GB2071139A - Sulfurized olefin compositions and lubricants and concentrates containing them - Google Patents

Abstract

Compositions comprising (A) at least one benzotriazole or reaction product thereof with an aliphatic amine and (B) a sulfurization product of at least one aliphatic or alicyclic C 3-30 olefinic compound are useful in lubricants, especially 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

SPECIFICATION Sulfurized olefin compositions and lubricants and concentrates containing them This invention relates to compositions for use 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 component selected from the 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 contain additives which maximize their capability of functioning under extreme pressure conditions. Among the compositions known to serve this purpose are various phosphorus- and sulfurcontaining compositions, chiefly salts and esters of dialkylphosphoridithioic acids, and sulfurization 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 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, therefore, to provide additive compositions in which the development of these deleterious effects is minimized.

Ways were therefore sought of providing additive compositions particularly useful in industrial and gear lubricants, said compositions being capable of affording long-lasting extreme pressure properties, antiwear capability and relative inertness to copper parts.

Component A in the compositions of this invention may, as previously indicated, be at least one benzotriazole which may be substituted or unsubstituted.

Examples of suitable compounds are benzotriazole and the tolytriazoles, ethylbenzotriazoles, hexylbenzotriazoles, octylbenzotriazoles, phenylbenzotriazoles, and substituted benzotriazoles wherein the substituents may be, for example, hydroxy, alkoxy, halo (especially chloro), nitro, carboxy or carbalkoxy.

Preferred are benzotriazole and the alkylbenzotriazoles in which the alkyl group contains about 1-20 and especially 1-8 carbon atoms, most desirably benzotriazole and tolyltriazole.

Also useful as component A are the reaction products of the above-described benzotriazoles with aliphatic amines. The amine may be any aliphatic monoamine or polyamine, with monoamines being preferred. It may be primary, secondary or tertiary, with amines containing at least one primary amino group being preferred. The most desirable amines are substintially 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, particularly those in which the alkyl group is a tertiary group.Illustrative amine mixtures of this type (available from Rohm & Haas Co.) are "Primene 81 R" which is a mixture of C12~,4 terti- ary alkyl primary amines, and "Primene JM-T" which is a similar mixture of C18#22 amines.

A second preferred class of amines 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 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 thereof) 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 andlor basic inorganic materials. Examples of these products are descirbed in many U.S. patents, of which 3,272,746 is one exampie.

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 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 pertinent disclosures of all of the above-listed patents and applications are incorporated by reference herein.

The carboxylic dispersants may be most conveniently and accurately described in terms of radical 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 radi cals, as defined by the Internation Union of Pure and Applied Chemistry, are as follows (each R' individually representing a hydrocarbon or similar group):

Radical 2 is preferably at least one radical in which a nitrogen or oxygen atom is attached directly to said acyl, acyloxy or acylimidoyl radical, said notrogen 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 nitrogen are satisfied at least in part by organic radicals 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 of amines useful for this purpose. Such compounds are the hydroxyhydrocarbyl-substituted compounds such as those having the formulas HNR1R2, wherein R' is an alkyl or hydroxy-substituted alkyl radical of up to 10 carbon atoms and R2 is hydrogen or a radical similar to R', at least one of R1 and R2 being hydroxy-substituted. Suitable hydroxy-substituted monoamines include ethanolamine, di-3propanolamine, 4-hydroxybutylamine, dieth anolamine, N-methyl-2-propylamine, N-hydroxyethylethylene diamine, N,N-di (hydroxyp- ropyl) 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 the carboxylic dispersant, provided they contain at least two amino groups of which at least one is primary or secondary. The heterocyclic ring can also incorporate unsaturation and can be substituted with hydrocarbon radicals such as alkyl, alkenyl, aryl, alkaryl or aralkyl. In addition, 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 or6, ring members.

Among such heterocycles are aziridines, azetidines, azolidines, pyridines, pyrroles, piperidines, imidazoles, indoles, piperazines, isoindoles, purines, morpholines, thiamo rpholines, azepines, azocines, azonines, azecines and tetrahydro; dihydro- and perhydro-derivatives of each of the above. Preferred heterocyclic amines are the saturated ones with 5and 6- membered rings, especially the piperidines, piperazines and morpholines described above.

Aliphatic polyamines are preferred for preparing the carboxylic dispersant Among the polyamines are alkylene polyamines (and mixtures thereof) including those having the formula

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 having up to about 30 atoms; and R3 is a divalent hydrocarbon radical having from about 1 to about 18 carbons. Preferably A is an aliphatic radical of up to about 10 carbon atoms which may be substituted with one ortwo hydroxy groups, and R3 is a lower alkylene radical having 1-10, 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 polyamines and heptylene 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, tris (2-aminoethyl)amine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di (heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di (trimethylene) triamine, 2-heptyl - 3 - (2aminopropyl) imidazoline, 1,3 - 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 polyamines (e.g., "Jeffamines").

The 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-Othmer, Encyclopedia of Chemical Technology, Second Edition, Vol. 7, pp.

2239. They are prepared mostconveniently by the reaction of an alkylene chloride with ammonia 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 such as piperazines. Because of their availability, these mixtures are particularly useful in preparing the compositions of this invention. Satisfactory products can also be obtained by the use 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 dispersant. Preferred hydroxyalkylsubstituted alkylene polyamines are 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, 1 - (2-hydroxethyl) - piperazine, monohydroxypropyl-substituted diethylene triamine, dihydroxypropyltetraethylene pentamine and N - l3-hYdroxybutyl) tetraniethylene diamine.

Higher homologs obtained by condensation of the above-illustrated hydrnxyalkyl-substituted a IEqf lene amines through amino radicals orthmugh hydroxy radicals are likewise useful.

The source of radical 1 in the carboxylic dispersant is an acylating agent comprising at least one carbon ylic acid-producing compound containing a hydrocarbon or substituted hydrocarbon substituent which has at least about 30 and preferably at least about 50 aliphatic carbon 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 (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 should be substantially saturated, i.e., at least about 95% of the total number of carbon-to-carbon covalent linkages should 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 which do not alter significantly their character or reactivity; examples are halide, hydroxy, ether, keto, carboxy, ester (especially lower carbolkoxy), amide, nitro, cyano, sulfoxy and sulfone radicals.The substituents, if present, generally comprise no more than about 10% by weight of the hydrocarbon source.

The preferred hydrocarbon sources are those derived from substantially saturated petroleum fractions and olefin polymers, particularly polymers of monoolefins having from 2 to about 30 carbon atoms. Thus, the hydrocarbon source may be derived from a polymer of ethylene, propene, 1-butene, isobutene, 1 -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 styrene, 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 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 acidproducing compound. 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 chromatography) are preferred, although higher polymers having molecu lar weights from about 10,000 to about 100,000 or higher may sometimes be used. Especially suitable as hydrocarbon sources are isobutene polymers within the prescribed molecular weight range, and chlorinated derivatives thereof.

Any one of a number of known reactions may be employed for the preparation of the carboxylic acid-producing 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-containing acid, such as acetoacetic acid, may be converted to 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 the desired molecular weight may be oxidized by means of the haloform reaction; an organometallic derivative of a halogenated 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 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, 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 halogensubstituted carboxylic acid or derivative thereof.

This latter reaction is preferred, especially when the acid-producing compound is unsaturated and preferably when it is maleic acid or anhydride. The resulting product is then a hydrocarbon-substituted succinic acid or derivative thereof. The reaction leading to its formation involves merely heating the two reactants at a temperature from about 1000 to about 200 C. The substituted succinic acid or anhydride thus obtained, may, if desired, be converted to the corresponding acid halide by reaction with known halogenating agents such as phosphorus trichloride, phosphorus pentachloride orthionyl chloride.

For the formation of the carboxylic dispersant, the hydrocarbon-substituted succinic anhydride or acid, or other carboxylic acid-producing compound, and the alkylene polyamine or other nitrogen-containing reagent are heated to a temperature above about 80 C., preferably from about 100"to about2500C. The product thus obtained has predominantly amide, imide andlor 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 80 C. to produce a product having predominantly amine salt linkages (containing acyloxy groups).The use of a diluent such as mineral oil, benzene, toluene, naptha or the like is often desirable to facilitate control of the reaction temperature.

The relative proportions of the carboxylic acidproducing compound and the alkylene polyamine or the like are such that at least about one-half the stoichiometrically equivalent amount of polyamine is used for each equivalent of carboxylic acidproducing compound. In this regard itwill be noted that the equivalent weight of the alkylene polyamine is based upon the number of amine radicals therein, and the equivalent is based upon the number of amine radicals therein, 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-carbonsubstituted succinic acid or anhydride is one-half 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 adverse effects.Ordinarily, about 1-2 equivalents of polyamine are used per equivalent of acylating agent In an alternative method for producing the carboxylic dispersant, the alkylene polyamine is first reacted with a low molecular weight, unsaturated or halogen-substituted carboxylic acid or derivative thereof (such as maleic anhydride or one of the other previously mentioned) and the resulting intermediate is subsequently reacted with the hydrocarbon source as previously described.

It is also possible to prepare carboxylic dispersants 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 hydroxy compound. The hydroxy compounds are usually alcohols 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 polyhydric alcohols including ethylene glycol, diethylene glycol, dipropylene glycol, tetramethylene glycol, pentaerythritol, glycerol and the like. Carbohydrates (e.g., sugars, starches, cellulose) are also suitable as are partially esterified derivatives of polyhydric alcohols having at least three hydroxy radicals.Aliphatic polyols containing 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 usu ally effected at a temperature above about 1 00 C.

and typically from about 1 500C to about 300 C. 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 in the preparation of component A are listed in Table I.

"Reagent 1" and "Reagent 2" are, respectively, the sources of radicals 1 and 2 as previously defined.

TABLE! Ratio of Reaction equivalents, temperature, Example Reagent 1 Reagent 2 1:2 C. Diluent 1 Polybutenyl (mol. wt. Ethylene polyamine 0.48 150 Mineral oil about 900) succinic mixture containing anhydride prepared about 3-7 amino from chlorinated poly- groups per molecule butene comprising principally isobutene units 2 Same as Example 1 Pentaethylene hexamine 0.41 150 Mineral oil 3 Like Example 1 Pentaethylene hexamine 0.61 150 Mineral oil except polybutene mol. wt. is about 1050 4 LikeExamplel, Diethylenetriamine 1.0 150 Mineral oil except polybutene mol. wt. is about 850 5 Same as Example 4 Ethylenediamine 1.0 150 Mineral oil 6 Same as Example 4 Di- (1,2-propylene)- 1.0 180-190 Mineral oil triamine toluene 7 Same as Example 4 N-(2-hydroxyethyl)- 1.06 150-155 Mineral oil trimethylene diamine 8 Same as Example 1 Pentaerythritol, 0.79 205-215 Xylene followed by ethylene polyamine of Example 1 (ratio of equivalents 3.4:1) 9 Same as Example 1 Same as Example 1 0.67 150 Mineral oil 10 Same as Example 1 Same as Example 1 1.0 150 Mineral oil 11 Like Example 1, ex- Pentaerythritol, 0.44 150-210 Mineral oil cept polybutene mol. followed by ethylene wt. is about 1100 polyamine of Example 1 (ratio of equivalents 7.7::1) 12 Acid produced by reac- Ethylene diamine 2.0 150 Xylene tion of chlorinated (3.6% Cl) polybutene (mol. wt. 750) with KCN, followed by hydrolysis 13 Methyl ester produced Triethylene tetramine 1.0 140-220 by reaction of chlori nated (4.7%CI) poly butene (mol. wt. 1000) with methyl methacrylate 14 Reaction product of Same as Example 1 0.4 150 Xylene sodiomalonic ester with C75 brominated wax 15 Reaction product of Pentaethylene hexamine 0.8 180-200 chlorinated (4.5% Cl) polybutene (mol. wt.

850) with acrylic acid 16 Acid produced by halo- Same as Example 1 0.8 180-210 form reaction with methyl heptacontanyl ketone In the preparation of carboxylic dispersants such as those described in Examples 1-16, reagent 1 is normally prepared by reacting approximately equimolaramountsofthe 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 prepared 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 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 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 prepared by a one-step procedure in which the hydrocarbon source is reacted with maleic anhydride; by a two-step procedure in which the hydrocarbon source is chlorinated and the chlorinated intermediate is reacted with maleic anhydride; or by various combinations of the two procedures.

The following examples illustrate typical methods for the preparation of suitable dispersants of this type.

Example 17 A mixture of 1000 parts (0.495 mole) of a polybutene comprising principally isobutene units and having a 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 184 C. over 6 hours as 85 parts (1.2 moles) of chlorine is added beneath the surface. At 184-189 C. an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is stripped by blowing with nitrogen at 186-190 C. for 26 hours to yield a polybutene-substituted succinic anhydride having a saponification number of 87 as determined by ASTM Procedure D94.

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 140-155 C. for3 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 demulsifierfrom Dow Chemical is heated at 150-210 C. for about 11 hours. The mixture is cooled to 190 C. and 8.5 parts (0.2 equivalent) of the ethylene polyamine mixture of Example 1 is added. The mixture is stripped by blowing with nit rogen for 3 hours at 205 C. 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 hereinabove with respect to the carboxylic dispersant. The polyamine 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 and German Application 2,551,256.

The following examples are also illustrative.

Example 19 A mixture of 3740 parts (2 equivalents) of a polybutenyl 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 480 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 undervacuum. The remaining water is removed by adding benzene and distilling azeotropically; 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 is added with stirring, at 90"C., parts (0.345 eq ui- valet; of the polyethylene amine mixture of Example 1. The mixture is heated at 90-120 C. for2 hours and then at 150-160 C. 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.

Example 20 A mixture of 564 parts (0.25 equivalent) of polybutenyl 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 isobutyl alcohol is heated to 650C., with stirring, and 2.15 parts (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 80-88 C. for 6 hours and then 5 parts (0.025 equivalent) of 18.5% aqueous hydrochloric acid is added slowly, with continued stirring, followed 36 parts (0.875 equivalent) of the polyethylene amine of Example 1, at 88 C. Mixing is continued at 88-91 'C.

for 30 minutes. The mixture is then heated to about 158 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 1500C., with stirring, after which the mixture is blown with nitrogen at 150-155 C. for 3 hours. The mixture is then cooled to 132 C. and filtered to yield the desired sulfurized Mannich 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 of Example 1 to 392 parts of mineral oil and 348 parts (0.52 equivalent) of the substituted succinic anhydride of Example 17. The mixture is heated to 1500C.

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 lubricant or concentrate containing the composition of this invention) such as mineral oil, benzene, toluene, xylene, petroleum naptha, an aliphatic ether or the like, whereupon it may take place at a temperature as low as about 15 C. Ordinarily, it is preferred to carry out the reaction at a temperature of at least about 50 C., especially when no diluent is used. Temperatures of about 70-200 C. 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 equivalentweightofthe amine is its molecularweight 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 equivalent of amine per equivalent or benzotriazole.

The precise molecular structures of the benzotriazole-amine reaction products are not known with certainty and are not 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 benzotriazole-amine reaction products useful as component A is illustrated by the following examples. All parts and percentages are by weight.

Example 22 Benzotriazole, 464 parts, is added in 20-30 part increments, with stirring, to 696 parts of "Primene 81 R" at61-680C. Stirring is continued as the reaction mixture is heated for 2-1 %2 hours at75-800C. 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.

Example 23 Benzotriazole, 1210 parts, is added over 20 minutes, with stirring, to 1820 parts of "Primene 81 R" maintained at 60 C. The mixture is stirred at BO"C. for45 minutes and 303 parts of an aromatic solvent with a distillation ranae of about 311 -3M (:.

is added. The mixture is stirred eJ50'C. f-or an eddi- tional 15 minutes and filtered to yield the desired product having a base number of 157 to bromphenol blue and acid number of 135 to phenolpthalein.

Example 24 Benzotriazole, 20 parts, is added over 10 minutes, with stirring, to 30 parts of "Primene JM-T" maintained at 60-80 C. 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 parts of "Primene 81 R" is heated for 8 hours under nitrogen at 120-140 C., 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 140 C. for 1 hour, cooled to 120C and filtered through a filter aid material to yield a mineral oil solution of the desired product 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, respectively).

Example 28 Tolyltriazole, 15 parts, is added with stirring at 90'C. to 485 parts of the dispersant of Example 21.

The mixture is heated to 140-145 C. for 1 hour, cooled to 130 C. and filtered to yield an oil solution of the desired product.

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 compound containing about 3-30 carbon atoms. The olefinic compounds 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 broadest sense, the olefin may be defined by the formula R1R26=6R3R4, wherein each of R1, R2 R3 and R4 is hydrogen or an organic radical.In general, the R val ues in the above formula which are not hydrogen may be satisified by such groups as-R5, -C(R5)a, -COOR5, #ON(R5)2, #OON(R5)4, -COOM, -CN,

Each R3 is independently hydrogen, alkyl, alkenyl, substituted alkyl or substituted alkenyl, with the proviso that any two R5 groups can be alkylene or substituted alkylene whereby a ring of up to about 12 carbon atoms is formed; M is one equivalent of a metal cation (preferably Group I or II, e.g., sodium, potassium, barium, calcium); X is halogen (e.g., chloro, bromo, or iodo); V is oxygen or diva lent sulfur.

Any two of R1, 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 of the invention and any such substituent is useful so long as it is or can be made compatible with lubricating environments and does not interfere under the contemplated reaction conditions. Thus, substituted compounds which are so unstable as to deleteriously decompose under the reaction conditions employed are not contemplated. However, 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 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 radical. Monoolefinic and diolefinic compounds, particularly the former, are preferred, and especially terminal monoolefinic hydrocarbons; that is, those compounds in which R3 and R4 are hydrogen and R' 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 thereof are especially preferred olefinic compounds. Of these compounds, isobutene and diisobutene are particularly desirable because of their availability and the particularly high sulfur-containing compositions which can be prepared therefrom.

The sulfurizing reagent used for the preparation of component B may be, for example, sulfur, a sulfur halide such as sulfur monochloride or sulfur dich bride, a mixture of hydrogen sulfide and sulfur or sulfur dioxide, or the like. Sulfur-hydrogen sulfide mixtures are often preferred and are frequently 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 or 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 50-350 C.

The preferred range is about 100-200 C. with about 125-180 C. being especially suitable. The reaction is often preferably conducted under superatmospheric pressure; this may be and usually is autogenous pressure (i.e., the pressure which naturally develops during the course of the reaction) but 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 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 mater ials useful as sulfurization catalysts in the reaction mixture. These materials may be acidic, basic or neutral, 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 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 preferred, and about 0.001-0.1 mole is especially desirable.

Following the preparation of the sulfurized mixture, it is preferred to remove substantially all low boiling materials, typically by venting the reaction vessel or by distillation at atmospheric pressure, vacuum distillation or stripping, or passage of an inert gas such as nitrogen through the mixture at a suitable temperature and pressure.

A further optional step in the preparation of component B is the treatment of the sulfurized product, obtained 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 are incorporated by reference herein for their disclosures of suitable 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 et-olefins is heated to 167 C. under nitrogen, and 17.4 parts of sulfur is added. The temperature of the mixture rises to 208 C. Nitrogen is blown over the surface at 165-200 C. for6 hours and the mixture is then cooled to 90 C. 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. Refrigerated 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 hydrogen sulfide and 7 parts of n-butylamine are charged to the reactor. The reactor is heated using steam in the external jacket, to a temperature of about 171 C. over about 1.5 hours. A maximum pressure of 720 psig. is reached at about 138'C. during this heat-up. Priorto 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 recovery system. After the pressure in the reactor has decreased to atmospheric, the sulfurized mixture is recovered as a liquid.

The compositions of this invention typically contain about 20-200 and preferably about 30-150 parts by weight of compenent B per part of component A.

They may be prepared by merely blending the ingredients, either undiluted or in substantially inert diluents. The 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 Ingredient Example A B C D E Tolyltriazole 1 1 - 0.41 1 Product of Example 25 - - 1 - "Primene 81 R" 81 - 0.59 Product of Example 29 - - - - 33.5 Product of Example 30 41 - - - - Reaction product of isobutene and sulfur monochloride - 148 41 37 33.5 As previously 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. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.These lubricants include chankcase lubricating oils for sparkignited 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, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants (in which their use is especially beneficial), metal-working lubricants, hydraulic fluids and other lubricating oil and 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 oils of the paraffinic, napthenic 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-substituted hydrocarbon oils such as polymerized and interpolymerized olefinsLe.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, poly(1-hexanes), poly(1 -octenes), poly(1 -decenes), etc. and mixtures thereof]; alkylbenzenes [ e.g., dodecylbenzenes, tetradecylbenzenes, dinonylben- zones, di(2-ethylhexyl)benzenes, 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 derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. 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., methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) ormonoand polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8Thtty acid esters, or the C12 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 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 alcohol, 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 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.

Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants [e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra - (4-methyl-2ethylhexyl) silicate, tetra - (p -tert-butylphenyl) silicate, hexa - (4-methyl - 2 - pentoxy) - disiloxane, poly (methyl) - siloxanes, poly (methylphenyl) siioxanes, etc. ] . Other synthetic lubricating 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 mixtures of each with each other) of the type disclosed hereinabove 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 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 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 purifica tion techniques are known to those of skill in the art such as solvent extraction, 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 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 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%, preferably about 0.01-5.0%, of the total weight of the 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 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 stabilizers and antifoam 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 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 agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or a phosphorothioic 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 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 heating a mineral oil solution of an acid with a stiochiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50 C. and filtering the resulting mass. The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known.Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenoiic substance; alcohols such as methanol, 2-propanol, octal alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenthiazine, phenyl -P- 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 promoter, and carbonating the mixture at an elevated temperature such as 60-200 C.

Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a nonvolatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarly contain metal and therefore does not yield a metalcontaining 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 illustrative: (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 3,271,310 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 3,697,428 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 carboxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exempiarly 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 oii-solubilizing monomers such as decyi methacrylate, vinyl decyl ether and high molecular weight olefines with monomers containing polar subst#tjents, e.g., amincalkyl acrylates or acrylamides and poly - (oxyothylene) - 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 The above-noted patents are incorporated by refer ence herein for their disclosures of ashless dispersants.

Auxiliary extreme pressure agents and corrosionand 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 methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500) - substituted phenyl phosphite, diisobutyl - substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di (heptylphenyl) phosphorodithioate, cadmium dinonylphosphorodithioate, and the 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 added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naptha, 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 described hereinabove.

Illustrative lubricants of this invention comprise principally mineral oil (e.g., SAE 10W-40 for an internal combustion engine lubricant and SAE 75W-90 for a gear lubricant) in combination with about 0.5-3.0% by weight of the composition of this invention (e.g., a composition of one of Examples A-E) and with other known gear lubricant or internal combustion engine lubricant additives.

Claims (15)

1. Acomposition comprising: (A) At least one component selected from 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 ortolyltriazole.

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

5. A method according to claim 1 wherein component 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 ortolyltriazole.

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 any of claims 1-12.

14. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a composition according to any of claims 1-12.

15. The invention in its several novel aspects.