MXPA97004194A - Oil soluble complexes of deaccies containing phosphoroethics as additives for lubricated oil - Google Patents

Abstract

This invention provides an oil-soluble complex of uninsulated phosphorus-containing, oil-insoluble and an alcohol this complex is an anti-wear additive in lubricating oils, particularly fluids for automatic transmission.

Description

SOLUBLE COMPLEXES IN ACID OIL CONTAINING USEFUL PHOSPHORUS AS ADDITIVES FOR LUBRICATING OILS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention concerns oil-soluble complexes of phosphorus-containing acids, useful as additives in lubricating oils, particularly fluids for automatic transmissions. 2. Description of the Related Art It is well known that phosphorus-containing compounds are useful as anti-wear additives in lubricating oils.

Traditionally, these materials are reaction products of acids and phosphorus oxides with alcohols or long chain amines (C10 to C20) to make them soluble in oleaginous media. Examples are shown in U.S. Patent No. 5,185,090, where short-chain phosphites (C2 to C4) are trans-esterified with longer chain alcohols (thioalcohols) and mixtures of alcohols (thioalcohols) to yield oil-soluble products. .

U.S. Patent No. 5,443,744 discloses that the reaction of P205 with alcohols (thioalcohols) yields oil soluble products. EP 622,444-A1 discloses oil compositions for wet clutches or wet brakes containing inorganic phosphorus compounds alone or in combination with an organic polyol having at least two hydroxyl groups in a molecule. EP 454, 110-A1 discloses supposedly improved corrosion inhibition brake fluids, consisting essentially of a glycol, a glycol-based inhibitor, and acid phosphate ester reaction products of a phosphorus-containing compound with a monofunctional alcohol and a polyol. GB 2, 557, 158-A concerns fluid functional systems based on oil containing an alcohol or polyol. A composition formed by heating an ash-free dispersant with a combination of at least one inorganic phosphorous acid, a boron compound, and a polyol is preferred. It has now been found that insoluble or substantially insoluble phosphorus-containing acids can be solubilized without the need to react the phosphorus-containing acids with alcohols or amines. In particular, phosphorus mineral acids, such as phosphorous and phosphoric acids, can be solubilized by dissolving them at low temperatures in alcohols containing either ether or thioether linkages. Once the hydroxy polyether and the acidic material are complexed, the acid remains completely soluble. These non-aqueous solutions of strong mineral acids allow their addition to concentrate additives for lubricating oils or lubricating oils without violent exothermic reactions. SUMMARY OF THE INVENTION An embodiment of this invention relates to an oil soluble additive, wherein the additive comprises the complex of an acid containing phosphorus substantially insoluble in oil and an alcohol, the alcohol being a simple alcohol or mixtures of alcohols represented by (I) or (II), where (I) and (II) are: [HO - (- CH2-) qk, R t * r 4 (-CH-CH-0-) SH) t] d > R2 Rl Rl I R-XE (-CH2-) q -C and -H (II) OH where: m + n is an integer from 1 to 4; m is 0 or an integer from 1 to 4 n is 0 or an integer from 1 to 4 q is 0 or an integer from 1 to 6, R is a hydrocarbyl group C ^ -C3 ,, in structure (I), and is a CÍ-CJO hydrocarbyl group or hydrogen in structure (II); X is sulfur, oxygen, nitrogen or -CH2-; r is 0, or an integer from 1 to 5, with the proviso that when X is oxygen or nitrogen, r is 1, when X is sulfur, r is 1 to 3, when X is -CH2-, r is 1 to 5; s is O, or an integer from 1 to 12; t is 0, or an integer from 1 to 2, with the proviso that when X is sulfur, oxygen or -CH2-, t is 1, when X is nitrogen, t is 1 or 2; and is 0, or an integer from 1 to 10; and R? And R2 are independently a C-L-Cg alkyl or hydrogen. In another embodiment, this invention concerns a lubricating oil composition comprising a lubricating oil base material and an amount of the additive disclosed to be at least effective for imparting anti-wear properties to the base material. In consecuense, a further embodiment of this invention relates to a method of inhibiting wear in lubricating oil systems, including fluid systems for power transmissions, and particularly fluid systems for automatic transmissions. Still another embodiment of this invention relates to the method of forming the additive. Detailed Description of the Invention Acids Containing Phosphorous Acids containing phosphorus include those that are insoluble in oil or substantially insoluble in oil.

The term "substantially insoluble in oil" is intended to include those acids whose limited solubility would be improved by following the teachings of this disclosure.

Generally, these phosphorus-containing acids are classified as acids that contain a fraction that dissociates hydrogen by having a pKa of about -12 to about 5. The term pKa is defined as the logarithm of negative base 10 of the equilibrium dissociation constant of the acid in an aqueous solution measured at 25 CC. Suitable phosphorus-containing acids are phosphoric acid (H3P04), phosphorous acid (H3P03), phosphinyl acids (including phosphinic acids and phosphinous acids), and phosphonic acids (including phosphonic acids and phosphonous acids).

Partial or total sulfur analogs of the above phosphorus-containing acids are also suitable, including phosphorotetrathioic acid (H3PS4), phosphoromonothioic acid (H3P03S), phosphorodithioic acid (H3POS3), and phosphorotetrathioic acid (H3PS "). Phosphorous and phosphoric acids are the most preferred acids. Also contemplated as phosphorus-containing acids for the purposes of this invention are phosphorus-containing acid esters that are insoluble or substantially insoluble in oleaginous compositions. These compounds are included in the following structure: Rl? L where Z is greater than P (X) - or greater than P-; And it is H or X3R3; R1, R2 and R3 are each independently H or hydrocarbyl containing 1 to 6 carbon atoms, and X1, X2, X3 and X are independently S u 0, with the proviso that Y is H when Z is greater than P (X) -, and that when X1 and X2 are S, and Z is greater than P-, Y is -SR3. Types of compounds within the above structure include phosphites, phosphates, thiophosphites, thiophosphates, thionophosphites, thionophosphates, and thiol-containing phosphites and phosphates. Examples of the phosphorus-containing acid esters that can be used in this invention include at least one compound of the formula: (i) monohydrocarbyl phosphite (Y = H) monohydrocarbyl phosphate (Y = 0H) monohydrocarbyl thiolphosphate (Y = SH); or (ii) dihydrocarbyl phosphite (Y = H) dihydrocarbyl phosphate (Y = 0H) dihydrocarbyl thiolphosphate (Y = SH), where R1 and R2 may be the same or different and are hydrocarbyl, generally from 1 to 6, preferably from 2 to 4 carbon atoms. The hydrocarbyl thiono compounds that can be used include: monohydrocarbyl thiophosphite (Y = H) monohydrocarbyl thiophosphate (Y = 0H) monohydrocarbyl dithiophosphate (Y = SH); or (ii) dihydrocarbyl thionophosphite (Y = H) dihydrocarbyl thiophosphate (Y = OH) dihydrocarbyl dithiophosphate (Y = SH) where R 1 and R 2 are the same or different and are as defined above. The hydrocarbyl thiol containing phosphite compounds that can be used include at least one compound of the formula: (i) Ris 11 monohydrocarbyl thiophosphite (Y = H) X * "? monohydrocarbyl thiolphosphate (Y = 0H) H0 monohydrocarbyl dithiolphosphate (Y = SH); or (ii) Ris \ || j > p -? dihydrocarbyl thiophosphite (Y = H) s ^ dihydrocarbyl thiolphosphate (Y = 0H) dihydrocarbyl dithiolphosphate (Y = SH) As used in the description and the appended claims, the terms hydrocarbyl or hydrocarbon-based denote a group having one carbon atom directly linked to the rest of the molecule and having a predominantly hydrocarbon character within the context of this invention. Such groups include the following: (1) Hydrocarbon groups, ie, aliphatic (eg, alkyl or alkenyl). (2) Substituted hydrocarbon groups, ie groups containing non-hydrocarbon substituents. Those skilled in the art will be aware of suitable substituents. Examples include halo, hydroxy, nitro, cyano, alkoxy, acyl, etc. (3) Hetero groups, ie groups which, although predominantly hydrocarbon in the context of this invention, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur. The hydrocarbyl groups R1 and R2 can be the same or different hydrocarbyl groups, and generally, the total number of carbon atoms in R1 and R2 will not be greater than about 6. In a preferred embodiment, the hydrocarbyl groups will contain from 2 to about 6 carbon atoms each, and preferably from about 2 to about 4 carbon atoms. The hydrocarbyl groups R1 and R2 are aliphatic such as alkyl and alkenyl. Examples of groups R1 and R2 include methyl, ethyl, propyl, n-butyl, n-pentyl and n-hexyl. The groups R1 and R2 may each comprise a mixture of commercially available hydrocarbyl groups derived from alcohols. Acid esters are usually prepared by reacting P205 or P2S5 with the desired alcohol or thiol to obtain substituted phosphorus-containing acids.

The hydroxy or thiol compound should contain hydrocarbyl groups of from about 2 to about 6 carbon atoms. In the preparation of the substituted hydrocarbon-substituted thiophosphoric acids, any conventional method, such as the preparation described in U.S. Patent Nos. 2,552.57s, -2,579,038; and 2,689,220. For the preparation of substituted hydrocarbyl thiophosphinic acids, such as conventionally known disubstituted thiophosphinic acids, see Organic Chemistry, by F.C. Witmore, published by Dover Publications, New York, New York (1961), page 848. Phosphites and phosphates having the formula Dio are preferred in the present hydrocarbyl. || P-D3? = Q ^ where D1 is a hydrocarbyl group containing 1 to 6 carbon atoms, D2 is a hydrocarbyl group containing 1 to 6 carbon atoms, and D3 is H or OH. Most preferred are hydrocarbyl phosphites and phosphates, where D1 and D2 are hydrocarbyl groups containing 1 to 3 carbon atoms, D3 is H or OH. D1 and D2 can be an alkyl or alkenyl group, preferably an alkyl group such as methyl or ethyl. D3 can be -OD2 where D2 is as defined above. Preferably, the unsaturated members contain only double bonds. Examples of useful compounds are dimethyl, diethyl, dibutyl, methylethyl, hexyl, phosphites and phosphates. The phosphites and phosphates employed in this invention can be made using a single diol or mixtures of monoalcohols and diols. Such mixtures may contain from about 5 to about 95% by weight of any constituent, the other constituent or constituents being selected such that together they comprise from about 95 to about 5% by weight of the mixture. Mixes over single member components are often preferred. The phosphite reaction can be carried out at about 70 to about 250 ° C, with about 100 being preferred to about 160 ° C. An amount less than the stoichiometric amount of phosphite can be used, and is often preferred over a stoichiometric amount. Preferred phosphorus-containing acid esters are the mono, di and phosphorous acid hydrocarbon esters. Examples are: dimethyl phosphite, diethyl phosphite, dibutyl phosphite, and ethylmethyl phosphite. Most preferred are diethyl phosphites, dimethyl phosphites. Alcohols: The alcohols represented by the structures (I) and (II) form a broad description of the alcohols useful in this invention. It should be noted that the hydrocarbyl groups represented by R can be straight chain, branched, or cyclic. Representative hydrocarbyl groups within this definition include alkyl, alkenyl, cycloalkyl, aralkyl, alkaryl, aryl, and their analogs containing hetero. Among the suitable alcohols within the structure (I) are the alkoxylated alcohols (s greater than or equal to 1) and the alkoxylated polyhydric alcohols (s greater than or equal to 1 and m + n + t greater than or equal to 2), and mixtures thereof. Examples of particularly useful alkoxylated alcohols are nonyl phenol pentaethoxylate, pentaproxylated butanol, hydroxyethyl octyl sulfide, and diethoxylated dodecyl mercaptan. Examples of particularly useful alkoxylated polyhydric alcohols are oleyl amine tetraethoxylate, 5-hydroxy-3-thio butanol triethoxylate, thiobisethanol, diethoxylated tallow amine, dithiodiglycol, tetrapropoxylated cocoamine, diethylene glycol, and 1,7-dihydroxy-3,5-dithioheptane. Among the suitable alcohols within the structure (II) are the polyhydric alcohols (and greater than or equal to 2). Examples of particularly useful polyhydric alcohols are pentaerythritol, l-phenyl-2,3-propane diol, polyvinyl alcohol, 1,2-dihydroxy hexadecane, and 1,3-dihydroxy octadecane. A particularly useful combination of alcohols within structure (I) are those represented by (III), (IV) and their mixtures, where (III) and (IV) are: A-OH (III) and OH-B-OH (IV) where:) "-; Yi is R2SCH2-, R2SCHCH2-, RCHCH2-, CH3 CH2 I CH3 R2SCH-, R2SCH2CH-, or R2SCH2CH-; CH3 CH3 ^ CH2 CH3 n is an integer of 0-12; B is -CH2CH2SCH2CH2-, -CH2CH2SSCH2CH2-O R3CHCH2SR4-; and R2 and R3 are the same or different and are H or a hydrocarbyl group containing up to 50 carbon atoms. R4 is a hydrocarbon group containing up to 50 carbon atoms. The groups R2, R3 and R4 of the alcohols (III) and (IV) are hydrocarbyl groups which can be straight chain, branched or cyclic. Representative hydrocarbyl groups include alkyl, alkenyl, cycloalkyl, aralkyl, alkaryl, and their analogs containing hetero. Heterobyl-containing hydrocarbyl groups may contain one or more hetero atoms. A variety of hetero atoms can be used and are readily apparent to those skilled in the art. Suitable hetero atoms include, but are not limited to nitrogen, oxygen, phosphorus and sulfur.

When the hydrocarbyl group is alkyl, straight chain alkyl groups are preferred, typically those which are alkyl of about C2 to C18, preferably about C4 to C12, most preferably about C6 to C10. When the hydrocarbyl group is alkenyl, straight chain alkenyl groups are preferred, typically those which are alkenyl of about C3 to C18, preferably about C4 to C12, most preferably about C6 to C10. When the hydrocarbyl group is cycloalkyl, the group typically has about 5 to 18 carbon atoms, preferably about 5 to 16, most preferably about 5 to 12. When the hydrocarbyl group is aralkyl and alkaryl, the aryl portion typically it contains about C6 to C12, preferably 6 carbon atoms, and the alkyl portion typically contains about 0 to 18 carbon atoms, preferably 1 to 10. Straight chain hydrocarbyl groups are preferred over branched or cyclic groups . However, if the hydrocarbyl group constitutes the less preferred cycloalkyl group, it can be substituted with a straight chain alkyl group C-L to C18, preferably C2 to C8. Representative examples of suitable hydrocarbyl groups for alcohols (III) and (IV) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, t-octyl, nonyl, isononyl, t-nonyl. , secondary nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, palmityl, stearyl, isostearyl, octenyl, nonenyl, decenyl, dodecenyl, oleyl, linoleyl and linolenyl, cyclooctyl, benzyl, octylphenyl, dodecylphenyl and phenyloctyl. Preferred hydrocarbyl groups for alcohol (III) are hexyl, octyl, decyl and dodecyl. Preferred hydrocarbyl groups for alcohol (IV) are, for R 3: methyl, ethyl and propyl; and for R4, methylene, ethylene, propylene and isopropylene. The alcohols (III) and (IV) can be prepared by conventional methods well known in the art. For example, a thioalcohol is produced by oxyalkylation of a mercaptan containing the desired hydrocarbyl group. Suitable oxyalkylating agents include alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. The most preferred alkylene oxide is ethylene oxide. In this way, the preferred thioalcohol can be prepared by the following reaction equation: RSH + ethylene oxide »- RSCH2CH2OH (V) where R is as defined above. To produce the desired alcohol, a more preferred reaction route is: RCH = CH2 + HSR2OH »-RCH2CH2SR2OH (VI) where R and R2 are as described above. The reaction equation (VI) is preferred because it yields a higher percentage of the desired alcohol, while the reaction equation (V) can produce a single alcohol of the formula RS (CH2CH20-) nH, where n is greater than 1 and it varies. Complex Formation: An example of this invention is illustrated below: (a) A-OH + (b) OH-B-OH + H3P04 _ complex (VII) where A and B are as defined above, and 1 minor or same as a + 2b less than or equal to 6. A preferred complex of this invention is formed by a monoalcohol and can be represented by the following equation: (a) RSCH2CH2OH + H3P04 »- complex (VIII) where R is as defined above. Typically, the formation of mineral acid and alcohol complexes is carried out under atmospheric pressure and at temperatures ranging from about -10 to 65, preferably to 55, most preferably 35 to 45 ° C. At these temperatures, a complex forms without producing water. At temperatures above 65 ° C, water will possibly be produced, which shows that an etherification reaction has occurred. However, preparation at temperatures below 65 ° C will make it less likely that an etherification reaction will occur, which can result in ether insoluble ether compounds. Complex formation times vary from around 0.5 to around 4 hours. Sufficient complex formation can typically be achieved in about two hours.

One method of forming the complex is first to dissolve the appropriate amount of the phosphorus-containing acid in water. The acid can be purchased as an aqueous concentrate, ie 70% in water, thereby eliminating the dissolution step. The alcohols (or thioalcohols) are then added to the aqueous acid solution and the temperature raised to the desired level with stirring until a homogeneous mixture is produced. After the phosphorus-containing acids and alcohols have sufficient time to form complexes, it may be desirable to remove water, ie water that may have been used to dissolve the acid. The water can be removed at atmospheric pressure or the complex can be placed under vacuum. The times and temperatures of dispossession vary according to the desired degree of dispossession. Vacuum can vary from about -65 to about -90 kPa, stripping times from about 1 to about 2 hours, and temperatures from 50 to 65 ° C. Typically, sufficient water removal can be achieved at a vacuum of about -60 kPa, which is maintained for about 1 hour at 55 ° C. A second method of forming a stable complex is to dissolve the anhydrous acid in the alcohol mixture. Sometimes it is desirable to add a small amount of water to the physical mixture. Typically, 1-5% by weight of water will give a homogeneous, stable material. The complexes shown in equations (VII) and (VIII) can be added to a lubricating oil base material in an amount sufficient to impart anti-wear properties. The typical range is from 0.05 to 1.0% by weight of active ingredient 100%, preferably 0.4 to 0.8% by weight, most preferably 0.5 to 0.7% by weight. The preferred range corresponds to approximately 0.02 to 0.04% of the phosphorus mass in the oil. Desirably, a boron source with the complex of this invention is present in the lubricating oil base material. The presence of boron tends to reduce the deterioration of silicone-based seals. The boron source may be present in the form of borated dispersants, borated amines, borated alcohols, borated esters, or alkyl borates. Accordingly, by adding an effective amount of the complex of this invention to a lubricating oil and then placing the resulting lubricating oil within a lubrication system, the oil will inhibit wear in metal-to-metal contact in the lubricating fluid. The lubrication oil base material may contain one or more additives to form a fully formulated lubricating oil. Such lubricating oil additives include corrosion inhibitors, detergents, pour point depressants, anti-oxidants, extreme pressure additives, viscosity improvers, friction modifiers, and the like. These additives are typically described, for example, in Lubricant Additives, by C.V. Smalheer and R. Kennedy Smith, 1967, pp. 1-11, and in U.S. Patent No. 4,105,571, the disclosure of which is incorporated herein by reference. A fully formulated lubricating oil normally contains from about 1 to about 20% by weight of these additives. Borated or non-borated dispersants can also be included as additives in the oil, if desired. However, the precise additives used (and their relative amounts) will depend on the particular application of the oil. Applications contemplated for formulations of this invention include gear oils, industrial oils, lubricating oils, and fluids for power transmission, especially fluids for automatic transmission. The following list shows representative amounts of additives in lubricating oil formulations: Detergent additives particularly suitable for use with this invention include basic ash-producing salts of group I (alkali metals) or group II (alkaline earth metals) and transition metals with sulfonic acids, carboxylic acids, or organic phosphorus acids. Particularly suitable types of anti-oxidants for use in conjunction with the complex of this invention are the amine-containing and aromatic hydroxy-containing antioxidants. Preferred types of these anti-oxidants are alkylated diphenyl amines and 2,6-di-t-butyl substituted phenols. The additive complex of this invention can also be physically mixed to form a concentrate. A concentrate will generally contain a larger portion of the complex together with other desired additives and a smaller amount of the lubricating oil or other solvent. The complex and the desired additives (ie, active ingredients) are provided in the concentrate in specific amounts to give a desired concentration in a finished formulation when combined with a predetermined amount of the lubricating oil. The collective amounts of active ingredient in the concentrate are typically from about 0.2 to 50, preferably from about 0.5 to 20, most preferably from 2 to 20% by weight of the concentrate, the remainder being a lubricating oil base material or a solvent. The complex of this invention can interact with the amines contained in the formulation (i.e., dispersant, friction modifier, and anti-oxidant) to form quaternary ammonium salts. The formation of amine salts and quaternary ammonium, however, will not adversely affect the anti-wear characteristics of this invention. Suitable lubricating oil base materials can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. In general, the lubricating oil base material will have a viscosity in the range of about 5 to about 10,000 mm2 / s (cSt) at 40 ° C, although typical applications will require an oil having a viscosity that varies from about 10 to around 1,000 mm2 / s (cSt) at 40 ° C. Natural lubricating oils include animal oils, vegetable oils (for example, castor oil and tallow oil), petroleum oils, mineral oils, and oils derived from coal or shale. Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (eg, polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes) , poly (l-tens), etc., and their mixtures); alkylbenzenes (for example, dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzene, etc.); polyphenyls (for example, biphenyls, terphenyls, alkylated polyphenyls, etc.); diphenyl alkylated ethers, alkylated diphenyl sulphides, as well as their derivatives, analogs and homologs; and similar. Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and their derivatives, where the terminal hydroxyl groups have been modified by esterification, etherification, etc. This class of synthetic oils is exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1,000, polyethylene glycol diphenyl ether having a molecular weight of 500-1,000, polypropylene glycol diethyl ether having a molecular weight 1,000-1,500); and their monocarboxylic and polycarboxylic esters (for example, acetic acid esters, mixed C3-C8 fatty acid esters, and C13 oxo acid diester of tetraethylene glycol). Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylomalonic acids, alkenyl malonic acids, etc. ) with a variety of alcohols (for example, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azeleto, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of dimer of linoleic acid, and the complex ester formed by reacting one mole of sebasic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like. The esters useful as synthetic oils also include those made from C5 to C2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentae-ritritol, and the like. Synthetic hydrocarbon oils are also obtained from hydrogenated oligomers of normal olefins. Silicone-based oils (such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra (pt-butylphenyl) silicate, hex- (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxanes, and poly (methylphenyl) siloxanes, and the like. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and decylphosphonic acid diethyl ester), polymeric tetrahydrofurans, polyalphaolefins, and the like. The lubricating oil can be derived from unrefined, refined, re-refined oils, or their mixtures. The unrefined oils are obtained directly from a natural source or a synthetic source (for example, coal, shales or bitumen of tar sands) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retort operation, a petroleum oil obtained directly from distillation, or an ester obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to unrefined oils, except that the refined oils have been treated in one or more purification steps to improve one or more of their properties. Suitable purification techniques include distillation, hydrotreatment, dewaxing, solvent extraction, acid or base extraction, filtration and percolation, all of which are known to those skilled in the art. Re-refined oils are obtained by treating refined oils in processes similar to those used to obtain refined oils. These re-refined oils are also known as re-circulated or re-processed oils and are often further processed by techniques for removal of spent additives and products of oil disintegration. This invention may be better understood by reference to the following examples, which are not intended to restrict the scope of the appended claims. EXAMPLES Example 1 In a 5 liter round-bottomed flask equipped with a stirrer, thermometer, gaseous nitrogen inlet and condenser with Dean-Stark trap were charged 246 g (3.0 moles) of solid phosphorous acid and 52 g of water. The mixture was stirred to dissolve the phosphorous acid. When the phosphorous acid was dissolved, 570.8 g (3.0 mol) of octylthioethanol and 463 g (3.0 mol) of dithiodiglycol were charged into the flask. The mixture was stirred and heated at 50 ° C for 2 hours. The temperature was then raised to 60-65 ° C and the distilled water to a vacuum of 40 mm. When the evolution of water stopped, the product was cooled. The product was a light yellow liquid which was calculated to have 7.2% P and 22.3% S. Example 2 The procedure of Example 1 was repeated, with the materials charged to the flask being: 570 g (3 moles) of octylthioethanol, 246 g (3 moles) of H3P03 and 367 g (3 moles) of thiobisethanol. The product was a light yellow liquid which was calculated to have 7.9% P and 16.2% S. Example 3 In a 1 liter flask equipped with a stirrer, Dean-Stark trap, thermometer and dry ice trap were placed 190 g ( 1 mol) of octylthioethanol, 154 g (1 mol) of dithiodiglycol and 115 g (1 mol) of 85% phosphoric acid. Agitation was initiated, when an exotherm of 10 ° C was observed. The mixture was slowly heated to 50 ° C, at which time another exotherm of 15 ° C occurred. The temperature was maintained at 50 ° C for two hours. The pressure was then reduced to -85 kPa and the temperature raised to 65 ° C. Agitation was continued under these conditions for one hour, during which approximately 2 cm3 of water was collected in the Dean-Stark trap. The mixture was cooled and filtered. It gave a light yellow product which was calculated to have 6.8% P and 21.1% S. Example 4 The procedure of Example 3 was repeated with the materials charged to the reactor being: 570 g (3 moles) of octylthioethanol, 115 g (1 mol) ) of 85% phosphoric acid. The product was a clear yellow solution calculated to have 4.5% P and 14% S. Example 5 To a one liter flask equipped with agitator, thermometer and nitrogen sweep was charged 290 g (1 mole) of diethoxylated dodecyl mercaptan and 39.9 g (0.35 moles) of 85% phosphoric acid. When mixing, a slight exotherm was observed. The mixture was stirred at 25-30 ° C for one hour. The resulting aqueous white product (ie, clear and colorless) was calculated to have 3.3% P and 9.7% S. Example 6 The above procedure was repeated using 40.3 g (0.35 mole) of 70% phosphorous acid instead of the acid phosphoric. The resulting light yellow liquid was calculated to have 3.3% P and 9.7% S. Example 7 To a one liter flask equipped with a stirrer, thermometer and nitrogen sweep was charged 300 g (approximately 0.7 mole) of pentaethoxylated isooctyl phenol ( commercially known as Plexol 305®) and 30.1 g (0.26 moles) of 85% phosphoric acid. The mixture was stirred at 25-30 ° C for one hour. The light yellow product was calculated to have 2.4% P. Example 8 The procedure of Example 7 was repeated except that 30.6 g (0.26 mole) of 70% phosphorous acid was used in place of the phosphoric acid. The light yellow product was calculated to have 2.4% P. Example 9 To a 500 ml flask equipped with stirrer, thermometer and nitrogen sweep were charged 150 g (1.4 moles) of diethylene glycol and 108.5 g (0.95 moles) of phosphoric acid. at 85%. The mixture was stirred at 25-30 ° C for one hour. The light yellow product was calculated to have 11.3% P. Example 10 The procedure of Example 9 was repeated except that 110 g (0.95 mole) of 70% phosphorous acid was replaced by the phosphoric acid. The product was calculated to have 11.3% P. Example 11 To a one liter flask equipped with a stirrer, thermometer and nitrogen sweep was charged 300 g (about 0.8 mole) of a pentapropoxylated butanol (commercially known as LB 135®) and 18.0 g (0.16 moles) of 85% phosphoric acid. The mixture was stirred at 25-30 ° C for one hour. The product was calculated to have 1.6% P. Example 12 The procedure of Example 11 was repeated, except that 18.3 g (0.16 mole) of phosphorous acid was replaced by phosphoric acid. The product was calculated to have 1.6% P. Example 13 To a 500 ml flask equipped with stirrer, thermometer and nitrogen sweep were charged 152 g (1.0 mol) of 1-phenyl-2,3-propanediol and 75.6 g (0.66 g). moles) of 85% phosphoric acid. The mixture was stirred at 25-30 ° C for one hour. The aqueous white product was calculated to have 9.0% of P. Example 14 The procedure of Example 13 was repeated, except that 77 g (0.66 mol) of 70% phosphorous acid was used instead of phosphoric acid. The product was calculated to have 9.0% P. The stability as a product of the samples of Examples 1 to 14 was determined by observing the samples stored at room temperature and at 0 ° C for 90 days. All samples remained clear, without evident separation.

Claims (10)

1. CLAIMS 1. An oil-soluble additive, wherein the additive comprises a non-water-forming complex of an acid containing phosphorus substantially insoluble in oil and an alcohol, the alcohol being a single alcohol or mixtures of alcohols represented by (I) or ( II), where (I) and (II) are:
2. [HO - (- CH2-) q * 3-your R -Exr-C (-CiH-ClH-0-) s-H) tln (I) R2 Rl
3. Rl I R-Xr ((- CH2-) q- C- and H (II) OH where: m + n is an integer from 1 to 4, n is 0 or an integer from 1 to 4 n is 0 or an integer from 1 to 4, q is 0 or an integer from 1 to 6 R is a hydrocarbyl group ^ - ^ X is sulfur, oxygen or nitrogen, in structure (I), and is sulfur, oxygen, nitrogen or -CH2- in the structure (II); r is an integer from 1 to 5, with the proviso that when X is oxygen or nitrogen, r is 1, when X is sulfur, r is 1 to 3, when X is -CH2-, r is 1 to 5; s is 0 or an integer from 1 to 12; t is 0 or an integer from 1 to 2, with the proviso that when X is sulfur, oxygen or -CH2-, t is 1, when X is nitrogen, t is 1 or 2; and is 0 or 1; and R 5 and R 2 are independently an alkyl or hydrogen. 2. The additive of claim 1, wherein the acid has a pKa of about -12 to about 5 in aqueous solutions measured at 25 ° C. The additive of claim 2, wherein the acid 10 is phosphorous acid, phosphoric acid, dimethyl phosphite, diethyl phosphite, or mixtures thereof. The additive of claim 3, wherein the alcohol is selected from the group consisting of (III), (IV), and mixtures thereof, wherein (III) and (IV) are: 15 A-OH (III) and OH -B-OH (IV) where: and IA is CH- (0CH2CH2) n- or Yi-CH-ÍOCHzCH-Jn! -; 20 xl Xl CH3 X1 is H or R2SCH2-; Yx is R2SCH2-, R2SCHCH2-, R2SCHCH2-, CH3 CH2 I CH3;
4. CH3 n-L is an integer from 0 to 12; B is - CH2CH2 (-H2 H2 -, - CH2CH2SSCH2CH - O
5. R3CHCH2SR4-; where R2 and R3 are the same or different and are H or a hydrocarbyl group containing up to 50 carbon atoms; and R4 is a hydrocarbyl group containing up to 50 carbon atoms. 5. The additive of claim 4, wherein (III) and
6. (IV) are mixed with the acid in the molar ratio of alcohol to acid from 1: 1 to 6: 1, and the amount of (III) is at least twice the amount of (IV). 6. The additive of claim 5, wherein R2, R3 and R4 represent alkyl, alkenyl, cycloalkyl, aralkyl or alkaryl.
7. 7. The additive of claim 6, wherein A is R2SCH2CH2-, R2 is a Cx-C15 alkyl.
8. 8. A lubricating oil composition, comprising a larger amount of lubricating oil base material and an effective anti-wear amount of the additive of claim 1.
9. 9. A concentrated composition, comprising the additive of claim 1.
10. 10. A method of forming the additive of claim 1, wherein the acid and the alcohol are mixed at a temperature of about -10 to 65 ° C.