EP0061823B1 - Fluide hydraulique ou fluide de coupe à base d'eau, et synergistiquement épaissi - Google Patents

Fluide hydraulique ou fluide de coupe à base d'eau, et synergistiquement épaissi Download PDF

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Publication number
EP0061823B1
EP0061823B1 EP82300360A EP82300360A EP0061823B1 EP 0061823 B1 EP0061823 B1 EP 0061823B1 EP 82300360 A EP82300360 A EP 82300360A EP 82300360 A EP82300360 A EP 82300360A EP 0061823 B1 EP0061823 B1 EP 0061823B1
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EP
European Patent Office
Prior art keywords
water
percent
carbon atoms
ethylene oxide
metalworking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82300360A
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German (de)
English (en)
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EP0061823A1 (fr
Inventor
Assadullah Nassry
Jerrold F. Maxwell
John W. Compton
Edward J. Panek
Pauls Davis
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BASF Corp
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BASF Wyandotte Corp
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Priority to AT82300360T priority Critical patent/ATE13689T1/de
Publication of EP0061823A1 publication Critical patent/EP0061823A1/fr
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Publication of EP0061823B1 publication Critical patent/EP0061823B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/081—Inorganic acids or salts thereof containing halogen
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/082—Inorganic acids or salts thereof containing nitrogen
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/22—Heterocyclic nitrogen compounds
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
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    • C10M2215/26—Amines
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    • C10M2215/30—Heterocyclic compounds
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    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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    • C10M2219/106—Thiadiazoles
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
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    • C10M2223/042—Metal salts thereof
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    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
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    • C10M2223/045—Metal containing thio derivatives
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Definitions

  • This invention relates to water-based hydraulic fluids and metalworking compositions.
  • a hydraulic fluid in the form of pressure by means of a hydraulic pump.
  • Power is utilized 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.
  • 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 utilized in conjunction with hydraulic fluids, (i.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 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.
  • 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.
  • 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.
  • Such fluids have found application in specially designed, high cost, large size equipment which, because of said large size and thus inflexibility, 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.
  • alkylene oxide derivatives of an alkyl, aryl or arylalkyl 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.
  • 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 (polyether) thickening agent.
  • the fluids of the invention can include a vapor or liquid phase corrosion inhibitor and a metal deactivator.
  • a polyether polyol thickening agent which is a high molecular weight polyether polyol derived from the reaction of ethylene oxide or ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with an active hydrogen-containing initiator containing at least two active hydrogens and have a molecular weight of 1000 to 75,000, preferably 1000 to 40,000, further modified by reaction with an alpha-olefin epoxide (oxide) having 12 to 18 carbon atoms, unexpectedly provides a surprising increase in viscosity, said increase not being simply additive.
  • 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 antiwear characteristics or as metalworking compositions used to cool and lubricate surfaces which are in frictional contact such as during the operations of turning, cutting, peeling, grinding metals and the like.
  • the hydraulic fluids and metalworking compositions of the invention are ecologically superior to those fluids and metalworking emulsions of the prior art containing mineral oil or a glycol/water mixture.
  • hydraulic fluids, metalworking fluids and lubricating concentrates which can be diluted with water as a base to prepare hydraulic fluids or metalworking compositions.
  • the disclosed compositions provide the desirable lubricity as well as antiwear properties which are necessary in a hydraulic fluid or a metalworking composition.
  • the thickened hydraulic fluids and metalworking fluids of the invention can be prepared 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.
  • corrosion inhibiting agents, defoamers, metal deactivators (chelating agents) can be used as part of the compositions of the invention.
  • water-soluble esters of the ethoxylated C S -C 36 aliphatic monohydric or polyhydric alcohols with aliphatic acids, and aliphatic dimer acids.
  • ethoxylated esters have a hydrophilic-lipophilic balance (HLB) in the range of 10 to 20.
  • HLB hydrophilic-lipophilic balance
  • 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 acid and stearic dimer acid.
  • Aliphatic acids can be either branched or straight-chain and can contain from 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 invention 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 polyester 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.
  • 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.
  • 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.
  • Useful representative monohydric alcohols are n-octyl, n-decyl, n-dodecyl (lauryl), n-tetradecyl (myristyl), n-hexadecyl (cetyl) and n-octadecyl alcohol.
  • Useful representative polyhydric alcohols are ethylene glycol, diethylene glycol, polyethylene glycol, sucrose, butanediol, butenediol, butynediol, hexanediol and polyvinyl alcohol.
  • Glycerol, sorbitol, pentaerythritol, trimethylolethane, and trimethylolpropane are particularly useful polyhydric alcohols which can by ethoxylated and subsequently esterified to produce the esters of ethoxylated aliphatic alcohols useful as essential components of the hydraulic fluids and metalworking compositions of the invention.
  • Suitable monohydric aliphatic alcohols are generally those having straight chains and carbon contents of Cg--C,8.
  • 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 C,2-C,5 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, sorbitan tristearate, sorbitan monopalmitate, sorbitan monoisostearate, and sorbitan monolaurate.
  • the sulfurized oxymolybdenum or oxyantimony organophosphorodithioate additives of the invention are represented by the formula: wherein M is molybdenum or antimony and R is organic and is selected from the group consisting of C 3 -C 20 alkyl, aryl, alkylaryl radicals and mixtures thereof.
  • Representative useful molybdenum and antimony compounds are sulfurized oxyantimony or oxymolybdenum organophosphorodithioate where the organic portion is alkyl, aryl or arylalkyl and wherein said alkyl has a chain length of 3 to 20 carbon atoms.
  • compositions of the invention contain a phosphate ester salt selected from the group consisting of 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 group have 6 to 30 carbon atoms, preferably 8 to 20 carbon atoms, wherein the alkyl groups have 6 to 30 carbon atoms, preferably 8 to 18 carbon atoms and
  • X is selected from the group consisting of the residue of ammonia or an amine and an alkali 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 generally obtained by esterifying 1 mole of phosphorus pentoxide with 2 to 4.5 moles of a nonionic surface active agent obtained by condensing at least 1 mole of ethylene oxide with 1 mole of a compound having at least 6 carbon atoms and a reactive hydrogen atom.
  • a nonionic surface active agent obtained by condensing at least 1 mole of ethylene oxide with 1 mole of a compound having at least 6 carbon atoms and a reactive hydrogen atom.
  • These nonionic surface active agents are well known in the art and are generally prepared by condensing a polyglycol ether containing a suitable number of alkanoxy groups or a 1,2-alkylene oxide, 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.
  • 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.
  • suitable nonionic surface active agent condensation products which can be in turn reacted with phosphorus pentoxide to produce the phosphate esters utilized as additives in the hydraulic fluids of the invention are exemplified below.
  • "EO” represents "ethylene oxide” and the number preceding this abbreviation refers to the number of moles thereof reacted with 1 mole of the given reactive hydrogen-containing compound.
  • the hydraulic fluids and metalworking compositions of the invention generally consist of 60 percent to 99 percent water and 40 percent to 1 percent of additives.
  • additives can consist of concentrates comprising combinations of the water-soluble esters of ethoxylated aliphatic acids and monohydric and polyhydric aliphatic alcohols, molybdenum and antimony compounds, a phosphate ester, and, in addition, can contain polymer thickening agents, defoamers, corrosion inhibitors and metal deactivators or chelating agents.
  • said fluids consist of 75 percent to 99 percent water and 25 percent to 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 concentrates are typically diluted with water in the proportion of 1:99 to 10:90.
  • the proportions of phosphate ester to sulfurized molybdenum or antimony compound of the invention are generally 0.1:1 to 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 0.5:1 to 2:1 based upon the weight of the sulfur in the sulfur-containing compound.
  • 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 1:1 to 1.5:1.
  • the concentration of sulfurized molybdenum or antimony compound to water in the hydraulic fluid or metalworking compositions of the invention is generally 0.05 percent to 3 percent by weight and the concentration of the phosphate ester to water in the hydraulic fluid or metalworking compositions of the invention is generally 0.05 percent to 1 percent by weight.
  • 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 0.1 percent to 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 modified polyether polyol thickening agents utilized to thicken the hydraulic fluids and metalworking fluids of the invention can be obtained in one embodiment of the invention by modifying a conventional polyether polyol thickening agent with an alpha-olefin epoxide having about 12 to about 18 carbon atoms or mixtures thereof.
  • the conventional polyether polyol thickening agent can be an ethylene oxide homopolymer or a heteric or block copolymer of ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms. Said ethylene oxide is used in the proportion of at least 10 percent by weight based upon the total weight of the polyether polyol. Generally, about 70 to 99 percent by weight ethylene oxide is utilized with 30 to 1 percent by weight of lower alkylene oxide having 3 to 4 carbon atoms.
  • Polyether polyols are generally prepared utilizing an active hydrogen-containing compound in the presence of an acid or basic oxyalkylation catalyst and an inert organic solvent at elevated temperatures in the range of 50°C to 150°C. under an inert gas pressure generally from 20 to 100 pounds per square inch gauge.
  • Polyether polyols suitable as thickeners can be prepared by further reacting a polyether polyol having a molecular weight of 1000 to 75,000, preferably 1000 to 40,000 with said alpha-olefin epoxide so as to provide an alpha-olefin epoxide cap on the polyether polyol.
  • Polyethers suitable as thickeners for the hydraulic fluids of the invention can be obtained by the heteric polymerization of ethylene oxide and said alphaolefin epoxide.
  • the amount of alpha-olefin epoxide required to obtain the modified polyether polyol thickening agents of the invention is 1 to 20 percent by weight based upon the total weight of the modified polyether polyol thickeners.
  • the modified polyether polyol thickening agents can be obtained by the heteric copolymerization of a mixture of ethylene oxide and at least one other lower alkylene oxide having 3 to 4 carbon atoms with an alpha-olefin epoxide having 12 to 18 carbon atoms or mixtures thereof.
  • At least 10 percent by weight, preferably 40 to 60 percent by weight of the modified polyether polyol is used together with 60 to 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 hydraulic fluid or metalworking compositions of the invention are as follows:
  • the liquid-vapor corrosion inhibitor can be any of the alkali metal nitrites, nitrates, phosphates, silicates and benzoates. Certain amines are also useful. The inhibitors can be used individually or in combinations. Representative 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, ethylenediamine, dimethylaminopropylamine, dimethylethanolamine, alpha- and gamma- picoline, piperazine and isopropylaminoethanol.
  • Particularly preferred vapor phase corrosion inhibiting compounds are morpholine and isopropylaminoethanol.
  • As corrosion inhibitors a proportion of from 0.05 percent to 2 percent by weight is used based upon the total weight of the hydraulic fluid or metalworking composition of the invention. Preferably, 0.5 percent to 2 percent by weight of these amines are used.
  • 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 derivatives of salicylidenes. Representative specific examples of these metal deactivators are as follows: benzotriazole, tolytriazole, 2-mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, and N,N'-disalicylidene-1,2-propanediamine.
  • 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 is as follows:
  • a typical high water-base hydraulic fluid or metalworking additive of the invention will contain the components shown in Table II.
  • the hydraulic fluid and metalworking compositions of the invention when formulated as above, are transparent liquids having a viscosity of up to 86 Centistrokes at 38°C, which are stable over long periods of storage at ambient temperature.
  • 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 fluids and metalworking additives of the invention are ecologically clean and non-polluting 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 independent of shortages of petroleum oil and not materially influenced by the economic impart of such shortages.
  • a test generally referred to as the Vickers Vane 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 to, a 25 horsepower, 1740 rpm electric motor.
  • the fluid is 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.
  • 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 front 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 connected 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 18.9 I (5 gallons) of the test fluid and running at temperatures ranging from 38°C to 57°C at 52 to 70 bars 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 disassembly for weighing, visual examination of the system was made for signs of deposits, varnish, corrosion, etc.
  • Hydraulic fluid concentrates were prepared having the compositions in percent by weight of:
  • the fluids were clear, dark amber in color, free flowing and showed no phase separation upon aging at room temperature.
  • 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.
  • a heteric copolymer of ethylene oxide and 1,2-propylene oxide is prepared having a molecular weight of about 23,000. Subsequently, this base heteric copolymer 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.
  • a conventional polyether derived from ethylene oxide and 1,2-propylene oxide in the ratio of 75 percent ethylene oxide and 25 percent 1,2-propylene oxide was prepared by reaction with trimethylol propane in two stages in a stainless steel autoclave.
  • An intermediate product was first prepared by reacting a mixture of trimethylol propane, potassium hydroxide, 1,2-propylene oxide, and ethylene oxide for a period of 18 hours at 120°C. The cooled liquid product was discharged into a glass container.
  • the base copolymer product was prepared by reacting this intermediate product with propylene oxide and ethylene oxide under a nitrogen atmosphere at 115°C. for 22 hours. The reaction mixture was then cooled and the viscous liquid product transferred to a glass container. The product had a molecular weight of about 23,000.
  • Tables III-V 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 5 to 7.5 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 hydraulic fluid concentrate is unexpected and advantageous in that lesser amounts of thickener would be required to produce a thickened hydraulic fluid or metalworking lubricant thus resulting in a cost saving.
  • a water-based hydraulic fluid having a viscosity of 72.2 cSt 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 689.104 Pa (1000 pounds per square inch) pressure at a temperature of 38°C for a period of 194 hours. Samples of the hydraulic fluid were taken at various time intervals during the test and the viscosity determined. The variation in viscosity is indicative of the shear stability of the hydraulic fluid.
  • the overall change in viscosity of the fluid after 194 hours running time is less than 20 percent which indicates good shear stability performance in the Vickers Vane Pump.
  • Example 5 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 38°C, for a period of 194 hours. Ring and vane wear losses were determined at various time intervals and the results are shown in Table VII.

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Claims (7)

1. Concentré de fluide hydraulique ou de fluide pour le travail des métaux susceptible de donner à l'eau les propriétés d'un lubrifiant telles que la résistance aux pressions extrêmes et l'inhibition à la corrosion, ce concentré consistant essentiellement en:
A. un ester aliphatique polyoxyéthylé, soluble dans l'eau, consistant en esters d'alcools mono- hydriques et polyhydriques aliphatiques éthoxylés et d'acides aliphatiques éthoxylés où lesdits acides ont 5 à 20 moles de d'oxyde d'éthylène ajoutées par mole d'acide et où lesdits alcools et acides ont des longueurs de chaîne carbonées de 8 à 36 atomes de carbone et où lesdits esters sont produits d'abord en polyoxyéthylant au moins un desdits acides ou alcools et ensuite en obtenant à partir deux, le produit de réaction d'ester,
B. un composé métallique sulfuré de la formule
Figure imgb0016
dans laquelle M est du molybdène ou de l'antimoine et où R est choisi dans le groupe constitué des radicaux alkyle, aryle, alkylaryle et leurs mélanges ayant 3 à 20 atomes de carbone dans le groupe alkyle et où le rapport entre ledit ester soluble dans l'eau et ledit composé métallique sulfuré est de 5:1 à 2:1 en poids, basé sur le poids du soufre dans le composé métallique,
C. un sel de phosphate ester choisi dans le groupe constitué par
Figure imgb0017
et leurs mélanges, où EO est de l'oxyde d'éthylène, R est choisi dans le groupe constitué de groupes alkyle à chaîne linéaire ou ramifiée ayant environ 6 à 30 atomes de carbone ou des groupes alkylaryle dans lesquels lesdits groupes alkyle ont 6 à 30 atomes de carbone; X est choisi parmi le reste d'ammoniac, une amine et un métal alcalin ou alcalino-terreux ou leurs mélanges, n est un nombre de 1 à 50, et où la proportion dudit phosphate ester audit composé métallique sulfuré est de 0,1:1 à 2:1 basée sur le poids du soufre dans ledit composé métallique, et
D. éventuellement, un inhibiteur de corrosion et un désactivateur métallique, caractérisé par le fait que ledit concentré en outre contient;
E. un épaississant, polyéther polyol, ayant un poids moléculaire de 1 000 à 75 000, préparé en faisant réagir de l'oxyde d'éthylène, ou de l'oxyde d'éthylène et au moins un oxyde d'alkylène inférieur ayant 3 à 4 atomes de carbone, avec au moins un composé contenant de l'hydrogène actif et contenant au moins deux hydrogène actifs et au moins un oxyde d'a-oléfine ou au moins un éther glycidylique ayant une longeur de chaîne de carbone de 12 à 18 atomes de carbone aliphatique et où ledit oxyde d'a-oléfine ou l'éther glycidylique est présent en proportion de 1 à 20% en poids, basé sur le poids total dudit épaississant.
2. Concentré selon la revendication 1, caractérisé par le fait que ledit phosphate ester est l'ester du produit de réaction de 4 moles d'oxyde d'éthylène avec 1 mole d'alcool oléylique estérifié en faisant réagir 1 mole dudit produit de réaction avec 2 moles de pentoxide de phosphore.
3. Fluide hydraulique ou fluide lubrifiant pour le travail des métaux, constitué essentiellement d'eau et du concentré de la revendication 1, caractérisé par le fait que ledit fluide consiste entre 60 et 99% d'eau et 40% à 1 % de concentré.
4. Concentré selon la revendication 1, constitué par 50% à 80% dudit épaississant.
5. Concentré selon la revendication 1, caractérisé par le fait que ledit polyéther polyol est préparé en copolymérisant un mélange desdits réactifs, pour produire un copolymère hétérogène liquide.
6. Concentré selon la revendication 1, caractérisé par le fait que le dit polyéther polyol est préparé en faisant réagir séquentiellement de l'oxyde d'éthylène avec au moins un desdits oxydes d'alkylène inférieurs pour produire un copolymère en blocs, intermédiaire, et ensuite en faisant réagir ledit intermédiaire avec au moins un desdits oxydes d'a-oléfine.
7. Concentré selon la revendication 1, dans laquelle ledit initiateur contenant de l'hydrogène actif, contenant au moins deux hydrogènes actifs, est un alkane polyol choisi dans le groupe constitué par au moins un des trimethylolpropane, glycerol, 2,3,5,6-hexane-tetrol, sorbitol, et pentaerythritol et le rapport molaire du dit initiateur aux quantités molaires combinées desdits oxyde d'éthylène, des oxydes d'alkylène inférieur et dudit oxyde d'a-oléfine est dans le rapport molaire de 1:5 à 1:15.
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EP0061823A1 (fr) 1982-10-06
DK30682A (da) 1982-10-02
ATE13689T1 (de) 1985-06-15
AU7978482A (en) 1982-10-07
IE820145L (en) 1982-10-01
JPS57167397A (en) 1982-10-15
BR8200371A (pt) 1982-11-23
AU546230B2 (en) 1985-08-22

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