CA1163041A

CA1163041A - Synergistically-thickened hydraulic fluid utilising alpha-olefin oxide modified polyethers

Info

Publication number: CA1163041A
Application number: CA000362905A
Authority: CA
Inventors: Assadullah Nassry; Jerrold F. Maxwell; Daniel R. Dutton; Ronald L. Camp
Original assignee: BASF Wyandotte Corp
Current assignee: BASF Corp
Priority date: 1979-10-22
Filing date: 1980-10-21
Publication date: 1984-02-28

Abstract

Abstract of the Disclosure Water-based hydraulic fluids and metalworking lubricants are disclosed which are thickened with a polyether polyol having a molecular weight of about 1000 to about 25,000 modified with an alpha-olefin epoxide having about 12 to about 18 carbon atoms. Unexpectedly, synergistic thickening results from a combination of said polyether polyol with the com-ponents of the water-based hydraulic fluid or metalworking lubricant. The particularly effective components of the hydraulic fluid or metalworking lubricant are the phosphate ester and water-soluble amine corrosion inhibitor components.
The hydraulic fluid and metalworking fluids of the invention also contain a water-soluble polyoxyethylated ester of an aliphatic acid and a monohydric or polyhydric aliphatic alcohol, either one or both said acid and said alcohol being polyoxyethylated, a sulfurized molybdenum or antimony compound and a metal deactivator as well as other adjuvants conven-tional in this art.

Description

WATER-BASED, SYNERGISTICALLY-THICKENED HYDRAULIC FLUID
Background of the Invention 1. Field of the Invention This invention relates to water-based hydraulic fluids and metalworking composi~ions.

2. Prior Art In the technology of hydraulic power transmission, mechanical power is imparted to a fluid called 'ia hydraulic fluid" in the form of pressure by means of a hydraulic pump.
Power is utili~ed where desired by tapping a source of said hydraulic fluid and thus transforming the power as pressure back to mechanical motion by a mechanism called a hydraulic motor. The hydraulic fluid is utilized as a pressure and volume transmitting medium. Any non-compressible fluid can perform this function. Water is the oldest fluid used for this purpose and is still sometimes used alone for this purpose. In the prior art, there has been a heavy emphasis on the development of petroleum oils for use as hydraulic fluids ` ~ and, consequently, much of the equipment utilized with hy-draulic fluids has been designed and manufactured specifically for use with petroleum oils. A petroleum oil in comparison with water as a hydraulic fluid possesses the advantage of inhibiting the development of rust of the ferrous components of the mechanical equipment utili~ed in conjunction with hydraulic fluids, li-e~, hydraulic pumps, motors, etc.) and in preventing wear of the machinery since the hydraulic fluid must lubricate the equipment. Petroleum oils have a second

3 ~3~

advantage over the use of water as a hydraulic fluid in that the petroleum oils normally exhibit a substantially higher viscosity than water and thus contribute to reduction of the leakage of the fluid in the mechanical equipment utilized. In addition, the technology relating to additives for petroleum oils has developed to such an extent that the viscosity, foam stability, wear prevention and corrosion prevention properties of such petroleum oil based hydraulic fluids can be further enhanced by the use of said additives.
Over the past 25 years, various substitutes for petroleum oil based hydraulic fluids have been developed in order to overcome one of the major deficiencies of petroleum oils, namely, flammability. Recent interest in the use of hydraulic fluids having up to 99 percent or more of water has resulted from the higher C05t of petroleum oils and recent emphasis on problems of ecologically suitable disposal of contamina~ed or spent petroleum oil based hydraulic fluids.
Metalworking fluids of the so-called "soluble oil"
type have been considered for use as hydraulic fluids. Such fluids contain mineral oil and emulsifiers as well as various additives to increase corrosion resistance and improve anti-wear and defoaming properties. Such fluids when used as hydraulic fluids are not generally suitable for use in ordinary industrial equipment designed specifically for use with the petroleum oil based hydraulic fluids since such fluids do not adequately prevent wear damage in pumps and valves of such equipment. However, such fluids have found ` `` ~.~63~

application in specially designed, high cost, large size equipment which, because of said large size and thus in-flexibility, is not suitable for use in most industrial plants. The soluble oil hydraulic fluid usage has thus been quite limited; usage has been largely confined to large installations where flexibility and size are not critical such as in steel mills.
It is known from U.5. Patent No. 3,249,538 to prepare an aqueous lubricant concentrate and lubricating composition consisting essentially of molybdenum disulfide and a water-soluble viscosity increasing agent such as polyvinyl alcohol and an emulsifiable mineral oil. It is also known from U.S. Patent No. 3,970,5~9 to prepare aqueous lubricating compositions containing a water-soluble mixed ester obtained by transesterification of a polyoxylethylene glycol and a triglyceride.
~ It is also known from U.S. Patent No. 3,933,65B that -~ a mixture of a phosphate ester and a sulfur compound can be - used in a water-based metalworking composition to obtain extreme pressure~ antiwear and corrosion inhibiting properties.
Such additives are used with a suitable vehicle such as mineral oil, vegetable oil, aliphatic acid ester, etc. The sulfur compounds disclosed are not sulfurized molybdenum compounds but rather are derivatives of 2-mercaptobenzo-thiazole. The phosphate esters of the invention, however, are similar to those disclosed in this reference. These are alkylene oxide derivatives of an alkyl, aryl or arylalkyl i ~ ~3~

phosphate which are useful in the form of the free acid or in the neutralized for wherein the phosphate ester is neutralized with a metal hydroxide or carbonate, ammonia or an amine. The use of these phosphate esters in water-based metalworking fluids is suggested in ASLE Transactions 7, pages 398 to 405, at page 405.
It is also known from U.S. Patent No. 4,151,099 and U.S. 4,138,346 to prepare water-based hydraulic fluids and metalworking lubricants. These hydraulic fluids which contain a phosphate ester and a sulfur compound or alternatively a phosphate ester, a sulfur compound and a water-soluble poly-oxyethylated aliphatic ester are optionally thickened with a polyglycol thickener but there is no suggestion in these references, or in any of the references above, that such fluids can be provided by the utilization of an alpha-olefin ; epoxide-modified polyether polyol thickener which reacts synergistically with certain components of the hydraulic fluid, particularly the phosphate ester or the phosphate ester and amine components to provide greatly increased viscosity in ~he resultant fluidso Summar~ of the Invention This invention relates to thickened high-viscosity, water-based hydraulic fluids and metalworking fluids. Said fluids comprise a water-soluble polyoxyethylated aliphatic ester, a sulfurized metallic compound, a phosphate ester salt, and a polyether polyol thickening agent. Optionally, the fluids of the invention can include a corrosion inhibitor and _~ _ ~ ~ ~3~ 1 a metal deactlvator. The use of a polyether polyol (poly-ether) thickening agent having a molecular weigh-t oE abou-t 1000 -to about ~5,000, preferably about 1000 -to about 10,000, derived from the reaction oE ethylene oxide or e-thylene oxide and at least one lower alkylene oxide haviny 3 to 4 carbon a-toms with an active hydrogen-containing inltiator having no more than one ac-tive hydrogen and further modified by reaction with an alpha-olefin epoxide (oxide) having about 12 to about 18 carbon atoms, unexpectedly provides a surprising increase in viscosity.
~ l-ternatively, the modified polyether polyol thickening agents can be obtained by copolymerizing a m:ixture of ethylene oxide, a-t least one other lower alkylene oxide having 3 to ~ carbon atoms, and an alpha-olefin expoxide having about I2 to about 18 carbon atoms, or mixtures thereof.
The concentrates of the invention can be used when blended with a substantial amount oE water as a flame-retardant hydraulic fluid having excellent lubricity and antiwear charac-teristics or as metalworking compositions used to cool and lubricate surfaces which are in fri.ctional contact such as during the operations of turning, cutting, peeling, grinding metals and the like. The hydraulic fluids and metalworking com-positions of the invention are ecologically superior to those fluids and metalworking emulsions of the prior ar-t containing mineral oil or a glycol/water mixture.

Detailed Description oE the Invention and the Preferred Embodiments In accordance with this invention, there are disclosed hydraulic fluids, metalworking fluids and lubri-cating concentrates which can be diluted with water as abase to prepare hydraulic fluids or metalworking composi-tions.

The disclosed composi-tions provide -the desirable lubricity as 1 1 ~3~ 1 well as antiwear properties which are necessary in a hydraulic 3~ 1 fluid or a metalworking composition. The thickened hydraulicfluids and metalworking fluids of the invention can be pre-pared at such viscosities as to substantially prevent internal and external leakage in the mechanical parts of a hydraulic system during the pumping of such hydraulic fluids and where the fluids are utilized as metalworking fluids, the thickened fluids reduce spattering of the fluids which can occur under high speed metalworking operations. As is conventional in this art, corrosion inhibiting agents, defoamers, metal deactivators (chelating agents) can be used as part of the compositions of the invention.
The Ester of an Ethoxylated Aliphatic Acid or Alcohol As an antiwear lubricant component of the lubri-cating concentrates of the invention and of the hydraulic fluids and metalworking additives of the invention, there are preferably utilized water-soluble esters of the ethoxylated Cg-C36 aliphatic monohydric or polyhydric alcohols with aliphatic acids, and aliphatic dimer acids. Such ethoxylated esters have a hydrophilic-lipophilic balance (HLB) in the range of 10 to 20. The most desirable adducts are in the range of 13 to 18.
Useful ethoxylated aliphatic acids have about 5 to about 20 moles of ethylene oxide added per mole of acid.
Examples are ethoxylated oleic acid, ethoxylated stearic acid and ethoxylated palmitic acid. Useful ethoxylated dimer acids are oleic dimer acid and stearic dimer acid. Aliphatic acids can be either branched or straight-chain and can contain from ` ;
`3 ~ ~0~ 1 about 8 to about 36 carbon atoms. Useful aliphatic acids include azelaic acid, sebacic acid, dodecanedioic acid, caprylic acid, capric acid, lauric acid, oleic acid, stearic acid, palmitic acid and the like. Especially useful for the purpose of obtaining the water-soluble esters of this inven-tion are aliphatic, preferably the saturated and straight-chain, mono- and dicarboxylic acids containing from about 8 to 18 carbon atoms.
The dimer acids employed in the formation of the water-soluble esters employed in the aqueous lubricants of the present invention are obtained by the polymerization of unsaturated fatty acids having from 16 to 26 carbon atoms, or their ester derivatives. The polymerization of fatty acids to form the dimer fatty acids has been described extensively in the literature and thus need not be amplified here. The preferred dimer acids employed in the formation of the poly~
ester are those which have 36 carbon atoms such as the dimer of linoleic acid and eleostearic acid. Other dimer acids having from 32 to 54 carbon atoms can be similarly employed.
The dimer acids need not be employed in pure form and can be employed as mixtures in which the major constituent, i.e~, greater than 50 percent, is the dimer acid and the remainder is unpolymerized acid or more highly polymerized acid such as trimer and tetramer acid.
The esters of the ethoxylated aliphatic acids and dimer acids utilized in the hydraulic fluids and metalworking lubricant compositions of the invention are reaction products with the ethoxylated monohydric or polyhydric alcohols.

~3~

Useful representative monohydric alcohols are n-octyl, n~decyl, n-dodecyl (lauryl), n-tetradecyl (myristyl~, n-hexadecyl (cetyl) and n-octadecyl alcohol. Useful represen-tative polyhydric alcohols are ethylene glycol, diethylene glycol, polyethylene glycol, sucrose, butanediol, butenediol, butynediol, hexanediol and polyvinyl alcohol. Glycerol, sorbitol, pentaerythritol, trimethylolethane, and trimethylol-propane are particularly useful polyhydric alcohols which can be ethoxylated and subsequently esterified to produce the esters of e~hoxylated aliphatic alcohols useful as essential components of the hydraulic fluids and metalworking composi-tions of the invention.
Suitable monohydric aliphatic alcohols are generally those having straight chains and carbon contents of Cg-C~g.
The alcohols are ethoxylated so as to add about 5 moles to about 20 moles of ethylene oxide by conventional ethoxylation procedures known to those skilled in the art. Such procedures are carried out under pressure in the presence of alkaline ; catalysts. The preferred monohydric aliphatic alcohols useful in producing the esters of the ethoxylated aliphatic alcohols of the invention are the linear primary alcohols having a chain length of C12-C1s and sold under the trademark "Neodol 25-3" and "Neodol 25-7" by the Shell Chemical Company.
Representative water-soluble polyoxyethylated esters having about 5 to about 20 moles of oxide per mole are the ` polyoxyethylene derivatives of the following esters; sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, ~ 1 630~ ~

sorbitan tri.stearate, sorbitan mon.opalmi:tate, sorbitan mono-isostearate, and sorbitan. monola.urate..
Sulu~ d Molybdenum a~Antimony Compounds The sulfurized oxymolyddenum.or oxiantimony organo-phosphorodithioate additi.ves of the invention are represented._ .

~ 1 63~4~
,, by the formula:
I R\
\O S I

,, \P~ S I M2S202 O
R / _12 wherein M is molybdenum or antimony and R is organi-~ and is selected from the group consisting of C3-C20 alkyl, aryl, alkylaryl radicals and mixtures thereof.
Representativ~ useul molybdenum and antimony compounds are sulfurized oxyantimony or oxymolybdenum organo-phosphorodithioate where the organic portion is alkyl, aryl or arylalkyl and wherein said alkyl has a chain length of 3 to 20 carbon atoms.

The Phosphate Esters ~ he compositions of the invention contain a phos-phate ester salt selected rom the group consisting of .. ... _ . . ..

~ ~ ~3~

o o 1~ 11 J
RO--(EO~n--P----OX and ~O--(EO)n~~P---(EO)n--OR
OX OX

and mixtures thereof wherein ethylene oxide is represented by EO; R is selected from the group consisting of linear or branched chain alkyl groups or alkylaryl groups wherein said alkyl groups have about 6 to about 30 carbon atoms, preferably about 8 to about 20 carbon atoms, wherein the alkyl groups have about 6 to about 30 carbon atoms, preferably about 8 to about 18 carbon atoms and X is selected from the group con-sisting of the residue of ammonia or an amine and an aIkali or alkaline earth metal or mixtures thereof and n is a number from 1 to 50. Metals such as lithium, sodium, potassium, ribidium, cesium, calcium, strontium, and barium are examples of X.
The phosphate ester salt composition utilized in the compositions of the invention are those more fully disclosed in U.S. Patent No. 3,004,056 and U.S. Patent No. 3,004,057, The phosphate esters utilized are génerally obtained by esteriying 1 mole of phosphorus pentoxide with 2 to 4.5 moles of a nonionic surface active agent obtained by con-densing at least 1 mole of ethylene oxide with 1 mole of a compound having at least 6 carbon atoms and a reactive hydro-gen atom. These nonionic sur~ace active agents are well known 3~

in the art and are generally prepared by condensing a poly-glycol ether containing a suitable number of alkanoxy groups or a 1,2-alkylene oxider or a substituted alkylene oxide such as a substituted propylene oxide, butylene oxide or preferably ethylene oxide with an organic compound containing at least 6 carbon atoms and a reactive hydrogen atom. Examples of compounds containing a reactive hydrogen atom are alcohols, phenols, thiols, primary and secondary amines and carboxylic and sulfonic acids and their amides. The amount of alkylene oxide or equivalent condensed with a reactive chain will generally depend upon the particular compound employed. About 20 to 85 percent by weight of combined alkylene oxide is generally obtained in a condensation product, however, the optimum amount of alkylene oxide or equivalent utilized will depend upon the desired hydrophobic~lipophilic balance desired.
Preferably, the nonionic surface active agents utilized are derivatives of alkylated and polyalkylated phenols, multibranched chain primary aliphatic alcohols having the molecular configuration of an alcohol and are produced by the Oxo process from a polyolefin of at least 7 carbon atoms or straight chain aliphatic alcohols of at least 10 carbon atoms. Examples of suitable nonionic surface active agent condensation products which can be in turn reacted with phos-phorus pentoxide to produce the phosphate esters utilized as additives in the hydraulic fluids of the invention are exem-plified below. In this list, "EO" represents "ethylene oxide"
and the number preceding this abbreviation refers to the ~ ~ ~3~ ~

number of moles thereof reacted with 1 mole of the given reactive hydrogen-containing compound.
Nonylphenol + 9 - 11 EO
Nonylphenol + 2 EO
Dinonylphenol + 7 EO
Dodecylphenol + 18 EO
Castor oil + ~0 EO
Tall oil + 18 EO
Oleyl alcohol + 4 EO
Oleyl alcohol + 20 EO
- Lauryl alcohol + 4 EO
Lauryl alcohol + 15 EO
Hexadecyl alcohol + 12 EO
Hexadecyl alcohol + 20 EO
Octadecyl alcohol + 20 EO
Oxo tridecyl alcohol:
(From tetrapropylene) + 7 EO
(From tetrapropylene) + 10 EO
(From tetrapropylene) + 15 EO
Dodecyl mercaptan + 9 EO
Soya bean oil amine + 10 EO
Rosin amine + 32 EO
Coconut fatty acid amine + 7 EO
Cocoa fatty acid + 10 EO
Dodecylbenzene sulfonamide + 10 EO
Decyl sulfonamide + 6 EO
Oleic acid + 5 EO
Polypropylene glycol (30 oxypropylene units) + 10 EO

The hydraulic fluids and metalworking compositions of the invention generally consist of about 60 percent to about 99 percen~ water and about 40 percent to about 1 percent of additives. These additives can consist of concen-trateS comprising combinations of the water-soluble esters of ethoxylated aliphatic acids and monohydric and polyhydric aliphatic alcohols, molybdenum or antimony compounds, a phosphate ester, and, in addition, can contain polymer thickening agents, defoamers, corrosion inhibitors and metal deactivatrs or chelating agents. Preferably, said fluids consist of about 75 percent to 99 percent water and about 25 percent to about 1 percent concentrate. The fluids are easily formulated at room temperature using distilled or deionized water although tap water can also be used without adverse effects on the fluid properties.
Stable concentrates of the hydraulic fluids and metalworking compositions of the invention can be prepared.
These can be completely free of water as indicated below or contain any desired amount of water but preferably contain up to 75 percent by weight of water to increase fluidity and provide ease of blending at the point of use. These concen-trates are typically diluted with water in the proportion of 1:99 to 10:90.
Representative concentrates are as follows:

_l ~_ ~ ~3~

Table I
Hydraulic Fluid Concentrates Ingredient % by Weight Thickener o Example 4 50.0 50.0 50.0 Alkylphosphate ester of Example 1 2.94 4.55 4.0 Polyoxye~hylene 20 sorbitan monostearate 11.75 18.17 19.0 Sulfurized oxymolybdenum or antimony organophosphorodithioate at 40~ solids 8.83 13.64 15.5 Sodium-2-mercaptobenzothiazole 11.77 6.Q6 4.0 Morpholine 14.71 7.58 7.5 100.00 1aO.00 100.00 The proportions of phosphate ester to sulfurized molybdenum or antimony compound of the invention are generally about 0.1:1 to about 2:1 based upon the weight of the sulfur in the sulfurized molybdenum or antimony compounds. The proportion of the water-soluble ester of the ethoxylated aliphatic acid or alcohol to the sulfurized molybdenum or sulfurized antimony containing compound is about 0.5:1 to about 2:1 based upon the weight of the sulfur in the sulfur-containing compound. Preferably, the proportion of phosphate ester to sulfurized molybdenum or antimony compound is 0.5:1 to 1:1 and~ preferably, the proportion of the ester of the ethoxylated aliphatic acid or alcohol to the sulfurized molybdenum compound is about 1:1 to about 1.5:1~
The concentration of sulfurized molybdenum or antimony compound to water in the hydraulic fluid or metal working compositions of the invention is generally about O.D5 ~ ~ 63~ ~

percent to about 3 percent by weight and the concentration of the phosphate ester to water in the hydraulic fluid or metal-working compositions of the invention is generally about 0.05 percent to about l percent by weightO The concentration of the water-soluble ester of the ethoxylated aliphatic acid or alcohol to water in the hydraulic fluid or metalworking compositions of the invention is generally about 0.1 percent to about 5 percent by weight. Preferably, these proportions by weight are respectively 0.75 percent to 0.5 percent, 0.25 percent to 0.5 percent, and 1 percent to 2 percent.

The Alpha-Olefin Epoxide Modified Polyether Polyol Thic_ening A~ent The modified polyether polyol thickening agents utilized to thicken the hydraulic fluids and metal-working fluids of the invention can be obtained by modifying a polyether polyol thickening agent derived from the reaction of ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-containing aliphatic or alkylaromatic initiator compound containing no more than one active hydrogen and 12 to 18 aliphatic carbon atoms. Useful initiators are selected from the group consisting of alkane monoalcohols, alkene monoalcohols, and alkyne monoalcohols. Specific examples of initiators include dodecylphenol, dodecylalcohol, dodecyl-carboxylic acid, dodecylmercaptan, octadecylphenol! octadecyl-alcohol, octadecylcarboxylic acidl octadecylmercaptan. The use of octadecylalcohol (stearyl alcohol) is particularly preferred. The modified polyether polyol thickening agents of ~ ~3~

the invention are prepared by reacting an alpha~olefin epoxide either by copolymerization with ethylene o~ide or ethylene oxide and said lower alkylene oxides or polymerization sub-sequent to the formation of a base polyether intermediate, said alpha-olefin epoxide having about 12 to about 18 carbon atoms. The polyether polyol thickening agent of the invention can be an alpha-olefin epoxide capped heteric or block co-polymer of ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms; an alpha-olefin epoxide capped ethylene oxide homopolymer; or a heteric copolymer of ethylene oxide, said lower alkylene oxide, and said alpha-olefin epoxide. Said ethylene oxide is used in the proportion of at least 10 percent by weight based upon the total weight of the polyether. Preferably, about 70 to 99 percent by weight ethylene oxide is utilized with about 30 to 1 percent by weiyht of lower alkylene oxide having 3 to 4 carbon atoms.
The preparation of polyether polyols is well known in the art~ Polyether polyols are generally prepared utilizing an active hydrogen-containing compound in the presence of an acidic or basic oxyalkylation catalyst and an inert-organic solvent at elevated temperatures in the range of about 50C to 150C under an inert gas pressure generally from about 20 to about 100 pounds per square inch gauge. Modification of these polyether polyols can be accomplished by further reacting the polyether polyol having a molecular weight of about 1000 to about 25,000 with said alpha-olefin epoxide so as to provide an alpha-olefin epoxide cap on the base polyether polyol~ The amount of alpha-olefin epoxide required to obtain ,.' 3~

the modified polyether polyol thic]cening agents of the inven-tion is about 7 to about 20 percent by weight based upon the total weight of the modified base polyether polyol thickeners.
Alternatively, the modified polyether polyol thickening agents can be obtained by copolymerizing a mixture of ethylene oxide, at least one other lower alkylene oxide having 3 to 4 carbon atoms, and an alpha-olefin epoxide having about 12 to about 18 carbon atoms, or mixtures thereof.
Further details of the preparation of the alpha-olefin epoxide modified polyether polyol thickening agents useful in the preparation of the hydraulic fluids and metalworking fluids of the invention can be obtained in co-pending Canadian.Patent application S rial Nos~ 362901, 362902, both filed on October 21, 1980.

Generally, at least 50 percent by weight, preferably about 40 to 60 percent by weight of the modified polyether polyol is used together with about 60 to about 40 percent by weight of an unthickened hydraulic fluid or metalworking fluid concentrate.
The metal deactivators and corrosion inhibitors which can be added either to the concentrate or to the hy-draulic fluid or metalworking compositions of the invention are as follows:
Liquid-Vapor Phase Corrosion Inhibitors The liquid-vapor corrosion inhibitor can be any o~
the alkali metal nitrites, nitrates, phosphates, silicates, ~ .~ 63~'1 1 and benzoates. Certain amines are also useful. The inhi bitors can be used individually or in combinations. Represen-tative examples of the preferred alkali metal nitrates and benzoates which are useful are as follows: sodium nitrate, potassium nitrate, calcium nitrate, barium nitrate, lithium nitrate, strontium nitrate, sodium benzoate, potassium benzoate, calcium benzoate, barium benzoate, lithium benzoate and strontium benzoate.
Representative amine type corrosion inhibitors are morpholine, N-methylmorpholine, N-ethylmorpholine, ethylene-diamine, dimethylaminopropylamine, dimethylethanolamine, alpha- and gamma- picoline, and piperazine. A particularly preferred vapor phase corrosion inhibiting compound is morpho-line. As corrosion inhibitors, a proportion of from about 0.05 percent to about 2 percent by weight is used based upon the total weight of the hydraulic fluid or metalworking composition of the invention. Preferably, about 0.5 percent to about 2 percent by weight of these amines are used.
Metal Deactivators (Chelating Agents) The metal deactivators are used primarily to chelate copper and copper alloys. Such materials are well known in the art and individual compounds can be selected from the broad classes of materials useful for this purpose such as the various triazoles and thiazoles as well as the amine deriva-tives of salicylidenes. Representative specific examples of these metal deactivators are as follows: benzotriazole, tolytriazole, 2-mercaptobenzothiazole, sodium 2-mercapto-benzothiazole, and N,N'-disalicylidene-1,2-propanediamine.

_l g_ I~ is also contemplated to add other known corrosion inhibitors. Besides the amines, alkali metal nitrates, benzoates and nitrates listed above, the alkoxylated fatty acids are useful as corrosion inhibitors.
The phosphate ester and the esters of ethoxylated aliphatic acids and monohydric and polyhydric alcohols, as described above, are water-soluble in the sense that no special method is required to disperse these materials in water and keep them in suspension over long periods of time.
The sulfurized molybdenum or antimony compounds on the other hand are insoluble in water and require emulsification prior to use, for instance, with anionic or nonionic surfactants.
Useful representative anionic or nonionic surfactants are:
sodium petroleum sulfonate, i.e., sodium dodecylbenzene sulfonate; polyoxyethylated fatty alcohol or fatty acid and polyoxyethylated alkyl phenol.
A typical recipe for the emulsification of the sulfurized molybdenum or antimony compound of the invention (sulfurized oxymolybdenum or oxyantimony organo-phosphorodi-20 thioates) is as follows:
Emulsifier ~ by Weight Sodium dodecylbenzene sulfonate 70 Ethylene glycol monobutyl ether 23 Butyl alcohol 7 `~ ~ 63V~ 1 % by Weight Emulsifiable concentrate (hereafter termed emulsion~

Sulfurized molybdenum or antimony compound 40 Emulsifier 60 A typical high water-base hydraulic fluid or metalworking additive of the invention will contain the components shown in Table II.
Table II

Typical Composition of Hydraulic Fluid or Metalworking Additive Component Parts by Weight water (distilled or deionized) 2.5-32.5 Polymeric thickener 80-5Q
Water-soluble ethoxylated ester 3-10 Molybdenum or antimony compound at 40% solids emulsion 1 5 Water-soluble alkyl phosphate ester0. 1-1. O
Me~al deactivator 0.1~0.5 Corrosion inhibitor 0.5-1.0 The hydraulic fluid and metalworking compositions of the invention, when formulated as above, are transparent liquids having a viscosity of up to 400 S.U.S. at 100F, which are stable over long periods of storage at ambient temperature.
In addition, the hydraulic fluids and metalworking additives of the invention are oil-free and will not support combustion in contrast to those flame-resistant fluids of the prior art based upon a glycol and water or petroleum oils. The hydraulic `~ 3 ~304 1 fluids and metalworking additives of the invention are ecologi-cally clean and nonpolluting compositions when compared to existing petroleum-based hydraulic fluids~ Since the hydraulic fluids and metalworking additives of the invention are largely based upon synthetic materials which are not derived from petroleum, the production of such fluids is relatively inde-pendent of shortages of petroleum oil and not materially influenced by the economic impact of such shortages.
The hydraulic fluids of the invention can be used in various applications requiring hydraulic pressures in the range of 200-2000 pounds per square inch since they have all the essential properties required such as lubricity, viscosity and corrosion protection. The hydraulic fluids of the inven-tion are suitable for use in various types of hydraulic systems and are especially useful in systems in which vane-type pumps or the axial-piston pumps are used. Such pumps are used in hydraulic systems where pressure is required for molding, clamping, pressing metals, actuating devices such as doors, elevators, and other machinery or for closing dies in die-casting machines and in injection molding equipment and other applications.
In evaluating the hydraulic fluids of the invention, a test generally referred to as the Vickers Van Pump Test is employed. The apparatus used in this test is a hydraulic system which functions as follows: Hydraulic fluid is drawn from a closed sump to the intake side of a Vickers V-104C
vane-type pump. The pump is driven by, and directly coupled ~ 3 ~3~

to, a 25 horsepower, 1740 rpm electric motor. The fluid i6 discharged from the pump through a pressure regulating valve.
From there it passes through a calibrated venturi (used to measure flow rate) and back to the sump. Cooling of the fluid is accomplished by a heat exchanger through which cold water is circulated. No external heat is required; the fluid temperature being raised by the frictional heat resulting from the pump's work on the fluid. Excess heat is removed by passing the fluid through the heat exchanger prior to return to the sump. The Vickers V-104C vane-type pump comprises a cylindrical enclosure ~the pump body) in which there is housed a so-called "pump cartridge". The "pump cartridge" assembly consists of fr~nt and rear circular, bronze bushings, a rotor, a cam-ring and rectangular vanes. The bushings and cam-ring are supported by the body of the pump and the rotor is con-nected to a shaft which is turned by an electric motor. A
plurality of removable vanes are inserted into slots in the periphery of the rotor. The cam-ring encircles the rotor and the rotor and vanes are enclosed by the cam-ring and bushings.
The inner surface of the cam-ring is cam-shaped. Turning the rotor results in a change in displacement of each cavity enclosed by the rotor, the cam-ring, two adjacent vanes and the bushings. The body is ported to allow fluid to enter and leave the cavity as rotation occurs.
The Vickers Vane Pump Test procedure used herein specifically requires charging the system with 5 gallons of the test fluid and running at temperatures ranging from 100 to ~ ~ ~30~ 1 135F at 750 to 1000 psi pump discharge pressure ~load). Wear data were made by weighing the cam-ring and the vanes of the "pump cartridge" before and after the test. At the conclusion of the test run and upon dissasembly for weighing, visual examination of the system was made for signs of deposits, varnish, corrosion, etc.
The following examples more fully describe the hydraulic fluids of the invention and show the unexpected results obtained by their use. The examples are intended for the purpose of illustration and are not to be construed as limiting in any way. All parts, proportions, and percentages are by weight and all temperatures are in degrees centigrade unless otherwise noted.

`3 ~ ~3~ 1 _amples 1 - 3 Elydraulic fluid concentrates were prepared having the compositions in percent by weight of:
Ingredient Example 1 Example 2 Example 3 Polyoxyethylene 20 sorbitan monostearate 23.53 36.36 38.00 Sulfurized oxymolybdenum organophosphordithioate 17.65 27.27 31.00 Alkylphosphate ester5.88 9.10 8.00 Morpholille 29.41 15.15 15.00 Sodium-2-mercaptoben~o-thiazole 23.53 12.12 8.00 The fluids were clear, dark amber in color, free flowing and showed no phase separation upon aging at room temperature. Upon diluting the concentrates with tap water to obtain hydraulic fluids containing 1, 3 and 5 percent of each of the concentrates, homogeneous mixtures were obtained.
The alkyl phosphate ester utilized in these examples was obtained by the reaction of two moles of phosphorus pentoxide with the surface-active agent condensation product obtained by reacting one mole of oleyl alcohol and 4 moles of ethylene oxide.
Example 4 In this example, a heteric copolymer of ethylene oxide and 1,2-propylene oxide is prepared having a molecular weight of about 8717. Subsequently, this base heteric co-polymer is further reacted with a mixture of alpha-olefin epoxides having 15 to 18 carbon atoms sold under the trademark VIKOLOX 15-18 by the Viking Chemical Company.

~ ~ ~30~. ~

Into a stainless steel one-gallon autoclave, there was charged 972 grams of stearyl alcohol, 89.6 grams of a 45 percent aqueous solution of potassium hydroxide and the mixture was heated with stirring at 115C at a pressure of less than 10 millimeters of mercury for 30 minutes. The vacuum was relieved with dry nitrogen to a pressure of 5 pounds per square inch gauge, and a mixture of 407 grams of propylene oxide and 1~20 grams of ethylene oxide were added over a period of 4 and 3/4 hours at a temperature of 115C.
After addition was complete, the mixture was stirred 70 minutes at 115C and cooled to 80C. The product labeled intermediate No. 1 was thereafter discharged to a one gallon glass bottle for use in the next step.
Using the previously prepared intermediate, 476 grams of said intermediate were charged to a one-gallon stainless steel autoclave which had been previously flushed with nitrogen and heated for 15 minutes at a temperature of 115C and a pressure of 10 millimeters of mercury. After relie~ing the vacuum to a pressure of 5 pounds per square inch gauge with nitrogen, a mixture of 1303 grams of propylene oxide and 3909 grams of ethylene oxide were added over a period of 14 hours at a temperature of 115C. After the addition of these ingredients was complete, the mixture was stirred for a period of two hours at a temperature of 115C
and then cooled to 80C. The second intermediate product was discharged to a one-gallon bottle in a yield of 55~9 grams of liquid intermediate.

3 ~ B304 1 Utilizing a 2600 grams portion of the above second intermediate product, a five-liter glass vessel was charged and thereafter the vessel and its contents were heated at a temperature of 120C under a nitrogen atmosphere at a pressure of 20 millimeters of mercury for a period of 30 minutes.
Thereafter, 76 grams of a mixture of alpha-olefin epoxides having 15 to 18 carbon atom chains and sold under the trade-mark VIKOLOX 15-18 by the Viking Chemical Company was added all at once. After heating this mixture for a period of 8 hours at a temperature of 120~C under a nitrogen atmosphere at atmospheric pressure, the product was cooled to 80C and discharged to a glass container. The product was character-ized as a viscous brown liquid at room temperature.
Tables III-V respectively show the viscosity of the concentrate of Example 3 when diluted with tap water to make a hydraulic fluid, the viscosity of the alpha-olefin epoxide modified polyether polyol thickener of Example 4 upon dilution with water, and the use of five percent by weight of the concentrate of Example 3 in combination with two and one-half to five percent of the alpha-olefin epoxide modified polyether polyol of Example 4. The surprising increase in viscosity shown in Table V for the combination of thickener and hy-draulic fluid concentrate is unexpected and advantageous in that lesser amounts of thickener would be required than expected to produce a thickened hydraulic fluid or metal-working lubricant thus resulting in a cost saving.

3 ~ 4 1 Table III
Viscosity of Hydraulic Fluid rom Concentrate of Example 3 in Water Concentration in Water Viscosity (SUS) (% by weight) at 100~F
1.0 34 3.0 54 5.0 56 Table IV
Viscosity of Thickener of Example 4 in Water Concentration in Water Viscosity (SUS) (% by weight) at 100 F
2.5 32 5.0 42 .0 77 Table V
Viscosity of Mixtures of the Concentrate of Example 3 & the Thickener of Example 4 in Water Concentration in Water Viscosity (SUS) (% by weight) at 100F
Example 3 Example 4 5.0 2.5 50 5.0 3.0 87 5.0 3.5 216 5.0 4.0 373 5.0 5.0 1299 Example 5 Usin~ 3.5 percent by weight of the thickener of Example 4 and 5 percent by weight of the hydraulic fluid ~ ~ 630~ ~1 concentrate of Example 3 with the remainder of the composition tap water, a water-based hydraulic fluid having a viscosity of 216 SUS was prepared and tested for stability under conditions of high shear in a Vickers V-104C hydraulic vane pump. The hydraulic fluid was tested at 1000 pounds per square inch pressure at a temperature of 100F for a period of 89 hours.
Samples of the hydraulic fluid were taken at various time intervals during the test and the viscosity determined. Tne reduction in viscosity is indicative of the relative degree of shear stability of the hydraulic fluid.

Table VI

Vickers Vane Pump Test -~ Shear Stability of Hvdraulic Fluid of Example 5 , Test Time Viscosity Viscosity (hours~ (SUS) at 100F ~ loss 3 213 1.4 8 209 3.2 ~06 4.6 24 196 9.3 195 g.7 89 194 10.~

As shown in Table VI, the overall change in vis-cosity of the fluid after 89 hours running time is about 10 percent which indicates good shear stability performance in the Vickers Vane Pump.

~ 1 ~3~

The hydraulic fluid of Example 5 was also tested for wear performance in a hydraulic vane pump. The test was conducted in the Vickers V-104C vane pump at 1000 pounds per square inch pressure, at a temperature of 100F, for a period of 89 hours. Ring and wear losses were determined at various time intervals and the results are shown in Table VII.

Table VII

Vickers Vane Pump Test - Wear Performance of Hydraulic Fluid of Example 5 Wear-loss in Weight (total) Test Time Ring and Vanes (hours) (grams) 0.66 1.19 89 1.76 The weight loss of the ring and vanes shown in Table VII is indicative of acceptable lubricity performance in the vane pump.
While this invention has been described with reference to certain embodiments, it will be recognized by those skilled in the art that many variations are possible without departing from the scope and spirit of the invention and it will be understood that it is intended to cover all changes and modifications of the invention disclosed herein for the purposes of illustration which do not constitute departures from the spirit and scope of the invention.

`~ 3 630~ ~L
SUPPLEMENTARY DISCLOSURE

The principal disclosure (-the entire contents of which are herein incorporated by reEerence) relates to -thickened high-viscosity, water-based hydraulic fluids and metal-working fluids. Said fluids comprise a water-soluble polyoxyethyla-ted aliphatic ester, a sulfurized metallic compound, a phosphate ester salt, and a polyether polyol thickening agent. Optionally, the fluids can include a corrosion inhibitor and a metal deac-tivator. The use of a polyether polyol (polyether) thickening agent having a molecular weight of about 1000 to about 25,000 preferably about 1000 to about 10,000, derived from the reac-tion of ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 -to 4 carbon atoms with an active hydrogen-containing initlator having no more than one active hydrogen and further modified by reaction with an alpha-olefin epoxide (oxide) having about 12 to about 18 carbon atoms, unexpectedly provides a surprising increase in viscosity.
Alternatively, the modified polyether polyol thickening agents can be ob-tained by copolymerizing a mixture of ethylene oxide, at least one other lower alkylene oxide having 3 to 4 carbon atoms, and an alpha-olefin epoxide having about 12 to about 18 carbon atoms, or mixtures thereof.
Alternatively to the use of the above-described alpha-olefin oxides, it is possible in accordance with the present invention , to substitute glycidyl ethers which can be prepared by reaction of an alcohol having 12 to about 18 carbon atoms with epichlorohydrin in accordance for example with the teachings of U.S. 4,086 " 79 and the references referred to thel'ein.
Thus, the present invention, in particular provides a hydraulic fluid or metalworking fluid concen-tra-te capab].e of . . 0.
.

i ~ ~3~

imparting to water the properties of a lubricant such as resis~
tance to extreme pressure and corrosion inhibition, said con-centrate consisting essentially of :
A. a water-soluble polyoxyethylated aliphatic ester consisting of esters of ethyoxylated aliphatic mohonydric and polyhydric alcohols or ethoxylated aliphatic acids wherein said acids or alcohols have about 5 to about 20 moles of ethylene oxide aclded per mole of acid or alcohol and wherein said alcohols and acids : have carbon chain lengths of 8 to 36 carbon atoms and wherein said esters are produced by first polyoxyethylating a-t least one-of said acids or alcohols, and , second, obtaining the ester reaction product therPof, B. a sulfurized metallic compound of the formula:

¦ \
\ ~ S M2S2 2 R _ wherein M is molybdenum or antimony and wherein R is selected from the group consisting of alkyl, aryl, alkylaryl radicals and mixtures thereof having 3 to 20 carbon atoms iD the alkyl group and wherein the rat1o of said water-soluble ester ; to said sulfurized metallic compound is Erom 5:1 to 2:1 by weight based upon the weight of the sulfur in said metallic compoundj C~ a phosphate ester salt selected from the group consisting of 3 ~ 4 1 o o Il 11 RO - (EO)n- P -OX and RO (EO)n -p (EO)n OR
OX OX

and mixtures thereof , wherein EO is e-thylene oxide, R is selected from the group consisting of linear or branched chain alkyl groups having about 6 to 30 carbon atorns or alkylaryl groups wherein said alkyl groups have 6 to 30 carbon atoms; X is selected from the residue of ammonia, an amine and an alkali or alkaline earth metal ;~ or mixtures thereof, n is a number from l to : 50 and wherein the proportion of said phosphate ; ester to said sulfurized metallic compound i5 about 0.1:1 to about 2:1 based upon the weight of the sulfur in said metallic compound, - D. a polyether thickener having a molecular weight of about 1000 to about 25,000, prepared by react-ing ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-contain-ing aliphatic or alkylaromatic initiator contain-ing no more than one active hydrogen and at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about l to about 20 percent by weight based upon the total weight of said thickener, and optionally E. a corrosion inhibitor and a metal deactivator.

~ : .

~ ~ ~30'1 1 In accordance with this invention, the polyether thickener may be prepared by copolymerizing a mixture of ethylene oxi.de and at least one of said lower al]cylene oxides in the presence of said initiator selected from -the group consisting of alkane monoalcohols, alkene monoalcohols , and alkyne monoalcohols to produce a liquid heteric copolymer intermediate and subse-quently reacting said intermediate with at least one of said ~lycidyl ether.
In accordance with the present invention, the polyether thickener may be prepared by sequentially reacting ethylene oxide with at least one of said lower alkylene oxides to produce a block copolymer intermediate and subsequently reacting said intermediate with at least one of said glycidyl ether.
In accordance with the present invention, the glycidyl ether may be in a mole ratio to said initiator of about 1:5 to about 1:15.
In accordance wi-th the invention, the lower alkylene oxides may be selected from the group consisting of 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide and tetrahydrofuran and the proportion of ethylene oxide residue in said thickener mav be at least 10 percent by weight of the total weight of said thickener.
' In accordance with,the invention, the proportion of ethylene oxide residue to the residue of the lower alkylene oxides may be from 70 to about 99 percent by weight of ethylene oxide residue to about 30 to about 1 percent by weight of the s,aid lower alkylene oxide residue and said active hydrogen-containing compound may be a monohydric aliphatic alcohol,.
In accordance with the invention, the initiator may 30 ' ,be selected from the group consisting of at least one of stearyl alcohol , lauryl alcohol and myristyl alcohol.

The glycidyl e-ther may be in a mole ra-tio to said initia-tor ~ 3~ -~ ~ ~30~ ~

of about 1:5 to about 1:15.
The concentrates of the invention can be used when blended with a substantial amount of water as a flame-retardant hydraulic fluid having excellent lubricity and an-tiwear charac-teristics or asmetalworking compositions used to cool and lubricate surfaces which are in frictional contac-t such as during the operat.ions of turning, cutting, peeling, grinding metals and the like. The hydraulic fluids and metalworking compositions oE the invention are ecologically superior to those fluids and metalworking emulsions of the prior art con-taining mineral oil or a glycol/water mixture.
' :

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A hydraulic fluid or metalworking fluid concentrate capable of imparting to water the properties of a lubricant such as resistance to extreme pressure and corrosion inhibi-tion, said concentrate consisting essentially of:
A. a water-soluble polyoxyethylated aliphatic ester consisting of esters of ethoxylated aliphatic monohydric and polyhydric alcohols or ethoxyl-ated aliphatic acids wherein said acids or alcohols have about 5 to about 20 moles of ethylene oxide added per mole of acid or alcohol and wherein said alcohols and acids have carbon chain lengths of 8 to 36 carbon atoms and wherein said esters are produced by first polyoxy-ethylating at least one of said acids or alcohols and second, obtaining the aster reaction product thereof, B. a sulfurized metallic compound of the formula:

wherein M is molybdenum or antimony and wherein R is selected from the group consisting of alkyl, aryl, alkylaryl radicals and mixtures thereof having 3 to 20 carbon atoms in the alkyl group and wherein the ratio of said water-soluble ester to said sulfurized metallic compound is from 5:1 to 2:1 by weight based upon the weight of the sulfur in said metallic compound, C. a phosphate ester salt selected from the group consisting of and and mixtures thereof, wherein EO is ethylene oxide; R is selected from the group consisting of linear or branched chain alkyl groups having about 6 to 30 carbon atoms or alkylaryl groups wherein said alkyl groups have 6 to 30 carbon atoms; X is selected from the residue of ammonia, an amine and an alkali or alkaline earth metal or mixtures thereof, n is a number from 1 to 50 and wherein the proportion of said phosphate ester to said sulfurized metallic compound is about 0.1:1 to about 2:1 based upon the weight of the sulfur in said metallic compound, D. a polyether thickener having a molecular weight of about 1000 to about 25,000, prepared by reacting ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-containing aliphatic or alkylaromatic initiator containing no more than one active hydrogen and at least one alpha-olefin oxide having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said alpha-olefin oxide is present in the amount of about 1 to about 20 percent by weight based upon the total weight of said thickener, and optionally E. a corrosion inhibitor and a metal deactivator.

2. The concentrate of claim 1 wherein said phosphate ester is the ester of the reaction product of 4 moles of ethylene oxide with 1 mole of oleyl alcohol esterified by reacting 1 mole of said reaction product with 2 moles of phosphorus pentoxide.

3. A hydraulic fluid or metalworking lubricant fluid consisting essentially of water and the concentrate of claim 2 wherein said fluid consists of about 60 percent to about 99 percent water and about 40 percent to about 1 percent con-centrate.

4. A hydraulic fluid or metalworking lubricant fluid consisting essentially of water and the concentrate of claim 2 wherein said concentrate consists of about 50 percent to about 80 percent of said thickener.

5. The hydraulic fluid or metalworking lubricant fluid of claim 3 wherein said corrosion inhibitor is selected from the group consisting of an alkali metal benzoate, nitrate, and nitrite, an amine, and mixtures thereof.

6. The hydraulic fluid or metalworking lubricant fluid of claim 5 wherein said amine corrosion inhibitor is morpholine.

7. The hydraulic fluid or metalworking lubricant fluid of claim 6 wherein said metal deactivator is the triethanolamine salt of 2-mercaptobenzothiazole.

8. The concentrate of claim 2 wherein said polyether thickener is prepared by copolymerizing a mixture of said reactants to produce a liquid heteric copolymer.

9. The concentrate of claim 2 wherein said polyether thickener is prepared by copolymerizing a mixture of ethylene oxide and at least one of said lower alkylene oxides in the presence of said initiator selected from the group consisting of alkane monoalcohols, alkene monoalcohols, and alkyne monoalcohols to produce a liquid heteric copolymer intermediate and subsequently reacting said intermediate with at least one of said alpha-olefin oxide.

10. The concentrate of claim 2 wherein said polyether is prepared by sequentially reacting ethylene oxide with at least one of said lower alkylene oxides to produce a block copolymer intermediate and subsequently reacting said inter-mediate with at least one of said alpha-olefin oxide.

11. The concentrate of claim 9 wherein said lower alkylene oxides are selected from the group consisting of 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, and tetrahydrofuran and wherein the proportion of ethylene oxide residue in said thickener is at least 10 percent by weight of the total weight of said thickener.

12. The concentrate of claim 11 wherein the propor-tion of ethylene oxide residue to the residue of said lower alkylene oxides is from about 70 to about 99 percent by weight of ethylene oxide residue to about 30 to about 1 percent by weight of the said lower alkylene oxide residue and said active hydrogen-containing compound is a monohydric aliphatic alcohol.

13. The concentrate of claim 12 wherein said initiator is selected from the group consisting of at least one of stearyl alcohol/ lauryl alcohol, and myristyl alcohol.

14. The concentrate of claim 13 wherein said alpha-olefin oxide is in a mole ratio to said initiator of about 1:5 to about 1:15.

15. A process of metalworking comprising working metal in the presence of the metalworking lubricant fluid of claim 4.

16. A process for the transmitting of force hydraulically comprising transmitting force utilizing the hy-draulic fluid of claim 3.

CLAIMS SUPPORTED BY SUPPLEMENTARY DISCLOSURE:

17. A hydraulic fluid or metalworking fluid concentrate capable of imparting to water the properties of a lubricant such as resistance to extreme pressure and corrosion inhibition, said concentrate consisting essentially of:
A. a water-soluble polyoxyethylated aliphatic ester consisting of esters of ethoxylated aliphatic monohydric and polyhydric alcohols or ethoxylated aliphatic acids wherein said acids or alcohols have about 5 to about 20 moles of ethylene oxide added per mole of acid or alcohol and wherein said alcohols and acids have carbon chain lengths of 8 to 36 carbon atoms and wherein said esters are produced by first polyoxyethylating at least one of said acids or alcohols and, second, obtaining the ester reaction product thereof, B. a sulfurized metallic compound of the formula:

M2S2O2 wherein M is molybdenum or antimony and wherein R is selected from the group consisting of alkyl, aryl, alkylaryl radicals and mixtures thereof having 3 to 20 carbon atoms in the alkyl group and wherein the ratio of said water-soluble ester to said sulfurized metallic compound is from 5:1 to 2:1 by weight based upon the weight of the sulfur in said metallic compound, C. A phosphate ester salt selected from the group consisting of and mixtures thereof, wherein EO is ethylene oxide; R is selected from the group consisting of linear or branched chain alkyl groups having about 6 to 30 carbon atoms or arylalkyl groups wherein said alkyl groups have 6 to 30 carbon atoms; X is selected from the residue of ammonia, an amine and an alkali or alkaline earth metal or mixtures thereof, n is a number from 1 to 50 and wherein the proportion of said phosphate ester to said sulfurized metallic compound is about 0.1:1 to about 2:1 based upon the weight of the sulfur in said metallic compound, D. a polyether thickener having a molecular weight of about 1000 to about 25,000, prepared by reacting ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-containing aliphatic or alkylaromatic initiator containing no more than one active hydrogen and at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based upon the total weight of said thickener, and optionally, E. a corrosion inhibitor and a metal deactivator.

18. The hydraulic fluid concentrate of claim 17 wherein said polyether thickener is prepared by copolymerizing a mixture of ethylene oxide and at least one of said lower alkylene oxides in the presence of said initiator selected from the group con-sisting of alkane monoalcohols, alkene monoalcohols, and alkyne monoalcohols to produce a liquid heteric copolymer intermediate and subsequently reacting said intermediate with at least one of said glycidyl ether.

19. The hydraulic fluid concentrate of claim 17 wherein said polyether thickener is prepared by sequentially reacting ethylene oxide with at least one of said lower alkylene oxides to produce a block copolymer intermediate and subsequently reacting said intermediate with at least one of said glycidyl ether.

20. The hydraulic fluid concentrate of claim 17 wherein said glycidyl ether is in a mole ratio to said initiator of about 1:5 to about 1:15.

21. The concentrate of claim 18 wherein said lower alkylene oxides are selected from the group consisting of 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, and tetrahydrofuran and wherein the proportion of ethylene oxide residue in said thickener is at least 10 percent by weight of the total weight of said thickener.

22. The concentrate of claim 21 wherein the proportion of ethylene oxide residue to the residue of said lower alky-lene oxides is from about 70 to 99 percent by weight of ethylene oxide residue to about 30 to about 1 percent by weight of the said lower alkylene oxide residue and said active hydrogen-con-taining compound is a monohydric aliphatic alcohol.

23. The concentrate of claim 22 wherein said initiator is selected from the group consisting of at least one of stearyl alcohol, lauryl alcohol, and myristyl alcohol.

24. The concentrate of claim 23 wherein said gly-cidyl either is in a mole ratio to said initiator of about 1:5 to about 1:15.

25. A hydraulic fluid or metalworking fluid concentrate capable of imparting to water the properties of a lubricant such as resistance to extreme pressure and corrosion inhibition, said concentrate consisting essentially of:
A. a water-soluble polyoxyethylated aliphatic ester consisting of esters of ethoxylated aliphatic monohydric and polyhydric alcohols or ethoxylated aliphatic acids wherein said acids or alcohols have about 5 to about 20 moles of ethylene oxide added per mole of acid or alcohol and wherein said alcohols and acids have carbon chain lengths of 8 to 36 carbon atoms and wherein said esters are produced by first polyoxyethylating at least one of said acids or alcohols and second, obtaining the ester reaction product thereof, B. a sulfurized metallic compound of the formula:

wherein M is molybdenum or antimony and wherein, R is selected from the group consisting of alkyl, aryl, alkylaryl radicals and mixtures thereof having to 20 carbon atoms in the alkyl group and wherein the ratio of said water-soluble ester to said sulfurized metallic compound is from 5:1 to 2:1 by weight based upon the weight of the sulfur in said metallic compound, C. a phosphate ester salt selected from the group consisting of and and mixtures thereof, wherein EO is ethylene oxide; R is selected from the group consisting of linear or branched chain alkyl groups having about 6 to 30 carbon atoms or alkylaryl groups wherein said alkyl groups have 6 to 30 carbon atoms; X is selected from the residue of ammonia, an amine and an alkali or alkaline earth metal or mixtures thereof, n is a number from 1 to 50 and wherein the proportion of said phosphate ester to said sulfurized metallic compound is about 0.1:1 to about 2:1 based upon the weight of the sulfur in said metallic compound, D. a polyether thickener having a molecular weight of about 1000 to about 25,000 prepared by reacting ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-containing aliphatic or alkylaromatic initiator containing no more than one active hydrogen and either at least one alpha-olefin oxide having a carbon chain length of about 12 to about 18 aliphatic carbon atoms or at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said alpha-olefin oxide or glycidyl ether is present in the amount of about 1 to about 20 percent by weight based upon the total weight of said thickener, and optionally, E. a corrosion inhibitor and a metal deactivator.