Multifunctional additives

A lubricant of fuel composition contains a multifunctional antioxidant/metal deactivating and thermal stabilizing amount of a tolyltriazole-derived Mannich base made from a tolyltriazole, an aliphatic amine, such as diisobutylamine or bis(2-ethylhexyl)amine, a cyclic amine, such as 1,4-diaminocyclohexane or ether amines exemplified by C.sub.6 to C.sub.13 alkoxypropylamines and polyether primary amines such as those derived from nonylphenol ethyoxylates and formaldehyde. The reaction products are, optionally, treated with epoxide.

FIELD OF THE INVENTION 
The invention relates to lubricants and fuel compositions. Particularly the 
invention relates to lubricant and fuel additives which have antioxidant 
and metal deactivating activity, good thermal stability and improved 
compatibility in mineral and synthetic lubricant compositions. 
BACKGROUND OF THE INVENTION 
Although base oils posses some aging stability and resistance to oxidation 
which is sufficient for normal demands, high load and temperature 
conditions, which are particularly found in internal combustion engines 
and gears, tend to increase the internal degradation of the lubricant. 
Metals reaching the lubricant by surface abrasion, acidic oxidation 
products and fuel combustion products mix with the lubricant and lead to 
premature aging of the lubricant. In an internal combustion engine, 
premature lubricant aging can lead to deposit formation on the Distorts 
which leads to ring sticking and eventual destruction of the engine. 
Increased acidity from oxidation products causes metal corrosion. 
Dissolved metals form salts which together with other aging products form 
sludge deposits which can block the filters and oil ducts and cause 
serious malfunction of the engine. The increase in viscosity which is 
caused by oxidation of gear oils can cause damage to the gear teeth and 
seizure due to reduced load-carrying capacity. Certain known metal 
deactivators or chelating agents include aromatic amines such as, 
dialkyldiphenylamines, heterocyclic amines, such as, imidazole, pyrazole, 
aminomercaptothiadiazole and dimercaptothiadiazole. The problem with these 
compounds, however, is that they are difficult to work with in lubricant 
blending operations because their bulkiness, polarity and reactivity makes 
them insoluble in most organic media. 
SUMMARY OF THE INVENTION 
The instant invention is directed to additives which are soluble in most 
base stocks. An additive has been discovered which has antioxidant, metal 
deactivating and thermal stability properties when incorporated into 
lubricating oils and fuels comprising the reaction product of an aldehyde 
or ketone, an alkylaryl triazole and an amine selected from the group 
consisting of an alkylamine, aliphatic diamine, alicyclic amine, 
heterocyclic amine and aliphatic etheramine. The synergism between the 
triazole metal deactivator and the amine antioxidant creates a very 
effective multipurpose additive which is soluble in lubricants because of 
the alkyl group of the triazole. 
The alkylaryltriazole is a 5-membered ring structure in which three of the 
ring members are nitrogen, the other ring members can be oxygen, sulfur or 
carbon atoms. Typical triazoles contemplated are those already known for 
their antioxidant characteristics. The triazole is characterized by the 
following structural formula: 
##STR1## 
where R.sub.1 is an alkyl group containing 1 to 60 carbon atoms or an 
alkyl group containing 2 to 60 carbon atoms and at least one heteroatom 
which is oxygen, sulfur or nitrogen. Representative examples of alkyl 
groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 
nonyl, decyl and dodecyl or any combination thereof. Non-limiting examples 
of suitable triazoles include tolyltriazole where R.sub.1 is methyl, 
propylbenzotriazole, butylbenzotriazole, the higher benzotriazoles such as 
dodecylbenzotriazole and oxygenated benzotriazoles such as 
carboxymethylbenzotriazole. The triazoles are known in the art and can be 
obtained from commercial sources. 
The carbonyl compound can be any compound containing the group (C.dbd.O) 
which occurs in aldehydes and ketones. This compound can be characterized 
by the structural formula 
##STR2## 
in which R.sub.2 and R.sub.3 are hydrogens or hydrocarbyl containing 1 to 
60 carbon atoms which are alkyl, aryl, arylalkyl or alkylaryl. The 
hydrocarbyl group can also contain 2 to 60 carbon atoms and at least one 
heteroatom which can be oxygen, sulfur or nitrogen. Typical compounds 
which are not limited to the following examples include formaldehyde, 
heptaldehyde, hexaldehyde, acetaldehyde, propionaldehyde, 
paraformaldehyde, benzaldehyde, salicylaldehyde, acetone, diethyl ketone, 
methyl ethyl ketone and 2-ethylhexanal. These compounds are known in the 
art and are readily available from commercial sources or are easily made 
using known methods. 
The alkylaryl triazole and the carbonyl compound are reacted with an 
aliphatic primary or secondary amine which can be an alkylamine, alicyclic 
amine, heterocyclic amine aliphatic etheramine or aliphatic diamine. The 
amines are characterized by at least one reactive hydrogen which is 
necessary for the reaction. 
The alkylamines are primary or secondary amines designated by the 
structural formula: 
##STR3## 
in which R.sub.4 or R.sub.5 is, independently, a hydrogen atom, in the 
case of a primary amine, or R.sub.4 and R.sub.5 are the same or different 
aliphatic hydrocarbon groups. R.sub.4 or R.sub.5 is a hydrocarbon group 
containing 1 to 60 carbon atoms and can contain at least one heteroatom 
which is oxygen, sulfur or nitrogen and 2 to 60 carbon atoms. The 
hydrocarbon group is paraffinic or olefinic containing at least one to 30 
at most 50 to 60 carbon atoms. Non-limiting examples of the aliphatic 
primary or secondary amines include the straight chain monoamines such as 
methyethylamine, proplylamine or butylamine. The particularly preferred 
amines are the long-chain aliphatic amines such as pentylamine, 
hexylamine, octylamine, dioctylamine, dicocoamine, dioleylamine and the 
like. The term "long chain" designates the amines containing hydrocarbyl 
groups of C.sub.5 and higher, preferably over C.sub.8 and in the range of 
C.sub.5 to C.sub.22, preferably C.sub.8 to C.sub.20. The branched chain 
aliphatic amines include, but are not limited to the short chain amines, 
i.e., isopropylamine, isobutylamine, diisobutylamine and longer chain 
branched amines such as bis(2-ethylhexyl)amine. The term "short chain 
amines" designates amines containing hydrocarbon groups of C.sub.5 and 
lower, preferably C.sub.3 and lower. 
The aliphatic diamines are also used. In general the long-chain diamines 
are contemplated and have the structural formula: 
##STR4## 
where R.sub.6 is an alkylene group containing 10 to 30 carbon atoms and 
R.sub.7 is an alkylene group containing 2 to 4 carbon atoms. Some 
nonlimiting examples of diamines include N-tallow-1,3-propylenediamine, 
N-oleyl-1,3-propylenediamine, N-linoleyl-1,3-propylenediamine, 
N-stearyl-1,3-propylenediamine, N-soya-1,3-propylenediamine, 
N-cocoyl-1,3-diaminopropane, and mixtures of two or more of these amines. 
Non-limiting examples of the alicyclic amines are dicyclohexylamine, 
1,4-diaminocyclohexane, piperidine and hexamethyleneimine. 
The contemplated amines are also heterocyclic in which the nitrogen atom is 
an integral member of a ring structure which is predominantly composed of 
carbon atoms. Most suitable, but not limiting examples of heterocyclic 
amines include morpholine, aminopropylmorpholine (APM) and 
aminoethylpiperazine (AEP). 
The oxygenated amines are also suitable. The oxygenated amines contemplated 
are the aliphatic etheramines such as the alkoxypropylamines having the 
structural formula 
##STR5## 
in which R.sub.8 is an alkyl group which contains 4 to 20, preferably 6 to 
18 carbon atoms. Nonlimiting examples of the alkoxypropylamines include 
3-methoxypropylamine, 3-ethoxypropylamine, 3-propyloxypropylamine, 
3-butyloxypropylamine, 3-octyloxypropylamine, 3-hexoxypropylamine, 
3-heptoxypropylamine, 3-nonyloxypropylamine and 3-decyloxypropylamine. 
The etherdiamines are another class of oxygenated amines which are 
suitable. Nonlimiting examples of the etherdiamines are those having the 
structure: 
##STR6## 
Where R.sub.8 is as defined above, but preferably contains 6 to 18 carbon 
atoms arranged in a straight or branched chain configuration. R.sub.9 is 
an alkyl group containing 2 to 4 carbon atoms, R.sub.11 is an alkyl group 
having at least 2 to 3 carbon atoms, at most 5 to 10 carbon atoms. 
Nonlimiting examples of etherdiamines include 
hexoxypropyl-1,3-propylenediamine, heptoxypropyl-1,3-propylenediamine, 
octoxypropyl-1,3-propylenediamine and nonoxypropyl-1,3-propylenediamine 
and any mixtures of the foregoing etherdiamines. 
The polyether primary amines are also contemplated. Suitable polyether 
primary amines have the following structural formula 
EQU R.sub.10 -O(C.sub.2 H.sub.3 (R.sub.11)O).sub.n C.sub.3 H.sub.6 NH.sub.2 
where R.sub.10 is an alkyl-substituted phenyl group containing 14 to 26 
carbon atoms, C.sub.6 to C.sub.30 alkyl group or C.sub.7 to C.sub.30 
aralkyl group, n is an integer ranging from 2 to 10 and R.sub.11 is 
independently hydrogen or methyl. These alkyl-substituted phenol-derived 
polyetheramines are sold by Texaco Chemical Co. under the trademark 
Surfonamine. Those available commercially include: 
______________________________________ 
Trademark Structure 
______________________________________ 
Surfonamine MNPA-380 
nonylphenyl-1EO-2PO-NH.sub.2 
Surfonamine MNPA-510 
nonylphenyl-4EO-2PO-NH.sub.2 
Surfonamine MNPA-750 
nonylphenyl-9.5EO-2PO-NH.sub.2 
Surfonamine MNPA-860 
nonylphenyl-12EO-2PO-NH.sub.2 
______________________________________ 
Contemplated polyether primary amines are those derived from nonylphenol 
ethoxylates such as where R.sub.10 is nonylphenyl. Specific examples of 
these polyether primary amines include the compounds sold by Texaco under 
the tradename SURFONAMINE MNPA. 
The triazole, the carbonyl compound and the amine can be reacted together 
in any sequence. However, for illustrative purposes, the amine is added to 
a solvated mixture of the triazole and the carbonyl compound. The triazole 
and the carbonyl compound are reacted in an equimolar proportion such that 
one equivalent amount of the carbonyl compound is used for each equivalent 
amount of the triazole and the amine. The reaction is a condensation 
reaction in which water is formed as the product evolves. The amount of 
water produced by the reaction is used to monitor the course of reaction: 
one mole of water being formed for each mole of product formed. 
For illustrative purposes, it is believed that the following reaction 
occurs when the reactants are combined: 
##STR7## 
where R.sub.1, R.sub.2, R.sub.3, R.sub.4 are described above. 
The reaction is carried out at a temperature of less than 50.degree. C., 
preferably less than 40.degree. C., which increases to at least 60.degree. 
C. to 70.degree. C., at most 110.degree. C. to 150.degree. C. during the 
course of the reaction. After the reactants have been contacted for at 
least 10 minutes to 1 hour, at most 3 hours to 8 hours, any solvent used 
to facilitate the reaction and any water present which is produced by the 
reaction is removed, usually by azeotropic and/or vacuum distillation. A 
solvent or diluent inert to the reactants :can be used to facilitate the 
reaction and which provide good solubility for the triazole. Nonlimiting 
examples of suitable solvents include methanol, ethanol, isopropyl 
alcohol, butanol and other similar alcohols. 
The reaction product is, optionally, treated with an epoxide to further 
enhance the solubility and stability of the product. The epoxide treatment 
converts any secondary amines to tertiary amines and creates a pendant 
hydroxy group which lends improved stability and solubility to the 
product. The pendant hydroxy groups also produce a site for further 
reaction with functionalizing compounds. The epoxide is generally added in 
stoichiometrically equivalent amounts such that one equivalent amount is 
added for each equivalent amount of the amine. Suitable epoxides include 
ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene 
oxide and higher alkylene oxides, isomers, polymers and copolymers 
thereof. 
The reaction products are blended with lubricants in a concentration of 
about 0.01% to 10%, preferably, from 0.05% to 5% by weight of the total 
composition. 
As previously mentioned, the additives are suitable for use in engine oils 
and gear oils. The engine oils which will benefit from these additives 
include oils for gasoline burning engines and diesel engines. The 
contemplated gear oils which will benefit from the additives are hypoid 
gear oils which are exposed to the most severe service conditions. Other 
gear oils contemplated include automotive spiral-bevel and worm gear axle 
oils. 
Although the additives are successful in internal combustion engine oils 
and gear oils, it is contemplated that the additives will successfully 
perform in other functional fluids and industrial lubricants. Other 
lubricant applications contemplated include the use of the instant 
additives in circulation oils and steam turbine oils, gas turbine oils 
(both heavy-duty gas turbines and aircraft gas turbines), machine tool 
lubricants and hydraulic fluids. 
The contemplated lubricants are liquid oils in the form of either a mineral 
oil or synthetic oil or mixtures thereof. Also contemplated are greases in 
which any of the foregoing oils are employed as a base. Still further 
materials which it is believed would benefit from the reaction products of 
the present invention are fuels and plastic materials. 
In general, the mineral oils, both paraffinic and naphthenic and mixtures 
thereof can be employed as a lubricating oil or as the grease vehicle. The 
lubricating oils can be of any suitable lubrication viscosity range, for 
example, from about 45 SSU at 100.degree. F. to about 6000 SSU at 
100.degree. F., and preferably from about 50 to 250 SSU at 210.degree. F. 
Viscosity indexes range from about 70 and higher, preferably 90 to 130. 
The average molecular weights of these oils can range from about 250 to 
about 800. 
It is also desirable to employ the additive in greases. The additive is 
particularly useful when used in gear greases. However, other classes of 
greases which will benefit from the additive include greases for 
automobile chassis lubrication, greases for journal and wheel bearings, 
etc. Typically, the range of application includes the automotive industry, 
railways and aviation industries. 
Where the lubricant is employed as a grease, the lubricant is generally 
used in an amount sufficient to balance the total grease composition, 
after accounting for the desired quantity of the thickening agent, and 
other additive components included in the grease formulation. A wide 
variety of materials can be employed as thickening or gelling agents. 
These can include any of the conventional metal salts or soaps, such as 
calcium, or lithium stearates or hydroxystearates, which are dispersed in 
the lubricating vehicle in grease-forming quantities in an amount 
sufficient to impart to the resulting grease composition the desired 
consistency. Other thickening agents that can be employed in the grease 
formulation comprise the non-soap thickeners, such as surface-modified 
clays and silicas, aryl ureas, calcium complexes and similar materials. In 
general, grease thickeners can be employed which do not melt or dissolve 
when used at the required temperature within a particular environment; 
however, in all other respects, any material which is normally employed 
for thickening or gelling hydrocarbon fluids for forming greases can be 
used in the present invention. 
Where synthetic oils, or synthetic oils employed as the vehicle for the 
grease are desired in preference to mineral oils, or in mixtures of 
mineral and synthetic oils, various synthetic oils may be used. Typical 
synthetic oils include the polyalphaolefins, polypropylene glycol, 
polyethylene glycol, trimethylol propane esters, neopentyl and 
pentaerythritol esters, di(2-ethylhexyl) sebacate, di(2-ethylhexyl) 
adipate, dibutyl phthalate, silicate esters silanes, esters of 
phosphorus-containing acids, hydrogenated synthetic oils, chain-type 
polyphenyls, siloxanes and silicones (polysiloxanes) and alkyl-substituted 
diphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenyl) 
ether and phenoxy phenylethers. 
The lubricating oils and greases contemplated for blending with the 
reaction product can also contain other additives generally employed in 
lubricating compositions such as corrosion inhibitors, detergents, extreme 
pressure agents, viscosity index improvers, friction reducers, antiwear 
agents and the like. Typical examples of these additives include but are 
not limited to phenates, sulfonates, imides, heterocyclic compounds, 
polymeric acrylates, amines, amides, esters, sulfurized olefins, 
succinimides, succinate esters, metallic detergents such as those 
containing calcium or magnesium, arylamines, hindered phenols and the 
like. 
It is also contemplated that the additives are useful in fuels, the fuels 
contemplated are liquid hydrocarbon and liquid oxygenated fuels such as 
alcohols and ethers. The additives can be blended in a concentration from 
about 25 to about 500 pounds of additive per 1000 barrels of fuel. Liquid 
hydrocarbon fuels include gasoline, fuel oils, diesel oils and alcohol 
fuels which include methyl and ethyl alcohols and ethers such as 
diisopropyl ether and methyl-tert-butyl ether. 
Specifically, the fuel compositions contemplated include gasoline base 
stocks such as a mixture of hydrocarbons boiling in the gasoline boiling 
range which is from about 90.degree. F. to about 450.degree. F. This base 
fuel may consist of straight chains or branched chains, paraffins, 
cycloparaffins, olefins, aromatic hydrocarbons, or mixtures thereof. The 
base fuel can be derived from among others, straight run naphtha, polymer 
gasoline, natural gasoline or from catalytically cracked or thermally 
cracked hydrocarbons and catalytically cracked reformed stock. The 
composition and octane level of the base fuel are not critical and any 
conventional motor fuel base can be employed in the practice of this 
invention. Further examples of fuels of this type are petroleum distillate 
fuels having an initial boiling point from about 75.degree. F. to about 
135.degree. F. and an end boiling point from about 250.degree. F. to about 
750.degree. F. It should be noted in this respect that the term distillate 
fuels is not intended to be restricted to straight-run distillate 
fractions. These distillate fuel oils can be straight-run distillate fuel 
oils, alkylate, catalytically or thermally cracked (including 
hydrocracked) distillate fuel oils etc. Moreover, such fuel oils can be 
treated in accordance with well-known commercial methods, such as acid or 
caustic treatment, dehydrogenation, solvent refining, clay treatment and 
the like. 
Particularly contemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils 
used in heating and as Diesel fuel oils, gasoline, turbine fuels and jet 
combustion fuels. 
The fuels may contain alcohols and/or gasoline in amounts of 0 to 50 
volumes per volume of alcohol. The fuel may be an alcohol-type fuel 
containing little or no hydrocarbon. Typical of such fuels are methanol, 
ethanol and mixtures of methanol and ethanol. The fuels which may be 
treated with the additive include gasohols which my be formed by mixing 90 
to 95 volumes of gasoline with 5-10 volumes of ethanol or methanol. A 
typical gasohol may contain 90 volumes of gasoline and 10 volumes of 
absolute ethanol. 
The fuel compositions of the instant invention may additionally comprise 
any of the additives generally employed in fuel compositions. Thus, 
compositions of the instant invention may additionally contain 
conventional carburetor detergents, anti-knock compounds such as 
tetraethyl lead, anti-icing additives, upper cylinder and fuel pump 
lubricity additives and the like.

EXAMPLES 
Example 1 
Tolyltriazole-Formaldehyde-Bis(2-ethlyhexyl)amine 
Approximately 40.0 gm (0.3 mole) of tolyltriazole (commercially obtained 
from PMC Specialties Group, Inc. under the tradename Cobratec TT-100), 
25.1 gm (0.31 mole) aqueous formaldehyde (37 wt. % solution in water), and 
50 ml of methanol were charged into a 500 ml reactor equipped with a 
reflux condenser, thermometer, dropping funnel, and mechanical stirrer. 
The reaction mixture became homogeneous after stirring for about 5 
minutes. Then 72.5 gm (0.3 mole) of bis(2-ethylhexyl)amine was slowly 
added to the reactor at a temperature less than 40.degree. C. (moderate 
exotherm is observable). Thereafter, the mixture was heated to .sup.- 
70.degree. C. and maintained at reflux for 3 hrs. Then the reactants were 
heated at 110.degree. C. during which methanol and water was 
azeotropically collected in the Dean-Stark trap. Finally, house vacuum was 
used to remove the trace amount of water at 110.degree. C. for a half 
hour. A final filtration to remove possible unreacted tolyltriazole is 
optional. Small amounts of residual water could make the final product 
appear hazy. Approximately 115.3 gm of yellow liquid was recovered as 
desired product (&gt;99% yield). 
Example 2 
Tolyltriazole-Formaldehyde-Diisobutylamine 
Approximately 80.1 gm (0.6 mole) of tolyltriazole, 200 ml 2-propanol, and 
78.0 gm (0.6 mole) diisobutylamine were mixed in a 500 ml reactor until a 
homogeneous phase was formed. 51.0 gm (0.618 mole) of aqueous formaldehyde 
was slowly added while maintaining a reactor temperature 
.ltoreq.40.degree. C. Thereafter, the reactants were heated at 
82.+-.2.degree. C. for 4 hrs., then at 110.+-.2.degree. C. for two 
additional hours during which isopropanol and water were removed by 
distillation. The final product (163.5 gm) is a yellowish liquid which 
solidifies upon standing at ambient temperature (m.p. 
49.degree.-51.degree. C.). A final filtration to remove possibly unreacted 
tolyltriazole is optional. However, small amounts of residual water could 
make the final product appear hazy. 
Example 3 
The procedure of Example 1 was followed with only one exception: equimolar 
commercial arylalkyl etheramine surfonamine MNPA 380 was used instead of 
bis(2-ethylhexyl)amine. 
Example 4 
The procedure of Example 1 was followed with only one exception: equimolar 
dibutylamine was used instead of bis (2-ethylhexyl)amine. 
Example 5 
The procedure of Example 1 was followed with only one exception: equimolar 
dicyclohexylamine was used instead of bis (2-ethylhexyl)amine. 
Example 6 
The procedure of Example 1 was followed with only one exception: equimolar 
dipentylamine was used instead of bis(2-ethylhexyl)amine. 
Example 7 
The procedure of Example 1 was followed with only one exception: equimolar 
Exxon Etheramine PA-14 was used instead of bis(2-ethylhexyl)amine. 
Example 8 
The procedure of Example 1 was followed with only one exception: equimolar 
2-ethyl-1-hexylamine was used instead of bis(2-ethylhexyl)amine. 
Example 9 
The procedure of Example 1 was followed with only one exception: equimolar 
hexamethylene imine was used instead of bis(2-ethylhexyl)amine. 
Example 10 
The procedure of Example 1 was followed with only one exception: equimolar 
N-aminoethyl piperazine was used instead of bis(2-ethylhexyl)amine. 
Example 11 
The procedure of Example 1 was followed with only one exception: equimolar 
4-(3-aminopropyl)morpholine was used instead of bis(2-ethylhexyl)amine. 
Example 12 
The procedure of Example 1 was followed with only one exception: equimolar 
morpholine was used instead of bis(2-ethylhexyl)amine. 
Example 13 
The procedure of Example 1 was followed with only one exception: equimolar 
diisobutylamine was used instead of bis(2-ethylhexyl)amine. 
Example 14 
The procedure of Example 1 was followed with one exception: equimolar 
1,4-diaminocyclohexane was used instead of bis(2-ethylhexyl)amine. 
Example 15 
The procedure of Example 1 was followed with one exception: one half molar 
Exxon etherdiamine DA-14 was used instead of bis(2-ethylhexyl)amine. 
Example 16 
The procedure of Example 1 was followed with one exception: one half molar 
Exxon etherdiamine DA-17 was used instead of bis(2-ethylhexyl)amine. 
Example 17 
The procedure of Example 1 was followed with the following exceptions: 
N-oleyl-1,3-diaminopropane (Akzo Duomeen O) was used instead of 
bis(2-ethylhexyl)amine, and only one half molar Duomeen O was employed for 
this reaction. 
Example 18 
The procedure of Example 17 was followed with one exception: equimolar 
N-cocoyl-1,3-diaminopropane (Akzo Duomeen C) was used instead of 
N-oleyl-1,3-diaminopropane. 
Example 19 
The procedure of Example 18 was followed with one additional subsequent 
reaction: the reaction adduct of Example 18 was further treated with 
equimolar 1,2-epoxide propane. 
EVALUATION OF THE PRODUCT 
A significant feature of the additives is that they impart enhanced thermal 
stability and oxidation and corrosion inhibition to the fluid compositions 
into which they are incorporated. The ability of the products of the 
examples to withstand severe performance conditions was tested in the CMCo 
Heat Test (the test data were reported in Table 1) and the Pressure 
Differential Calorimetry Test (PDSC) for oxidation (the test data were 
reported in Table 2). 
In the CMCo Heat Test procedure, a thermal stability test, clean, polished, 
preweighed copper and steel rods were placed in a 250 ml Griffin beaker 
containing 200 cc of the lubricant sample to be tested. The beaker and its 
contents were placed in an aluminum fixture in an electric gravity 
convection oven which maintained the temperature was maintained at 
375.degree. C. for about one week. After about one week, the samples were 
removed and allowed to cool to room temperature. The copper rod was 
removed from the oil sample, washed with acetone to remove all oil and 
dried. The dry, clean rod was weighed and its condition was visually 
evaluated for any signs of corrosion. The copper rod was then placed in a 
solution of potassium cyanide (KCN) at room temperature until all visible 
deposits were removed. The rod was then washed with distilled water 
followed by an acetone wash and air dried. The rod was then weighed to the 
nearest 0.1 mg. The steel rod was removed from the sample washed with 
naphtha and air dried. The rod was weighed and visually evaluated for 
discoloration.. The rod was then placed in a 20% solution of sodium 
hydroxide (NaOH) and any softened lacquer was wiped away. The rod was then 
washed with acetone, dried and weighed to the nearest 0.1 mg. A visual 
comparison between the test copper and steel rods and a reference set of 
copper and steel rods was made. The reference set was rated on a scale of 
1 to 9, depending upon the degree of discoloration .and corrosion. A score 
of 9 was given to the most severely corroded reference rod. A score of 1 
was given to the cleanest reference rod which was essentially free of any 
signs of deterioration. The reference rods which fell within the lower 
range of this scale were acceptable even though slightly discolored or 
slightly to moderately tarnished and were rated from 3-5. The reference 
rods which fell within the upper range of the scale were unacceptably 
discolored or corroded and were rated from 6-8. The test rods were 
compared with the reference rods and were rated based on their degree of 
corrosion relative to the reference set. All of the products of the 
examples achieved acceptable copper rod ratings under the vigorous, 
severely corrosive conditions of the test. The base oil containing a 
conventional additive package, but without the additive of the present 
invention, obtained a rating of 9 indicating a high corrosivity to copper. 
As shown in Table 1, adding a small amount of the present additive to the 
base oil composition remarkably elevated the copper and steel rod ratings. 
TABLE 1 
______________________________________ 
CMCo Heat Test (one week, 375.degree.) 
Copper Steel 
Item Conc. wt % Rod Rating 
Rod Rating 
______________________________________ 
Base oil (a formulated 
-- 9 1 
mineral oil containing 
defoamant/demulsifier/ 
antioxidant/antiwear/ 
dispersant performance 
package) 
Example 1 0.03 3 1 
(in above base oil) 
0.10 3 1 
Example 2 0.03 3 1 
(in above base oil) 
0.10 3 1 
Example 3 0.03 3 1 
(in above base oil) 
Example 4 0.10 3 1 
(in above base oil) 
Example 8 0.10 3 1 
(in above base oil) 
Example 17 0.10 4 1 
(in above base oil) 
Example 18 0.10 4 1 
(in above base oil) 
Example 19 0.10 4 1 
(in above base oil) 
______________________________________ 
In the Pressure Differential Calorimetry test (PDSC) for oxidation 
inhibition, the thermal stability of the lubricant containing the additive 
of the present invention was measured. The results of tile test were 
reported in Table 2. In the PDSC test, the test instrument measured the 
oxidation onset temperature: the temperature at which the lubricating oil 
started to degrade (oxidize). The onset temperature was measured by 
gradually increasing the temperature at a specified rate over a certain 
temperature range. The higher the onset temperature, the more thermally 
stable the lubricant and the better the lubricating oil was at resisting 
oxidative change. A more detailed description of the PDSC procedure will 
be found in "Characterization of Lubricating Oils by Differential Scanning 
Colorimetry," Walker et al., SAE Technical Paper Series No. 803,383, 1980 
and "Characterization of Lube Oils and Fuel Oils by DSC Analysis, F. Noel, 
Journal of the Institute of Petroleum, Vol. 57, No. 568, November 1971, pp 
354-358, which are both incorporated herein by reference. 
The data show that a small 0.1% concentration of the additive can raise the 
onset temperature of the base oil sample T(.degree. C.) up to 13.8.degree. 
C. 
TABLE 2 
______________________________________ 
PDSC Oxidation Test 
(500 psi oxygen pressure, ramp 10.degree. C./minute 
from 30.degree. C. to 275.degree. C.) 
Onset 
Item Concentration 
Temp. T (.degree.C.) 
______________________________________ 
Base oil (200 sec solvent 
-- 216.1 -- 
refined paraffinic neutral 
mineral oil 
Example 2 0.1% 228.5 +12.4 
(in above base oil) 
Example 3 0.1% 229.9 +13.8 
(in above base oil) 
Example 16 0.1% 222.4 +6.3 
(in above base oil) 
Example 18 0.1% 227.5 +11.4 
(in above base oil) 
Example 19 0.1% 227.4 +11.3 
(in above base oil) 
______________________________________ 
As can be seen from the above test results, the products of the invention 
exhibited considerable corrosion inhibiting activity, antioxidation 
characteristics and thermal stability in lubricating oils and greases.