CA1163998A - Benzotriazole compositions dispersible in compounded lubricants - Google Patents

Abstract

BNZOTRIAZOLE COMPOSITIONS DISPERSIBLE
IN COMPOUNDED LUBRICANTS

Abstract The reaction products of water-insoluble ali-phatic amines with benzotriazoles are dispersible in compounded lubricants and are convenient for the incor-poration of benzotriazoles therein as oxidation and corrosion inhibitors and suppressors of copper activity.
The preferred benzotriazole is tolyltriazole, and the preferred amines are tertiary alkyl primary amines and oil-soluble basic nitrogen-containing dispersants.

Description

~l63~sa BENZOTRIAZOLE COMPOSITIONS DISPERSIBLE
IN CO~IPOUNDED LUB~ICANTS

This invention relates to new compositions of matter, methods for their preparation, and lubricants S containing them. More particularly, it relates to composi-tions of matter dispersible in compounded lubricants, said compositions being prepared by reacting at least one sub-stantially wa~er-insoluble aliphatic amine with at least one benzotriazole.
It is known that improved oxidation and corrosion resistance and decreased copper activity can be imparted to lubricants by the incorporation therein of minor amounts of benzotriazoles. The preparation of lubricants containing benzotriazoles is difficult, however, because many benzo-15 triazoles are solid and most are substantially insoluble in lubricating oils. It is of interest, therefore, to develop methods for increasing the compatibility of benzo-triazole-containing compositions with formulated lubricants.
A principal object of the present invention, 20 therefore, is to provide novel benzotriazole compositions and a method for their preparation.
A further object is to provide benzotriazole compositions which may be stably incorporated in lubrica-ting oils, especially gear lubricants.
A further object i5 to produce lubricants, es-pecially gear lubricants, which are highly rssistant to .
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corrosion and oxidation and which are low in copper ac-tivity.
Other objects will in part be ob~ious and will in part appear hereinafter.
The benzotriazole used in the method of this invention may be substituted or unsubstituted. Examples of suitable compounds are benzotriazole and the tolyltriazoles, ethylbenzotriazoles, hexylbenzot:riazoles, octylbenzotria~
zoles, phenylbenzotriazoles, chlorobenzotriazoles and 10 nitrobenzotriazoles. Preferred are benzotriazole and the alkylbenzotriazoles in which the alkyl group contains about 1-8 carbon atoms, especially benzotriazole and tolyltria-zole.
The amine may be any substantially water-insoluble 15 aliphatic monoamine or polyamine, with monoamines being pre-ferred. It may be primary, secondary or tertiary, with amines containing at least one primary amino group being preferred. For the most part, the water-insoluble aliphatic amines contain at least one alkyl group having at least 20 about 10 carbon atoms. Suitable ones include the decyl-amines, didecylamines, tridecylamines, dodecylamines, tetradecylamines and octadecylamines, with all isomers being suitable. Mixtures of these amines are also useful for the purposes of this invention. A preferred class of amines, 25 especially for the preparation of compositions for use in gear lubricants, comprises the primary amines in which the alkyl group contains about 10-30 carbon atoms, particularly those in which the alkyl group is a tertiary group. Illus-trative amine mixtures of this type (a~ailable from Rohm &
30 ~aas Co.) are "Primene 81R" which is a mixture of Cl 2-1~
tertiary alkyl primary amines, and "Primene JM-T" which is a similar mixture of C 18-2 2 amines.
A second preferred class of amines, especially for preparing compositions for use in internal combustion engine lubricants, comprises the oil-soluble basic nitrogen-containing dispersants, preferably those containing no more than 100 and usually no more than about 25 aliphatic carbon atoms per basic amino group. Dispersants of this type are .

~ 1~399~

known in the art and include such subclasses as the "carboxylic dispersants", "amine dispersants" and "Mannich dispersants".

The carboxylic dispersants are :reaction products of carboxylic acids (or derivatives the:reof) containing at least about 44 and preferably at least about 54 aliphatic carbon atoms with polyamines and optionally also with organic hydroxy compounds such as phenols and alcohols and/or basic inorganic materials.
Examples of these products are described in many U.S. patents, of which 3,272,746 is one example.

The amine dispersants are reaction products of aliphatic or alicyclic halides containing at least about 40 carbon atoms with polyamines, preferably polyalkylene polyamines. Examples thereof are described, for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 The Mannich dispersants are reaction products of alkyl phenols in which the alkyl group contains at least about 40 carbon atoms with aliphatic aldehydes containing at most about 7 carbon atoms (especially formaldehyde) and polyamines (especially alkylene polyamines). The materials described in the :Eollowing U.S. patents are illustrative:

2,459,112 3,442,808 3,591,598 2,962,442 3,448,047 3,600,372 2,984,550 3,454,497 3,634,515

3,036,003 3,459,661 3,649,229 3,166,516 3,461,172 3,697,574 3,236,770 3,493,520 3,725,277 3,355,270 3,539,633 3,725,480 3,368,972 3,558,743 3,726,882 3,413,347 3,586,629 3,980,569 The carboxylic dispersants may be most conveniently and accurately described in terms of radicals 1 and 2 present therein.
Radical 1 is usually an acyl, acyloxy or acylimidoyl radical ~l containing at least about 34 carbon ............................
;i, .

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atoms. The structures of these radicals, as defined by the International Union of Pure and Applied Chemistry, are as follows (each R' individually repreSeTIting a hydrocarbon or similar grouP):

Acyl: R'-C-o Acyloxy: R'-C-O-NR' ~cylimidoyl: R'-C-Radical 2 is preferably at least one radical in which a nitrogen or oxygen atom is attached directly to said 10 acyl, acyloxy or acylimidoyl radical, said nitrogen or oxygen atom also being attached to a hydrocarbon-based radical containing at least one basic amino group.
The preferred carboxylic dispersants are those disclosed (for example) in the above-mentioned U.S. Patents 15 3,219,666 and 3,272,746 which also describe a large number of methods for their preparation. Radical 2 therein is derived from compounds characterized by a radical of the structure ~ N~ wherein the two remaining valences of nitro-gen are satisfied at least in part by organic radicals 20 bonded to said nitrogen atom through direct carbon-to-nitrogen linkages, said organic radicals containing at least one basic nitrogen atom. These compounds include aliphatic, heterocyclic and carbocyclic amines.
Hydroxy amines are included in the class o~
25 useful amines. Such compounds are the hydroxyhydrocarbyl-substituted compounds such as those having the formulas HNRIR2, wherein Rl is an alkyl or hydroxy-substituted alkyl radical of up to lO carbon atoms and R2 is hydrogen or a radical similar to Rl, at least one of R1 and R2 being 30 hydroxy-substituted. Suitable hydroxy-substituted mono-amines include ethanolamine, di-3-propanolamine, 4-hydroxy-butylamine, diethanolamine, N-methyl-2-propylamine, N-hydroxyethylethylene diamine, N,~-di(hydroxypropyl)propylene diaminP and tris(hydroxymethyl)methylamine. While in ~ ~63~

general, hydroxy amines containing only one hydroxy group will be employed as reactants, those containing more can also be used.
Heterocyclic polyamines are also useful in making 5 the carboxylic dispersant, prov:Lded they contain at least two amino groups of which at least one is primary or secon-dary. The heterocyclic ring can also incorporate unsatu-ration and can be substituted with hydrocarbon radicals such as alkyl, alkenyl, aryl, alkaryl or aralkyl. In addition, 10 the ring can also contain other hetero atoms such as oxygen, sulfur, or other nitrogen atoms including those not having hydrogen atoms bonded to them. Generally, these rings have 3-10, preferably 5 or 6, ring members. Among such hetero~
cycles are aziridines, azetidines, azolidines, pyridines, 15 pyrroles, piperidines, imidazoles, indoles, piperazines, isoindoles, purines, morpholines, thiamorpholines, azepines, azocines, azonines, azecines and tetrahydro-, dihydro- and perhydro-derivatives of each of the above. Preferred heterocyclic amines are the saturated ones with 5- and 6-20 membered rings, especially the piperidines, piperazines andmorpholines described above.
Aliphatic polyamines are preferred for preparing the carboxylic dispersant. Among the polyamines are alkylene polyamines (and mixtures thereof) including those 25 having the formula A-N-~R3-N~-nH
A A
wherein n is an integer between about 1 and 10, preferably between 2 and 8; each A is independently hydrogen or a hydrocarbon or hydroxy-substituted hydrocarbon radical 30 having up to about 30 atoms; and R3 is a divalent hydro-carbon radical having from about 1 to about 18 carbons.
Preferably A is an aliphatic radical of up to about 10 car-bon atoms which may be substituted with one or two hydroxy groups, and R3 is a lower alkylene radical having 1-10, 35 preferably 2-6, carbon atoms. Especially preferred are the alkylene polyamines wherein each A is hydrogen. Such 1 l63s~a alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologs of such amines and related 5 aminoalkyl-substituted piperazines are also included.
Specific examples of such polyamines include ethylene diamine, triethylene tetramine, tris(2-aminoethyl)amine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, 10 di(heptamethylene) triamine, tripropylene tetramine, tetra-ethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine, 2-heptyl-3-(2-amino-propyl)imidazoline, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and 15 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs, obtained by condensing two or more of the above-illustrated alkylene amines, are also useful, as are the polyoxy-alkylene polyamines (e.g., "Jeffamines").
The ethylene polyamines, examples of which are 20 mentioned above, are especially useful for reasons of cost and effectiveness. Such polyamines are described in detail under the heading "Diamines and Higher Amines" in Kirk-Othmer, Encyclopedia of Chemical Technolo~y, Second Edition, Vol. 7, pp. 22-39. They are prepared most con-25 veniently by the reaction of an alkylene chloride withammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products 30 such as piperazines. Because of their availability, these mixtures are particularly useful in preparing the composi-tions of this invention. Satisfactory products can also be obtained by the use of pure alkylene polyamines.
Hydroxy polyamines, e.g., alkylene polyamines 35 having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing the carboxylic dispersant.
Preferred hydroxyalkyl-substituted alkylene polyamines are 1 16~9g8 those in which the hydroxyalkyl group has less than about 10 carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)ethylene diamine, l-(2-hydroxyethyl)-5 piperazine, monohydroxypropyl~substituted diethylene tri-amine, dihydroxypropyltetraethylene pentamine and N-(3-hydroxybutyl)tetramethylene dialmine. Higher homologs obtained by condensation of the above-illustrated hydroxy-alkyl-substituted alkylene amines through amino radicals or lO through hydroxy radicals are likewise useful.
The source of radical l in the carboxylic dis-persant is an acylating agent comprising at least one carboxylic acid-producing compound containing a hydrocarbon or substituted hydrocarbon substituent which has at least 15 about 30 and preferably at least about 50 aliphatic carbon atoms. By "carboxylic acid-producing compound1' is meant an acid, anhydride, acid halide, ester, amide, imide, amidine or the like; the acids and anhydrides are preferred.
The carboxylic acid-producing compound is usually 20 prepared by the reaction (more fully described hereinafter) of a relatively low molecular weight carboxylic acid or derivative thereof with a hydrocarbon source containing at least about 30 and preferably at least about 50 carbon atoms. The hydrocarbon source is usually aliphatic and 25 should be substantially saturated, i.P. ~ at least about 95%
of the total number of carbon-to-carbon covalent linkages should be saturated. It should also be substantially fxee from pendant groups containing more than about six aliphatic carbon atoms. It may be a substituted hydrocarbon source.
30 By "substituted" is meant sources containing substituents which do not alter significantly their character or reac-tivity; examples are halide, hydroxy, ether, keto, carboxy, ester (especially lower carbalkoxy), amide, nitro, cyano, sulfoxy and sulfone radicals. The substituents, if present, 35 generally comprise no more than about 10% by weight of the hydrocarbon source.

~ ~ ~i 3 ~9~ a The preferred hydrocarbon sources are those de~
rived from substantially saturated petroleum fractions and olefin polymers, particularly polymers of monoolefins having from 2 to about 30 carbon atoms. Thus, the hydro-5 carbon source may be derived from a polymer of ethylene,propene, l-butene, isobutene, l-octene, 3-cyclohexyl~l-butene, 2-butene, 3-pentene or the like. Also useful are interpolymers of olefins such as those illustrated above with other polymerizable olefinic substances such as 10 styrene, chloroprene, isoprene, p-methylstyrene, piperylene and the like. In general, these interpolymers should con-tain at least about 80~, preferably at least about 95~, on a weight basis of uni~s derived from the aliphatic mono-olefins.
Another suitable hydrocarbon source comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or synthetic alkanes.
In many instances, the hydrocarbon source should contain an activating polar radical to facilitate its 20 reaction with the low molecular weight acid-producing com-pound. The preferred activating radicals are halogen atoms, especially chlorine, but other suitable radicals include sulfide, disulfide, nitro, mercaptan, ketone and aldehyde groups.
As already pointed out, the hydrocarbon sources generally contain at least about 40 and preferably at least about 50 carbon atoms. Among the olefin polymers those having a number average molecular weight between about 600 and about 5000 (as determined by gel permeation chromato-30 graphy) are preferred, although higher polymers having molecular weights from about 10,000 to about 100,000 or higher may sometimes be used. Especially suitable as hydro-carbon sources are isobutene polymers wi~hin the prescribed molecular weight range, and chlorinated derivatives thereof.
Any one of a number of known reactions may be em-ployed for the preparation of the carboxylic acid-producing 1 ~6399~
_9_ compound. Thus, an alcohol of the desired molecular weight may be oxidized with potassium permanganate, nitric acid or a similar oxidizing agent; a halogenated olefin polymer may be reacted with a ketene; an ester of an active hydrogen-5 containing acid, such as acetoacetic acid, may be convertedto its sodium derivative and the sodium derivative reacted with a halogenated high molecular weight hydrocarbon such as brominated wax or brominated polyisobutene; a high molecular weight olefin may be ozonized; a methyl ketone of 10 the desired molecular weight may be oxidized by means of the haloform reaction; an organometallic derivative of a halo-genated hydrocarbon may be reacted with carbon dioxide; a halogenated hydrocarbon or olefin polymex may be converted to a nitrile, which is subsequently hydrolyzed; or an olefin 15 polymer or its halogenated derivative may undergo a reaction with an unsaturated carboxylic acid or derivative thereof such as acrylic acidl methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, 20 glutaconic acid, chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, 2-pentene-1,3,5-tricarboxylic acid, and the like, or with a halogen-substituted carboxylic acid or derivative thereof. This latter reaction is preferred, es-25 pecially when the acid-producing compound is unsaturated and preferably when it is maleic acid or anhydride. The result-ing product is then a hydrocarbon-substituted succinic acid or derivative thereof. The reaction leading to its forma-tion involves merely heating the two reactants at a temper-30 ature from about 100 to about 200C. The substitutedsuccinic acid or anhydride thus obtained, may, if desired, be converted to the corresponding acid halide by reaction with known ha].ogenating agents such as phosphorus tri-chloride, phosphorus pentachloride or thionyl chloride.
For the formation of the carboxylic dispersant, the hydrocarbon-substituted succinic anhydride or acid, or 3s~a other carboxylic acid-producing compound, and the alkylene polyamine or other nitrogen-containing reagent are heated to a temperature above about 80C., preferably from about 100 to about 250C. The product thus obtained has predominantly 5 amide, imide and/or amidine linkages (containing acyl or acylimidoyl groups), or, if a hydroxy amine is used, may contain ester linkages. The process may in some instances be carried out at a temperature below 80C. to produce a product having predominantly amine salt linkages (containing 10 acyloxy groups). The use of a diluent such as mineral oil, benzene, toluene, naphtha or the like is often desirable to facilitate control of the reaction temperature.
The relative proportions of the carboxylic acid-producing compound and the alkylene polyamine or the like 15 are such that at least about one-half the stoichiometrically equivalent amount of polyamine is used for each equivalent of carboxylic acid-producing compound. In this regard it will be noted that the equivalent weight of the alkylene polyamine is based upon the number of amine radicals therein, 20 and the equivalent weight of the carboxylic acid-producing compound is based on the number of acidic or potentially acidic radicals. (Thus, the equivalent weight of a hydro-carbon-substituted succinic acid or anhydride is one-half its molecular weight.) Although a minimum of one-half 25 equivalent of polyamine per equivalent of acylating agent should be used, there does not appear to be an upper limit for the amount of polyamine. If an excess is usecl, it merely remains in the product unreacted without any apparent adverse effects. Ordinarily, about 1-2 equivalents of 30 polyamine are used per equivalent of acylating agent.
In an alternative method for producing the car boxylic dispersant, the alkylene polyamine is first reacted with a low molecular weight, unsaturated or halogen-substituted carboxylic acid or derivative thereof (such as 35 maleic anhydride or one of the others previously mentioned) and the resulting intermediate is subsequently reacted with the hydrocarbon source as previousl~ described.

1 ~639~8 It is also possible to prepare carboxylic dis-persants by reacting the acylating agent simultaneously or, preferably, sequentially with at least one of the above-described nitrogen-containing reagents and with at least one 5 hydroxy compound. The hydroxy compounds are usually alco-hols containing up to about 40 aliphatic carbon atoms.
These may be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, neopentyl alcohol, monomethyl ether of ethylene glycol and the like, or poly-10 hydric alcohols including ethylene glycol, diethyleneglycol, dipropylene glycol, tetramethylene glycol, penta-erythritol, glycerol and the like. Carbohydrates (e.g., sugars, starches, cellulose) are also suitable as are par-tially esterified derivatives of polyhydric alcohols having 15 at least three hydroxy radicals. Aliphatic polyols contain-ing up to 10 carbon atoms and at least 3 hydroxy groups, especially those with up to 6 carbon atoms and 3-6 hydroxy groups, are preferred.
The reaction with the hydroxy compound is usually 20 effected at a temperature above about 100C. and typically from about 150 to about 300C. The relative amounts of the nitrogen-containing and hydroxy reagents may be between about 10:1 and 1:10, on an equivalent weight basis.
Typical carboxylic dispersants suitable for use 25 according to this invention are listed in Table I. "Reagent 1" and "Reagent 2" aré, respectively, ~he sources of radi-cals 1 and 2 as previously defined.

g ~ 8 --12 ~
r~ ~ r~
r~ r~ rl r~ rl r~
1~ O O O O O O O
r~ ~ r-l r~ a) r-l ~1 ~ a) h ~::
r~
.r~ r~ r~rt O

O ~ o Ln Ll~
rl ~) c~ Ln r-o o o or--l r--u ~ ~ Ln Ln Ln Ln Ln o ~I r-l r-l r--P~ E3 co ~ o tn L~
O
C) co r--l r~
O r~
r~
r-l O O r--l r--l~I r-l O
1~ r I
tr a) a .r~ .r~
~ r ~ X ~ r--l r~
r~ r ,5~ r~ r--l.C r ~ ~- S: r h E~ ~ $ ~
H ~: r~ 4 ~ al .r l L~ 5-1 a) O ~ a~ a) a) .r-~O X ~ h ~ o-- u~
1~1 tJ ~ O h ~I r-l (I) ~ h O O .
~ ~ U 1`
tq (I) ~ rd ~ rc~
lC p; ~ O ~) ~) ~I r~ h 0 -1 a) r-l E~ a1 h ut ~ -r~ ~ ~ al 3 ~ r-l 0 r~ r--l ~1 ~i I al a~ O
.5 X O O s ~ I r~ r-l r~l 11~ ~
-1 R h ~) ~ rl ~rl h I ~1 a) O O X til æ ~ ~:
. ~, ~ o r~ Ln 3 0 O a~ s o r~ r~

r--I r~ h r~ ~ Q
Q u ~ ~ ~rl O ~D ~D O ~ a) O
r-l~; u ~ ~ r~ r-l ~) R ~Ir-l r-l r--- ~ r~ r~
h ~ h ~ R Cl r4 ~ E3 O::>1~ h ~ r-l X ~r-l rl ~~ rl X X X X
r~ 3 0 .~; O 1~ W
rc~ r-l u ~¦
a~ ~ cn~l S ~1 u~ X ~ X ~ tQU~
r~ \ 3 1~1 ~ 3 fd U ~ ~ o a) ~ a)a~ a) (D
.r~ r~ ) r-l Ln ~ u ~ ~ k E~ ~i O Q ~ h ~ h S:: ~ r~ X O O ~rl X O

r-l X

39~8 .,~ .~ .,1 O O O
a) ~ ~1 ~1 ~ 0 _l S~
.~ a~a) a~ ~ I a .,1 .,~ .,1 ~, ~ ~ ~ ~ X X
a~
~ S~
O ~ o o ,1 ~ ~1 ~
. o o ~ o ~ o o ~ O ~ 0 ~1 P; ~ U~ ~

U~
q~
O ~
a) ,~ ~r O ~I N ~ O el' O O
-O ~ O ~ ~1 0 a O--~1 `~ O '-~ ~ 'I O
H ~ ~ ~ O ~
~ d ~ ~ a) G) ~1 p:~~ ~n ~ h E~ ~ O
a)a~ ~ k o o x ~ ~s~

I o ~ .
. ~ o ~ 3 ~ ~ ~ ~O o ~1 o ~
X Q S~0 ~I t) O ~ X
~1~1 a~ ~ o ~ ~ R 3 ~ ~ C) Q. ~a) ~ h ,1 o ~:1 0 E~ ~a) ~ ~ a) o o Ln a~ ~ ~ o o ~:: ~ u ~ ~ 3a) ~ o~o ~ ,~
X ~~R Q ~ ~ u~~ o r~
~1 ~ X O ~ q~ U 3 0 :~ v~ a) O ~ O
~; ~1 ~ 0~ ~ ~o 1 0 o Z
~ Q) ~ V rl ~ ~ U ~ o u~I V 3 ~ ; S:~ R ~:: Q 3 ~:; ~ U
a) ~ ~ c~
X

-~ 1639~8 ~ l l ~ l ,~

~ 5 o ~
,1 ~ o o . o o s~ U
~o o o ~; ~ oo CO
_ ..
U~
o a~
O ~I N CO CO
-~ ~1 O O
P; ~
.~
X
a~
S
~1 ~1 ~ ,, x ~ ~ s ~q E~
U~
~a I
~ ~rl O
0 3 ss ~ i c~o o U~
3 o o a~ ~ aJ ~

~ ~ ~ ~D ~ O ~ S
a~ o rJ ,~ ~ 3 r~
O O ~1'` ~ E3 S O
~ o ,~
a~ o o G) C~

L~
~1 X

B

In the preparation of carboxylic dispersants such as those described in Examples 1-16, reagent 1 is normally prepared by reacting appro~imately equimolar amounts of the hydrocarbon source and the low molecular weight carboxylic 5 acid or derivative thereof. It is also within the scope of the invention, however, to use a carboxylic dispersant pre-pared by initially reacting substantially more than one mole of acid or acid derivative with one mole of hydrocarbon source. In the preferred dispersants of this type, as in 10 those previously described herein, the hydrocarbon source is an olefin polymer such as polybutene and the carboxylic acid derivative is maleic anhydride. Dispersants of this type usually contain up to about 3.5 and most often from about 1.3 to about 3.5 succinic groups for each group derived from 15 the hydrocarbon source.
The method of preparation of dispersants o~ this type is basically the same as for the carboxylic dispersants already described. Reagent 1, in particular, may be pre-pared by a one-step procedure in which the hydrocarbon 20 source is reacted with maleic anhydride; by a two-step procedure in which the hydrocarbon source is chlorinated and the chlorinated intermedia~e is reacted with maleic anhy-dride; or by various combinations of the two procedures.
The following examples illustrate typical methods 25 for the preparation of suitable dispersants of this type.

Example 17 A mixture of lO00 parts (0.~95 mole) of a poly-butene comprising principally isobutene units and having a number average molecular weight of 2020 and a weight average 30 molecular weight of 6049 and 115 parts (1.17 moles) of maleic anhydride is heated to 184C. over 6 hours as 85 parts (1.2 moles) of chlorine is added beneath the surface.
At 184-189C. an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is stripped by 35 blowing with ~itrogen at 186-190C. fox 26 hours to yield a polybutene-substituted succinic anhydride having a saponifi-cation number of 87 as determined by ASTM Procedure D94.

~ lfi39~8 To 893 parts (1.38 equivalents) of this substituted succinic anhydride is added 1067 parts of mineral oil and 57 parts (1.38 equivalents) of a commercial ethylene polyamine mixture containing from about 3 to about 10 nitrogen atoms per molecule.
The mixture is heated to 140-155C. for 3 hours and is then stripped by blowing with nitrogen. The stripped liquid is filtered and the filtrate is the desired dispersant (approximately 50% solution in oil).

Example 18 A mixture of 334 parts (0.52 equivalent) of the polybutenyl succinic anhydride of Example 17, 548 parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Polyglycol 112-2 demulsifier from Dow Chemical Company is heated at 150-210C. for about 11 hours. The mixture is cooled to 190C. and 8.5 parts (0.2 equivalent) of the ethylene polyamine mixture of Example 1 is added. The mixture is stripped by blowing with nitrogen for 3 hours at 205C. and is filtered to yield the desired dispersant as an approximately 40% solution in oil.

Also suitable as an alternative to the carboxylic dispersants hereinabove described, are the Mannich dispersants. These are, as previously noted, reaction products of certain alkyl phenols with aldehydes (usually lower aliphatic aldehydes and especially formaldehyde) and polyamino compounds. The structure of the alkyl substituent on the phenol is subject to the same preferences as to source, structure, molecular weight and the like expressed herein-above with respect to the carboxylic dispersant. The polyamino compounds are the same as those described with reference to carboxylic dispersants and are subject to the same preferences.

Suitable Mannich dispersants are illustrated in the working examples of the aforementioned U.S. Patent 3,980,569. The following examples are also illustrative.

1~3gn~d Example 19 A mixture of 3740 parts (2 equivalents) of a poly-butenyl phenol in which the polybutene substituent comprises principally isobutene units and has a molecular weight of about 1600, 1250 parts of textile spirits and 2000 parts of isopropyl alcohol is stirred as 352 parts (2.2 equivalents) of 50% aqueous sodium hydroxide is added, followed by ~80 parts (6 equivalents~ of 38~ aqueous formaldehyde solution.
The mixture is stirred for 2 hours, allowed to stand for 2 days and then stirred again for 17 hours. Acetic acid, 150 parts (2.5 equivalents), is added and the mixture is stripped of volatile materials under vacuum. The remaining water is removed by adding benzene and distilling azeo-tropically; during the distillation, 1000 parts of mineral 15 oil is added in two portions. The distillation residue is filtered.
To 430 parts (0.115 equivalent) of the filtrate is added with stirring, at 90C., 14.1 parts (0.345 equivalent) of the polyethylene amine mixture of Example 1. ~he mixture 20 is heated at 90-120C. for 2 hours and then at 150-160C.
for 4 hours, with nitrogen blowing to remove volatiles. The resulting solution is filtered to yield the desired Mannich dispersant (52~ solution in mineral oil) which contains 1.03% nitrogen.

25 Example 20 A mixture of 564 parts (0.25 equivalent) of poly-butenyl phenol in which the polybutene substituent comprises principally isobutene units and has a molecular weight of about 2020, 400 parts of mineral oil and 16.5 parts of iso-30 butyl alcohol is heated to 65C., with stirring, and 2.15parts (0.025 equivalent) of 50~ aqueous sodium hydroxide solution is added, followed by 16.5 parts (0.5 equivalent) of paraformaldehyde. The mixture is stirred at 80-88C. for 6 hours and then 5 parts (0.025 equivalent) of 18.5~ aqueous 35 hydrochloric acid is added slowly, with continued stirring, followed by 36 parts (0.875 equivalent) of the polyethylene amine of Example 1, at 88C. ~ixing is continued at ~t~3~

88-91C. for 30 minutes. The mixture is then heated to about 15~C. with nitrogen blowing to remove volatiles.
Sulfur, 16 parts (0.5 mole), and 25 parts of a filter aid material are added slowly at 150C., with 5 stirring, after which the mixture is blown with nitrogen at 150-155C. for 3 hours. The mixture is then cooled to 132C. and filtered to yield the desired sulfurized Mannich product as a 60% solution in mineral oil; it contains about 0.63~ sulfur.

10 Example 21 A mixture is prepared by the addition of 18.2 parts (0.433 equivalent) of the ethylene polyamine mixture of Example 1 to 392 parts of mineral oil and 348 parts (0.52 equivalent) of the substituted succinic anhydride of E~ample 17. The mixture is heated to 150C. over 1.8 hours, stripped by blowing with nitrogen, and iltered to yield an oil solution of the desired dispersant.
The compositions of this invention may be prepared by merely blending the benzotriazole with the amine and 20 allowing the reaction between the two to proceed. If blend-ing takes place in a substantially inert, normally liquid organic ailuent such as mineral oil, benzene, toluene, xylene, petroleum naphtha, an aliphatic ether or the li~e, the reaction may take place at a temperature as low as about 15C. Ordinarily, it is preferred to carry out the reaction at a temperature of at least about 50C., especially when no diluent is used. Temperatures of about 70-200C. are pre-ferred.
The proportions of the benzotriazola and amine may vary widely. In general, it is intended to incorporate as much of the benzotriazole as possible in an oil-dispersible medium and this is best done by using about 1 equivalent of amine per equivalent of benzotriazole. (The equivalent weight of the amine is its molecular weight divided by the number of basic nitrogen atoms therein, and that of the benzotriazole is its molecular weight divided by the number of triazole rings therein.) In some instances, however, it ~ ~ ~3g~3 may be desirable to use more or less than 1 equivalent of amine per equivalent of benzotriazole. For example, an effective amount of benzotriazole for use in an internal combustion engine lubricant may be less than the equivalent 5 amount based on the dispersant present in the lubricant, in which case it may be desirable to incorporate a rela-tively minor amount of benzotriazole in the dispersant for incorporation in the lubricant.
The precise molecular structuras of the composi-10 tions of this invention are not known with certainty and arenot critical. It is known, however, that the benzotriazoles are more acidic than the amines and it is believed that the compositions may be amine salts of the benzotriazoles.
The preparation of the compositions of this inven-15 tion is illustrated by the following examples. All partsand percentages are by weight.

Example 2_ Benæotriazole, 464 parts, is added in 20-30 part increments, with stirring, to 696 parts of "Primene 81R" at 20 61-68C. Stirring is continued as the reaction mixture is heated for 2-1/2 hours at 75-80C. The mixture is filtered through a filter aid material to yield the desired product which has a base number of 172 to bromphenol blue and an acid number of 187 to phenolphthalein.

25 Example 23 Benzotriazole, 1210 parts, is added over 20 minutes, with stirring, to 1820 parts of "Primene 81R"
maintained at 60C. The mixture is stirred at 80C. for 45 minutes and 303 parts of an aromatic solvent with a dis-30 tillation range of about 311-344C. is added. The mixture is stirred at 80C. for an additional 15 minutes and filtered to yield the desired product having a base number of 157 to bromphenol blue and acid number of 135 to phenol-phthalein.

~ 1~3~

Example 24 Benzotriazole, 20 parts, is added over 10 minutes, with stirring, to 30 parts of "Primene JM-T" maintained at 60-80C. Xylene, 5 parts, is added and the mixture is 5 filtered to yield the desired product.

Example 25 A mixture of 500 parts of tolyltriazole and 718 parts of "Primene 81R" is heated for 8 hours under nitrogen at 120-140C., with stirring. Mineral oil, 135 parts, is added and the solution is filtered to yield the desired product.

Example 26 Four mixtures of tolyltriazole and the dispersant of Example 10 are prepared, respectively containing 3, 5, 7 and 9 parts of tolyltriazole and 97, 95, 93 and 91 parts of the dispersant. Each mixture is heated to 140C. for 1 hour, cooled to 120 and filtered through a filter aid material to yield a mineral oil solution of the desired product.

20 Example 27 Following the procedure of Example 26, products are made from tolyltriazole (3, 5 and 7 parts, respectively) and the dispersant of Example 17 (97, 95 and 93 parts, respec-tively).

25 Example 28 Tolyltriazole, 15 parts, is added with stirring at 90C. to 485 parts of the dispersant of Example 21. The mixture is heated to 140-145C. for 1 hour, cooled to 130C.
and filtered to yield an oil solution o the desired pro-30 auct.

~ s previously indicated, the compositions of thisinvention are useful as additives for lubricants, in which ~ '3 ~ 5~

they function primarily as oxidation and corrosion in-hibitors and inhibitors of copper activity. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic 5 lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compress~on-ignited internal combustion engines, including automobile and truck engines, two-cycle en~ines, aviation piston engines, marine and rai:lroad diesel engines, and the 10 like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic trans-missiOn fluids, transaxle lubr:icants, gear lubricants (in which ~heir use is especially beneficial), metal-working lubricants, hydraulic ~luids and other lubricating oil and 15 grease compositions can also benefit from the incorporation therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating 20 oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils and halo-substi-tuted hydrocarbon oils such as polymerized and interpoly-25 merized olefins [e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof~; alkylbenzenes [e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)ben-30 zenes, etc.]; polyphenyls (e.g., biphenyls, terphenyls,alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and 35 derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc.
constitute another class of known synthetic lubricating ~ l~3s~a oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an 5 average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed 10 C3-Ca fatty acid esters, or the Cl 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and 15alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alco-hol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, 20ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl 25sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid wi~h two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those 30 made from Cs to Cl 2 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Sil:icon-based oils such as the polyalkyl-, poly-aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili~
35 cate oils comprise another useful class of synthetic lubri-cants [e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) ~ 1639g~

silicate, tetra-(p-tert~butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly(methylphenyl)siloxanes, etc.]. Other synthetic lubri-cating oils include liquid esters of phosphorus-containing 5 acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-10 inabove can be used in the lubricant compositions of thepresent invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained 15 directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or 20 more properties. Many such purification techniques are known to those of skill in the art such as solvent extrac-tion, acid or base extraction, filtration, percolation, etc.
Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which 25 have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
` Generally, the lubricants of the present inven-30 tion contain an amount of the composition of this invention sufficient to provide it with oxidation, corrosion or cop-per activity inhibiting properties. Normally this amount will be about 0.01-10.0~, preferably about 0.01-5.0~, of the total we:ight of the lubricant. In lubricants operated 35 under extremely adverse conditions, the reaction products of this invention may be present in amounts up to about 20%
by weight.

ll63ssa -2~-The invention also contemplates the use of other additives in combination with the compositions of this invention. Such additives include, for example, detergents and dispersants of the ash~producing or ashless type, 5 auxiliary corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti~foam agents.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline 10 earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing 15 agent such as phosphorus trichloride, phosphorus heptasul-fide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphoro-thioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, 20 strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involve heat-25 ing a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid 30 the incorporation of a large excess of metal likewise is known. Examples o compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation pro-ducts of formaldehyde with a phenolic substance; alcohols 35 such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as anilina, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A

~l~3~a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated tem-5 perature such as 60-200C.
Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it 10 does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are illus-trative:
(1) Carboxylic dispersants such as those described hereinabove, and corresponding ester dispersants. These are described in British Patent 1,306,529, in the aforementioned U.S. Patent 3,272,746, and in many other U.S. patents including the following:
3,163,603 3,351,552 3,522,179 3,184,474 3,381,022 3,541,012 3,215,707 3,399,141 3,542,678 3,219,666 3,415,750 3,542,680 3,271,31~ 3,433,744 3,567,637 3,281,357 3,4~4,170 3,574,101 3,306,908 3,448,04~ 3,576,743 3,311,558 3,448,049 3,630,904 3,316,177 3,451,933 3,632,510 3,340,281 3,454,607 3,632,511 3,341,542 3,467,668 3,697,428 3,346,493 3,501,405 3,725,441 Re 26,433 (2) "Amine dispersants" and "Mannich dispersants"
such as those described hereinabove.
(3) Products obtained by post-treating the car-boxylic~ amine ox Mannich dispersants with such r~agents as ~ 163g~

urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like~
Exemplary materials of this kind are described in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,936 3,367,943 3,533,945 3,658/836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522

(4) Interpolymers of oil-solubilizing monomers such as decvl methacrylate, vinyl decyl ether and high molecuIar weight olefins with monomers containing polar substituents, e.g., amino-alkyl acrylates or acrylamides and poly-(oxyethylene~-substituted acrylates. These may be characterized as "polymeric dispersants" 0 and examples thereof are disclosed in the following U.S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 Extreme pressure agents and auxiliary corrosion- and oxidation-inhibiting agents are exemplified by chloroinated aliphatic hydrocarbons such as chlorinated wax; organic suIfides and poly-sulfides such as benzyl disulfide, bis(chlorobenzyl~disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulEurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate;
phosphorus esters including principally dihydrocarbon and tri-hydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, 1 1639g8 dicyclohexyl phosphite, pentylphenyl phosphite, dipentyl-phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl

5 phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such as zinc clioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phos-phorodithioates such as zinc cLicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)-10 phosphorodithioate, cadmium dinonylphosphorodithioate, andthe zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.
The compositions of this invention can be diluted 15 with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate which usually contains about 20-90% by weight of said composition and may contain, in addition, one or more other additives known in the art or 20 described hereinabove. However, their use is advantageous largely because, while not always s~luble in oil in amounts suitable for concentrate formation, they are soluble or at least stably dispersible in compounded lubricants ~e.g., gear lubricants) containing other additives. ~hus, 25 it is usually convenient to add them in the desired amount to the otherwise fully compounded lubricant. For example, a suitable gear lubricant consists of an SAE 90 mineral oil base in combination with 0.04% (by weight) of the product of Example 25 and 3.25~ of "Anglamol 99", a commercially 30 available additive package ~or gear lubricants. A suitable internal combustion engine lubricant may comprise an SAE 10 mineral oil and 1~ of the product of ~xample 23.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for preparing a composition of matter dispersible in compounded lubricants which comprises reacting, at a temperature within the range of about 15-200°C, at least one substantially water-insoluble tertiary alkyl primary monoamine with at least one triazole selected from the group consisting of benzotriazole and substituted benzotriazoles wherein the substituent is an alkyl group containing from 1 to 8 carbon atoms, a phenyl, a halo or a nitro group.

2. A method according to claim 1 wherein the amine is a mixture of C12-14 tertiary alkyl primary monoamines.

3. A method according to claim 2 wherein the triazole is tolyltriazole.

4. A method for preparing a composition of matter dispersible in compounded lubricants which comprises reacting, at a temperature within the range of about 15-200°C:
at least one triazole selected from the group consisting of benzotriazole and substituted benzotriazoles wherein the substitutent is an alkyl group containing from 1 to 8 carbon atoms, a phenyl, a halo or a nitro group with at least one oil-soluble dispersant selected from the group consisting of:
carboxylic dispersants which are the reaction products of alkylene polyamines with carboxylic acid-producing compounds containing at least about 34 aliphatic carbon atoms;
amine dispersants which are the reaction products of aliphatic or alicyclic halides containing at least about 40 carbon atoms with polyamins; and Mannich dispersants which are the reaction products of alkyl phenols in which the alkyl group contains at least about 40 carbon atoms with aliphatic aldehydes containing at most about 7 carbon atoms and polyamines.

5. A method according to claim 4 wherein the dispersant is a carboxylic dispersant.

6. A method according to claim 5 wherein the carboxylic acid-producing compound is a substituted succinic acid-producing compound and the substituent is a hydrocarbon or substituted hydrocarbon having at least about 50 aliphatic carbon atoms.

7. A composition prepared by the method of claim 1.

8. A composition prepared by the method of claim 2.

9. A composition prepared by the method of claim 3.

10. A composition prepared by the method of claim 4.

11. A composition prepared by the method of claim 6.

12. A lubricating composition comprising a major amount of a lubricating oil and a minor amount, effective to inhibit oxidation, corrosion or copper activity, of a composition according to claim 7 or 8.

13. A lubricating composition comprising a major amount of a lubricating oil and a minor amount, effective to inhibit oxidation, corrosion or copper activity, of a composition according to claim 9, 10 or 11.