WO1989006237A1

WO1989006237A1 - Basic metal dihydrocarbylphosphorodithioates

Info

Publication number: WO1989006237A1
Application number: PCT/US1988/001083
Authority: WO
Inventors: Richard Yodice; Alan Curtis Clark
Original assignee: The Lubrizol Corporation
Priority date: 1988-01-04
Filing date: 1988-03-31
Publication date: 1989-07-13
Also published as: ZA883230B; IN172404B; AU1625688A

Abstract

Basic metal dihydrocarbylphosphorodithioates and phosphoromonothioates are prepared by employing a catalytic amount of an alkali metal or alkaline earth metal hydroxide or mixtures thereof. Also basic, multiple metal complexes of various dihydrocarbylphosphorodithioic acids have been developed. These salts and complexes are highly effective antiwear and antioxidant additives for functional fluids, e.g., lubricating oils.

Description

BASIC METAL DIHYDROCARBYLPHOSPHORODITHIOATES

INTRODUCTION TO THE INVENTION

This invention relates to basic metal dihydroca- rbylphosphorodithioates which impart effective antiwear properties and antioxidant properties to functional fluids such as lubricants, and to fuels. The invention also relates to a method for preparing basic mixed metal dihydrocarbylphosphorodithioates. Alkali metal hydroxides and specifically sodium hydroxide have been used in the preparation of various metal dihydrocarbylphosphorodithioates, such as zinc dialkyldithiophosphates. Stoichiometric amounts of the alkali metal hydroxides have been reacted with phosphorus- containing acids to form salts; these salts can subse¬ quently be reacted with zinc chloride and the like to prepare the desired dihydrocarbyldithiophosphate. Such methods and variations thereof are illustrated in U.S. Patents 2,794,780 to Wystrach et al; 2,797,238 to Miller et al; 3,843,530 to Niedzielski; and 4,123,370 to Meinhardt. U.S. Patent 2,797,238 to Miller et al discloses the preparation of various phosphinodithioic metal compounds, including zinc compounds, utilizing a stoichiometric amount of sodium hydroxide. U.S. Patents 3,347,790 and 4,089,793 to Meinhardt disclose generally the preparation of various zinc dialkyldithiophosphate compounds, including "normal" or "neutral" compounds and "basic" compounds. U.S. Patent 4,094,800 to Warne discloses a basic zinc dialkyldithiophosphate derived from primary alcohols containing from about 6 to about 20 carbon atoms.

In U.S. Patent 4,466,895 to Schroeck metal salts of one or more dialkylphosphorodithioic acids are disclosed that contain specific alkyl groups.

Mixed metal salts of dialkylphosphorodithioic acids and carboxylic acids are disclosed in U.S. Patent 4,308,154 to Clason et al.

The ammonia catalyzed preparation of zinc dihydro- carbyldithiophosphates is disclosed in U.S. Patent 4,377,527 to Sabol et al.

U.S. Patent 4,495,075 to Buckley discloses a method for preventing the precipitation of zinc dialkyldith- iophosphates, which contain a high percentage of lower alkyl group, from functional fluids.

The preparation of a mixture of zinc salts of O,0-dialkyldithiophosphoric acids are disclosed in U.S. Patent 4,101,428 to Crawford.

Lubricants containing zinc dithiophoεphates which exhibit both antiwear and antioxidant properties are disclosed in U.S. Patent 3,290,246 to Perotti et al.

U.S. Patent 2,552,570 to McNab et al, U.S. Patent

4,582,920 to Bridges, and European Patent 24146, granted

October 9 , 1985 to Exxon Research and Engineering Company, each disclose copper salts of phosphorus- and sulfur-containing acids.

Other salts, and processes for their production, are the subjects of U.S. Patents 3,428,662 to

Millendorf et al, 3,595,792 to Elliot et al, 4,085,053 to Caspari, 4,376,711 to Shaub, and 4,392,966 to Schlicht. Basic zinc O,0-dialkylphosphorodithioates are discussed in papers by: Burn et al, "The Structure of Basic Zinc 0 O-Dialkyl Phosphorodithioates," Chemical Communications, No. 17, pp. 394-396 (1965) ; Wystrach et al, "Basic Zinc Double Salts of 0, O-Dialkyl Phosphorodithioic Acids, "Journal of Organic Chemistry, Vol. 21, pp. 705-707 (1956); and Burn et al, "EXAFS Determination of the Structure of Basic Zinc OO-Di-n-butyl Phosphorodithioate" Journal of the Chemical Society, Chemical Communication, pp. 982-984 (1986) .

SUMMARY OF THE INVENTION

In accordance with the present invention, a novel method for preparing basic mixed metal dihydrocarbyl- phosphorodithioate compounds and complexes has been discovered. Further in accordance with the invention, novel basic, multiple metal complexes of the dialkyl¬ phosphorodithioates have been developed. Still further in accordance with the present invention, it has been found that the basic mixed metal dialkylphosphorodithioates and complexes thereof are useful as highly effective antiwear and antioxidant additives for functional fluids, including lubricant and fuel compositions. Still further in accordance with the present invention, a method for preparing basic mixed metal dihydrocarbylphosphorodi- thioates in the absence of a catalyst or promoter is provided. Still further in accordance with the invention, various functional fluids, including lubricants, automatic transmission fluids, hydraulic fluids and the like, comprising basic mixed metal dihydrocarbylphosphorodithio- ates and complexes thereof of the present invention are provided. In accordance with one aspect of the invention, a basic metal dihydrocarbylphosphorodithioate is prepared by reacting (A) at least one dihydrocarbylphosphorodithioic acid, or a normal acid metal salt thereof, with (B) at least one metal salt thereof, with (B) at least one metal oxide or hydroxide, wherein the metal is zinc, copper, nickel, chromium, iron, cobalt, manganese, calcium, barium, antimony, lead, aluminum, or tin in the presence of (C) a catalytic amount of at least one alkali metal or alkaline earth metal hydroxide , oxide, carbonate, or halide, wherein the metal of (C) is different from the metal of (B) .

These and other aspects of the invention will become more clear to those skilled in the art upon the reading and understanding of the following specification.

DETAILED DESCRIPTION OF THE INVENTION

A novel method for preparing basic metal dihydro- carbylphosphorodithioates and complexes thereof has been developed. In one embodiment of the invention, the method involves employing a catalytic amount of: at least one alkali metal hydroxide, -oxide, carbonate or halide; or at least one alkaline earth metal hydroxide, oxide, carbonate or halide, or mixtures thereof. The method further involves reacting at least one dihydrocarbylphosphoro- dithioic acid or the normal or acid metal salt of at least one of these acids with a metal oxide, or hydroxide, wherein the metal is selected from zinc, copper, nickel, chromium, iron, cobalt, manganese, barium, calcium, lead, antimony, aluminum or tin in the presence of a catalytic amount of at least one alkali metal hydroxide, oxide, halide or carbonate, or alkaline earth metal hydroxide, oxide, halide or carbonate; or mixtures thereof. It should be recognized that the metal of the catalyst will not be the same as the metal of the metal-containing reactant, e.g., when the reactant is a calcium or barium salt.

The term "catalytic amount," as used herein, denotes an amount of a material which promotes the efficient reaction of a dihydrocarbylphosphorodithioic acid, or salt, with a metal-containing reactant to form a basic salt; in general, a catalytic amount contains about 0.001 to 0.05 equivalents of an alkali or alkaline earth metal, per equivalent of phosphorus in the acid or its salt. Another embodiment of the invention involves the preparation of basic metal dihydrocarbylphoεphorodithio- ates by contacting a normal or acid metal salt of a dihydrocarbylphosphorodithioic acid with a metal- containing reactant in the absence of a catalyst or promoter. This aspect of the invention has been found to be particularly useful for preparing basic metal dihydrocarbylphosphorodithioates where the hydrocarbyl groups are aryl, aralkyl or long chain alkyl (e.g., greater than 24 carbon atoms) . As still another aspect of the invention, basic, multiple metal complexes of dialkylphosphorodithioic acids have been developed and may be represented by the follow¬ ing general formula:

[Z]_dt(RO)₂PSS] M_aX_b (I)

wherein M and X represent different metal cations selected from the group consisting of zinc, copper, chromium, iron, copper, manganese, calcium, barium, lead, antimony, tin and aluminum; Z is an anion selected from oxygen, hydroxide and carbonate; R is independently a linear or branched alkyl group of 1 to about 200 carbon atoms, or a substituted or unεubstituted aryl group of 6 to about 50 carbon atoms; a and b are integers of at least one and are dependent upon the respective oxidation states of M and X; y is a whole integer which is dependent upon the oxidation states of M and X; and d is an integer of 1 or 2. As used herein, the terms "hydrocarbyl" or "hydro¬ carbon-based" denote a radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention. Such radicals include the following:

(1) Hydrocarbon radicals; that is, aliphatic, e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl or cyclo- alkenyl) , aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic radicals, and the like, as well as cyclic radicals wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic radical) . (2) Substituted hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predomi¬ nantly hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents; examples are halo (particularly chloro and fluoro) , alkoxy, mercapto, nitro, nitroso, sulfoxy, and other groups.

(3) Hetero radicals; that is, radicals which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present 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. Terms such as "alkyl-based radical," "aryl-based radical" and the like have meaning analogous to the above with respect to alkyl and aryl radicals and the like.

The preferred radicals are usually hydrocarbon, that is, composed most often of carbon and hydrogen atoms, and are straight- or branched-chain alkyl.

By "basic" metal phosphorodithioate, it is intended, for the purposes of the present invention, to include those salts and/or complexes that have a higher ratio of equivalents of total metal to equivalents of the dihydrocarbylphosphorodithioic acid moiety, than that of the corresponding "neutral" or "normal" salt and/or complex. Partially neutralized dihydrocarbyl phospho- rodithioic acids, denoted "acid salts" herein, have a lower ratio of equivalents than that of the "Neutral" or "normal" salts. More specifically, a "neutral" or "normal" zinc phosphorodithioate has one equivalent of zinc per one equivalent of the phosphorodithioic acid moiety, i.e., a 1:1 ratio in this case. The corresponding "basic" zinc phosphorodithioate has more than one equivalent of zinc per one equivalent of the phosphorodithioic acid moiety, e.g., in certain instances the equivalent ratio will be 4:3 of zinc to phosphorodithioate.

In a preferred embodiment of the present invention, the salts and/or complexes of the present invention are derived from oxides or hydroxides of a metal selected from the group consisting of Zn, Cu, Ca, Ba, Ni, Cr, Fe, Co, Mn, Sn, Sb or mixtures thereof. In a most preferred embodiment, metal oxides are used and the metal is selected from Zn, Cu, Ca, Sb, Co or mixtures thereof.

Also in a preferred embodiment, the catalyst used in the method of the present invention is calcium hydroxide, potassium hydroxide or sodium hydroxide. In a most preferred embodiment, the catalyst is sodium hydroxide.

In a further preferred embodiment, the hydrocarbyl groups of the phosphorodithioic acid are, independently, linear or branched alkyl groups of 1 to about 200 carbon atoms or substituted or unsubstituted aryl group of 6 to about 50 carbon atoms. Representative of such alkyl or aryl groups include octyl, butyl, pentyl, propyl, oleyl, heptyl, hexyl , heptylphenyl, dodecylphenyl, nonylphenyl, cresyl and the isomers thereof. In a more preferred embodiment, the total number of carbon atoms in the dihydrocarbylphosphorodithioate moiety is at least 8. In a most preferred embodiment, the hydrocarbyl groups are, independently, selected from isooctyl, isopropyl, 4-methyl-2-pentyl and heptylphenyl.

With respect to the multiple metal complexes of the present invention, it has been found that the complex includes at least two different metals where one metal is included as the oxide or hydroxide and the other metal is included in the form of a salt of a phosphorodithioic acid, generally in a 1:3 molar ratio. More specifically, one mole of a metal oxide, for example, is complexed with 3 moles of a neutral metal dihydrocarbylphosphorodi- thioate. This ratio, of course, may vary dependent upon the ratio of reactants used to prepare the complex and the like.

A presently preferred basic salt for use in lubricating compositions is a mixed zinc and copper salt of a dihydrocarbylphosphorodithioic acid. This salt can be conveniently prepared by reacting a normal or acid zinc salt of the acid with a cuprous compound, such as cuprous oxide, in the presence of a catalytic amount of a material such as sodium hydroxide.

When the method of the invention is carried out in the absence of a catalyst, the reaction is conducted- by contacting a metal dihydrocarbylphosphorodithioate with a metal oxide. The metal-of the phosphorodithioate and the metal of the oxide may be the same or different and preferably are, independently, Zn, Cu, Ca, Sb and Co. This embodiment of the invention is most effective in preparing "basic" metal dihydrocarbylphosphorodithioa-tes where at least one hydrocarbyl group is aralkyl, e.g., heptylphenyl or dodecylphenyl, or is long-chain alkyl, e.g., greater than 24 carbon atoms.

The following examples are provided to illustrate various salts/complexes prepared by the method of the present invention as described above. These examples are provided for illustrative purposes only and are not to serve as a limitation on the scope of the invention, such scope being set out solely in the appended claims. EXAMPLE I

354 grams of zinc oxide and 225 grams of diluent oil were charged to the reaction container. At ambient temperature, 5.28 grams of a 50% sodium hydroxide solution was charged with stirring to the reaction container. After which, 1,982 grams of zinc 0,0-isobutyl/amyl (65:35) dithiophosphate was charged to the reaction container. After the initial exotherm, the reaction container was heated to 80°C and held at that temperature for 5 hours. The material was vacuum stripped at 100°C and lOmmHg. After filtering, 1,773 grams of product resulted.

EXAMPLE II

1,030 grams of zinc diheptylphenyldithiophosphate, 1.6 grams of a 50% sodium hydroxide solution, 50 grams of water and 32.1 grams of zinc oxide were charged to a reaction container with stirring. This mixture was heated to 80°C and held at that temperature. After filtering, 982.1 grams of product was produced.

EXAMPLE III

To a reaction container was charged 369 grams of zinc oxide and 309 grams of diluent oil. With stirring 4.8 grams of 50% sodium hydroxide solution was charged to the reaction container. After the addition was complete, 2,472 grams of zinc diisooctyldithiophosphate was charged to the reaction container. The reaction container was heated to 80°C and held at that temperature for 5 hours. After vacuum stripping at 100°C and 20mmHg, the material was filtered to yield 2,383 grams of product. EXAMPLE IV

A reaction container was charged with 147 grams of zinc diisooctyldithiophosphate, 4.1 grams of calcium hydroxide and 10 grams of water. The mixture was heated to 95°C and maintained at that temperature for 5 hours. The mixture was vacuumed stripped under reduced pressure at 110°C. Final product yielded 148 grams after filtering through diatomaceous earth filter aid.

EXAMPLE V

A reaction container was charged with 1,945 grams of zinc dialkyldithiophosphate (the alkyl groups are a 65/35 mixture of isobutyl/primary amyl respectively) , 77 grams of calcium hydroxide, 22 grams of water and 700 grams of toluene. This mixture was stirred and heated to 80°C and maintained at the temperature for 5 hours. The contents were then vacuum stripped at 100°C and lOmmHg. The product was filtered through diatomaceous earth filter aid yielding 2,000 grams of product.

EXAMPLE VI

The same procedure in the previous examples was followed utilizing 11 grams of calcium hydroxide, 10 grams of water and 291.4 grams of zinc dialkyldithiophosphate (the alkyl groups were a 65/35 mixture of isobutyl/amyl respectively) . 250 grams of product was obtained. EXAMPLE VII

A reaction container was charged with 1,000 grams of zinc diisooctyldithiophosphate, 26.88 grams of copper (I) oxide, 2.54 grams of a 50% sodium hydroxide solution and 25.4 grams of distilled water. This mixture was heated with stirring to 80°C and maintained at that temperature for 2.5 hours. The reaction mixture was then vacuumed stripped at 100°C and 15mmHg. The mixture was then filtered through diatomaceous earth filter aid to obtain 1,022 grams of product.

EXAMPLE VIII

A reaction container was charged with 30.1 grams of copper oxide, 2.0 grams of a 50% solution of sodium hydroxide, 25 grams of water and 350 grams of zinc di- alkyldithiophosphate (the alkyl groups are a 65/35 mixture of isobutyl/amyl respectively) . This mixture was heated to 100°C and maintained at that temperature for 1.5 hours. The mixture was then vacuum stripped and filtered through diatomaceous earth filter aid to give 320 grams of product.

EXAMPLE IX

The procedure for the above examples was followed to prepare the following product which was prepared from 34 grams of zinc oxide, 18 grams of copper (I) oxide, 33 grams of diluent oil and 256 grams of a dialkyldithiophoε- phoric acid (the alkyl groups are a 60/40 mixture of methylamyl/isopropyl, respectively) . The addition of these reactants took place over a period of 1.5 hours where the temperature was maintained at leεε than 60°C. After the addition was complete, the mixture was heated to 75°C and maintained at that temperature for 4.5 hours. After filtering through diatomaceous earth filter aid, 270 grams of product was obtained.

EXAMPLE X

The same procedure was followed as with the previous examples where the following reactants were used to prepare the desired product. 483 grams of a 1:1.1 equivalents mixture of diisooctyldithiophosphoric acid and copper (I) oxide, 13.43 grams of zinc oxide and 9.6 grams of distilled water. From this reaction mixture was obtained 450 grams of product.

EXAMPLE XI

A one liter reaction container was charged with 32 gramε of diluent oil and 25 grams of zinc oxide. 200 grams of di-4-methyl-2-=-pentyldithiophosphoric acid were added dropwiεe to the reaction mixture over a period of one hour. This mixture was then heated to 65°C and maintained at that temperature for one hour. After this one-hour period, 22 grams of manganese carbonate were added to the reaction mixture. Thiε addition waε followed by the addition of an additional 60 gramε of di-4-methyl- 2-pentyldithiophosphoric acid. This final reaction mixture waε heated to 75°C and maintained at that tempera¬ ture for 4 hours. The reaction mixture was then vacuum stripped at 95°C and lOmmHg and filtered through diatomaceous earth filter aid. 242 grams of the mixed metal product was obtained. The salts and complexes according to the present invention, which specific specieε have been illustrated in the above Examples I-XI, are versatile additiveε for lubricating compoεitionε and fuelε aε well as other functional fluids. The compositionε of the preεent invention are uεeful additives for imparting antioxidant propertieε and antiwear propertieε to various lubricant compositions. The complexes, i.e., additives, of the present invention also find use in functional fluids including fuel compositions, automatic transmission fluids, hydraulic fluids and the like. The salts and complexes of the present invention may also be uεed aε curing agentε for epoxy reεinε and the like.

The additiveε of the present invention may be formu- lated with a functional fluid by the direct blending of the compoεition to the particular functional fluid, e.g., lubricating oil, or it may be formulated with the func¬ tional fluid in the form of a concentrate. Such a concen¬ trate may be prepared by adding 1% to about 99% by weight of the composition or additive of the present invention to a εubεtantially inert, normally liquid organic diluent or εolvent εuch aε benzene, toluene, xylene, petroleum naphtha, mineral oil, ethylene glycol monomethyl ether or the like. The compoεitionε of the present invention, formulated with the particular functional fluid or concentrate, may contain other additiveε and chemiεtrieε εuch aε diεper- εantε, antioxidantε and the like. Such other additiveε and chemistrieε include, for example, detergents and disperεants of the ash-producing or ashleεε- type, corro¬ sion- and oxidation-inhibiting agents, pour point depressing agents, extreme preεsure agentε, color εtabilizers, antifoam agents and VI improvers. These other additiveε and chemistrieε are fully described and discloεed in U.S. Patents 3,541,014, 4,289,635, and 4,266,945, which disclosures of these patents relating to εuch other additiveε and chemistries are hereby incorporated by reference for such discloεureε.

A preferred diεperεant for uεe with the preεent invention is at least one substituted succinic acid or derivative thereof containing of subεtituent groups, wherein the substituent groups are derived from poly-alkylene, said polyalkylene being characterized by a Mn value of 500 to about 10,000 and a Mw/Mn value of 1.0 to about 4.0. It has alεo been found that the additive compounds of the present invention are useful in formulating various lubricant compoεitionε. The salt and/or metal complex additiveε of the preεent invention are uεeful in both mineral and synthetic lubricating oilε and greaεeε . Synthetic oilε include polyolefin oilε (e.g., polybutene oil, decene oligomer, and the like) , εynthetic eεters

(e.g., dinonyl sebacate, trioctanoic acid ester of tri- methylolpropane, and the like) , polyglycol oils, and the like. Greases are made from these oilε by adding a thickening agent such as sodium, calcium, lithium, or aluminum saltε of fatty acidε εuch aε εtearic acid. Theεe and similar thickening agentε are described in U.S. Patents 2,197,263, 2,564,561 and 2,999,066. The oilε and greases of the present invention are prepared by blending an amount of at least one salt or metal complex additive of the present invention sufficient to impart antiwear properties and antioxidant properties into the oil or grease. A useful concentration may range from about Q.l to about 5 weight percent. To further illustrate various functional fluid compositionε, specifically lubricant compoεitionε, com¬ prising the salts and complexes of the present invention, the following illustrative examples are provided. It is again pointed out that the following examples are provided for illustrative purposes only and are not to place any limitation on the scope of the invention where such scope iε εet out only in the claimε. All partε and percentages are by weight.

Typical compositions according to this invention are listed in the following table.

Reaction Product of Polybutenyl

Succinic Anhydride with Ethylene

Polyamine and

Pentaerythritol 2.50 Reaction Product of Polybutenyl

Succinic Anhydride with Ethylene

Polyamine and Carbon Disulfide 2.00 2.00

Reaction Product of Polybutenyl Succinic Anhydride with Ethylene Polyamine and

Boric Acid 1.00 1.00 Baεic Calcium Alkylbenzene- sulfonate 1.79 1.79 1.10

Basic Magnesium Alkylbenzene- sulfonate 1.35 0.65

Reaction Product of Maleic Anhydride- styrene Copolymer with Alcohol and

Amine 3.50 3.50 1.11 0.20

Hydrogenated Styrene- diene Block Copolymer Viscoεity Improver 9.00 Ethylene-propylene

Copolymer Viεcosity

Improver 7.00

Sulfurized Fat 0.50

Reaction Product of an Organo Sulfur Cmpd. with an Epoxide 0.50 0.50

Sulfurized Olefin 2.50 1.50

Ester of Dimercapto- thiadiazole 0.17 0.10 0.06 Sulfurized Diels-

Alder Adduct 0.60

Oil Soluble Phoεphoruε-Containing Extreme Preεεure Agent 1.47

The products of the various examples, contained in a fully formulated lubricating composition aε is described in Table I, were tested with regard to a Timken "OK" load teεt as well as a contact presεure teεt in accordance with ASTM D 2782, with the exception that in the "OK" load test the following procedural differences were made: 1. Test cup and block surfaces are merely "wetted" with test lubricant (approximately 5 drops on block) . No test sample is recirculated over the surfaces during the test.

2. Test duration is 5 minutes under load. 3. This procedure is run as an "OK" Load teεt, determining "OK" Load as in ASTM Test D 2782 except utilizing the following load increments: a. "OK" Load is lesε than or equal to 20 lbε.: Determine "OK" Load to the nearest 1 lb. b. "OK" Load is greater than 20 lbs.: Deter¬ mine "OK" Load using standard load incrementε aε deεcribed in ASTM Teεt D 2782.

The reεults from testing productε of the preεent invention according to the above teεt procedure are set out in Table II below.

n the sample.

Productε of the preεent invention illustrated in the above examples were also tested in the copper εtrip test in accordance with ASTM D 130. The results from testing productε of the preεent invention according to the above test procedure are set out in Table III below.

The invention also includes aqueous compositionε characterized by an aqueous phase with at least one salt or complex of the present invention disperεed or dissolved in said aqueous phase. Preferably, this aqueous phaεe iε a continuouε aqueous phase although, in some embodiments, the aqueous phase can be a discontinuouε phase. These aqueous compositionε uεually contain at leaεt about 25% by weight water. Such aqueouε compoεitions encompass both concentrates containing about 25% to about 80% by weight, preferably from about 40% to about 65% water; and water- based functional fluids containing generally over about 80% by weight of water. The concentrates generally contain from about 10% to about 90% by weight of at least one of the salt or complex materials of the invention. The water-baεed functional fluidε generally contain from about 0.05% to about 15% by weight of the εalt or complex materialε of the invention. The concentrates generally contain leεε than about 50%, preferably leεε than about 25%, more preferably lesε than about 15%, and still more preferably lesε than about 6% hydrocarbon oil. The water-baεed functional fluidε generally contain leεs than about 15%, preferably leεs than about 5%, and more prefer¬ ably leεε than about 2% hydrocarbon oil.

Theεe concentrateε and water-baεed functional fluidε can optionally include other conventional additives commonly employed in water-baεed functional fluids. These other additives include surfactantε; thickenerε; oil- soluble, water-insoluble functional additiveε εuch as antiwear agents, extreme pressure agentε, diεperεants, etc.; and supplemental additives such as corrosion- inhibitors, shear stabilizing agentε, bactericides, dyes, water-softeners, odor masking agents, anti-foam agents and the like.

The concentrateε are analogouε to the water-baεed functional fluidε except except that they contain less water and proportionately more of the other ingredients. The concentrates . can be converted to water-based functional fluids by dilution with water. This dilution iε uεually done by standard mixing techniques. This is often a convenient procedure εince the concentrate can be εhipped to the point of uεe before additional water is added. Thuε, the cost of shipping a subεtantial amount of the water in the final water-baεed functional fluid iε εaved. Only the water necessary to formulate the concen¬ trate (which iε determined primarily be ease of handling and convenience factors) , need be shipped.

Generally these water-based functional fluidε are made by diluting the concentrates with water, wherein the ratio of water to concentrate is usually in the range of about 80:20 to about 99:1 by weight. As can be seen when dilution iε carried out within these ranges, the final water-based functional fluid contains, at most, an insig¬ nificant amount of hydrocarbon oil.

In various preferred embodimentε of the invention, the water-based functional fluids are in the form of solutions while in other embodiments they are in the form of micelle disperεionε or microemulεionε which appear to be true εolutionε. Whether a solution, micelle diεpersion or microemulsion iε formed is dependent, inter alia, on the particular components employed. Also included within this invention are methods for preparing aqueouε compositions, including both concen- trates and water-based functional fluids, containing other conventional additives commonly employed in water-based functional fluids. These methods comprise the stepε of:

(1) mixing at leaεt one salt or complex additive of the invention with such other conventional additiveε either simultaneously or sequentially to form a dispersion or solution; optionally

(2) combining said dispersion or solution with water to form said aqueous concentrate; and/or (3) diluting said dispersion or solution, or concen¬ trate with water wherein the total amount of water used is in the amount required to provide the desired concentration of the components of the invention and other functional additives in said concentrates or said water- based functional fluids.

These mixing steps are preferably carried out using conventional equipment and generally at room or slightly elevated temperatures, usually below 100°C and often below^' 50°C. As noted above, the concentrate can be formed and then εhipped to the point of uεe where it iε diluted with water to form the deεired water-baεed functional fluid. In other inεtanceε, the finiεhed water-baεed functional fluid can be formed directly in the εame equipment uεed to form the concentrate or the diεperεion or solution. The surfactantε that are uεeful in the aqueouε compoεitionε of the invention can be of the cationic, anionic, nonionic or amphoteric type. Many εuch εurfac- tantε of each type are know to the art. See, for example, McCutcheon'ε "Emulsifiers & Detergentε," 1981, North American Edition, publiεhed by McCutcheon Diviεion, MC Publiεhing Co., Glen Rock, New Jerεey, U.S.A., which iε hereby incorporated by reference for its discloεureε in thiε regard.

Among the nonionic εurfactant typeε are the alkylene oxide-treated products, εuch aε ethylene oxide-treated phenols, alcohols, esters, a ineε and amides. Ethylene oxide/propylene oxide block copolymerε are alεo uεeful nonionic surfactantε. Glycerol esters and sugar esters are also known to be nonionic surfactantε. A typical nonionic εurfactant class useful with the present inven- tion are the alkylene oxide-treated alkyl phenols such as the ethylene oxide alkyl phenol condenεateε sold by the Rohm & Haaε Company. A specific example of theεe iε Triton X-100 which containε an average of 9-10 ethylene oxide unitε per molecule, haε an HLB value of about 13.5 and a molecular weight of about 628. Many other suitable nonionic surfactants are known; see, for example, the aforementioned McCutcheon's aε well as the treatise "Non-Ionic Surfactants" edited by Martin J. Schick, M. Dekker Co., New York, 1967, which is herein incorporat- ed by reference for itε diεcloεureε in thiε regard.

Aε noted above, cationic, anionic and amphoteric εurfactantε can also be used. Generally, these are all hydrophilic surfactantε. Anionic surfactantε contain negatively charged polar groupε while cationic εurfactantε contain poεitively charged polar groups. Amphoteric disperεantε contain both typeε of polar groupε in the εa e molecule. A general εurvey of useful εurfactantε iε found in Kirk-Othmer Encyclopedia of Chemical Technology, Second Edition, Volume 19, page 507 et seq. (1969, John Wiley and Son, New York) and the aforementioned compilation pub¬ lished under the name of McCutcheon's. These references are both hereby incorporated by reference for their discloεureε relating to cationic, amphoteric and anionic εurfactantε. Among the uεeful anionic surfactant types are the widely known carboxylate soaps, organo sulfateε, εulfo- nateε, εulfocarboxylic acids and their saltε, and phos- phateε. Uεeful cationic εurfactantε include nitrogen compoundε εuch aε amine oxides and the well-known quaternary ammonium salts. Amphoteric εurfactantε include amino acid-type materials and εimilar typeε. Various cationic, anionic and amphoteric diεperεantε are available from the induεtry, particularly from such companies aε Rohm & Haas and Union Carbide Corporation, both of Ameri¬ ca. Further information about anionic and cationic surfactants also can be found in the texts "Anionic Surfactants," Parts II and III, edited by W. M. Linfield, published by Marcel Dekker, Inc., New York, 1976, and "Cationic Surfactants," edited by E. Jungermann, Marcel Dekker, Inc., New York, 1976. Both of these references are incorporated by reference for their discloεureε in thiε regard.

Theεe εurfactantε, when used, are generally employed in effective amounts to aid in the diεperεal of the variouε additiveε, particularly the functional additiveε diεcussed below, in the concentrates and water-based functional fluids of the invention. Preferably, the concentrates can contain up to about 75% by weight, more preferably from about 10% to about 75% by weight of one or more of these surfactants. The water-based functional fluids can contain up to about 15% by weight, more prefer¬ ably from about 0.05% to about 15% by weight of one or more of these εurfactantε.

Often the aqueous compoεitionε of thiε invention contain at least one thickener for thickening said compo- sitions. Generally, these thickeners can be polysac- charideε, synthetic thickening polymers, or mixtures of two or more of these. Among the poly-εaccharideε that are useful are natural gums such as those disclosed in "Indus¬ trial Gums" by Whiεtler and B. Miller, publiεhed by Academic Preεε, 1959. Diεcloεureε in thiε book relating to water-εoluble thickening natural gumε in hereby incor¬ porated by reference. Specific exampleε of εuch gumε are gum agar, guar gum, gum arabic, algin, dextranε, xanthan gum and the like. Alεo among the polyεaccharideε that are uεeful aε thickenerε for the aqueouε compoεitionε of thiε invention are cellulose ethers and esters , including hydroxy hydrocarbyl celluloεe and hydrocarbylhydroxy cellulose and its saltε. Specific exampleε of εuch thickenerε are hydroxyethyl celluloεe and the εodium εalt of carboxymethyl celluloεe. Mixtureε of two or more of any such thickeners are also useful.

It is a general requirement that the thickener used in the aqueouε compositions of the preεent invention be soluble in both cold (10°C) and hot (about 90°C) water. This excludes such materials as methyl celluloεe which is soluble in cold water but not in hot water. Such hot- water-insoluble materials, however, can be used to perform other functions such as providing lubricity to the aqueous compositions of this invention.

These thickeners can also be synthetic thickening polymers. Many such polymers are known to those of skill in the art. Representative of them are polyacrylates, polyacrylamideε, hydrolyzed vinyl esterε, water-soluble homo- and interpolymers of acrylamidoalkane sulfonates containing 50 mole percent at least of acryloamido alkane sulfonate and other comonomers such as acrylonitrile, styrene and the like. Poly-n-vinyl pyrrolidones, homo- and copolymerε aε well aε water-εoluble εaltε of εtyrene, maleic anhydride and iεobutylene maleic anhydride copoly¬ merε can also be used as thickening agents. Other useful thickeners are known to those of skill in the art and many can be found in the list in the afore-mentioned McCutcheon Publication: "Functional Materials," 1976, pp. 135-147, incluεive. The disclosures therein, relative to water-εoluble polymeric thickening agentε meeting the general requirements set^' forth above are hereby incorporated by reference.

Preferred thickeners, particularly when the composi- tionε of the invention are required to be εtable under high shear applicationε, are the water-disperεible reac- tion products formed by reacting at least one hydro- carbyl-subεtituted εuccinic acid and/or anhydride repreεented by the formula

CHCOOH or R CHC

\ 0 /

CH.-COOH CH-C

wherein R iε a hydrocarbyl group of from about 8 to about 40 carbon atomε, with at least one water-disperεible ami e terminated poly(oxyalkylene) or at leaεt one water- dispersible hydroxy-terminated polyoxyalkylene. R prefer¬ ably has from about 8 to about 30 carbon atoms, more preferably from about 12 to about 24 carbon atoms, still more preferably from about 16 to about 18 carbon atoms. In a preferred embodiment, R is represented by the formula

R"CH=CH-CH- f R -

wherein R' and R" are independently hydrogen or straight chain or substantially straight chain hydrocarbyl groupε, with the proviεo that the total number of carbon atomε in R is within the above-indicated ranges. Preferably R' and R" are alkyl or alkenyl groups. In a particularly advan¬ tageous embodiment, R has from about 16 to about 18 carbon atoms, R' is hydrogen or an alkyl group of from 1 to about 7 carbon atoms or an alkenyl group of from 2 to about 7 carbon atoms, and R" iε an alkyl or alkenyl group of from about 5 to about 15 carbon atoms.

The water-diεperεible amine terminated poly(oxyalkyl¬ ene) ε are preferably alpha omega diamino poly(oxyethyl- ene)ε, alpha omega diamino pcly(oxypropylene) pol (oxyethylene) poly(oxypropylene) s or alpha omega diamino propylene oxide capped poly(oxyethylene) ε. The amine-terminated poly(oxyalkylene) can alεo be a urea condensate of such alpha omega diamino poly(oxytheylene) s, alpha omega diamino poly(oxypropylene) poly(oxyethylene) poly(oxypropylene) s or alpha omega diamino propylene oxide capped poly(oxyethylene) s. The amine-terminated poly(oxy¬ alkylene) can also be a polyamine (e.g., triamino, tetra- mino, etc.) polyoxyalkylene provided it is amine-terminated and it is water-dispersible.

Examples of water-dispersible amine-terminated poly(oxyalkylene) s that are useful in accordance with the present invention are disclosed in U.S. Patents 3,021,232; 3,108,011; 4,444,566; and RE 31,522. The disclosures of these patents are incorporated herein by reference. Water-dispersible amine terminated poly(oxyalkylene) s that are uεeful are commercially available from the Texaco Chemical Company under the trade name "Jeffamine."

The water-diεperεible hydroxy-terminated polyoxy- alkyleneε are conεtituted of block polymers of propylene oxide and ethylene oxide, and a nucleus which is derived from organic compounds containing a plurality of reactive hydrogen atoms. The block polymerε are attached to the nucleuε at the εites of the reactive hydrogen atoms. Examples of these compounds include the hydroxy-terminated polyoxyalkylenes which are represented by the formula

H(OH₄C₂)_b(OH₆C₃)_a ^0) _&(C^O)_bH

NCH₂CH₂N

H(0H₄C₂)_b(0H₆C₃)_a^ ^ (C₃H₆0)_a(C₂H₄0)_bH

wherein a and b are integers such that the collective molecular weight of the oxypropylene chains range from about 900 to about 25,000, and the collective weight of the oxyethylene chains constitute from about 20% to about 90%, preferably from about 25% to about 55% by weight of the compound. These compoundε are commercially available from BASF Wyandotte Corporation under the trade name "Tetronic." Additional examples include the hydroxy- terminated polyoxyalkylenes represented by the formula

HO(C₂H₄0)_χ(C₃H₆0)_y(C₂H₄0)_zH

wherein y is an integer such that the molecular weight of the oxypropylene chain is at least about 900, and x and z are integers εuch that the collective weight of the oxyethylene chains constitute from about 20% to about 90% by weight of the compound. These compounds preferably have a molecular weight in the range of about 1,100 to about 14,000. These compounds are commercially available from BASF Wyandotte Corporation under the trade name "Pluronic." Useful hydroxy-terminated polyoxyalkylenes are diεcloεed in U.S. Patents 2,674,619 and 2,979,528, which are incorporated herein by reference. The reaction between the carboxylic agent and the amine- or hydroxy-terminated polyoxyalkylene can be carried out at a temperature ranging from the highest of the melt temperatures of the reaction components up to the loweεt of the decompoεition temperatureε of the reaction componentε or products. Generally, the reaction is carried out at a temperature in the range of about 60°C-^*"to about 160°C, preferably about 120°C to about 160°C. The ratio of equivalentε of carboxylic agent to polyoxy¬ alkylene preferably rangeε from about 0.1:1 to about 8:1, preferably about 1:1 to about 4:1, and advantageously about 2:1. The weight of an equivalent of the carboxylic agent can be determined by dividing itε molecular weight by the number of carboxylic functionε preεent-. The weight of an equivalent of the amine-terminated polyoxyalkylene can be determined by dividing itε molecular weight by the number of terminal amine groups present. The weight of an equivalent of the amine-terminated polyoxyalkylene can be determined by dividing itε molecular weight by the number of terminal amine groupε preεent. The number of terminal amine and hydroxyl groups can usually be determined from the structural formula of the polyoxyalkylene or empiri¬ cally through well-known procedures. The amine/acids and ester/acidε formed by the reaction of the carboxylic agent and amine-terminated or hydroxy-terminated polyoxyalkylene can be neutralized with, for example, one or more alkali metals, one or more amines, or a mixture thereof, and thus converted to amide/salts or ester/salts, reεpectively. Additionally, if theεe amide/acidε or eεter/acidε are added to concentrateε or functional fluids containing alkali metals or amines, amide/salts or eεter/salts uεually form, in situ.

South African Patent 85/0978 is incorporated herein by reference for its teachings with respect to the use of hydrocarbyl-substituted εuccinic acid or anhydride/ hydroxy-terminated poly(oxyalkylene) reaction productε as thickeners for aqueouε compoεitionε.

When the thickener iε formed uεing an amine- terminated poly (oxyalkylene) , the thickening characteris- ticε of εaid thickener can be enhanced by combining it with at least one εurfactant. Any of the surfactants identified above under the subtitle "Surfactants" can be uεed in this regard. When such surfactantε are used, the weight ratio of thickener to εurfactant iε generally in the range of from about 1:5 to about 5:1, preferably from about 1:1 to about 3:1.

Typically, the thickener iε preεent in a thickening amount in the aqueouε compoεitionε of thiε invention. When uεed, the thickener iε preferably preεent at a level of up to about 70% by weight, preferably from- about 20% to about 50% by weight of the concentrates of the invention. The thickener is preferably preεent at a level in the range of from about 1.5% to about 10% by weight, prefera¬ bly from about 3% to about 6% by weight of the functional fluids of the invention.

The functional additives that can be used in the aqueouε systemε are typically oil-εoluble, water-inεoluble additiveε which function in conventional oil-baεed εyεtemε aε extreme preεεure agentε, antiwear agents, load-carrying agents, dispersants, friction modifierε, lubricity agentε, etc. They can also function as anti-slip agents, film formers and friction modifiers. As is well known, such additives can function in two or more of the above- mentioned wayε; for example, extreme preεεure agentε often function aε load-carrying agents. The term "oil-soluble, water-insoluble functional additive" refers to a functional additive which iε not εoluble in water above a level of about 1 gram per 100 milliliters of water at 25°C, but is soluble in mineral oil to the extent of at least 1 gram per liter at 25°C. These functional additives can also include certain solid lubricants such as graphite, molybdenum disulfide and polytetrafluoroethylene and related solid polymers.

These functional additives can alεo include friction- al polymer formerε. Briefly, theεe are potential polymer forming materialε which are diεperεed in a liquid carrier at low concentration and which polymerize at rubbing or contacting εurfaceε to form protective polymeric filmε on the εurfaceε. The polymerizationε are believed to reεult from the heat generated by the rubbing and, poεεibly, from catalytic and/or chemical action of the freεhly expoεed surface. A specific example of such materialε iε dili- noleic acid and ethylene glycol combinationε which can form a polyeεter frictional polymer film. Theεe materialε are known to the art and deεcriptionε of them are found, for example, in the journal "Wear," Volume 26, pageε 369-392, and Weεt German Publiεhed Patent Application 2,339,065. Theεe diεcloεureε are hereby incorporated by reference for their diεcuεεions of frictional polymer formers. Typically these functional additives are known metal or amine εaltε of crgano εulfur, phoεphorus, boron or carboxylic acids which are the same as or of the same type as used in oil-baεed fluids. Typically εuch εaltε are of carboxylic acids of 1 to 22 carbon atoms including both aromatic and aliphatic acidε; εulfur acidε εuch aε alkyl and aromatic sulfonic acids and the like; phosphorus acids such as phosphoric acid, phosphoruε acid, phoεphinic acid, acid phoεphate esters and analogous sulfur homologs such aε the thiophosphoric and dithiophosphoric acid and related acid eεters; boron acids include boric acid, acid borateε and the like. Useful functional additives also include metal dithiocarbamateε such as molybdenum and antimony dithiocarbamates; aε well aε dibutyl tin εulfide, tributyl tin oxide, phoεphateε and phoεphiteε; borate amine εaltε, chlorinated waxeε; trialkyl tin oxide, molybdenum phoεphateε, and chlorinated waxes.

Many such functional additives are known to the art. For example, descriptionε of additives useful in conven¬ tional oil-based syεtems and in the aqueous εystems of thiε invention are found in "Advanceε in Petroleum Chemiε- try and Refining," Volume 8, edited by John J. McKetta, Interεcience Publiεherε, New York, 1963, pageε 31-38 incluεive; Kirk-Othmer "Encyclopedia of chemical Technolo¬ gy," Volume 12, Second Edition, Interscience Publisherε, New York, 1967, page 575 et εeq.; "Lubricant Additiveε" by M. W. Ranney, Noyes Data Corporation, Park Ridge, New Jerεey, U.S.A., 1973; and "Lubricant Additiveε" by C. V. Smalheer and R. K. Smith, The Leziuε-Hileε Co., Cleveland, Ohio, U.S.A. Theεe referenceε are hereby incorporated by reference for their diεclosures of functional additives useful in the compositionε of thiε invention..

In certain of the typical aqueous compoεitionε of the invention, the functional additive iε a sulfur or chloro- εulfur extreme preεεure agent, known to be uεeful in oil-baεe εystemε. Such materials include chlorinated aliphatic hydrocarbons, εuch as chlorinated wax; organic εulϊides and polyεulfideε, εuch as benzyl-diεulfide, biε- (chlorobenzyl) diεulfide, dibutyl tetraεulfide, εulfu- rized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adductε; phoεphoεul- furized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esterε such aε the dihydrocarbon and trihydro- carbon phosphites, i.e., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phoεphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; metal thiocarbamateε, such as zinc dioctyl-dithiocarbamate and barium heptylphenol dithiocarbamate; and Group II metal salts of a phosphorodithioic acid, such as zinc dicyclohexyl phosphorodithioate.

The functional additive can alεo be a film former such as a synthetic or natural latex or emulsion thereof in water. Such latexes include natural rubber latexes and polystyrene butadienes synthetic latex. The functional additive can alεo be an anti-chatter or anti-squawk agent. Examples of the former are the amide metal dithiophosphate combinationε εuch aε disclosed in West German Patent 1,109,302; amine εalt-azomethene combinationε εuch aε diεcloεed in Britiεh Patent Specification 893,977; or amine dithiophoεphate εuch aε diεclosed in U.S. Patent 3,002,014. Examples of anti-squawk agents are N-acyl-εarcoεineε and derivatives thereof such as disclosed in U.S. Patents 3,156,652 and 3,156,653; εulfurized fatty acidε and eεterε thereof εuch aε diεcloεed in U.S. Patentε 2,913,415 and 2,982,734; and eεterε of dimerized fatty acidε εuch aε disclosed in U.S. Patent 3,039,967. The above-cited patents are incorporated herein by reference for their discloεure aε pertinent to anti-chatter and anti-εquawk agentε uεeful aε a functional additive in the aqueouε εyεtems of the preεent invention. Specific examples of functional additives uεeful in the aqueouε εyεtemε of thiε invention include the follow¬ ing commercially available productε.

TABLE IV

Functional Addi- tive Trade Name

Anglamol 32

Anglamol 75

Molyvan L

Lubrizol-5315

Emcol TS 230

The Lubrizol Corporation, Wickliffe, Ohio, U.S.A. 2

R. T. Vanderbilt Company, Inc., New York, New York, U.S.A.

3 Witco Chemical Corp., Orgamcε Divi.si.on, Houston,

Texas, U.S.A.

Mixtures of two or more of any of the afore-described functional additives can alεo be uεed. Typically, a functionally effective amount of the functional additive iε preεent in the aqueous compositionε of thiε invention.

The term "functionally effective amount" referε to a εufficient quantity of an additive to impart deεired propertieε intended by the addition of said additive. For example, if an additive is a ruεt-inhibitor, a functional¬ ly effective amount of εaid ruεt-inhibitor would be an amount εufficient to increaεe the ruεt-inhibiting charac¬ teristics of the composition to which it is added. Similarly, if the additive is an antiwear agent, a func- tionally effective amount of εaid antiwear agent would be a sufficient quantity of the antiwear agent to improve the antiwear characteristics of the composition to which it is added. The aqueous systemε of this invention often contain at least one inhibitor for corrosion of metalε. These inhibitors can prevent corrosion of either ferrous or non-ferrous metals (e.g., copper, bronze, brasε, titanium, aluminum and the like) or both. The inhibitor can be organic or inorganic in nature. Usually it is sufficient¬ ly soluble in water to provide a satisfactory inhibiting action though it can function as a corrosion-inhibitor without dissolving in water, it need not be water-soluble. Many suitable inorganic inhibitors uεeful in the aqueouε εystemε of the preεent invention are known to those εkilled in the art. Included are thoεe described in "Protective Coatings for Metalε" by Burnε and Bradley, Reinhold Publiεhing Corporation, Second Edition, Chapter 13, pageε 596-605. Thiε disclosure relative to inhibitors are hereby incorporated by reference. Specific examples of uεeful inorganic inhibitors include alkali metal nitrites, sodium di- and tripolyphosphate, potassium and dipotassium phoεphate, alkali metal borate and mixtureε of the same. Many suitable organic inhibitors are known to those of skill in the art. Specific examples include hydrocarbyl amine and hydroxy-substituted hydrocarbyl amine neutralized acid compound, such aε neutralized phoεphateε and hydrocarbyl phoεphate eεterε, neutralized fatty acidε (e.g., thoεe having about 8 to about 22 carbon atomε), neutralized aromatic carboxylic acidε (e.g., 4-tertiarybutyl benzoic acid) , neutralized naphthenic acidε and neutralized hydrocarbyl εulfonateε. Mixed εalt eεters of alkylated succinimideε are alεo uεeful. Partic¬ ularly uεeful amineε include the alkanol amineε εuch aε ethanol amine, diethanolamine. Mixtureε of two or more of any of the afore-deεcribed corroεion-inhibitorε can alεo be uεed. The corroεion-inhibitor iε uεually preεent in concentrations in which they are effective in inhibiting corrosion of metals with which the aqueous composition comes in contact. Certain of the aqueous systemε of the present inven¬ tion (particularly those that are used in cutting or shaping of metal) can also contain at least one polyol with inverse solubility in water. Such polyols are those that become less soluble aε the temperature of the water increases. They thus can function as surface lubricity agents during cutting or working operations since, aε the liquid iε heated aε a reεult of friction between a metal workpiece and work tool, the polyol of inverεe εolubility "plateε out" on the surface of the workpiece, thus improv- ing itε lubricity characteriεtics.

The aqueous εyεtems of the present invention can also include at leaεt one bactericide. Such bactericideε are well known to thoεe of εkill in the art and εpecific exampleε can be found in the afore-mentioned McCutcheon publication "Functional Materials" under the heading "Antimicrobials" on pages 9-20 thereof. Thiε diεclosure is hereby incorporated by reference as it relates to suitable bactericides for use in the aqueous compositionε or εyεtemε of this invention. Generally, these bacteri- cides are water-soluble, at least to the extent to allow them to function aε bactericideε.

The aqueouε syεtemε of the preεent invention can alεo include εuch other materialε aε dyeε, e.g., an acid green dye; water softeners, e.g., ethylene diamine tetraacetate sodium salt or nitrilo triacetic acid; odor masking agents, e.g., citronella, oil of lemon, and the like; and anti-foamantε, εuch aε the well-known εilicone anti- foamant agentε.

The aqueouε εyεtems of this invention may alεo include an antifreeze additive where it iε desired to use the composition at a low temperature. Materialε such as ethylene glycol and analogous polyoxyalkylene polyols can be used as antifreeze agents. Clearly, the amount used will depend on the degree of antifreeze protection deεired and will be known to thoεe of ordinary εkill in the art. It should also be noted that many of the ingredients described above for use in making the aqueous syεtemε of this invention are industrial products which exhibit or confer more than one property on such aqueous composi¬ tions. Thus, a single ingredient can provide several functions thereby eliminating or reducing the need for some other additional ingredient. Thus, for example, an extreme presεure agent such aε tributyl tin oxide can alεo function aε a bactericide.

While the invention haε been described and illus¬ trated with reference to certain preferred embodimentε thereof, thoεe skilled in the art will appreciate that variouε changes, modifications and subεtitutions can be made therein without departing from the spirit of the invention. For example, different concentration ranges- other than the preferred ranges set forth hereinabove may be applicable as a consequence of variationε in the oil baεe εtock or the type of engine or the like. It iε intended, therefore, that the invention be limited only by the εcope of the claimε which follow.

Claims

WHAT IS CLAIMED IS:

1. A method for preparing a baεic metal dihydro- carbylphoεphorodithioate wherein said method compriεeε reacting: (A) at leaεt one dihydrocarbyl phoεphorodithioic acid or the normal or acid metal εalt thereof; with

(B) at least one metal oxide or hydroxide wherein the metal is zinc, copper, nickel, chromium, iron, cobalt, manganese, calcium, barium, antimony, lead, aluminum or tin; in the presence of

(C) a catalytic amount of at least one alkali metal hydroxide, oxide, carbonate or halide; alkaline earth metal hydroxide, oxide, carbonate or halide; or mixtures thereof; wherein the metal of (C) is different from the metal of (B) .

2. The method according to claim 1 wherein said metal of (A) and (B) are, independently, selected from the group consiεting of zinc, copper, calcium, barium, nickel, chromium, iron, cobalt, tin, manganeεe, antimony or mixtureε thereof and each of the hydrocarbyl groupε iε, independently, selected- from linear or branched alkyl groups of 1 to about 200 carbon atoms, and subεtituted or unεubεtituted aryl groupε of 6 to about 50 carbon atoms.

3. The method according to claim 2 wherein each of the alkyl or aryl groups iε, independently, εelected from the group conεisting of butyl, propyl, pentyl, hexyl , heptyl, octyl, oleyl, heptylphenyl, nonylphenyl, dodecylphenyl, cresyl and iεomerε thereof. 4. The method according to claim 2 wherein said metals are selected from zinc, copper, calcium, cobalt or mixtureε thereof and wherein εaid alkyl or aryl groupε are, independently, εelected from isooctyl, iεopropyl,

4-methyl-2-pentyl and heptylphenyl.

5. The method according to claim 1 wherein the metal of (A), (B) , or both (A) and (B) iε zinc.

6. The method according to claim 1, wherein (C) iε εodium hydroxide or potassium hydroxide.

7. The method according to claim 1 wherein (C) is εodium hydroxide.

8. A baεic multiple metal complex of dialkyl- phoεphorodithioic acid defined by the general formula

[Z]_d[(R0)₂PSS]_yM_aX_b

wherein M and X repreεent different metal cationε εelected from the group conεiεting of zinc, copper, nickel, chromium, iron, cobalt, manganeεe, calcium, barium, lead,, tin, antimony, and aluminum; Z is an anion selected from oxygen, hydroxide and carbonate; each R iε hydrocarbyl; a and b are integerε of at leaεt 1 and are dependent upon the reεpective oxidation εtateε of M and X; y iε a whole integer which iε dependent upon the oxidation εtateε of M and X; and d iε an integer of 1 or 2.

9. The complex according to claim 8 wherein each hydrocarbyl iε, independently, a linear or branched alkyl group of 1 to about 200 carbon atomε or a εubεtituted or unεubεtit red aryl group of 6 to about 50 carbon atoms.

10. The complex according to claim 8 wherein M and X, independently, are selected from zinc, copper, calcium, barium, nickel, chromium, iron, cobalt, antimony, manganese, tin and each of said R groups is, indepen- dently, selected from propyl, butyl, pentyl, octyl, hexyl, heptyl, oleyl, heptylphenyl, nonylphenyl, dodecylphenyl, cresyl and isomers thereof.

11. The complex according to claim 8 wherein M and X, independently, are selected from zinc, copper, calcium, and cobalt and each R, independently, iε εelected from isooctyl, isopropyl, 4-methyl-2-pentyl and heptylphenyl.

12. The complex according to claim 8 wherein M is zinc, X is copper, Z is oxygen, a is 3; b is 1; y is 6; and d is 1.

13. The complex according to claim 8 wherein M is zinc; X is calcium; Z is oxygen; a is 3; b is 1; y iε 6; and d is 1.

14. A basic metal εalt or a baεic, multiple metal complex of dihydrocarbylphoεphorodithioic acid wherein said εalt or complex is the reaction product of:

(A) dihydrocarbyl phosphorodithioic acid or a normal or acid metal salt thereof; with

(B) at leaεt one metal oxide or hydroxide wherein the metal iε zinc, copper, nickel, chromium, iron, cobalt, manganeεe, calcium, barium, antimony, lead, aluminum or tin; in the preεence of

(C) a catalytic amount of at leaεt one alkali metal hydroxide, oxide, carbonate or halide; alkaline earth metal hydroxide, oxide, carbonate or halide; or mixtureε thereof; wherein the metal of (C) is different from the metal of (B) .

15. The complex according to claim 14 wherein said metals of (A) and (B) independently are selected from the group consisting of zinc, copper, calcium, barium, nickel, chromium, iron, cobalt, tin, manganese, antimony or mixtures thereof and each hydrocarbyl group independently is εelected from the group consisting of octyl, butyl, pentyl, propyl, hexyl, oleyl, heptyl, heptylphenyl, nonylphenyl, dodecylphenyl, cresyl and the isomerε thereof.

16. The complex according to claim 14 wherein the metalε of (A) and (B) are selected from zinc, copper, calcium, and cobalt and wherein each hydrocarby group independently is selected from isooctyl, isopropyl, 4-methyl-2-pentyl and heptylphenyl.

17. The complex according to claim 14 wherein one of the metalε of (A) and (B) is zinc and the other is copper.

18. The complex according to claim 14 wherein the metal of (A) iε Zn and the metal of (B) iε calcium.

19. The complex according to claim 17 wherein the metal of (A) iε zinc and- the metal of (B) is copper.

20. The complex according to claim 14 where (C) is sodium hydroxide.

21. A lubricating composition comprising a major amount of an oil of lubricating viscoεity and a minor amount of a complex of claim 8.

22. A lubricating compoεition compriεing a major amount of an oil of lubricating viεcoεity and a minor amount of a εalt or complex of claim 14.

23. A concentrate for formulating lubricating compoεitionε compriεing a normally liquid, εubεtantially inert organic solvent or diluent and from about 1% to about 99% by weight of a complex defined in claim 8.

24. A concentrate for formulating lubricating compositions comprising a normally liquid, subεtantially inert organic εolvent or diluent and from about 1% to about 99% by weight of a salt or complex defined in claim 14.

25. A greaεe compoεition compriεing a minor amount of a complex of claim 8.

26. A greaεe compoεition compriεing a minor maount of a εalt or complex of claim 14.

27. An aqueouε functional fluid compriεing a minor amount of a complex of claim 8.

28. An aqueouε functional fluid compriεing a minor amount of a εalt or complex of claim 14.

29. A method for -preparing a baεic metal dihydro- carbylphoεphorodithioate compriεing reacting: (A) a normal or acid metal dihydrocarbylphoεpho- rodithioate; with

(B) a metal oxide; in the abεence of a catalyεt wherein said metals of (A) and (B) are the same or different and are selected from the group consiεting of zinc, copper, nickel, chromium, iron, cobalt, anganeεe, calcium, barium, lead, antimony, tin and aluminum.

30. The method according to claim 29 wherein said metals of (A) and (B) are, independently, selected from the group consisting of zinc, copper, calcium, barium, nickel, chromium, iron, cobalt, tin, manganese, antimony or mixtures thereof and each hydrocarbyl group is, independently, selected from linear or branched alkyl groups of 1 to about 200 carbon atoms, and substituted or unsubstituted aryl groups of 6 to about 50 carbon atoms.

31. The method according to claim 30 wherein each alkyl or aryl group is, independently, selected from the group consisting of butyl, propyl, pentyl, hexyl, heptyl, octyl, oleyl, heptylphenyl, nonylphenyl, dodecylphenyl, cresyl and iεomerε thereof.

32. The method according to claim 30 wherein the metalε of (A) and (B) are εelected from zinc, copper, calcium, cobalt, or mixtures thereof and wherein each alkyl or aryl group is, independently, selected from isooctyl, isopropyl, 4-methyl-2-pentyl and heptylphenyl.

33. The method according to claim 29 wherein the metal of (A) and (B) is zinc.

34. The method according to claim 29 wherein each hydrocarbyl group iε a εubεtituted or unεubεtituted aryl of 6 to about 50 carbon atoms or alkyl of greater than 24 carbon atoms.

35. The method according to claim 29 wherein the metals of (A) and (B) are different and are selected from zinc and calcium.

36. The method according to claim 29 wherein the metalε of (A) and (B) are different and selected from zinc and copper.