CA1168222A

CA1168222A - Benzotriazole-sulfurized olefin compositions and lubricants and concentrates containing them

Info

Publication number: CA1168222A
Application number: CA000372094A
Authority: CA
Inventors: James A. Taglia; Donald L. Clason
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1980-03-10
Filing date: 1981-03-02
Publication date: 1984-05-29
Also published as: FR2485031A1; IT1170786B; JPS56136898A; GB2071139B; FR2485031B1; IT8147961A0; GB2071139A

Abstract

BENZOTRIAZOLE-SULFURIZED OLEFIN COMPOSITIONS

AND LUBRICANTS AND CONCENTRATES CONTAINING THEM

Abstract Compositions comprising (A) at least one benzo-triazole or reaction product thereof with an aliphatic amine and (B) a sulfurization product of at least one aliphatic or alicyclic olefinic compound are useful in lubricants, espe-cially gear lubricants, as additives capable of affording long-lasting extreme pressure properties and antiwear capability and having relative inertness to copper parts.
Component A is preferably benzotriazole or tolyltriazole, and component B is preferably the reaction product of a sulfur-hydrogen sulfide mixture with propene, isobutene, or a dimer, trimer or tetramer thereof.

Description

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B~NZOTRIAZOLE-SULFURIZED OLEFIN COMPOSITIONS
AND LUsRICANTS AND CONCENTRATES CONTAINING THEM

This invention relates to new compositions of matter useful as additives for lubricants, especially for industrial and gear lubricants. In its broadest sense, the invention is directed to compositions comprising:
(A) At least one composition selected from the group consisting of benzotriazoles and reaction products of said benzotriazoles with at least one aliphatic amine; and (B) an extreme pressure agent comprising the sulfurization product of at least one aliphatic or alicyclic olefinic compound containing about 3-30 carbon atoms.
Because of the severe conditions under which they are used, industrial and gear lubricants must ordinarily 15contain additives which maximize their capability of func-tioning under extreme pressure conditions. Among the compositions known to serve this purpose are various phos-phorus- and sulfur-containing compositions, chiefly salts and esters of dialkylphosphorodithioic acids, and sulfuri-20zation products of various aliphatic olefinic compounds.These two types of compositions are frequently used in combination in lubricants of this type, and both serve to increase the effectiveness of the lubricant under conditions of extreme pressure.
Many of the known sulfurization products of olefinic compounds contain substantial amounts of active Z2~

sulfur. Active sulfur is a form of relatively loosely bound sulfur, and its presence often has deleterious side effects such as staining of copper parts, increased wear on the metal components being lubricated, and a decrease in extreme pressure properties with the passage of time. It is of interest, thererore, to provide additive compositions in which the development of these deleterious effects is minimized.
A principal object of the present invention, therefore, is to provide improved lubricant additive com-positions and lubricants containing the same.
A further object is to provide additive composi-tions particularly useful in industrial and gear lubricants, said compositions being capable of affording long-lasting 15 extreme pressure properties, antiwear capability and rela-tive inertness to copper parts.
Other objec~s will in part be obvious and will in part appear hereinafter.
Component A in the compositions of this invention 20 may, as previously indicated, be at least one benzotriazole which may be substituted or unsubstituted. Examples of suitable compounds are benzotriazole and the tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles, octylbenzotria-zoles, phenylbenzotriazoles, and substituted benzotriazoles 25 wherein the substituents may be, for example, hydroxy, alkoxy, halo (especially chloro), nitro, carboxy or carb-alkoxy. Preferred are benzotriazole and the alkylbenzo-triazoles in which the alkyl group contains about 1-20 and especially 1-8 carbon atoms, most desirably benzotriazole 30 and tolyltriazole.
Also useful as component A are the reaction pro-ducts of the above-described benzotriazoles with aliphatic amines. The amine may be any aliphatic monoamine or poly-amine, with monoamines being preferred. It may be primary, 35 secondary or tertiary, with amines containing at least one

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primary amino group being preferred. The most desirable amines are substantially water-insoluble aliphatic amines, which ordinarily contain at least one alkyl group having at least about 10 carbon atoms. Suitable ones include the decylamines, didecylamines, tridecylamines, dodecylamines, tetradecylamines and octadecylamines, with all isomers being suitable. Mixtures of these amines are also useful. A
preferred class of amines comprises the primary amines in which the alkyl group contains about 10-30 carbon atoms, 10 particularly those in which the alkyl group is a tertiary group. Illustrative amine mixtures of this type (available B from Rohm & Haas Co.) are "Primene 81R" which is a mixture of Cl 2-14 tertiary alkyl primary amines, and "Primene JM-T"
which is a similar mixture of Cl 8-22 amines.
A second preferred class of amines comprises the oil-soluble basic nitrogen-containing dispersants, prefer-ably 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 known in the art and include 20 such subclasses as the "carboxylic dispersants", "amine dispersants" and "Mannich dispersants".
The carboxylic dispersants are reaction products of carboxylic acids (or derivatives thereof) containing at least about 44 and preferably at least about 54 aliphatic 25 carbon atoms with polyamines and optionally also with organic hydroxy compounds such as phenols and alcohols and/or basic inorganic materials. Examples of these pro-ducts 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 poly~lkylene polyamines. Examples thereof are described, for example, in the following U.S. patents:

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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 following 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 containing at least about 34 carbon atoms. The structures of these radicals, as defined by the International Union of Pure and Applied Chemistry, are as follows (each R' individually representing a hydrocarbon or similar group):
o Il Acyl: R'-C-c) Acyloxy: R'-C-O-NR' Il Acylimidoyl: R'-C-Radical 2 is preferably at least one radical in which a nitrogen or oxygen atom is attached directly to said ~ -t~3 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 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 NH wherein the two remaining valences of nitro-10 gen are satisfied at least in part by organic radicalsbonded to said nitrogen atom through direct carbon-to-nitrogen linkages, said organic radicals containing at least one basic nitrogen atom. ~hese compounds include aliphatic, heterocyclic and carbocyclic amines.
Hydroxy amines are included in the class of amines useful for this purpose. 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 10 carbon atoms 20 and R2 is hydrogen or a radical similar to Rl, at least one of Rl and R2 being hydroxy-substituted. Suitable hydroxy-substituted monoamines include ethanolamine, di-3-propanol-amine, 4-hydroxybutylamine, diethanolamine, N-methyl-2-propylamine, N-hydroxyethylethylene diamine, N,N-di(hy-25 droxypropyl)propylene diamine and tris(hydroxymethyl)-methylamine. While in 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 30 the carboxylic dispersant, provided they contain at least two amino groups of which at least one is primary or secon-dary. ~he heterocyclic ring can also incorporate unsatu-ration and can be substituted with hydrocarbon radicals such as alkyl, alkenyl, aryl, alkaryl or aralkyl. In addition, 35 the ring can also contain other hetero atoms such as oxygen, z~;~

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, pyrroles, piperidines, imidazoles, indoles, piperazines, isoindoles, purines, morpholines, thiamorpholines, azep nes, azocines, azonines, azecines and tetrahydro~, dihydro- and perhydro-derivatives of each of the above. Preferred heterocyclic amines are the saturated ones with 5- and 6-10 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 15 having the formula A-N tR3-~t-nH

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 20 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, 25 preferably 2-6, carbon atoms. Especially preferred are the alkylene polyamines wherein each A is hydrogen. Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene pol~amines and heptylene 30 polyamines. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.
Specific examples of such polyamines include ethylene diamine, triethylene tetramine, trist2-aminoethyl)amine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, 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 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 polyoxyalkylene 10 polyamines (e.g., "Jeffamines").
~ he ethylene polyamines, examples of which are 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-15 Othmer, Encyclopedia of Chemical Technology, Second Edition,Vol. 7, pp. 22-39. They are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction o~ an ethylene imine with a ring~opening reagent such as ammonia. These reactions result in the production 20 of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.
Because of their availability, these mixtures are particu-larly useful in preparing the compositions of this inven-tion. Satisfactory products can also be obtained by the use 25 of pure alkylene polyamines.
Hydroxy polyamines, e.g., alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing the carboxylic disper-sant. Preferred hydroxyalkyl-substituted alkylene polyamines 30 are those in which the hydroxyalkyl group has less than about 10 carbon atoms. ~xamples of such hydroxyalkyl-substituted polyamines include N-t2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-pipera7ine, monohydroxypropyl-substituted 35 diethylene triamine, dihydroxypropyltetraethylene pentamine and N-(3-hydroxybutyl)tetramethylene diamine. Higher homo-logs obtained by condensation of the above-illustrated hydroxyalkyl-sùbstituted alkylene amines through amino radicals or through hydroxy radicals are iikewise useful.
The source of radical 1 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 about 30 and preferably at least about 50 aliphatic carbon 10 atoms. By "carboxylic acid-producing compound" 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 prepared by the reaction tmore fully described hereinafter) 15 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 aource is usually aliphatic and should be substantially ~aturated, i.e., at least about 95%
20 of the total number of carbon-to-carbon covalent linkages shoud be saturated. It should also be substantially free from pendant groups containing more than about six aliphatic carbon atoms. It may be a substituted hydrocarbon source.
By "substituted" is meant sources containing substituents 25 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, generally comprise no more than about 10% by weight of the 30 hydrocarbon source.
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-35 carbon source may be derived from a polymer of ethylene, :~lfi8 propene, l-butene, isobutene, l-octene, 3-cyclohexyl-1-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 sty-rene, chloroprene, isoprene, p-methylstyrene, piperylene and the like. In general, these interpolymers should contain at least about 80%, preferably at least about 95~, on a weight basis of units derived from the aliphatic monoolefins.
Another suitable hydrocarbon source comprises 10 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 reaction with the low molecular weight acid-producing com-15 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 20 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-graphy) are preferred, although higher polymers having 25 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 within the prescri~ed molecular weight range, and chlorinated derivatives thereof.
Any one of a number of known reactions may be em-30 ployed for the preparation of the carboxylic acid-producing compound. Thus, an alcohol of ~he 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-35 containing acid, such as acetoacetic acid, may be converted to its sodium derivative and the sodium derivative reactedwith 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 the de-sired molecular weight ~.ay be oxidized by means of thehaloform reaction; an organometallic derivative of a halo-genated hydrocarbon may be reacted with carbon dioxide; a halogenated hydrocarbon or olefin polymer may be converted to a nitrile, which is subsequently hydrolyzed; or an olefin 10 polymer or its halogenated derivative may undergo a reaction with an unsaturated carboxylic acid or derivative thereof such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, 15 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-20 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-25 ature from about 100 to about 200C. The substituted succinic acid or anhydride thus obtained, may, if desired, be converted to the corresponding acid halide by reaction with ~nown halogenating agents such as phosphorus trichlo-ride, phosphorus pentachloride or thionyl chloride.
For the formation of the carboxylic dispersant, the hydrocarbon-substituted succinic anhydridP or acid, or 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 35 to about 250C. The product thus obtained has predominantly 11ti~22Z

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 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-10 producing compound and the alkylene polyamine or the likeare 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 15 polyamine is based upon the number of amine radicals therein, and the equivalent weight of the carboxylic acid-producing compound is ~ased 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 20 its molecular weight.) Although a minimum of one-half 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 used, it merely remains in the product unreacted without any apparent 25 adverse effects. Ordinarily, about 1-2 equivalents of 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-sub-30 stituted carboxylic acid or derivative thereof (such asmaleic anhydride or one of the others previously mentioned) and the resulting intermediate is subsequently reacted with the hydrocarbon source as previously described.
It is also possible to prepare carboxylic dis-35 persants by reacting the acylating agent simultaneously or, 8Z2~-12-preferably, sequentially with at least one of the above-described nitrogen-containing reagents and with at least one 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-hydric alcohols including ethylene glycol, diethylene glycol, dipropylene glycol, tetramethylene glycol, penta-10 erythritol, glycerol and the like. Carbohydrates (e.g.,sugars, starches, cellulose) are also suitable as are par-tially esterified derivatives of polyhydric alcohols having at least three hydroxy radicals. Aliphatic polyols contain-ing up to 10 carbon atoms and at least 3 hydroxy groups, 15 especially those with up to 6 carbon atoms and 3-6 hydroxy groups, are preferred.
The reaction with the hydroxy compound is usually effected at a temperature above about 100C. and typically from about 150 to about 300C. The relative amounts of the 20 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 in the preparation of component A are listed in Table I.
"Reagent 1" and "Reagent 2" are, respectively, the sources 25 of radicals 1 and 2 as previously defined.

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In the preparation of carboxylic dispersants such as those described in Examples 1-16, reagent 1 is normally prepared by reacting approximately equimolar amounts of the hydrocarbon source and the low molecular weight carboxylic 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 of 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 pro-cedure in which the hydrocarbon source is chlorinated and the chlorinated intermediate is reacted with maleic anhy-dride; or by various combinations of the two procedures.
The following examples illustrate typical 25 methods for the preparation of suitable dispersants of this type.

Example 17 A mixture of 1000 parts (0.495 mole) of a poly-butene comprising principally isobutene units and having a 30 number average molecular weight of 2020 and a weight average 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 tO-83 mole) of chlorine 35 is added over 4 hours. The reaction mixture is stripped by blowing with nitrogen at 186-190C. for 26 hours to yield a 2~,Z

polybutene-substituted succinic anhydride having a saponifi-cation number of 87 as determined by ASTM Procedure D9a.
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 poly-amine 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 10 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 15 and 8.6 parts (0.0057 equivalent) of Polyglycol~112-2 aemul-sifier from Dow Chemical Company is heated at 150-210C. for about 11 hours. The mixture is cooled to 190C. and 8.5 part8 (0.2 equivalent~ of the ethylene polyamine mixture of Example 1 is added. The mixture is stripped by blowing with 20 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 disper-sants. These are, as previously noted, reaction products 25 of certain alkyl phenols with aldehydes (usually lower aliphatic aldehydes and especially formaldehyde~ and poly-amino compounds. The structure of the alkyl substituent on the phenol is subject to the same preferences as to source, structure, molecular weight and the li~e expressed 30 hereinabove 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 35 the working examples of the aforementioned U.S. Patent t~aJe ~n~rl( 2~'~

3,980,569 and German Application 2,551,256. The following examples are also illustrative.

Example 19 A mixture of 3740 parts (2 equivalents) of a poly-butenyl phenol in which the polybutene substituent comprisesprincipally 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 480 10 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 15 water is removed by adding benzene and distilling azeo-tropically; during the distillation, 1000 parts of mineral oil is added in two portions. The distillation residue is filtered.
To 430 parts (0.115 equivalent) of the filtrate 20 is added with stirring, at 90C., 14.1 parts (0.345 equiva-lent) of the polyethylene amine mixture of Example 1. The mixture 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 25 the desired Mannich dispersant (52% solution in mineral oil) which contains 1.03% nitrogen.

Example 20 A mixture of 564 parts tO.25 equivalent) of poly-butenyl phenol in which the polybutene substituent comprises 30 principally isobutene units and has a molecular weight of about 2020, 400 parts of mineral oil and 16.5 parts of iso-butyl alcohol is heated to 65C., with stirring, and 2.15 parts (0.025 equivalent) of 50% aqueous sodium hydroxide l~t~ 2Z

solution is added, followed by 16.5 parts (0.5 equivalent) of paraformaldehyde. The mixture is stirred at 80-88C.
ior 6 hours and then 5 parts (0.025 equivalent) of 18.5%
aqueous hydrochloric acid is added slowly, with continued stirring, followed by 36 parts (0.875 equivalent) of the polyethylene amine of Example 1, at 88C. Mixing is con-tinued at 88-91C. for 30 minutes. The mixture is then heated to about 158C. 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 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 15 product as a 60~ solution in mineral oil; it contains about 0.63% sulfur.

Example 21 A mixture is prepared by the addition of 18.2 parts (0.433 equivalent) of the ethylene polyamine mixture 20 of Example 1 to 392 parts of mineral oil and 348 parts t0.52 equivalent) of the substituted succinic anhydride of Example 17. The mixture is heated to 150C. over 1.8 hours, stripped by blowing with nitrogen, and filtered to yield an oil solution of the desired dispersant.
The benzotriazole-amine reaction product may be prepared by merely blending the two reagents and allowing the reaction to proceed. The reaction may be effected in a substantially inert, normally liquid organic diluent (which may be the oil or diluent constituent of the lubri-30 cant or concentrate containing the composition of this invention) such as mineral oil, benzene, toluene, xylene, petroleum naphtha, an aliphatic ether or the like, whereupon it may take place at a temperature as low as about 15C. Ordinarily, it is preferred to caxry out the reaction z~

at a temperature of at least about 50C., especially when no ~diluent is used. Temperatures of about 70-200C. are preferred.
The proportions of the benzotriazole and amine used for the preparation of the reaction products useful as component A 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 10 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 may be desirable to use more or less than 1 15 equivalent of amine per equivalent of benzotriazole.
The precise molecular structures of the benzo-triazole-amine reaction products are not known with cer-tainty and are not critical. It is known, however, that the benzotriazoles are more acidic than the amines and it is 20 believed that the compositions may be amine salts of the benzotriazoles.
The preparation of benzotriazole-amine reaction products useful as component A is illustrated by the fol-lowing examples. All parts and percentages are by weight.

25 Example 22 Benzotriazole, 464 parts, is added in 20-30 part increments, with stirring, to 696 parts of "Primene 81R" at 61-68C. Stirring is continued as the reaction mixture is heated for 2-1/2 hours at 75-80C. The mixture is filtered 30 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.

Example 23 Benzotriazole, 1210 parts, is added over 20 35 minu~es, ~ith 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-tillation range of about 311-344C. is added. The mixture is stirred at 80C. for an additional 15 minutes and fil-tered to yield the desired product having a base number of157 to bromphenol blue and acid number of 135 to phenol-phthalein.

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

Example 25 A mixture of 500 parts of tolyltriazole and 718 15 parts of "Primene 81R" is heated for 8 hours under nitrogen at 120-140C., with stirring. ~ineral 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 25material to yield a mineral oil solution of the desired product.

Example 27 Following the procedure of Example 26, products are made from tolyltriazo~e (3, 5 and 7 parts, respectively) 30and the dispersant of Example 17 (97, 95 and 93 parts, respectively).

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 of the desired pro-duct.
Component B in the compositions of this invention is an extreme pressure agent comprising the sulfurization product of at least one aliphatic or alicyclic olefinic com-10 pound containing about 3-30 carbon atoms. The olefinic com-pounds which may be sulfurized to form component B are diverse in nature. They contain at least one olefinic double bond, which is defined as a non-aromatic double bond; that is, one connecting two aliphatic carbon atoms. In its 15 broadest sense, the olefin may be defined by the formula RlR2C=~R3R4, wherein each of Rl, R2, R3 and R4 is hydrogen or an organic radical. In general, the R values in the above formula which are not hydrogen may be satisfied by such groups as -Rs, -C(R5)3, -CooR5, -CoN(R5)2, -CooN(R5)4, IlR
20 -COOM, -CN, -C-R5, -X or -YRs, wherein:
Each Rs is independently hydrogen, alkyl, alkenyl, substituted alkyl or substituted alkenyl, with the proviso that any 'cwo Rs groups can be alkylene or substituted alkylene whereby a ring of up to about 12 carbon atoms is 25 formed;
M is one equivalent of a metal cation (preferably Group I or II, e.~., sodium, potassium, barium, calcium~;
X is halogen (e.g., chloro, bromo, or iodo);
Y is oxygen or divalent sulfur.
Any two of Rl, R2, R3 and R4 may also together form an alkylene or substituted alkylene group; i.e., the olefinic compound may be alicyclic.
The natures of the substituents in the substituted moieties described above are not normally a critical aspect Z~
_~3_ of the invention and any such substituent is useful so long as; it is or can be made compatible with lubricating environ-ments and does not interfere under the contemplated reaction conditions. Thus, substituted compounds which are so un-stable as to deleteriously decompose under the reactionconditions employed are not contemplated. Howevex, certain substituents such as keto or aldehydo can desirably undergo sulfurization. The selection of suitable substituents is within the skill of the art or may be established through lO routine testing. Typical of such substituents include any of the above-listed moieties as well as hydroxy, carboxy, carbalkoxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mercapto and the like.
The olefinic compound is usually one in which each R value which is not hydrogen is independently alkyl or alkenyl, or (less often) a corresponding substituted radi-cal. Monoolefinic and diolefinic compounds, particularly the former, are preferred, and especially terminal mono-20 olefinic hydrocarbons; that is, those compounds in which R3 and R4 are hydrogen and Rl and R2 are alkyl (that is, the olefin is aliphatic). Olefinic compounds having about 3-30 and especially about 3-20 carbon atoms are particularly desirable.
Propylene, isobutene and their dimers, trimers and tetramers, and mixtures ~hereof are especially preferred olefinic compounds. Of these compounds, isobutene and diisobutene are particularly desirable because of their availability and the particularly high sulfur-containing 30 compositions which can be prepared therefrom.
The sulfuri2ing reagent used for the preparation of component B may be, for example, sulfur, a sulfur halide such as sulfur monochloride or sulfur dichloride, a mixture of hydrogen sulfide and sulfur or sulfur dioxide, or the 35 like. Sulfur-hydrogen sulfide mixtures are often preferred 32~

zlnd are requently referred to hereinafter; however, it will be understood that other sulfurization agents may, when appropriate, be substituted therefor.
The amounts of sulfur and hydrogen sulfide per mole of olefinic compound are, respectively, usually about 0.3-3.0 gram-atoms and about 0.1-1.5 moles. The preferred ranges are about 0.5-2.0 gram-atoms and about 0.4-1.25 moles respectively, and the most desirable ranges are about 1.2-1.8 gram-atoms and about 0.4-0.8 mole respectively.
The temperature range in which the sulfurization reaction is carried out is generally about 50-350C. The preferred range is about 100-200C., with about 125-180C.
being especially suitable. ~he reaction is often preferably conducted under superatmospheric pressure; this may be and 15 usually is autogenous pressure (i.e., the pressure which naturally develops during the course of the reaction) kut may also be externally applied pressure. The exact pressure developed during the reaction is dependent upon such factors as the design and operation of the system, the reaction 20 temperature, and the vapor pressure of the reactants and products and it may vary during the course of the reaction.
It is frequently advantageous to incorporate materials useful as sulfurization catalysts in the reaction mixture. These materials may be acidic, basic or neutral, 25 but are preferably basic materials, especially nitrogen bases including ammonia and amines. The amount of catalyst used is generally about 0.05-2.0% of the weight of the olefinic compound. In the case of the preferred ammonia and amine catalysts, about 0.0005-0.5 mole per mole of olefin is 30 preferred, and about 0.001-0.1 mole is especially desirable.
Following the preparation of the sulfurized mix-ture, it is preferred to remove substantially all low boiling materials, typically by ~enting the reaction vessel or by distillation at atmospheric pressure, vacuum dis-35 tillation or stripping, or passage of an inert gas such as ~;822Z

nitrogen through the mixture at a suitable temperature and pressure.
A further optional step in the preparation of CODnpOnent B is the treatment of the sulfurized product, ob1ained as described hereinabove, to reduce active sulfur.
An illustrative method is treatment with an alkali metal sulfide as described in U.S. Patent 3,498,915. Other optional treatments may be employed to remove insoluble by-products and improve such qualities as the odor, color and staining characteristics of the sulfurized compositions.
U.S. Patents 3,926,822 and 4,119,549 disclose suit-able sulfurization products useful as component B. Several specific sulfurized compositions are described in the working examples thereof. The following examples illustrate the preparation of two such compositions.
Example 29 A mixture of 100 parts of soybean oil, 5.25 parts of tall oil acid and 44.8 parts of commercial C15-18 straight chain a-olefins is heated to 167C. under nitrogen, and 17.4 parts of sulfur is added. The temperature of the mixture rises to 208C. Nitrogen is blown over the surface at 165-200C. for 6 hours and the mixture is then cooled to 90C. and filtered. The filtrate is the desired product and contains 10.6% sulfur.
Example 30 Sulfur (629 parts, 19.6 moles) is charged to a jacketed high-pressure reactor which is fitted with an agitator and internal cooling coils. Refrigera-ted brine is circulated through the coils to cool the reactor prior to the introduction of the gaseous reactants. After sealing the reactor, evacuating to about 6 torr and cooling, 1100 parts (19~6 moles) of isobutene, 334 parts (9.8 moles) of ~', ~ ~ ~i*22~

hydrogen sulfide and 7 parts of n-butylamine are char~ed to the reactor. The reactor is heated using steam in the external jacket, to a temperature of about 171C. over about 1.5 hours. A maximum pressure of 720 psig. is reached at about 138C. during this heat-up. Prior to reaching the peak reaction temperature, the pressure starts to decrease and continues to decrease steadily as the gaseous reactants are consumed. After about 4.75 hours at about 171~C., the unreacted hydrogen sulfide and isobutene are vented to a 10 recovery system. After the pressure in the reactor has decreased to atmospheric, the sulfurized mixture is re-covered as a liquid.
The compositions of this invention typically contain about 20-200 and preferably about 30-150 parts by 15 weight of component B per part of component A. They may be prepared by merely blending the ingredients, either un-diluted or in substantially inert diluents. ~he diluent, if any, may be the oil used as a lubricant base and may include other additives such as those described hereinafter.
The following are illustrative of the compositions of this invention.

Parts by weight In redient Exam le A B C D E
g P
Tolyltriazole 1 1 - 0.41 25 Product of Example 25 - - 1 - -"Primene 8lR" - - - 0.59 Product of Example 29 - - - - 33.5 Product of Example 30 41 - - - -Reaction product of iso-30 butene and sulfur monochloride - 148 41 37 33.5 As pre~iously indicated, the compositions of this invention are useful as additives for lubricants, in which they function primarily as extreme pressure and antiwear agents having a relatively long period of effectiveness.
l'hey can be employed in a variety of lubricants based on cliverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, sta-10 tionary power engines and turbines and the like. Automatictransmission fluids, transaxle lubricants, gear lubricants (in which their use is especially beneficial), metal-~70rking lubricants, hydraulic fluids and other lubricating oil and grease compositions can also benefit from the incorporation 15 therein of the compositions of the present invention.
Matural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liq~id petro-leum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, napthenic and mixed 20 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-substituted hydrocarbon oils such as polymerized and interpolymerized olefins ~e.g., polybutylenes, polypro-25 pylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof]; alkylbenzenes [e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, dit2-ethylhexyl)benzenes, etc.]; polyphenyls (e.g., biphenyls, 30 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 derivatives thereof where the terminal hydroxyl groups have 35 been modified by esterification, etherification, etc.

t~ih~

--~8--constitute another class of known synthetic lubricating 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 average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, d~ethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic 10 esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids te.g., 15 phthalic acid, succinic acid, al~yl succinic acids and alkenyl 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-20 hol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene 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 25 azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
3~ Esters useful as synthetic oils also include those made from C5 to Cl 2 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, poly-35 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-cate oils comprise another useful class of synthetic lubri-2~;~

cants [e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) s:Llicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, polytmethyl)-siloxanes, poly(methylphenyl)siloxanes, etc.]. Other synthetic lubri-cating oils include liquid esters of phosphorus-containing 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-inabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further 15 purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained 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 20 similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to tho~e of skill in the art such as solvent extrac-tion, acid or base extraction, filtration, percolation, etc.
25 Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which 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 30 spent additives and oil breakdown products.
Generally, the lubricants of the present invention contain an amount of the composition of this invention sufficient to provide it with extreme pressure and antiwear properties. Normally this amount will be about 0.01-10.0~, 35 preferably about 0.01-5.0%, of the total t~eight of the L t:j~2 lubricant. In lubricants operated under extremely adverse conditions, the reaction products of this invention may be present in amounts up to about 20% by weight.
The invention also contemplates the use of other 5 additives in combination with the compositions of this invention. Such additives include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, auxiliary extreme pressure agents, color lOstabilizers and anti-foam agents.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acias characterized by at least one 15direct 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 agent such as phosphorus trichloride, phosphorus heptasul-fide, phosphorus pentasulfide, phosphorus trichloride and 20sulfur, 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, strontium and barium.
The term "basic salt" is used to designate metal 25salts 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-ing a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal 30oxide, hydroxide, carbonate, bicaxbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutxalization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include 35phenolic substances such as phenolt naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation pro-ducts of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. 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 pro-10 moter, and carbonating the mixture at an elevated tempera-ture 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 15 such as boric oxide or phosphorus pentoxide; however, it 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-20 trative:
(1) Carboxylic dispersants such as those des-cribed 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.
25 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 3,271,310 3,433,744 3,567,637 3,281,357 3,444,170 3,574,101 3,306,908 3,448,048 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 3,597,428 3,346,493 3,501,405 3,725,441 Re 26,433 2Z~

(2) "Amine dispersants" and "Mannich dispersants" such as those described hereinabove.
(3) Products obtained by post-treating the carboxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydro-carbon-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 decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substitutents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These may be characterized as "polymeric dispersants" 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 Auxiliary extreme pressure agents and corrosion- and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; aromatic or arylaliphatic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) disulfide and sulfurized alkylphenol;
phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or ................. ...

lltj~Z~

methyl oleate; phosphorus esters including principally dihydrocarbon and ~rihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, Ipentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-sub-stituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl di-10 thiocarbamate; Group II metal phosphorodithioates such aszinc dicyclohexylphosphorodithioate, zinc dioctylphosphoro-dithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phos-15 phorus pentasulfide with an equimolar mixture of isopropylalcohol and n-hexyl alcohol.
The compositions of this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic 20 diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate which usually con-tains about 20-90% by weight of said composition and may contain, in addition, one or more other additives known in the art or described hereinabove.
Illustrative lubricants of this invention comprise principally mineral oil (e.g., SAE lOW-40 for an internal combustion engine lubricant and SAE 75W-90 for a gear lubri-cant) in combination with about 0.5-3.0~ by weight of the composition of this invention te.g-, a composition of one of 30 Examples A-E) and with other known gear lubricant or in-ternal combustion engine lubricant additives.

Claims

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

1. A composition comprising:
(A) At least one composition selected from the group consisting of benzotriazoles and reaction products of said benzotriazoles with at least one aliphatic amine; and (B) an extreme pressure agent comprising the sulfurization product of at least one aliphatic or alicyclic olefinic compound containing about 3-30 carbon atoms.

2. A composition according to claim 1 wherein component A is benzotriazole or an alkylbenzotriazole in which the alkyl group contains about 1-8 carbon atoms.

3. A composition according to claim 2 wherein component A is benzotriazole or tolyltriazole.

4. A composition according to claim 3 wherein component A is tolyltriazole.

5. A method according to claim 1 wherein com-ponent A is a reaction product of said benzotriazole with at least one tertiary alkyl primary monoamine.

6. A composition according to claim 1 wherein component A is a reaction product of said benzotriazole with an oil-soluble basic nitrogen-containing dispersant.

7. A composition according to claim 1 wherein component B is a sulfurization product of at least one aliphatic olefinic compound containing about 3-20 carbon atoms.

8. A composition according to claim 7 wherein the olefinic compound is at least one of propylene, isobutene and dimers, trimers and tetramers thereof.

9. A composition according to claim 8 wherein the sulfurization agent is a mixture of sulfur and hydrogen sulfide.

10. A composition according to claim 9 wherein the olefinic compound is isobutene.

11. A composition according to claim 10 wherein component A is benzotriazole or tolyltriazole.

12. A composition according to claim 11 wherein component A is tolyltriazole.

13. An additive concentrate comprising a substantially inert, normally liquid organic diluent and about 20-90% by weight of a composition according to claim 1.

14. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 1.