Technical Field of the Invention

This invention relates to compositions which a useful as additives for lubricants and functional fluids These additives provide lubricants and functional flui with thermal stability and improved antiwear, extre pressure, load-carrying and/or corrosion-inhibiting proper ties.

Introduction to the Invention Historically antiwear hydraulic fluids have con tained zinc in the form of zinc dithiophosphates. Thes hydraulic fluids typically have excellent thermal stabilit and antiwear properties. However, in recent years ther has been growing concern about the accumulation in the wor place and environment of heavy metals such as zinc. Thi concern has lead to the demand for hydraulic fluids whic contain only ashless antiwear agents. Ashless antiwea agents are available but often fluids containing thes agents lack thermal stability. One test which measures lubricant's thermal stability is the Cincinnati Milicro test. Hydrocarbyl phosphites are antiwear agents whic are useful in replacing zinc dithiophosphates in hydrauli fluids. However, under high temperature operating condi tions, phosphites form products which are corrosive to th yellow metal components in the hydraulic systems. Withou a means to stabilize phosphites, they are ineffective i replacing zinc dithiophosphates in hydraulic fluids.

PCT publication WO 89/04358 relates to a composi tion comprising (A) a neutral or basic metal salt or boron containing neutral or basic metal salt of at least on acidic organic compound, (B) a metal deactivator and (C) sulfur- and/or phosphorus-containing compound. Thes compositions are used in lubricants and functional fluids

βimm rγ o the Invention This invention relates to a composition, compris ing:

(A) at least one basic alkali or alkaline eart metal salt of an acidic organic compound;

(B) at least one metal deactivator other tha dimercaptothiadiazole or derivatives thereof; and

(C) at least one hydrocarbyl phosphite, wherei the equivalents of (A) based on total base number to th equivalents of (C) based on phosphorus atoms is at leas one, provided that the composition is free of zin dithiophosphate and provided that when (A) is an overbased magnesiu salicylate then the composition contains (D) up to abou 0.40% by weight of a sulfur-, phosphorus-, or sulfur- an phosphorus-containing antiwear agent. These compositions are useful as additives for lubricants and functional fluids, particularly hydraulic fluids, gear oils, greases and the like. The lubricants and fluids having this particular combination of components have improved thermal stability and do not contain zinc dithiophosphate. These lubricants and fluids are also not corrosive to the hydrau¬ lic system components. Description of the Invention

The term "hydrocarbyl" includes hydrocarbon, as well as substantially hydrocarbon, groups. Substantially hydrocarbon describes groups which contain non-hydrocarbon substituents which do not alter the predominately hydrocar- bon.nature of the group.

Examples of hydrocarbyl groups include the following:

(1) hydrocarbon substituents, that is, aliphatic

(e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic-, aliphatic- and

alicyclic-substituted aromatic substituents and the like a well as cyclic substituents wherein the ring is complete through another portion of the molecule (that is, fo example, any two indicated substituents may together for an alicyclic radical) ;

(2) substituted hydrocarbon substituents, tha is, those substituents containing non-hydrocarbon group which, in the context of this invention, do not alter th predominantly hydrocarbon substituent; those skilled in th art will be aware of such groups (e.g., halo (especiall chloro and fluoro) , hydroxy, alkoxy, ercapto, alkylmer capto, nitro, nitroso, sulfoxy, etc.);

(3) hetero substituents, that is, substituent which will, while having a predominantly hydrocarbo character within the context of this invention, contai other than carbon present in a ring or chain otherwis composed of carbon atoms. Suitable heteroatoms will b apparent to those of ordinary skill in the art and include for example, sulfur, oxygen, nitrogen and such substituent as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc. I general, no more than about 2, preferably no more than one, non-hydrocarbon substituent will be present for every te carbon atoms in the hydrocarbyl group. Typically, ther will be no such non-hydrocarbon substituents in the hydro carbyl group. Therefore, the hydrocarbyl group is purel hydrocarbon. (A) Basic Metal Salts

The lubricating compositions of the presen invention contain (A) at least one basic alkali or alkalin earth metal salt of an acidic organic compound. Thes salts are generally referred to as overbased materials. Overbased materials are single phase, homogeneous Newtonia systems characterized by a metal content in excess of tha which would be present according to the stoichio etry o

the metal and the particular acidic organic compou reacted with the metal.

The amount of excess metal is commonly express in terms of metal ratio. The term "metal ratio" is t ratio of the total equivalents of the metal to the equiv lents of the acidic organic compound. A neutral metal sa has a metal ratio of one. A salt having 4.5 times as mu metal as present in a normal salt will have metal excess 3.5 equivalents, or a ratio of 4.5. The basic salts of t present invention have a metal ratio of about 1.5, mo preferably about 3, more preferably about 7, up to abo 40, preferably about 25, more preferably about 20.

The basicity of the overbased materials of t present invention generally is expressed in terms of total base number. A total base number is the amount o acid (perchloric or hydrochloric) needed to neutralize al of the overbased material's basicity. The amount of aci is expressed as potassium hydroxide equivalents. Tota base number is determined by titration of one gram o overbased material with 0.1 Normal hydrochloric aci solution using bromophenolblue as an indicator. Th overbased materials of the present invention generally hav a total base number of at least about 20, preferably abou 100, more preferably about 200. The overbased materia generally have a total base number up to about 600, prefer ably about 500, more preferably about 400. The total bas number is essential to the invention because the inventor have discovered that the ratio of the equivalents o overbased material based on total base number to th equivalents of hydrocarbyl phosphite based on phosphoru atoms must be at least one to make the thermally stabl lubricating compositions of the present invention. Th equivalents of overbased material is determined by th following equation: equivalent weight = (56,100/total bas number) . For instance, an overbased material with a tota

base number of 200 has an equivalent weight of 280.5 (eq « 56100/200) . The equivalents of phosphite are determin by dividing the molecular weight of the phosphite by t number of phosphorus atoms in the phosphite. The overbased materials (A) are prepared reacting an acidic material (typically an inorganic acid lower carboxylic acid, preferably carbon dioxide) with mixture comprising an acidic organic compound, a reacti medium comprising at least one inert, organic solve (mineral oil, naphtha, toluene, xylene, etc.) for sa acidic organic material, a stoichiometric excess of a met base, and a promoter.

The acidic organic compounds useful in making t overbased compositions of the present invention inclu carboxylic acids, sulfonic acids, phosphorus-containi acids, phenols or mixtures of two or more thereof. Prefe ably, the acidic organic compounds are carboxylic acids sulfonic acids with sulfonic and salicylic acids mo preferred. Throughout this specification and in t appended claims, any reference to acids, such as carboxy ic, or sulfonic acids, is intended to include the acid-pr ducing derivatives thereof such as anhydrides, lower alk esters, acyl halides, lactones and mixtures thereof unle otherwise specifically stated. The carboxylic acids useful in making the ove based salts (A) of the invention may be aliphatic aromatic, mono- or polycarboxylic acid or acid-produci compounds. These carboxylic acids include lower molecul weight carboxylic acids (e.g., carboxylic acids having to about 22 carbon atoms such as acids having about 4 about 22 carbon atoms or tetrapropenyl-substituted succini anhydride) as well as higher molecular weight carboxyli acids.

The carboxylic acids of this invention ar preferably oil-soluble. Usually, in order to provide th

desired oil-solubility, the number of carbon atoms in th carboxylic acid should be at least about 8, more preferabl at least about 18, more preferably at least about 30, mor preferably at least about 50. Generally, these carboxyli acids do not contain more than about 400 carbon atoms pe molecule.

The lower molecular weight monocarboxylic acid contemplated for use in this invention include saturate and unsaturated acids. Examples of such useful acid include dodecanoic acid, decanoic acid, oleic acid, steari acid, linoleic acid, tall oil acid, etc. Mixtures of tw or more such agents can also be used. An extensive discus sion of these acids is found in Kirk- Othmer "Encyclopedi of Chemical Technology" Third Edition, 1978, John Wiley Sons New York, pp. 814-871; these pages being incorporate herein by reference.

The monocarboxylic acids include isoaliphati acids. Such acids often contain a principal chain havin from about 14 to about 20 saturated, aliphatic carbon atoms and at least one but. usually no more than about four pendant acyclic lower alkyl groups. Specific examples of such isoaliphatic acids include 10-methyl-tetradecanoic acid, 3-ethyl-hexadecanoic acid, and 8-methyl-octadecanoic acid. The isoaliphatic acids include mixtures of branch- chain acids prepared by the isomerization of commercial fatty acids (oleic, linoleic or tall oil acids) of, for example, about 16 to about 20 carbon atoms.

High molecular weight carboxylic acids may also be used in the present invention. These acids have a sub- stituent group derived from a polyalkene. The polyalkene is characterized as containing at least about 30 carbon atoms, preferably at least about 35, more preferably at least about 50, and up to about 300 carbon atoms, prefera¬ bly about 200, more preferably about 150. In one embodi- ment, the polyalkene is characterized by an Mn (number

average molecular weight) value of at least about 50 generally about 500 to about 5000, preferably about 800 about 2500. In another embodiment, Mn varies between abo 500 to about 1200 or 1300. The polyalkenes include homopolymers and inte polymers of polymerizable olefin monomers of 2 to about carbon atoms. The olefins may be monoolefinε such ethylene, propylene, 1-butene, isobutene, and 1-octene; a polyolefinic monomer,, preferably diolefinic, monomer su 1,3-butadiene and isoprene. Preferably the monome contain from 2 to about 6 carbon atoms, more preferably to about 4, more preferably 4. The interpolymers inclu copolymers, terpolymers, tetrapolymers and the lik Preferably, the interpolymer is a homopoly er. An examp of a preferred homopolymer is a polybutene, preferably polybutene in which about 50% of the polymer is deriv from isobutylene. The polyalkenes are prepared by conve tional procedures.

The higher molecular weight mono- and polyca boxylic acids suitable for use in making the overbas salts (A) are well known in the art and have been describ in detail, for example, in the following U.S., British a Canadian patents: U.S. Patents 3,024,237; 3,172,89

3,219,666 3,245,910; 3,271,310; 3,272,746; 3,278,55 3,306,907 3,312,619; 3,341,542; 3,367,943; 3,374,17 3,381,022 3,454,607; 3,470,098; 3,630,902; 3,755,16 3,912,764 and 4,368,133; British Patents 944,13 1,085,903 1,162,436; and 1,440,219; and Canadian Pate

956,397. These patents are incorporated herein by refe ence for their disclosure of higher molecular weight on and polycarboxylic acids and methods for making the same

Illustrative carboxylic acids include palmit acid, stearic acid, myristic acid, oleic acid, linole acid, behenic acid, hexatriacontanoic acid, tetrapropy enyl-substituted glutaric acid, polybutenyl-substitut

succinic acid derived from a polybutene (Mn » 200-1500 preferably 300-1000) , polypropenyl-substituted succini acid derived from a polypropene, (Mn ■ 200-1000, preferabl

300-900) , octadecyl-substituted adipic acid, chlorosteari acid, 9-methylstearic acid, dichlorostearic acid, stearyl benzoic acid, eicosanyl-substituted naphthoic acid, di lauryl-decahydronaphthalene carboxylic acid, mixtures o any of these acids, their alkali and alkaline earth meta salts, and/or their anhydrides. A preferred group o aliphatic carboxylic acids includes the saturated an unsaturated higher fatty acids containing from about 12 t about 30 carbon atoms. Illustrative of these acids ar lauric acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, oleostearic acid, stearic acid, myristi acid, and undecalinic acid, alpha-chlorostearic acid, an alphanitrolauric acid.

In another embodiment, the carboxylic acid is a alkylalkyleneglycol-acetic acid, more preferably alkylpoly ethyleneglycol-acetic acid. Some specific examples o these compounds include: iso-stearylpentaethyleneglycol- acetic acid; iso-stearyl-0-(CH ₂ CH ₂ 0) ₅ CH ₂ C0 ₂ Na; lauryl-o- lauryl-0-(GH ₂ CH ₂ 0) ₃ jCH ₂ C0 ₂ H; oleyl-0-(CH ₂ C-

H ₂ 0) ₄ -CH ₂ Cθ ₂ H; lauryl-0-(CH ₂ CH ₂ 0) ₄ jCH ₂ C0 ₂ H; lauryl-O-(CH ₂ CH ₂ O), ₀ -

CH ₂ CC- ₂ H; lauryl-0-(CH ₂ CH ₂ 0)ι ₆ CH ₂ C0 ₂ H; octyl-phenyl-0-(CH ₂ CH ₂ 0),- CH _i CO _j H octyl-phenyl-0-(CH ₂ CH ₂ 0) _w CH ₂ C0 ₂ H; 2-octyl-decanyl-O-

(CH ₂ CH ₂ 0) ₆ CH ₂ C0 ₂ H. These acids are available commercially from Sandoz Chemical under the tradename Sandopan acids.

In another embodiment, the carboxylic acids are aromatic carboxylic acids. A group of useful aromatic carboxylic acids are those of the formula

wherein R _j is an aliphatic hydrocarbyl group of prefera about 4 to about 400 carbon atoms, a is a number in range of zero to about 4, usually 1 or 2, Ar is an aroma group, each X is independently sulfur or oxygen, prefera oxygen, b is a number in the range of from 1 to about usually 1 or 2 , c is a number in the range of zero to ab 4, usually 1 to 2, with the proviso that the sum of a and c does not exceed the number of valences of Ar Preferably, ] and a are such that there is an average of least about 8 aliphatic carbon atoms provided by the groups. Examples of aromatic carboxylic acids incl substituted and non-substituted benzoic, phthalic salicylic acids or anhydrides.

The R _! group is a hydrocarbyl group that directly bonded to the aromatic group Ar. R, prefera contains about 6 to about 80 carbon atoms, preferably ab 6 to about 30 carbon atoms, more preferably about 8 about 25 carbon atoms, and advantageously about 8 to ab 15 carbon atoms. j groups may be derived form one or m of the above-described polyalkenes. Examples of R, gro include butyl, isobutyl, pentyl, octyl, nonyl, dodec 5-chlorohexyl, 4-ethoxypentyl, 3-cyclohexyloctyl, 2,3, trimeth lhepty1, and substituents derived from polymeri olefins such as polyethylenes, polypropylenes, polyi butylenes, ethylene-propylene copolymers, chlorina olefin polymers, oxidized ethylene-propylene copolyme propylene tetramer and tri(isobutene) .

Examples of the Rj groups include butyl, isobut pentyl, octyl, nonyl, dodecyl, and substituents deri from the above-described polyalkenes such as polyethylen polypropylenes, polyisobutylenes, ethylene-propyl copolymers, oxidized ethylene-propylene copolymers, and like.

The aromatic group Ar may have the same struct as any of the aromatic groups Ar discussed below. Exampl

of the aromatic groups that are useful herein include t polyvalent aromatic groups derived from benzene, nap thalene, anthracene, etc., preferably benzene. Specif examples of Ar groups include phenylenes and naphthylen e.g., ethylphenyleneε, ethoxyphenylenes, isopropylpheny enes, hydroxyphenylenes, dipropoxynaphthylenes, etc.

Within this group of aromatic acids, a usef class of carboxylic acids are those of the formula

wherein Rj is defined above, a is a number in the range o from zero to about 4, preferably 1 to about 2; b is number in the range of 1 to about 4, preferably 1 to abou 2, c is a number in the range of zero to about 4, prefera bly 1 to about 2, and more preferably 1; with the provis that the sum of a, b and c does not exceed 6. Preferably R _t and a are such that the acid molecules contain at leas an average of about 12 aliphatic carbon atoms in th aliphatic hydrocarbon substituents per acid molecule Preferably, b and c are each one and the carboxylic acid i a salicylic acid.

The salicylic acids can be aliphatic hydrocarbon substituted salicyclic acids wherein each aliphatic hydro carbon substituent contains an average of at least about carbon atoms per substituent and 1 to 3 substituents pe molecule. Overbased salts prepared from such salicycli acids wherein the aliphatic hydrocarbon substituents ar derived from the above-described polyalkenes, particularl polymerized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene ethylene/propylene copoly

mers and the like and having average carbon contents about 30 to about 400 carbon atoms are particularly usefu The above aromatic carboxylic acids are we known or can be prepared according to procedures known the art. Carboxylic acids of the type illustrated by the formulae and processes for preparing their neutral a basic metal salts are well known and disclosed, for exa ple, in U.S. Patents 2,197,832; 2,197,835; 2,252,66 2,252,664; 2,714,092; 3,410,798; and 3,595,791. The sulfonic acids useful in making the overbas salts (A) of the invention include the sulfonic and thi sulfonic acids. Generally they are salts of sulfon acids. The sulfonic acids include the mono- or polynucle aromatic or cycloaliphatic compounds. The oil-solub sulfonates can be represented for the most part by one the following foirmulae: R ₂ -T-(Sθ ₃ ), and R ₃ -(S0 ₃ ) _b , wherein is a cyclic nucleus such as, for example, benzene, naphth lene, anthracene, diphenylene oxide, diphenylene sulfid petroleum naphthenes, etc.; R ₂ is an aliphatic group such alkyl, alkenyl, alkoxy, alkoxyalkyl, etc.; (R^+T contai a total of at least about 15 carbon atoms; and R ₃ is aliphatic hydrocarbyl group containing at least about carbon atoms. Examples of R ₃ are alkyl, alkenyl, alkox alkyl, carboalkoxyalkyl, etc. Specific examples of R ₃ a groups derived from petrolatum, saturated and unsaturat paraffin wax, and the above-described polyalkenes. T groups T, ₂ , and R ₃ in the above Formulae can also conta other inorganic or organic substituents in addition those enumerated above such as, for example, hydrox mercapto, halogen, nitro, amino, nitroso, sulfide, disu fide, etc. In the above Formulae, a and b are at least In one embodiment, the sulfonic acids have a substituent ( or R ₃ ) which is derived from one of the above-describ polyalkenes.

Illustrative examples of these sulfonic aci include monoeicosanyl-subεtituted naphthalene sulfon acids, dodecylbenzene sulfonic acids, didodecylbenze sulfonic acids, dinonylbenzene sulfonic acids, cetylchlor benzene sulfonic acids, dilauryl beta-naphthalene sulfon acids, the sulfonic acid derived by the treatment o polybutene having a number average molecular weight (Mn) i the range of 500 to 5000, preferably 800 to 2000, mor preferably about 1500 with chlorosulfonic acid, nitronaph thalene sulfonic acid, paraffin wax sulfonic acid, cetyl cyclopentane, sulfonic acid, lauryl-cyclohexane sulfoni acids, polyethylenyl-substituted sulfonic acids derive from polyethylene (Mn=300-1000, preferably 750), etc Normally the aliphatic groups will be alkyl and/or alkeny groups such that the total number of aliphatic carbons i at least about 8, preferably at least 12 up to about 40 carbon atoms, preferably about 250.

Another group of sulfonic acids are mono-, di- and tri-alkylated benzene and naphthalene (includin hydrogenated forms thereof) sulfonic acids. Illustrativ of synthetically produced alkylated benzene and naphthalen sulfonic acids are those containing alkyl substituent having from about 8 to about 30 carbon atoms, preferabl about 12 to about 30 carbon atoms, and advantageously abou 24 carbon atoms. Such acids include di-isododecyl-benzen sulfonic acid, polybutenyl-substituted sulfonic acid, polypropylenyl-substituted sulfonic acids derived fro polypropene having an Mn=300-1000, preferably 500-700, cetylchlorobenzene sulfonic acid, di-cetylnaphthalen sulfonic acid, di-lauryldiphenylether sulfonic acid, diisononylbenzene sulfonic acid, di-isooctadecylbenzen sulfonic acid, stearylnaphthalene sulfonic acid, and the like.

Specific examples of oil-soluble sulfonic acids are mahogany sulfonic acids; bright stock sulfonic acids;

sulfonic acids derived from lubricating oil fracti having a Saybolt viscosity from about 100 seconds at 10 to about 200 seconds at 210°F; petrolatum sulfonic aci mono- and poly-wax-substituted sulfonic and polysulfo acids of, e.g., benzene, naphthalene, phenol, diphe ether, naphthalene disulfide, etc.; other substitu sulfonic acids such as alkyl benzene sulfonic acids (wh the alkyl group has at least 8 carbons) , cetylphe mono-sulfide sulfonic acids, dilauryl beta naphthyl sulf ic acids, and alkaryl sulfonic acids such as dode benzene "bottoms" sulfonic acids.

Dodecyl benzene "bottoms" sulfonic acids are material leftover after the removal of dodecyl benz sulfonic acids that are used for household detergen These materials are generally alkylated with higher olig ers. The bottoms may be straight-chain or branched-ch alkylates with a straight-chain dialkylate preferred.

The production of sulfonates from deterg manufactured by-products by reaction with, e.g., S0 ₃ , well known to those skilled in the art. See, for examp the article "Sulfonates" in Kirk-Othmer "Encyclopedia Chemical Technology", Second Edition, Vol. 19, pp. 291 seq. published by John Wiley & Sons, N.Y. (1969).

The phosphorus-containing acids useful in mak the basic metal salts (A) of the present invention incl any phosphorus acids such as phosphoric acid or esters; thiophosphorus acids or esters, including mono and dith phosphorus acids or esters. Preferably, the phospho acids or esters contain at least one, preferably t hydrocarbyl groups containing from 1 to about 50 car atoms, typically 1 to about 30, preferably 3 to about more preferably about 4 to about 8.

In one embodiment, the phosphorus-contain acids are dithiophosphoric acids which are readily obtai able by the reaction of phospherus pentasulfide (P ₂ S ₅ )

an alcohol or a phenol. The reaction involves mixing at temperature of about 20°C to about 200°C four moles o alcohol or a phenol with one mole of phosphorus pentasul fide. Hydrogen sulfide is liberated in this reaction. Th oxygen-containing analogs of these acids are convenientl prepared by treating the dithioic acid with water or stea which, in effect, replaces one or both of the sulfur atom with oxygen.

In another embodiment, the phosphorus-containin acid is the reaction product of the above-described poly alkene and phosphorus sulfide. Useful phosphorus sulfide containing sources include phosphorus pentasulfide, phos phorus sesquisulfide, phosphorus heptasulfide and the like The reaction of the polyalkene and the phosphoru sulfide generally may occur by simply mixing the two at temperature above 80 ^β C, preferably between 100 ^β C and 300 ^β C Generally, the products have a phosphorus content fro about 0.05% to about 10%, preferably from about 0.1% t about 5%. The relative proportions of the phosphorizin agent to the olefin polymer is generally from 0.1 part t 50 parts of the phosphorizing agent per 100 parts of th olefin polymer.

The phosphorus-containing acids useful in th present invention are described in U.S. Patent 3,232,883 issued to Le Suer. This reference is herein incorporated by reference for its disclosure to the phosphorus-contain¬ ing acids and methods for preparing the same.

The phenols useful in making the basic metal salts (A) of the invention can be represented by the formula (Rι),-Ar-(OH) _b , wherein Rj is defined above; Ar is an aromatic group; a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar. Preferably, a and b are indepen- dently numbers in the range of 1 to about 4, more prefera-

bly 1 to about 2. Rj and a are preferably such that th is an average of at least about 8 aliphatic carbon at provided by the R, groups for each phenol compound.

While the term "phenol" is used herein, it is be understood that this term is not intended to limit aromatic group of the phenol to benzene. Accordingly, is to be understood that the aromatic group as represen by "Ar", as well as elsewhere in other formulae in t specification and in the appended claims, can be mononuc ar such as a phenyl, a pyridyl, or a thienyl, or polynuc ar. The polynuclear groups can be of the fused t wherein an aromatic nucleus is fused at two points another nucleus such as found in naphthyl, anthranyl, e The polynuclear group can also be of the linked t wherein at least two nuclei (either mononuclear or poly clear) are linked through bridging linkages to each oth These bridging linkages can be chosen from the gr consisting of alkylene linkages, ether linkages, k linkages, sulfide linkages, polysulfide linkages of 2 about 6 sulfur atoms, etc.

The number of aromatic nuclei, fused, linked both, in Ar can play a role in determining the inte values of a and b. For example, when Ar contains a sin aromatic nucleus, the sum of a and b is from 2 to 6. W Ar contains two aromatic nuclei, the sum of a and b is f 2 to 10. With a tri-nuclear Ar moiety, the sum of a an is from 2 to 15. The value for the sum of a and b limited by the fact that it cannot exceed the total num of displaceable hydrogens on the aromatic nucleus or nucl of Ar.

The metal compounds useful in making the bas metal salts (A) are generally any Group I or Group II met compounds (CAS version of the Periodic Table of the El ments) . The Group I metals of the metal compound inclu alkali metals (sodium, potassium, lithium, etc.) as well

Group IB metals such as copper. The Group I metals ar preferably sodium, potassium, lithium and copper, mor preferably sodium or potassium, and more preferably sodium The Group II metals of the metal base include the alkalin earth metals (magnesium, calcium, barium, etc.) as well a the Group IIB metals such as zinc or cadmium. Preferabl the Group II metals are magnesium, calcium, or zinc preferably magnesium or calcium, more preferably magnesium Generally the metal compounds are delivered as metal salts The anionic portion of the salt can be hydroxyl, oxide carbonate, borate, nitrate, etc.

An acidic material is used to accomplish th formation of the basic metal salt (A) . The acidic materia may be a liquid such as formic acid, acetic acid, nitri acid, sulfuric acid, etc. Acetic acid is particularl useful. Inorganic acidic materials may also be used suc as HC1, S0 ₂ , S0 ₃ , C0 ₂ , H ₂ S, etc, preferably C0 ₂ . A preferre combination of acidic materials is carbon dioxide an acetic acid. A promoter is a chemical employed to facilitat the incorporation of metal into the basic metal composi tions. Among the chemicals useful as promoters are water, ammonium hydroxide, organic acids of up to about 8 carbon atoms, nitric acid, sulfuric acid, hydrochloric acid, metal complexing agents such as alkyl salicylaldoxime, and alkali metal hydroxides such as lithium hydroxide, sodium hydrox¬ ide and potassium hydroxide, and mono- and polyhydric alcohols of up to about 30 carbon atoms. Examples of the alcohols include methanol, ethanol, isopropanol, dodecanol, behenyl alcohol, ethylene glycol, monomethylether of ethylene glycol, hexamethylene glycol, glycerol, penta¬ erythritol, benzyl alcohol, phenylethyl alcohol, amino- ethanol, cinnamyl alcohol, allyl alcohol, and the like. Especially useful are the monohydric alcohols having up to

about 10 carbon atoms and mixtures of methanol vith hi monohydric alcohols.

Patents specifically describing techniques making basic salts of the above-described sulfonic aci carboxylic acids, and mixtures of any two or more of th include U.S. Patents 2,501,731; 2,616,905; 2,616,9 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,3 3,320,162; 3,318,809; 3,488,284; and 3,629,109. disclosures of these patents are hereby incorporated this present specification for their disclosures in t regard as well as for their disclosure of specific suita basic metal salts. (B_ Metal Deactivator

The composition also contains (B) at least metal deactivator other than a dimercaptothiadiazole derivatives thereof. Metal deactivators reduce the cor sion of metals, such as copper. Metal deactivators also referred to as metal passivators. Metal deactivat are typically nitrogen and/or sulfur containing hete cyclic compounds, such as triazoles, amino-mercaptoth diazoles, imidazoles, thiazoles, tetrazoles, hydroxyqui lines, oxazolines, imidazolines, thiophenes, indol indazoles, quinolines, benzoxazines, dithiols, oxazol oxatriazoles, pyridines, piperazines, triazines, derivatives of any one or more thereof. The metal deac vator preferably comprises at least one triazole which be substituted or unsubstituted. Examples of suita compounds are benzotriazole, alkyl-substituted benzot azole (e.g., tolyltriazole, ethylbenzotriazole, hexylben triazole, octylbenzotriazole, etc.), aryl-substitu benzotriazole (e.g., phenol benzotriazoles, etc.), al ylaryl- or arylalkyl-substituted benzotriazole substituted benzotriazoles where the substituent may hydroxy, alkoxy, halo (especially chloro) , nitro, carb and carboxyalkoxy. Preferably, the triazole is a benzot

azole or an alkylbenzotriazole in which the alkyl grou contains 1 to about 20 carbon atoms, preferably 1 to abou 8 carbon atoms. Benzotriazole and tolyltriazole ar particularly preferred. The metal deactivator (B) may also be the reac tion product of at least one of the above benzotriazole with at least one amine. The amine can be one or more mon or polyamines. These monoamines and polyamines can b primary amines, secondary amines or tertiary amines. The monoamines generally contain from 1 to abou

24 carbon atoms, with 1 to about 12 carbon atoms being mor preferred, with 1 to about 6 being more preferred. Exam ples of monoamines useful in the present invention includ methylamine, ethylamine, propylamine, butylamine, octyl amine, and dodecylamine. Examples of secondary amine include dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, etc. Tertiary amines include trimethylamine, tributylamine, methyldiethylamine, ethyldibutylamine, etc. The polyamines may be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of the polyamines include alkylene polyamines and heterocyclic polyamines.

Alkylene polyamines are represented by the formula

HN-(Alkylene-N) _B R,

R, R, wherein n has an average value between about 1 and about 10, preferably about 2 to about 7 and the "Alkylene" group has from 1 to about 10 carbon atoms, preferably about 2 to about 6. As noted above, * is preferably an aliphatic or hydroxy-substituted aliphatic group of up to about 30 carbon atoms.

Such alkylene polyamines include methylene poly¬ amines, ethylene polyamines, butylene polyamines, propylene

polyamines, pentylene polyamines, etc. The higher homol and related heterocyclic amines such as piperazines N-amino alkyl-substituted piperazines are also includ Specific examples of such polyamines are ethylene diami triethylene tetramine, trie-(2-aminoethyl)amine, propyl diamine, trimethylene diamine, tripropylene tetrami tetraethylene pentamine, hexaethylene heptamine, pen ethylenehexamine, etc.

Higher homologs obtained by condensing two more of the above-noted alkylene amines are simila useful as are mixtures of two or more of the aforedescri polyamines.

Ethylene polyamines, such as some of those me tioned above, are useful. Such polyamines are described detail under the heading Ethylene Amines in Kirk Othmer "Encyclopedia of Chemical Technology", 2d Edition, Vol. pages 22-37, Interscience Publishers, New York (1965). Su polyamines are most conveniently prepared by the reacti of ethylene dichloride with ammonia or by reaction of ethylene imine with a ring opening reagent such as wate ammonia, etc. These reactions result in the production a complex mixture of polyalkylene polyamines includi cyclic condensation products such as piperazines. Ethyle polyamine mixtures are useful. The amine may also be a heterocyclic polyamin

Among the heterocyclic polyamines are aziridine azetidines, azolidines, tetra- and dihydropyridine pyrroles, indoles, piperidines, imidazoles, di- and tetr hydroimidazoles, piperazines, isoindoles, purines, morph lines, thiomorpholines, N-aminoalkylmorpholines, N-amin alkylthiomorpholines, N-aminoalkylpiperazines, N,N'-d aminoalkylpiperazines, azepines, azocines, azonine azecines and tetra-, di- and perhydro derivatives of ea of the above and mixtures of two or more of these heteroc clic amines. Preferred heterocyclic amines are the sat

rated 5- and 6-membered heterocyclic amines containing onl nitrogen, oxygen and/or sulfur in the hetero ring, espe cially the piperidines, piperazines, thiomorpholines orpholines, pyrrolidines, and the like. Piperidine aminoalkylsubstituted piperidines, piperazine, aminoalkyl substitutedpiperazines, morpholine, aminoalkyl-εubstitute morpholines, pyrrolidine, and aminoalkyl-subεtitute pyrrolidines, are especially preferred. Usually th aminoalkyl substituents are substituted on a nitrogen ato forming part of the hetero ring. Specific examples of suc heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-diaminoethylpiperazine.

Other useful types of polyamine mixtures ar those resulting from stripping of the above-describe polyamine mixtures to leave as residue what is often termed "polyamine bottoms". In general, alkylene polyamine bottoms can be characterized aε having less than two, usually less than 1% (by weight) material boiling below about 200°C. A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Texas designated "E-100" has a specific gravity at 15.6 ^β c of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40°C of 121 centistokes. Gas chromatography analysis of such a sample contains about 0.93% "Light Ends" (most probably DETA) , 0.72% TETA, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and higher (by weight) . These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like. These alkylene polyamine bottoms can be reacted solely with the acylating agent, in which case the amino reactant consists essentially of alkylene polyamine bot¬ toms, or they can be used with other amines, polyamines, or mixtures thereof.

Amines useful in the present invention described in U.S. Patents 3,219,666 and 4,234,435, these patents are hereby incorporated by reference their disclosures of amines. Another useful polyamine is a condensation re tion between at least one hydroxy compound with at le one polyamine reactant containing at least one primary secondary amino group. The hydroxy compounds are prefe bly polyhydric alcohols and amines. The polyhydric al hols contain from 2 to about 10, preferably 2 to about preferably 2 to about 4 hydroxyl groups and up to aliphatic carbon atoms, preferably from 2 to about 30, m preferably 2 to about 10. The polyhydric alcohols incl ethylene glycols, including di-, tri- and tetraethyl glycols; propylene glycols, including di-, tri- and tet propylene glycols; glycerol; butane diol; hexane di sorbitol; arabitol; mannitol; sucrose; fructose; gluco cyclohexane diol; erythritol; and penterythritolε, incl ing di- and tripentaerythritol. Preferably the hydro compounds are polyhydric amines. Polyhydric amines inclu any of the above-described monoamines reacted with alkylene oxide (e.g., ethylene oxide, propylene oxi butylene oxide, etc.) having two to about 20 carbon ato preferably two to about four. Examples of polyhydr amines include tri-(hydroxypropyl)amine, tris-(hydrox methyl)amino methane, 2-amino-2-methyl-l,3-propanedio N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, a N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine,prefer bly tris(hydroxymethyl)aminomethane (THAM) . Polyamine reactants, which react with the pol hydric alcohol or amine to form the condensation produc or condensed amines, are described above. Preferred pol amine reactants include triethylenetetramine (TETA tetraethylenepentamine (TEPA) , pentaethylenehexami

(PEHA) , and mixtures of polyamines such as the above described "amine bottoms".

The condensation reaction of the polyamin reactant with the hydroxy compound is conducted at a elevated temperature, usually about 60°C to about 265°C

(preferably about 220°C to about 250°C) in the presence o an acid catalyst.

The amine condensates and methods of making th same are described in PCT publication WO86/05501 which i incorporated by reference for its disclosure to the conden sates and methods of making. The preparation of suc polyamine condensates may occur as follows: A 4-necke 3-liter round-bottomed flask equipped with glass stirrer, thermowell, subsurface N ₂ inlet, Dean-Stark trap, and Friedrich condenser is charged with: 1299 grams of HPA Taft Amines (amine bottoms available commercially from Union Carbide Co. with typically 34.1% by weight nitrogen and a nitrogen distribution of 12.3% by weight primary amine, 14.4% by weight secondary amine and 7.4% by weight tertiary amine), and 727 gramε of 40% aqueous tris(hydroxy- methyl)aminomethane (THAM). This mixture is heated to 60°C and 23 grams of 85% H ₃ P0 ₄ is added. The mixture is then heated to 120°C over 0.6 hour. With N ₂ sweeping, the mixture is then heated to 150 ^β C over 1.25 hour, then to 235 ^β C over 1 hour more, then held at 230-235 ^β C for 5 hours, then heated to 240 ^β C over 0.75 hour, and then held at 240-245 ^β C for 5 hours. The product is cooled to 150 ^β C and filtered with a diatomaceous earth filter aid. Yield: 84% (1221 grams) . The metal deactivator may also be the reaction product of one or more of the above triazoles and at least one compound selected from acylated nitrogen compounds, hydrocarbyl substituted amines and Mannich reaction prod¬ ucts.

The acylated nitrogen compounds include reacti products of amines, hydrocarbyl-substituted carboxyl acylating agents such as substituted carboxylic acids derivatives thereof. The amines are described abov typically the amines are polyamines, preferably the amin are ethylene amines, amine bottoms or amine condensates.

The hydrogen-substituted carboxylic acylati agent may be derived from a monocarboxylic acid or polycarboxylic acid. Polycarboxylic acids generally a preferred. The acylating agentε may be a carboxylic ac or derivatives of the carboxylic acid such as the halide esters, anhydrides, etc., preferably acid, esterε anhydrides, more preferably anhydrides. Preferably t carboxylic acylating agent is a succinic acylating agent The hydrocarbyl-substituted carboxylic acylati agent includes agentε which have a hydrocarbyl gro derived from the above-described polyalkenes.

In another embodiment, the hydrocarbyl groups a derived from polyalkenes having an Mn value of at lea about 1300 up to about 5000, and the Mw/Mn value is fr about 1.5 to about 4, preferably from about 1.8 to abo 3.6, more preferably about 2.5 to about 3.2. The prepar tion and use of substituted succinic acylating agen wherein the substituent is derived from such polyolefi are deεcribed in U.S. Patent 4,234,435, the disclosure which is hereby incorporated by reference.

The hydrocarbyl-substituted carboxylic acylati agents are prepared by a reaction of one or more polya kenes with one or more unsaturated carboxylic reagent. T unsaturated carboxylic reagent generally contains alpha-beta olefinic unsaturation. The carboxylic reagen may be carboxylic acids per se and functional derivativ thereof, such as anhydrides, esterε, amides, imides, salt acyl halides, and nitriles. These carboxylic acid reagen may be either monobasic or poly^asic in nature. When th

are polybasic they are preferably dicarboxylic acids although tri- and tetracarboxylic acids can be used Specific examples of useful monobasic unsaturated carboxyl ic acids are acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, 2-phenylpropenoic acid, etc. Exemplar polybasic acids include aleic acid, fumaric acid, mesa conic acid, itaconic acid and citraconic acid. Generally, the unsaturated carboxylic acid or derivative is malei anhydride or maleic or fumaric acid or ester, preferably, maleic acid or anhydride, more preferably maleic anhydride.

The polyalkene may be reacted with the carboxylic reagent such that there is at least one mole of reagent for each mole of polyalkene. Preferably, an excess of reagent is used. This excess is generally between about 5% to about 25%.

In another embodiment, the acylating agents are prepared by reacting the above described polyalkene with an excess of maleic anhydride to provide substituted succinic acylating agents wherein the number of succinic groups for each equivalent weight of substituent group is at least

1.3. The maximum number will not exceed 4.5. A suitable range is from about 1.4 to 3.5 and more specifically from about 1.4 to about 2.5 succinic groups per equivalent weight of substituent groups. In this embodiment, the polyalkene preferably has an Mn from about 1300 to about

5000 and a Mw/Mn of at least 1.5, as described above, the value of Mn is preferably between about 1300 and 5000. A more preferred range for Mn is from about 1500 to about

2800, and a most preferred range of Mn valueε iε from about 1500 to about 2400.

The conditions, i.e., temperature, agitation, solvents, and the like, for reacting an acid reactant with a polyalkene, are known to those in the art. Exampleε of patents describing various procedureε for preparing uεeful acylating agents include U.S. Patents 3,215,707 (Rense) ;

3,219,666 (Norman et al) ; 3,231,587 (Rense) ; 3,912,7 (Palmer); 4,110,349 (Cohen); and 4,234,435 (Meinhardt al) ; and U.K. 1,440,219. The disclosures of these paten are hereby incorporated by reference. The hydrocarbyl-substituted amines, which may reacted with a triazole, are well known to those skilled the art. These amines are disclosed in U.S. paten 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; a 3,822,289. These patents are hereby incorporated reference for their disclosure of hydrocarbyl amines a methods of making the same.

Typically, hydrocarbyl-subεtituted amineε a prepared by reacting olefinε and olefin polymers (polya kenes) with amines (mono- or polyamines) . The polyalke may be any of the polyalkenes described above. The amin may be any of the amines described above. Examples these substituted amines include poly(propylene)amine; N, dimethy1-N-poly(ethylene/propylene)amine, (50:50 mole rat of monomers); polybutene amine; N,N-di(hydroxyethyl)- polybutene amine; N-(2:-hydroxypropyl)-N-polybutene amin N-polybutene-aniline; N-polybutenemorpholine; N-pol (butene)ethylenediamine; N-poly(propylene)trimethylen dia ine; N-poly(butene)diethylenetria ine; N',N'-pol (butene)tetraethylenepentamine; N,N-dimethyl-N'-pol (propylene)-1,3-propylenediamine and the like.

The triazole may also be reacted with a Manni reaction product. Mannich reaction products are formed the reaction of at least one aldehyde, at least one of t above described amine and at least one hydroxyaromat compound. The reaction may occur from room temperature 225 ^β C, uεually from 50° to about 200 ^β C (75 ^β C-125°C mo preferred) , with the amounts of the reagents being su that the molar ratio of hydroxyaromatic compound to formal dehyde to amine is in the range from about (1:1:1) to abou (1:3:3).

The first reagent is a hydroxyaromatic compound This term includes phenols (which are preferred) , carbon-, oxygen-, sulfur- and nitrogen-bridged phenols and the lik as well as phenols directly linked through covalent bond (e.g.4,4'-bis(hydroxy)biphenyl) , hydroxy compounds derive from fused-ring hydrocarbon (e.g., naphthols and the like) ; and polyhydroxy compounds such as catechol, resorcinol an hydroquinone. The hydroxyaromatic compound may be any o the above-described phenols. Mixtures of one or more hydroxyaromatic compounds can be used aε the first reagent.

The hydroxyaromatic compound is preferably one of the above-described phenols. In one embodiment, the hydroxyaromatic compound is phenol subεtituted with an aliphatic or alicyclic hydrocarbon-based group having an Mn of about 420 to about 10,000.

The second reagent is a hydrocarbon-based alde¬ hyde, preferably a lower aliphatic aldehyde. Suitable aldehydeε include formaldehyde, benzaldehyde, acetaldehyde, the butyraldehydeε, hydroxybutyraldehydes and heptanals, as well as aldehyde precursors which react aε aldehydeε under the conditionε of the reaction such as paraformaldehyde, paraldehyde, formalin and methanal. Formaldehyde and its precursors (e.g., paraformaldehyde, trioxane) are pre¬ ferred. Mixtures of aldehydes may be used as the second reagent.

The third reagent is any amine deεcribed above. Preferably the amine is a polyamine as deεcribed above.

Mannich reaction products are described in the following patents: U.S. Patent 3,980,569; U.S. Patent 3,877,899; and U.S. Patent 4,454,059 (herein incorporated by reference for their disclosure to Mannich reaction products, also referred to as Mannich disperεantε) .

The triazole-amine, -acylated amine, -hydrocarbyl substituted amine and -Mannich reaction products may be prepared by blending the reagents and allowing the reaction

to proceed. The reaction may occur at a temperature aε lo as about 15°C, up to about 160°C, with temperatures in th range of about 60*C to about 140 ^β C being preferred. Th triazole-amine, -acylated nitrogen compound, -hydrocarby substituted amine and -Mannich reaction products may b reacted in any proportion but are preferably reacted at a equal equivalent ratio. fC. Hvdrocarbvl Phosphites

Compositions of the present invention alε include (C) a hydrocarbyl phosphite. The phosphite may b represented by the following formulae:

or wherein each Rj is independently hydrogen or a hydrocarby group, provided at least one Rj is hydrocarbyl. Preferably each ₅ is independently a hydrogen o hydrocarbyl group having from 1 to about 24, more prefera bly from 1 to about 18, and more preferably from about 2 t about 8 carbon atoms. Each ₅ may be independently alkyl alkenyl or aryl. When Rj is aryl it contains at least carbon atoms; preferably 6 to about 18 carbon atoms Examples of alkyl or alkenyl groups are propyl, butyl hexyl, heptyl, octyl, oleyl, linoleyl, εtearyl, etc Examples of aryl groups are phenyl, napthyl, heptylphenol etc. Preferably each R ₅ is independently propyl, butyl pentyl, hexyl, heptyl, oleyl or phenyl, more preferabl butyl, oleyl or phenyl and more preferably butyl or oleyl

The R ₅ groups may alεo comprise a mixture o hydrocarbyl groups derived from commercial alcohols

Exampleε of preferred monohydric alcohols and alcoho mixtures include commercially available "Alfol" alcohol marketed by Continental Oil Corporation. Alfol 810 is mixture containing alcohols consisting essentially o straight-chain, primary alcohols having 8 to 10 carbo atoms. Alfol 812 is a mixture comprising mostly C ₁₂ fatt alcohols. Alfol 1218 is a mixture of synthetic, primary, straight-chain alcohols having from 12 to 18 carbon atoms. Alfol 20+ alcohols are mixtures of 18-28 primary alcohol having mostly, on an alcohol basis, C^ alcohols as deter mined by GLC (gas-liquid-chromatography) .

Another group of commercially available alcoho mixtures includeε the "Neodol" productε available fro Shell Chemical Company. For example, Neodol 23 is a mixture of C ₁₂ and C ₁₃ alcohols; Neodol 25 is a mixture of C ₁₂ and C ₁₅ alcohols; and Neodol 45 is a mixture of C ₁₄ and C ₁₅ linear alcohols. Neodol 91 is a mixture of G,, C _I0 and C _n alcohols.

Phosphites and their preparation are known and many phosphites are available commercially. Particularly useful phosphites are dibutylhydrogen phosphite, trioleyl phosphite and triphenyl phosphite. Phosphite esters are generally dialkyl hydrogen phosphites.

A number of dialkyl hydrogen phosphites are commercially available, such as lower dialkyl hydrogen phosphites, which are preferred. Lower dialkyl hydrogen phosphites include dimethyl, diethyl, dipropyl, dibutyl, dipentyl and dihexyl hydrogen phosphites. Also mixed alkyl hydrogen phosphites are useful in the present inven- tion. Examples of mixed alkyl hydrogen phoεphiteε include ethyl, butyl; propyl, pentyl; and methyl, pentyl hydrogen phoεphiteε.

fD. Sulfur-. Phoεphorus-. or Sulfur- and Phosohorus-Co talninσ Antiwear Aσents

Although not required, the compoεition of t present invention may include a supplemental sulfur phosphorus-, or sulfur- and phosphorus-containing antiwe agent. The term antiwear agent is used in the specific tion and claims to refer to compounds which provide we protection properties to lubricating compositionε a functional fluids. The antiwear agent is useful in co trolling wear and may also act as an extreme presεu agent. These antiwear agents include (D-l) sulfuriz organic compounds, (D-2) hydrocarbyl phosphates, (D- phosphoruε-containing amides, (D-4) phosphorus-containi carboxylic esters, (D-5) phosphorus-containing ethers, a (D-6) dithiocarbamate-containing compounds. Of course, t above antiwear agents may provide other useful propertie such as friction modification. lΩzJΔ Sulfurized Organic Compositions

In one embodiment, the antiwear agent (D) is sulfurized organic composition (D-l) , preferably a sulf rized olefin, more preferably a mono-, or disulfide mixtures thereof. The sulfurized organic compounds usef in the present invention are generally characterized having sulfide linkages having from about 1 to about sulfur atoms, preferably about 1 to about 4, more prefer bly about 1 or about 2.

Materials which may be sulfurized to form t sulfurized organic compositionε of the preεent inventi include oilε, fatty acids or esters, olefins or polyolefi made thereof, turpeneε, or Diels-Alder adducts.

Oilε which may be εulfurized are natural synthetic oils including mineral oils, lard oil, carboxyl acid esters derived from aliphatic alcohols and fatty aci or aliphatic carboxylic acids (e.g., myristyl oleate a

oleyl oleate) sperm whale oil and synthetic sperm whale o substitutes and synthetic unsaturated esters or glyceride

Fatty acids generally contain from about 4 about 22 carbon atoms. The unsaturated fatty acids gene ally contained in the naturally occurring vegetable animal fats and oils may contain one or more double bon and such acids include palmitoleic acid, oleic acid linoleic acid, linolenic acid, and erucic acid. Th unsaturated fatty acids may comprise mixtures of acids suc aε those obtained from naturally occurring animal an vegetable oilε such as lard oil, tall oil, peanut oil soybean oil, cottonseed oil, sunflower seed oil, or whea germ oil. Tall oil is a mixture of rosin acids, mainl abietic acid, and unsaturated fatty acids, mainly oleic an linoleic acids. Tall oil is a by-product of the εulfat proceεε for the manufacture of wood pulp.

The most particularly preferred unsaturated fatt acid esters useful in this invention are the fatty oilε that is, naturally occurring esterε of glycerol with th fatty acidε deεcribed above, and synthetic esterε o similar structure. Examples of naturally occurring fat and oils containing unsaturation include animal fats suc as Neat'ε-foot oil, lard oil, depot fat, beef tallow, etc. Examples of naturally, occurring vegetable oils includ cottonseed oil, corn oil, poppy-seed oil, safflower oil, sesame oil, soybean oil, sunflower seed oil and wheat ger oil.

The fatty acid esters also may be prepared fro aliphatic olefinic acids of the type described above suc as oleic acid, linoleic acid, linolenic acid, and beheni acid by reaction with alcohols and polyols. Examples of aliphatic alcohols which may be reacted with the above- identified acids include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, the butanolε, etc.; and polyhydric alcohols including ethylene glycol,

propylene glycol, trimethylene glycol, neopentyl glyco glycerol, etc.

The olefinic compounds which may be sulfuriz are diverse in nature. They contain at least one olefin double bond, which is defined as a non-aromatic doub bond; that iε, one connecting two aliphatic carbon atom In its broadest sense, the olefin may be defined by t formula R R ^*2 C=CR' ³ R ^, \ wherein each of R' ¹ , R ^*2 , R ^*3 and R' ⁴ hydrogen or an organic.group. In general, the R ^* groupε the above formula which are not hydrogen may be satisfi by such groups as -C(R' ⁵ ) ₃ , -COOR ^*5 , -CON(R' ⁵ ) ₂ , -COON(R ^*5 ) -COOM, -CN, -X, -YR" ⁵ or -Ar, wherein: each R ^*5 is independently hydrogen, alkyl, alk nyl, aryl, substituted alkyl, substituted alkenyl substituted aryl, with the proviso that any two R ^*s grou can be alkylene or substituted alkylene whereby a ring up to about 12 carbon atoms is formed;

M is one equivalent of a metal cation (preferab Group I or II, e.g., sodium, potassium, barium, calcium) X is halogen (e.g., chloro, bromo, or iodo) ;

Y is oxygen or divalent sulfur; Ar is an aryl or substituted aryl group of up about 12 carbon atoms.

Any two of R ^*1 , R ^*2 , R ^*3 and R ^N may also togeth form an alkylene or substituted alkylene group; i.e., t olefinic compound may be alicyclic.

The olefinic compound is usually one in whi each R group which is not hydrogen is independently alky alkenyl or aryl group. Monoolefinic and diolefinic co pounds, particularly the former, are preferred, and esp cially terminal monoolefinic hydrocarbons; that is, tho compounds in which R ^*3 and R ^*4 are hydrogen and R ^*1 and R ^*2 a alkyl or aryl, especially alkyl (that is, the olefin aliphatic) having 1 to about 30, preferably l to about 1 more preferably 1 to about 8, and more preferably 1

about 4 carbon atoms. Olefinic compounds having about 3 30 and especially about 3 to 16 (most often less than carbon atoms are particularly desirable.

Isobutene, propylene and their dimers, trime and tetramers, and mixtures thereof are especially pr ferred olefinic compounds. Of these compounds, isobutyle and diisobutylene are particularly desirable because their availability and the particularly high εulfurcontai ing compositions which can be prepared therefrom. In another embodiment, the sulfurized organ compound (D-l) is a sulfurized terpene compound. The ter "terpene compound" as used in the specification and claim is intended to include the various isomeric terpene hydro carbonε having the empirical formula C ₁₀ H, ₆ , εuch aε con tained in turpentine, pine oil and dipenteneε, and th variouε synthetic and naturally occuring oxygen-containin derivatives. Mixtures of these various compounds generall will be utilized, especially when natural products such a pine oil and turpentine are used. Pine oil, for example which is obtained by destructive distillation of waste pin wood with super-heated steam comprises a mixture of terpen derivatives such as alpha-terpineol, beta-terpineol alpha-fenchol, camphor, borneol/isoborneol, fenchone estragole, dihydro alpha-terpineol, anethole, and othe mono-terpene hydrocarbons. The specific ratios and amount of the various components in a given pine oil will depen upon the particular source and the degree of purification. A group of pine oil-derived products are available commer cially from Hercules Incorporated. It has been found tha the pine oil productε generally known aε terpene alcohol available from Hercules Incorporated are particularl useful in the preparation of the sulfurized productε of th invention. Examples of such productε include alpha-Terpin eol containing about 95-97% of alpha-terpineol, a hig purity tertiary terpene alcohol mixture typically contain-

ing 96.3% of tertiary alcohols; Terpineol 318 Prime wh iε a mixture of isomeric terpineols obtained by dehydrat of terpene hydrate and contains about 60-65 weight perc of alpha-terpineol and 15-20% beta-terpineol, and 18-20% other tertiary terpene alcohols. Other mixtures and gra of useful pine oil products also are available from Herc les under such designations as Yarmor 302, Herco pine oi Y rmor 302W, Yarmor F and Yarmor 60.

In one embodiment, sulfurized olefins are p duced by (1) reacting sulfur monochloride with a sto chiometric excess of a low carbon atom olefin, (2) treati the resulting product with an alkali metal sulfide in t presence of free sulfur in a mole ratio of no less than 2 in an alcohol-water solvent, and (3) reacting that produ with an inorganic base. This procedure is described U.S. Patent 3,471,404, and the discloεure of U.S. Pate 3,471,404 is hereby incorporated by reference for i discussion of this procedure for preparing εulfuriz olefins and the sulfurized olefins thus produced. Genera ly, the olefin reactant contains from about 2 to 5 carb atoms and examples include ethylene, propylene, butylen isobutylene, amylene, etc.

The sulfurized olefins which are useful in t compositions of the present invention also may be prepar by the reaction, under superatmospheric pressure, olefinic compounds with a mixture of sulfur and hydrog sulfide in the presence of a catalyst, followed by remov of low boiling materials. This procedure for prepari sulfurized compositions which are useful in the prese invention is described in U.S. Patent 4,191,659, t disclosure of which is hereby incorporated by reference f its description of the preparation of useful sulfuriz compositionε.

In another embodiment, the sulfurized organ composition (D-l) is at least one sulfur-containing mater

al which comprises the reaction product of a sulfur sour and at least one Diels-Alder adduct in a molar ratio of least 0.75:1. Generally, the molar ratio of sulfur sour to Diels-Alder adduct is in a range of from about 0.75 about 4.0, preferably about 1 to about 2.0, more preferab about 1 to about 1.8. In one embodiment the molar ratio sulfur to adduct is from about 0.8:1 to 1.2:1.

The Diels-Alder adducts are a well-known, ar recognized class of compounds prepared by the diene εynth sis or Diels-Alder reaction. A summary of the prior a relating to this class of compounds is found in the Russi monograph, Dienovyi Sintes, Izdatelstwo Akademii Nauk SSS 1963 by A.S. Onischenko. (Translated into the Engli language by L. Mandel as A.S. Onischenko, Diene Synthesi N.Y., Daniel Davey and Co., Inc., 1964.) This monogra and references cited therein are incorporated by referen into the present specification.

Basically, the diene synthesis (Diels-Ald reaction) involves the reaction of at least one conjugat diene with at least one ethylenically or acetylenical unsaturated compound, these latter compounds being known a dienophiles. Piperylene, isoprene, methylisoprene, chlor prene, and 1,3-butadiene are among the preferred dienes fo use in preparing the Diels-Alder adducts. In addition, to these linear 1,3-conjugate dienes, cyclic dienes are also useful as reactants in th formation of the Diels-Alder adducts. Examples of thes cyclic dienes are the cyclopentadienes, fulveneε, l,3-cy clohexadieneε, 1,3-cycloheptadienes, 1,3,5-cycloeptatri enes, cyclooctatetraene, and 1,3,5-cyclononatrienes

Various substituted derivatives of these compounds ente into the diene synthesis.

Dienophiles, useful in preparing the Diels-Alde adducts, include those having at least one electron-accept ing groups selected from groups such aε formyl, cyano

nitro, carboxy, carbohydrocarbyloxy, hydrocarbyl- carbon hydrocarbylsulfonyl, carbamyl, acylcarbamyl, N-acyl-N- drocarbylcarbamyl, N-hydrocarbylcarbamyl, and N,N-dihyd carbylcarbamyl. The dienophiles include: nitroalken alpha,beta-ethylenically unsaturated carboxylic este acids or amides; ethylenically unsaturated aldehydes vinyl ketones. Specific examples of dienophiles include nitrobutene-1, alkylacrylates, acrylamide, dibutylacry amide, methacrylamide, crotonaldehyde; crotonic aci dimethyldivinyl ketone, methylvinyl ketone and the like.

Another clasε of dienophiles are those having least one carboxylic ester group represented by -C(0)0 where R„ is the residue of a saturated aliphatic alcohol up to about 40 carbon atoms, the aliphatic alcohol fr which -R,, is derived can be a mono or polyhydric alcoh such aε alkyleneglycols, alkanolε, aminoalkanols, alkox substituted alkanols, ethanol, ethoxy ethanol, propano beta-diethylamino-ethanol, dodecyl alcohol, diethyle glycol, tripropylene glycol, tetrabutylene glycol, hexano octanol, isooctyl alcohol, and the like. In this especia ly preferred class of dienophiles, not more than t -CfOJ-O- ^ groups will be present, preferably only o -CfOJ-O-R _o group.

In addition to the ethylenically unsaturat dienophiles, there are many useful acetylenically unsat rated dienophiles such as propiolaldehyde, methyl-ethyny ketone, propylethynylketone, propenylethynylketone, propi lic acid, propiolic acid nitrile, ethyl-propiolate, tetr lic acid, propargylaldehyde, acetylene-dicarboxylic aci the dimethyl ester of acetylenedicarboxylic acid, dibe zoylacetylene, and the like.

Cyclic dienophiles include cyclopentenedion coumarin, 3-cyanocoumarin, dimethyl maleic anhydrid 3,6-endomethylene-cyclohexenedicarboxylic acid, etc. Wi the exception of the unsaturated dicarboxylic anhydrid

derived from linear dicarboxylic acids (e.g., mal anhydride, methylmaleic anhydride, chloromaleic anhydrid this class of cyclic dienophiles are limited in commerc usefulness due to their limited availability and ot economic considerations.

Normally, the adducts involve the reaction equimolar amounts of diene and dienophile. However, if dienophile has more than one ethylenic linkage, it possible for additional diene to react if present in reaction mixture.

The sulfur-containing Diels-Alder adducts readily prepared by heating a mixture of a sulfur sour preferably sulfur and at least one of the Diels-Al adducts of the types discussed hereinabove at a temperat within the range of from about 110 ^β C to just below t decomposition temperature of the Diels-Alder adduct Temperatures within the range of about 110° to about 200 will normally be used.

The reaction can be conducted in the presence suitable inert organic solvents such as mineral oil alkanes of 7 to 18 carbons, etc., although no solvent generally necessary. After completion of the reaction, t reaction mass can be filtered and/or subjected to oth conventional purification techniques. The following examples illustrate the preparati of the sulfurized organic compound (D-l) useful in t present invention. Unless otherwise indicated, in t following examples as well as elsewhere in the specific tion and claims, temperature is in degrees Celsiuε, par and percentages are by weight and pressures are atmosphe ic.

EXAMPLE 1 A reaction mixture comprising 1175 parts moles) of the Diels-Alder adduct of butyl aerylate a isoprene, and 384 parts (12 moles) of sulfur flowers

heated for 0.5 hour at 108-110°C, and then to 155-165°C 6 hours while bubbling nitrogen gas through the react mixture at 0.25 to 0.5 SCFH. At the end of this heat period the reaction mixture is allowed to cool and filtered at room temperature. The product is allowed stand at room temperature for one day and is then ref tered. The filtrate which is the desired product wei 1278 parts.

EXAMPLE 2 A mixture of 910 parts (5 moles) of a bu aerylate-butadiene adduct prepared as in Example 7, parts (4 moles) of sulfur and 9 parts of triphenyl ph phite is prepared and heated with stirring while sweep with nitrogen to a temperature of 142°C over a period about one hour. The heating is continued to raise temperature to 185-186°C over about 2 hours and the mixt is maintained at 185-187°C for 3.2 hours. After allow the reaction mixture to cool to 96°C, the mixture filtered with filter aid, and the filtrate is the desi product containing 12.0% sulfur.

EXAMPLE 3 The general procedure of Example 2 is repea except that the mixture contain 259 parts (8.09 mole) sulfur. The product obtained in this manner contains 21. sulfur.

EXAMPLE 4 Sulfur (526 parts, 16.4 moles) is charged to jacketed, high-pressure reactor which is fitted with agitator and internal cooling coils. Refrigerated brine circulated through the coils to cool the reactor prior the introduction of the gaseous reactants. After seal the reactor, evacuating to about 2 torr and cooling, parts (16.4 moles) of isobutene and 279 parts (8.2 mol of hydrogen sulfide are charged to the reactor. reactor is heated using steam in the external jacket, t

temperature of about 182*C over about 1.5 hours. A maxim pressure of 1350 psig is reached at about 168°C during th heat-up. Prior to reaching the peak reaction temperatur the pressure starts to decrease and continues to decrea steadily as the gaseous reactants are consumed. Aft about 10 hours at a reaction temperature of about 182° the pressure is 310-340 psig and the rate of pressu change is about 5-10 psig per hour. The unreacted hydrog sulfide and isobutene are vented to a recovery syste After the pressure in the reactor has decreased to atmo pheric, the sulfurized mixture is recovered as a liquid.

The mixture is blown with nitrogen at about 100 to remove low boiling materials including unreacted isob tene, mercaptans and monosulfides. The residue aft nitrogen blowing is agitated with 5% Super Filtrol a filtered, using a diatomaceous earth filter aid. T filtrate is the desired sulfurized composition whi contains 42.5% sulfur.

EXAMPLE 5 Sulfur monochloride (2025 parts, 15.0 moles) i heated to 45°C. Through a sub-surface gas sparger, 146 partε (26.2 moles) of isobutylene gas are fed into th reactor over a 5-hour period. The temperature is main tained between 45-50°C. At the end of the εparging, th reaction mixture increases in weight of 1352 parts.

In a separate reaction vessel are added 215 parts (16.5 moles) of 60% flake sodium sulfide, 240 part

(7.5 moleε) sulfur, and a solution of 420 ml. of isopropa nol in 4000 ml. of water. The contents are heated to 40°C The adduct of the sulfur monochloride and isobutylen previouεly prepared iε added over a three-quarter hou period while permitting the temperature to riεe to 75°C

The reaction mixture iε refluxed for 6 hourε, and afterwar the mixture is permitted to form into separate layers. Th lower aqueous layer is discarded. The upper organic laye

is mixed with two liters of 10% aqueous sodium hydroxi and the mixture is refluxed for 6 hours. The organic la is again removed and washed with one liter of water. washed product iε dried by heating at 90°C and 30 mm. pressure for 30 minutes. The residue is filtered throu diatomaceous earth filter aid to give 2070 parts of a cle yellow-orange liquid.

EXAMPLE 6 A mixture of 100 parts of soybean oil and parts of commercial C ₁₆ α-olefins is heated to 175°C. und nitrogen and 17.4 parts of sulfur is added graduall whereupon an exothermic reaction causes the temperature rise to 205°C. The mixture is heated at 188°-200 ^β C. for hours, allowed to cool gradually to 90°C. and filtered yield the desired product containing 10.13% sulfur.

EXAMPLE 7 A mixture of 100 parts of soybean oil, 3.7 par of tall oil acid and 46.3 parts of commercial C ₁₅ _ _u α-olefi is heated to 165°C. under nitrogen and 17.4 parts of sulf is added. The temperature of the mixture rises to 191° It is maintained at 165 ^β -200 ^β C. for 7 hourε and iε th cooled to 90°C. and filtered. The product contains 10.1 sulfur. fD-2. Hydrocarbyl Phosphate In one embodiment, the antiwear agent (D) is hydrocarbyl phosphate (D-2). The phosphate may be a mono di- or trihydrocarbyl phosphate. The hydrocarbyl grou each independently contain from 1 to about 30 carbon atom preferably 1 to about 24 carbon atoms, more preferably 1 about 12 carbon atoms. In a preferred embodiment, ea hydrocarbyl is independently an alkyl or aryl group. Wh any group is an aryl group it contains from 6 to about carbon atoms, more preferably 6 to about 18 carbon atom Examples of hydrocarbyl groups include a butyl, amy

hexyl, octyl, oleyl or cresyl, with octyl and cresyl be preferred.

The hydrocarbyl phosphates (D-2) of the pres invention may be prepared by reacting phosphorus acid anhydride, preferably phosphorus pentaoxide with an alco at a temperature of about 30 ^β C to about 200°C, prefera 80°C to about 150 ^β C. The phosphorus acid is genera reacted with the alcohol in a ratio of about 1:3.5, pref ably 1:3. The hydrocarbyl groups may be derived from mixture of hydrocarbyl groups derived from the abo described commercial alcohols (see phosphite) . Also usef hydrocarbyl groups derived from Alfol 22+ alcohols a C _j g-C _j , primary alcohols having mostly, on an alcohol basi C _JJ alcohols. These Alfol alcohols can contain a fair large percentage (up to 40% by weight) of paraffin compounds which can be removed before the reaction desired.

Another example of a commercially availab alcohol mixture is Adol 60 which comprises about 75% weight of a straight chain C _Q primary alcohol, about 15% a C _JO primary alcohol and about 8% of C, ₈ and C^ alcohol Adol 320 comprises predominantly oleyl alcohol. The Ad alcohols are marketed by Ashland Chemical. A variety of mixtures of monohydric fatty alc hols derived from naturally occurring triglycerides a ranging in chain length of from C, to C _1S are available fr Procter & Gamble Company. These mixtures contain vario amounts of fatty alcohols containing mainly 12, 14, 16, 18 carbon atomε. For example, CO-1214 is a fatty alcoh mixture containing 0.5% of C ₁₀ alcohol, 66.0% of C ₁₂ alcoho 26.0% of C ₁₄ alcohol and 6.5% of C ₁₆ alcohol. Another gro of commercially available mixtures include the above described "Neodol" products available from Shell Chemica Co.

Fatty vicinal diols also are useful and th include those available from Ashland Oil under the gene trade designation Adol 114 and Adol 158. The former derived from a straight chain alpha olefin fraction C _j ,-C ₁₄ , and the latter is derived from a C^-Cn fraction.

In another embodiment, the hydrocarbyl phosph (D-2) may be a hydrocarbyl thiophosphate. Thiophospha may contain from one to about three sulfur atoms, prefe bly one or two sulfur atoms. The thiophosphates may h the same hydrocarbyl group as described above. Thioph phates are prepared by reacting one or more of the abo described phosphites with a βulfurizing agent includ sulfur, εulfur halideε, and sulfur containing compoun such as sulfurized olefins, sulfurized fats, mercapt and the like.

The following example relates to preparation thiophosphates.

EXAMPLE 8 A reaction vessel is charged with 1204 par (3.69 equivalents) of triphenylphosphite. The phoεphite heated to 160°C. where 112 parts (3.51 equivalents) sulfur is added over three hours. The reaction temperatu is maintained at 160°C. for four hours. The mixture filtered through diatomaceous earth and the filtrate is t desired product. The filtrate containε 8.40% phosphoro (8.7% theory) and 8.4% sulfur (8.50% theory). (D-3) Phosphorus-Containing Amides

In another embodiment, the antiwear agent (D) m be a phosphorus-containing amide (D-3). Phosphorus-co taining amides are generally prepared by reacting one the above-described phosphorus acids such as a phosphori phosphonic, phosphinic, thiophoεphoric, including d:*-_hi phoεphoric as well as monothiophosphoric, thiophosphinic thiophosphonic acids with an unsaturated amide, such as acrylamide. Preferably the ph&sphorus acid is a dithi

phosphorus acid prepared by reacting a phosphorus sulfi with an alcohol or phenol to form dihydrocarbyl dithiopho phoric acid. The hydrocarbyl groups may be those describ above for hydrocarbyl phosphates.

In one embodiment, the antiwear agent (D) is phosphorus-containing amide (D-3) repreεented by t formula:

wherein each X' ¹ , X' ² , X' ³ , X' ⁴ and X' ⁵ is independent oxygen or sulfur; each R' ¹ and R' ² is independently a hydrocarb group; each R' ³ , R' ⁴ , R' ⁵ , R' ⁶ and R' ⁷ is independently hydrogen, halogen or hydrocarbyl group; a and b independently are zero or 1; n is zero or 1; n' iε 1, 2 or 3; with the proviso that:

(1) when n' is 1, R' ¹ is hydrogen, -R ^# , -RO -ROR, -RSR or

R' -R'-N-R ^f ;

(2) when n' is 2, R' ¹ iε a coupling grou εelected from -R'-, -R*-, -R'-O-R'-, -R'-S-R'-, 0 S H R'

II I I I

-R'-C-R'-, -R'-C-R'-, -R'-N-R'- or -R'-N-R'- ; and

(3) when n' iε 3, R'* iε the coupling grou -R'-N-R'-

R'

Hherein each R ^# is independently a hydrocarbyl group of 1 about 12 carbon atoms; and each R' is independently arylene, or an alkylene or alkylidene group having from to about 12 carbon atoms. X' ¹ , X' ² and X' ⁵ are preferably oxygen. X' ³ and are preferably sulfur and a and b are preferably 1.

Each R' ¹ and R' ² is independently a hydrocarb group of from 1 to about 50 carbon atoms, more preferab from 1 to about 30 carbon atoms, more preferably from abo 3 to about 18 carbon atoms, more preferably from about 4 about 8 carbon atoms. Each R' ¹ and R' ² is preferably alkyl group. Examples of R' ¹ and R ^/2 are independent t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl, eicosy 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylpheny alkylnaphtyl, phenylalkyl, naphthylalkyl, alkylphenylalky alkylnaphthylalkyl groups, and the like.

Each R' ³ , R' ⁴ , R' ⁵ , R' ⁶ and R' ⁷ iε independently hydrogen or hydrocarbyl group of 1 from about 50 carb atoms, more preferably 1 to about 30, more preferably 1 about 18, more preferably 1 to about 8. Advantageousl each R' ³ , R' ⁴ , R' ⁵ , R' ⁶ and R' ⁷ is independently a hydroge an alkyl group of from 1 to about 22 carbon atoms; a cycl alkyl group of from about 4 to about 22 carbon atoms; or aromatic, an alkyl-εubεtituted aromatic or an aromatic-su stituted alkyl group of from about 4 to about 34 carb atomε.

Preferably each R' is independently an alkyle or alkylidene group having from 1 to about 12, more pr ferably from 1 to about 6, more preferably 1 carbon ato R' is preferably methylene, ethylene, or propylene wi preferably methylene.

The phosphorus-containing amides (D-3) may prepared by the reaction of a phosphoruε-containing aci preferably a dithiophosphoric acid, as described above wi an acrylamide such as acrylamide, N,N'-methylenebisacry

amide, ethacrylamide, crotonamide, and the like. T reaction product from above may be further reacted wi linking or coupling compounds, such as formaldehyde paraformaldehyde to form coupled compounds. The phosphorus-containing amides are known in t art and are disclosed in U.S. Patents 4,876,374, 4,770,8 and 4,670,169 which are incorporated by reference for i disclosure of the phosphorus amides, and their preparatio The following examples illustrate the phosphor containing amides (D-3) of the present invention.

EXAMPLE 9 To 1017 parts (3.0 equivalents) of 0,0-di- methyl-2-pentyl phosphorodithioic acid under nitrogen added 213 parts (3.0 equivalents) of acrylamide. T reaction exotherms to 65°C. and is held for one to thr hours at 65 ^β -75 ^β C. The product is filtered through diat maceouε earth and the filtrate is the desired product. T product contains 7.65% phosphorus (7.82% theory), 3.5 nitrogen (3.50% theory), and 16.05% sulfur (16.06% theory) EXAMPLE 10

To a mixture of 1494 parts (3.79 equivalents) O,0-di-isooctyl phosphorodithioic acid and 800 parts toluene under a nitrogen atmosphere are added 537 part (3.79) equivalents of 50% aqueous acrylamide solution ove a period of one hour. The reaction mixture exotherms t about 53°C. and 64 partε (1.93 equivalents) of paraforma ldehyde and 18 parts (0.095 equivalent) of p-toluenesulfo nic hydrate are added. Heating iε continued at reflu (91 ^β -126 ^β C.) for four hourε while collecting 305 partε o water. The mixture iε cooled to about 90°C. and 7.6 part (0.095 equivalent) of 50% aqueous sodium hydroxide solutio are added. Cooling iε continued to about 30°C. and vacuum is applied (15 mm. Hg) . Toluene solvent iε remove while raiεing the temperature to 110 ^β C. The reεidue i filtered through diatomaceous earth and the filtrate is th

desired product. The product contains 6.90% phosphor (6.75% theory) and 2.92% nitrogen (2.97% theory). fD-4. Phosphorus-containing carboxylic ester

In one embodiment, the antiwear agent (D) is phosphorus-containing carboxylic ester (D-4) . The pho phorus-containing esters may be prepared by reaction of o of the above-described phosphoruε acids, such as a dithi phoεphoric acid, and an alpha, beta unsaturated carboxyl compounds, such as acrylic and methacrylic acids or ester If the carboxylic acid is used, the ester may then formed by subsequent reaction with an alcohol. The unsat rated carboxylic esters may contain from about 4 to abo 40 carbon atoms, preferably 4 to about 24, more preferab 4 to about 12. Preferably, the unsaturated carboxylic ac is an allyl or vinyl ester of a carboxylic acid or an eεt of an unsaturated carboxylic acid.

The vinyl ester of a carboxylic acid may represented by the formula R ₆ CH=CH-0(0)CR ₇ wherein R ₆ is hydrogen or hydrocarbyl group having from 1 to about carbon atoms, preferably hydrogen or a hydrocargyl gro having 1 to about 12, more preferably hydrogen and R ₇ is hydrocarbyl group having 1 to about 30 carbon atom preferably 1 to about 12, more preferably 1 to about 8. Examples of vinyl esterε include vinyl acetate, vinyl ethylhexanoate, vinyl butanoate, vinyl crotonate.

In another embodiment, the unsaturated carboxyl ester is an ester of an unsaturated carboxylic acid such maleic, fumaric, acrylic, methacrylic, itaconic, citracon acids and the like. In one embodiment, the ester represented by the formula RgO-(0)C-HC=CH-C(0)OR, where each Rg is independently a hydrocarbyl group having 1 about 18 carbon atoms, preferably 1 to about 12, mo preferably 1 to about 8.

Examples of unsaturated carboxylic esters, usef in the present invention, include methylacrylate, ethy

acrylate, 2-ethylhexylacrylate, 2-hydroxyethylacrylat ethylmethacrylate, 2-hydroxyethylmethacrylate, 2-hydrox propylmethacrylate, 2-hydroxypropylacrylate, ethylmaleat butylmaleate and 2-ethylhexylmaleate. The above li includeε mono- aε well aε diesters of maleic, fumaric a citraconic acids.

In one embodiment, the phosphorus-containi carboxylic ester (P-4) is represented by the formula:

wherein each X" ¹ , X" ² , X" ³ and X" ⁴ iε independently oxygen sulfur;

R" ¹ and R" ² are independently hydrocarbyl group R" ³ , R" ⁴ and R" ⁵ are independently hydrogen hydrocarbyl groups;

R" ⁶ is a hydrocarbyl group; and a and b are independently zero or 1.

X" ¹ and X" ² are preferably oxygen, and X" ³ and X are preferably sulfur.

Each R" ¹ and R" ² is independently a hydrocarby group of from 1 to about 50 carbon atoms, more preferabl from 1 to about 30 carbon atoms, more preferably from 3 t about 18 carbon atoms, more preferably from 4 to about carbon atoms. Each R" ¹ and R" ² is preferably independentl an alkyl group. Exampleε of R" ¹ and R" ² include indepen dently t-butyl, iεobutyl, amyl, iεooctyl, decyl, dodecyl eicosyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkyl phenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkyl phenylalkyl, alkylnaphthylalkyl groups, and the like.

Preferably each R" ³ , R" ⁴ and R" ⁵ is independentl a hydrogen or hydrocarbyl group of from l to about 5

carbon atoms. More preferably, each R" ³ , R" ⁴ and R" ⁵ independently a hydrogen; alkyl group of from 1 to about carbon atoms; cycloalkyl groups of from about 4 to about carbon atoms; or aromatic, alkyl-subεtituted aromatic aromatic-εubstituted alkyl group of from about 4 to ab 34 carbon atoms.

R" ⁶ is preferably an alkyl group of from 1 about 22 carbon atoms; a cycloalkyl group of from about to about 22 carbon atomε; or an aromatic, alkyl-substitu aromatic or aromatic-substituted alkyl group of from abo 4 to about 34 carbon atoms.

In a particularly preferred embodiment, each and each R" ² is independently an alkyl group of from abo 3 to about 18 carbon atoms; X" ¹ and X" ² are oxygen; X" ³ a X" ⁴ are sulfur; R" ³ , R" ⁴ and R" ⁵ independently are hydrog or methyl; and n" is 1. fP-5. Phosphorus-Containing Ether

In one embodiment, the antiwear agent (D) is t reaction product of a phosphorus acid and vinyl ether. T vinyl ether is repreεented by the formula Rg-CH ₂ =CH- wherein each Rg iε hydrogen or a hydrocarbyl group having to about 30, preferably 1 to about 24, more preferably 1 about 12 carbon atomε and R, is a hydrocarbyl group havi 1 to about 30 carbon atoms, preferably 1 to about 24, mo preferably 1 to about 12. Examples of vinyl ethers inclu vinyl methylether, vinyl propylether, vinyl 2-ethylhexy ether and the like. fD-6. Dithiocarbamate Compounds

In one embodiment, the antiwear agent (D) is dithiocarbamate-containing compound (D-6) . The dithioca bamate-containing compounds may be dithiocarbamate ester dithiocarbamate amides, dithiocarbamic ethers, or alkylen coupled dithiocarbamates. The dithiocarbamate amide ether, and esters are prepared in a manner similar as th described above for phosphoruε-containing amides a

esters. Generally, the dithiocarbamic acid is reacted w an unsaturated amide, ether, or ester to form the dithio rbamate-containing compounds.

The dithiocarbamates used in making the dith carbamate-containing compound (D-6) are prepared by rea ing an amine with carbon disulfide or carbonyl sulfi The amines are generally any of the amines described abo Preferably, the amines are secondary amines. Speci amines include dimethyl amine, diethyl amine, dipro amine, dibutyl amine, diamyl amine, dihexyl amine diheptyl amine. Nonsymmetrical amines may also be used they include methylethyl amine, ethylbutyl amine, ethyla amine and the like. The unsaturated amide, ether, esters are preferably alpha, beta unsaturated compoun These compounds are deεcribed above. Preferably, the compounds include methylacrylate, ethylacrylate, 2-ethy hexylacrylate, 2-hydroxyethylacrylate, ethylmethacrylat 2-hydroxyethylmethacrylate, 2-hydryxypropylmethacrylate, hydroxypropylacrylate, an acrylamide, and acrylonitril preferably acrylamides. Acrylamides include acrylamid methacrylamide, bisacrylamide, bismethacrylamide, bi methyleneacrylamide, N-hydroxymethylacrylamide, N-mercapt methylacrylamide, N-(methyl, ethyl, bioether) acrylamid and N-(methyl, ethyl, ether) acrylamide. The dithiocarbamates are reacted with the unsat rated compounds at a temperature of about 25°C. to abo 125°C., preferably about 50°C. to about 100°C. , mo preferably 70°C. to about 90°C. The reaction may carrier out in the presence or absence of a εolven Solvents include hydrocarbons such aε toluene, xylen hexane, heptane, kerosene, fuel oil or oils of lubricati viscosity as well as chlorohydrocarbons including chlor form, carbon tetrachloride and the like. Alcohols may al be used, such as methanol, ethanol, bropanol, butanol, ethylhexanol and the like.

The following examples illustrate dithiocarba containing compounds (D-6) of the present invention.

EXAMPLE 11 A 1-liter flask is charged with 71g of acryla and 60 g of 95% ethanol. This mixture is stirred at temperature for % hour. An additional 40g of 95% eth is added to completely dissolve the acrylamide. To solution is added 76g of CS ₂ . Diamylamine (I57g) is a over 1.23 hours. An exotherm to 41°C. occurs. mixture is heated and the temperature is maintained at 5 55°C. for three hours. This mixture is subsequently vac stripped at 91°C. and 20 mm Hg to yield 113g of distilla The residue is filtered through diatomaceous earth fil aid with a filtrate yield of 281g of clear, yellow, visc liquid.

EXAMPLE 12

A 1-liter flask is charged with 172g of meth acrylate and 156g of CS ₂ . This mixture is stirred at r temperature and 146g of diethylamine are added over hours, producing an exotherm to 62°C. The mixture is t held at 55°C. for 2% hours and then is allowed to c while standing overnight. The reaction mixture is t stirred and is heated to approximately 55°C. and is held that temperature for two hours. The mixture is then vac stripped at 73°C. at 9 mm Hg. The residue is then filte through diatomaceous earth filter aid to give 447g o clear, brown filtrate.

In one embodiment, the dithiocarbamate-contain compound (D-6) is an alkylene-coupled dithiocarbama Alkylene-coupled dithiocarbamates may be represented by formula

S S

II II R, (RjoJN-C-S-Ru-S-fc-NfRjoJR,

wherein R _> , R ₁₀ and R _u are defined below.

Each R, is independently a hydrogen; a hydrocarb group having from 1 to about 18 carbon atoms, preferably to about 10, more preferably 1 to about 6; or K, tak together with R ₁₀ and the nitrogen atom form a five, six seven member heterocyclic group. Preferably, each R ₉ hydrogen or an alkyl group, more preferably hydrogen or propyl, butyl, amyl or hexyl group, more preferably a but group. The above list encompasses all stereo arrangemen these groups, including isopropyl, n-propyl, sec-buty isobutyl, and β-butyl.

Each R _I0 is independently a hydrocarbyl gro having from 1 to about 18 carbon atoms, or R _w taken toget er with R, and the nitrogen atom form a five, six or sev member heterocyclic group. When R _ϊ0 iε a hydrocarbyl grou it iε defined the same as when E, is a hydrocarbyl group.

When R and R ₁₀ are taken together with a nitrog atom to form a five, six or seven member heterocycl group, the heterocyclic group is a pyrrolidinyl, a pipe idinyl, a morpholinyl or a piperazinyl group. The heter cyclic group may contain one or more, preferably one three alkyl substituents on the heterocyclic ring. T alkyl substituents preferably contain from about one about six carbon atoms. Examples of heterocyclic grou include 2-methylmorpholinyl, 3-methyl-5-ethylpiperidinyl 3-hexylmorpholinyl, tetramethylpyrrolidinyl, piperazinyl 2,5-dipropylpiperazinyl, piperidinyl, 2-butylpiperazinyl 3,4,5-triethylpiperidinyl, 3-hexylpyrrolidinyl, and 3 ethyl-5-isopropylmorpholinyl groups. Preferably, th heterocyclic group is a pyrrolidinyl or piperidinyl group In one embodiment, each , iε independently hydrogen, or a hydrocarbyl group and each R ₁₀ iε indepen dently a hydrocarbyl group. In another embodiment, one and R ₁₀ taken together with a nitrogen atom form a five, si or seven member heterocyclic group while the other R ₉ i independently a hydrogen or a hydrocarbyl group and th

other io is a hydrocarbyl group. In another embodimen each R and Rι ₀ taken together with the nitrogen atom form five, six or seven member heterocyclic group.

R _u is a hydrocarbylene group having from 1 about 10 carbon atoms, preferably 1 to about 4, mo preferably 1 or 2. Preferably, R _n is an alkylene, arylen alkarylene, or arylalkylene. In one embodiment, R _u is alkylene group, preferably, a methylene or ethylene grou more preferably methylene. In one embodiment, R _n is an arylene grou alkarylene group, or arylalkylene group having from 6 about 10 carbon atoms, preferably 6 to about 8. Prefer bly, R _u is a phenylmethylene, phenylethylene, phenyld ethylene, phenylene, tolylene, etc. The alkylene-coupled dithiocarbamates useful the present invention may be prepared by the reaction of salt of a dithiocarbamic acid with a suitable dihalog containing hydrocarbon in the presence of a suitab reaction medium. Suitable reaction media include alcohol such as ethanol and methanol; ketones, such as acetone methylethylketone; ethers, such as dibutylether or dioxan and hydrocarbons, such as petroleum ether, benzene a toluene. The reaction is generally carried out at temperature within the range of about 25°C to about 150° more preferably about 25°C to about 100°C.

U.S. Patent 3,876,550 issued to Holubec describ lubricant compositionε containing alkylene dithiocarbam compoundε. U.S. Patentε 1,726,647 and 1,736,429 iεsued Cadwell describeε phenylmethylene bis(dithiocarbamates) a methods of making the same. These patents are incorporat by reference for their teachings related to dithiocarbama compounds and methods for preparing the same.

The following example relates to dithiocarbama containing compounds (D-6) .

EXAMPLE 13 A reaction vessel is charged with 1000 pa (7.75 moles) of di-n-butylamine, 650 parts (8.1 moles) a 50% aqueous solution of sodium hydroxide, and 1356 pa of water. Carbon disulfide (603 parts, 7.9 moles) iε ad to the above mixture while the temperature of the react mixture is maintained under about 63°C. After complet of the addition of the carbon disulfide, methylene dichl ide (363 parts, 4.3 moleε) is added over four hours wh the reaction mixture is heated to 88°C. After the addit of methylene dichloride, the mixture iε heated for additional three hourε at a temperature in the range 85°C-88 ^β C. The εtirring is stopped and the aqueous pha is drained off. The reaction mixture is stripped to 150 and 50 millimeters of mercury. The residue is filtere The filtrate has 6.5% nitrogen and 30.0% sulfur. Lubricating Compositionε

The inventors have discovered that the combin tion of (A) a basic alkali or alkaline earth metal salt an acidic organic compound, (B) a metal deactivator oth than a dimercaptothiadiazole and (C) a hydrocarbyl pho phite provide thermal stability to lubricating compos tionε. The basic metal salt (A) and hydrocarbyl phosphi (C) must be present so that the ratio of equivalents of ( based on total base number to equivalents of phosphite ( based on phosphorus atoms must be at least one. An exce of basic metal salt (A) may be used, i.e. the ratio total base number to equivalents of phosphite (C) may greater than one. The compoεitions of the present invention may used in lubricating compositions and functional fluid The compositions are useful in power transfer fluid including hydraulic, gear, automatic transmisεion a tractor fluidε, preferably hydraulic fluids.

In one embodiment, the compositions are fre zinc dithiophosphates. The use of the term "free refers to compositions which are substantially free of dithiophosphate. In another embodiment, the composit are free of phosphorus containing ester or amide. another embodiment, the compositions are free of zinc.

The lubricating compositions and functi fluids employ an oil of lubricating viscosity, inclu natural or synthetic lubricating oils and mixtures ther Natural oils include animal oils, vegetable oils, min lubricating oils, solvent or acid treated mineral oils, oils derived from coal or shale. Synthetic lubricating include hydrocarbon oils, halo-substituted hydroca oils, alkylene oxide polymers, eεters of dicarboxylic a and polyols, esters of phosphoruε-containing acidε, p meric tetrahydrofurans and silcon-based oils.

Specific examples of the oils of lubrica viscosity are described in U.S. Patent 4,326,972 European Patent Publication 107,282, both herein inco rated by reference for their disclosureε relating lubricating oilε. A basic, brief description of lubri base oils appears in an article by D. V. Brock, "Lubri Base Oils", Lubrication Engineerin . Volume 43, p 184-185, March, 1987. This article is herein incorpor by reference for its disclosures relating to lubrica oils. A description of oils of lubricating visco occurs in U.S. Patent 4,582,618 (column 2, line 37 thr column 3, line 63, inclusive), herein incorporated reference for its disclosure to oils of lubricating vis ity.

The overbased metal salt (A) is generall pre in an amount from about 0.005%, preferably about 0. more preferably about 0.075% up to about 5%, prefer about 1%, more preferably about 0.3% by weight of the t composition. The metal deactivator (B) is gener

present in an amount from about 0.001%, preferably 0.00 more preferably about 0.05% up to about 0.2%, prefera about 0.1%, more preferably about 0.05% by weight of total composition. The phosphite (C) is generally pres in an amount from about 0.01%, preferably about 0.05%, m preferably about 0.075% up to about 5%, preferably ab 1%, more preferably about 0.5% by weight of the to compoεition.

In another embodiment, the compositions of present invention include from about 0.01%, prefera about 0.05%, more preferably about 0.075% up to about 5 preferably about 2%, more preferably about 1% by weight a sulfur-, phosphorus- or sulfur- and phosphorus-containi antiwear agent (D) . When the basic metal salt (A) is basic magnesium salicylate then (D) is present in an amou up to about 0.40% by weight of the total compositio preferably from about 0.01%, more preferably about 0.05 up to about 0.4%, preferably about 0.3%, more preferab about 0.25%. The above combination of the present inventi may be used, in lubricants, in functional fluids or concentrates, by themselves or in combination with a other known additive which includes, but is not limited diεperεantε, antioxidants, anti-wear agents, extre pressure agents, emulsifiers, demulsifierε, fricti modifiers, anti-rust agents, corrosion inhibitors, viscoε ty improvers, pour point depressantε, dyes, and solvents improve handleability which may include alkyl and/or ar hydrocarbons. These additives may be present in vario amounts depending on the needs of the final product.

Disperεantε include but are not limited hydrocarbon substituted εuccinimides, succinamides, esters and Mannich disperεants as well aε materials functioni both as disperεantε and viscosity improvers. These dis persantε are deεcribed above as acylated nitrogen com

pounds, hydrocarbyl substituted amines and Mannich react products. The dispersants listed above may be post-trea with reagents such as urea, thiourea, carbon disulfi aldehydes, ketones, carboxylic acids, hydrocarbon subs tuted succinic anhydride, nitriles, epoxides, boron c pounds, phosphorus compounds and the like.

Antioxidants, corrosion inhibitors, extr pressure and anti-wear agents include but are not limi to chlorinated aliphatic hydrocarbons; boron-contain compounds including borate esters; and molybdenum c pounds.

Viscosity improvers include but are not limi to pol isobutenes, polymethyacrylate acid esterε, po acrylate acid esters, diene polymers, polyalkyl styren alkenyl aryl conjugated diene copolymerε, polyolefinε multifunctional viscosity improvers.

Pour point depressants are a particularly use type of additive often included in the lubricating o described herein. See for example, page 8 of "Lubric Additives" by C. V. Smalheer and R. Kennedy Smith (Lesi Hiles Company Publishers, Cleveland, Ohio, 1967) .

Anti-foam agents used to reduce or prevent formation of stable foam include silicones or orga polymers. Examples of these and additional anti-f compositions are described in "Foam Control Agents", Henry T. Kerner (Noyes Data Corporation, 1976) , pages 1 162.

These and other additives are described greater detail in U.S. Patent 4,582,618 (column 14, line through column 17, line 16, inclusive), herein incorpora by reference for its discloεure of other additiveε that be used in combination with the present invention.

The following are examples of lubricants use in the present invention.

Dibutylhydrogen phosphite

Triphenyl phosphite 10

Di-2-ethylhexyl phosphite

so Tolytriazole

I 15 Benzotriazole 0.01 0.01 0.01

Octyl imidazole

Sodium sulfonate (metal 0.08 20 ratio»20, total base number -440, and 36% by weight 100 neutral mineral oil)

Calcium sulfonate (metal 0.075 0.1 25 ratio-20, total base number "400, and 44% by weight 100 neutral mineral oil)

Calcium phenate (metal 0.1

! 30 ratio»5, total base number -•250, and 30% by weight 100

S. neutral mineral oil)

£

∞

s Table I

Lubricants (% by weight) (Continued) A P C D E F G _H_

Magnesium sulfonate (metal 0.1 0.1 0.1 ratio-15; total base number 10 -400; and 32% by weight 100 neutral mineral oil)

Magnesium salicylate (metal 0.1 0.1 0.1 ratio»6; total base number

I 15 »345; and 38% by weight 100 neutral mineral oil) I

Reaction product of 0.05 0.05 0.05 0.05 0.05 propylene oxide and tetra- 20 propenyl succinic acid

Phosphorus-containing amide 0.15 derived from diisooctyl di- thiophoεphoric acid, acryl- 25 amide and paraformaldehyde

o

00

S Table I

B CM Lubricants (% by weight) (Continued) A B C P _________ F _JL JL

Phosphorus-containing car¬ 0.1 0.2 boxylic ester derived from isobutyl-amyl dithiophos- 10 phoric acid, and methy1- acrylate, post-treated with propylene oxide

Dithiocarbamate containing 0.1 0.2

I

00 15 ester derived from dibutyl- m

I dithiocarbamate and methyl- aerylate

Methylene-bis(dibutyl 0.2 20 dithiocarbamate)

0.2 0.2

0.25 0.25 0.25 0.25 0.25 0.5 0.25 0.25 0.25 0.5 0.5 * * * * * * *

Dibutylhydrogen. hosphite

Triphenyl phosphite

10

Di-2-ethylhexyl phosphite

I Tolytriazole 0.005 0.05 0.005 0.01

¹ 15 Benzotriazole

Octyl i idazole 0.05

Sodium sulfonate (metal 20 ratio-20, total base number -440, and 36% by weight 100 neutral mineral oil)

Calcium sulfonate (metal 0.25 0.4 2.0 25 ratio-20, total base number -400, and 44% by weight 100 neutral mineral oil) g s^ Calcium phenate (metal ς 30 ratio=5, total base number §5 =250, and 30% by weight 100

O neutral mineral oil)

00

OS c_

P Table I

B PM Lubricants (% by weight) (Continued) K M W ^Q

Magnesium sulfonate (metal 1.0 0.4 ratio-15; total base number 10 -400; and 32% by weight 100 neutral mineral oil)

Magnesium salicylate (metal

I ratio—6; total base number o O 15 -345; and 38% by weight 100 neutral mineral oil)

Reaction product of 0.05 - 0.05 0.05 0.05 0.05 propylene oxide and tetra- 20 propenyl succinic acid

Phosphorus-containing amide derived from diisooctyl di- thiophosphoric acid, acryl- 25 amide and paraformaldehyde

I σv

I

00

© as en able I Lubricants (% by weight) (Continued) K L M N ^Q

Phosphorus-containing car¬ boxylic ester derived from isobutyl-amyl dithiophos- 10 phoric acid, and methyl aerylate, post-treated with propylene oxide o Dithiocarbamate containing

I 15 ester derived from dibutyl- dithiocarbamate and ethyl- acrylate

Methylene-bis(dibutyl 20 dithiocarbamate)

Tricresyl phosphate Product of Example 7 1.0 0.05 1.0 0.25

25 2,6-di-t-butyl phenol Di(nonylphenyl)amine

30 Mineral oil *=Balance

While the invention has been explained in rel tion to its preferred embodiments, it is to be understo that various modifications thereof will become apparent those skilled in the art upon reading the specificatio Therefore, it is to be understood that the inventi disclosed herein is intended to cover such modifications fall within the scope of the appended claims.