4 39.6
4 3 2.2 0.0361 0.0521
5 3 1.5 0.0404 0.0595
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