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WO2010053639A1 - Liquides fonctionnels à faible viscosité - Google Patents

Liquides fonctionnels à faible viscosité Download PDF

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Publication number
WO2010053639A1
WO2010053639A1 PCT/US2009/059181 US2009059181W WO2010053639A1 WO 2010053639 A1 WO2010053639 A1 WO 2010053639A1 US 2009059181 W US2009059181 W US 2009059181W WO 2010053639 A1 WO2010053639 A1 WO 2010053639A1
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fluid composition
percent
amount
weight
present
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Jin Zhao
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
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    • C10M2207/02—Hydroxy compounds
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2207/046—Hydroxy ethers
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    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
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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
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
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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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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/0615—Esters derived from boron used as base material
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • This disclosure relates to low viscosity functional fluids which are useful in a variety of applications, and in particular, as brake fluids.
  • FMVSS 1 16, SAE J1704, and ISO 4925 provide stringent physical property and performance requirements particularly with respect to minimum dry equilibrium reflux boiling point (ERBP), minimum wet equilibrium boiling point (WERBP) and maximum low temperature (-4O 0 C) viscosity while maintaining adequate resistance to corrosion, stability and meeting other physical property requirements such as pH, reserve alkalinity, rubber swell, etc.
  • ERBP minimum dry equilibrium reflux boiling point
  • WERBP minimum wet equilibrium boiling point
  • 4O 0 C maximum low temperature
  • the standards for DOT 4 fluid certification set forth in FMVSS 1 16 are comparable to those for J1704 Fluids and ISO 4925 Class 4 fluids, some of which are shown in Table 1 :
  • Brake fluids and other functional fluids may cause corrosion of different materials with which they come into contact over time.
  • FMVSS 1 16, J1704, and ISO 4925 each include corrosion specifications based on defined test procedures in which metal strips of various metals are submerged in a mixture of 5 percent water (by volume) and the brake fluid for a specified time (120 hours) at a specified temperature (100 0 C).
  • DOT 4 brake fluids comprising alkyl glycol borate esters, alkyl glycols, and a corrosion inhibitor package.
  • they do not address the issue of brake fluid contamination with salt water mixtures and provide no indication that the disclosed fluids could meet the DOT 4, J1704 or ISO 4925 corrosion standards when subjected to a salt water environment.
  • a need has arisen for a functional fluid which addresses the foregoing issues.
  • a fluid composition which comprises at least one glycol borate ester, at least one glycol, and an additive package that includes at least one corrosion inhibitor.
  • the fluid composition is combined with water and a chloride salt to yield a total composition in which water is present in an amount that is 5 percent by volume of the total composition and chloride ion is present in an amount that is 50 parts per million by weight of the total composition, and the total composition is subjected to the corrosion testing protocol set forth in SAE Standard J1704, the mass change per unit area of tinned iron is no more than 0.2 mg/cm 2 .
  • the total composition meets the maximum permissible weight change specification for tinned iron, steel, aluminum, cast iron, brass and copper set forth in SAE Standard J 1704.
  • a fluid composition which comprises at least one glycol borate ester, at least one glycol, and an additive package including at least one corrosion inhibitor.
  • the at least one corrosion inhibitor comprises at least one triazole, at least one amine, at least one inorganic borate, at least one inorganic nitrate, and at least one alkenyl succinic anhydride.
  • a fluid composition which comprises at least one glycol borate ester, at least one glycol, and an additive package comprising at least one corrosion inhibitor.
  • the at least one corrosion inhibitor is present in an amount effective to inhibit the corrosion of tinned iron when the fluid composition is combined with water and a chloride salt to yield a total composition in which water is present in an amount that is 5 percent by volume of the total composition and chloride ion is present in an amount that is 50 parts per million by weight of the total composition.
  • the at least one corrosion inhibitor comprises at least one triazole, at least one non-triazole amine, at least one inorganic borate, at least one inorganic nitrate, and at least one alkenyl succinic anhydride.
  • This disclosure relates to functional fluids comprising one or more glycols, one or more glycol borate esters, and an additive package that includes at least one corrosion inhibitor.
  • the corrosion inhibitors are preferably present in an amount that is effective to inhibit the corrosion of metals when the brake fluid is contaminated with salt water.
  • the corrosion inhibitors are present in an amount that is effective to inhibit the corrosion of tinned iron, brass, aluminum, copper, cast iron, and steel when the fluid is mixed with 5 percent water (by volume) and 50 ppm (by weight) of chloride ion.
  • the corrosion inhibitors are present in an amount that is effective to inhibit the corrosion of tinned iron, brass, aluminum, copper, cast iron, and/or steel when the fluid is mixed with 5 percent water (by volume) and 50 ppm (by weight) chloride ion and subjected to the SAE J1704 (Rev. April 2004) and FMVSS 1 16 (49 CFR ⁇ 571.116) corrosion test protocols.
  • the functional fluids meet the SAE J1704 and FMVSS 1 16 specifications for the maximum permissible weight change of tinned iron, steel, aluminum, cast iron, brass, and copper when the fluid is mixed with 5 percent (by volume) water and 50 ppm (by weight) chloride ion and the mixture is subjected to the SAE J1704 and FMVSS 1 16 corrosion testing protocols.
  • SAE J1704 Rev. April 2004
  • FMVSS 1 16 are hereby incorporated by reference.
  • the total amount of glycols (excluding glycol borate esters) present in the functional fluid formulation is preferably at least about 30 percent, more preferably at least about 35 percent and most preferably at least about 38 percent by weight of the total functional fluid formulation.
  • the total amount of glycols present in the functional fluid formulation is preferably no greater than about 50 percent, more preferably no greater than about 45 percent, and most preferably no greater than about 43 percent by weight of the total functional fluid formulation.
  • the glycol component can be formed partially, substantially entirely (at least 90 percent or at least 95 percent by weight) or entirely of one, two, three or more glycols, polyglycols, or both.
  • the glycols or polyglycols of the glycol component have the formula of EQUATION I:
  • Each of R-i, R 2 , R 3 , R 4 , R5 is either hydrogen (H) or an alkyl group containing 1 to 8 or more carbon atoms or mixtures thereof such as one disclosed in Provisional Application Ser. No. 60/976,010 (filed September 28, 2007) entitled "Functional Fluid Composition", which is hereby incorporated by reference for all purposes.
  • Ri be an alkyl group containing 1 to 8 carbon atoms such that the glycol or polyglycol is an alkoxy glycol ether (e.g., an alkyl end capped glycol ether) as opposed to being simply a glycol where Ri is H.
  • Ri is H for less than about 30 percent, more typically less than about 10 percent and even possibly less than about 5 percent or less than about 2 percent by weight of the glycol component.
  • polyglycol refers to a glycol such as that of EQUATION I in which n is at least 2 or greater.
  • glycol is inclusive of all polyglycols. It should also be understood that the glycol component can include both those glycols in which Ri is an alkyl group and those in which Ri is H.
  • the amount of glycol in which n is 2 or more is even more preferably at least about 90 percent by weight of the glycol component.
  • n is essentially 2 to 4.
  • Preferable glycol components include an Ri group comprising a methyl, an ethyl, a propyl, a butyl, or combinations thereof.
  • examples of useful glycols include methoxy triglycol, methoxy diglycol, methoxy tetraglycol, methoxy polyglycol (e.g., mixtures of methoxy triglycol, methoxy tetraglycol, and other glycols in which Ri is CH 3 and n is 5 or more), ethoxy triglycol, ethoxy diglycol, ethoxy tetraglycol, propoxy triglycol, butoxy triglycol (e.g., Methylene glycol monobutyl ether), butoxy diglycol (e.g., diethylene glycol monobutyl ether), butoxy tetraglycol, butoxy polyglycol (e.g., mixtures of butoxy triglycol, butoxy tetraglycol, and other glycols in which Ri is an alkyl having 4 carbon atoms and n
  • Preferable glycols (e.g., alkoxy glycols) of the glycol component include, without limitation, methoxy triglycol, methoxy diglycol, methoxy polyglycol, methoxy tetraglycol, ethoxy polyglycol, ethoxy triglycol, ethoxy diglycol, ethoxy tetraglycol, butoxy polyglycol, butoxy triglycol, butoxy diglycol, butoxy tetraglycol, triethylene glycol monohexyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monobutyl ether, polypropylene glycol monobutyl ether,
  • More preferable alkoxy glycol components comprise methoxy triglycol, methoxy diglycol, methoxy polyglycol, butoxy triglycol, butoxy diglycol, butoxy polyglycol, triethylene glycol monohexyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monopropyl ether, polypropylene glycol monobutyl ether or mixtures thereof.
  • alkoxy glycol components comprise a mixture of two or more of methoxy polyglycol, butoxy diglycol, butoxy triglycol, butoxy polyglycol, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monopropyl ether, or polypropylene glycol monobutyl ether.
  • useful glycols include, without limitation, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monopropyl ether, polypropylene glycol monobutyl ether, polybutylene glycol monopropyl ether, polybutylene glycol monopropyl ether, polybutylene glycol monobutyl ether, combinations thereof or the like.
  • methods of preparing useful alkoxy glycols include an alkoxylation reaction that reacts an alkylene oxide with an alcohol to produce an alkoxy glycol.
  • the glycol component comprises at least about 50 percent, more preferably at least about 60 percent, and most preferably at least about 65 percent methoxy triglycol based on the total weight of the glycols present in the fluid.
  • the glycol component preferably comprises no greater than about 80 percent, more preferably not greater than about 70 percent, and most preferably no greater than about 68 percent methoxy triglycol based on the total weight of the glycols present in the fluid.
  • the glycol component preferably comprises at least about 20 percent, more preferably at least about 25 percent, and most preferably at least about 28 percent butoxy triglycol based on the total weight of the glycols present in the fluid.
  • the glycol component preferably comprises no greater than about 40 percent, more preferably no greater than about 35 percent, and most preferably no greater than about 32 percent butoxy triglycol based on the total weight of the glycols present in the fluid.
  • glycol borate ester(s) of the functional fluid preferably include at least one ingredient having the formula:
  • R-i, R 2 , R3, R4, and R 5 can be any of groups as specified with respect to EQUATION I and n can be as specified with respect to EQUATION I.
  • the glycol borate ester component can have any of the repeat units of glycol component as discussed with respect to EQUATION I herein. In certain exemplary formulations, n is essentially 2 to 4. It is also understood that the glycol borate ester component and any borate containing compound is not considered as part of the glycol component, but rather is separate.
  • glycol borate ester components include alkoxy glycol borate ester components such as methoxy triethylene glycol borate ester, ethoxy triethylene glycol borate ester, butoxy triethylene glycol borate ester and mixtures thereof disclosed in U.S. Patent No. 6,558,569, hereby incorporated by reference.
  • the amount of glycol borate ester in the functional fluid is preferably at least about 30 percent by weight of the total fluid composition, more preferably at least about 40 percent by weight of the total fluid composition and most preferably at least about 50 percent by weight of the total fluid composition. In an especially preferred embodiment, the amount of glycol borate ester is at least about 52 percent by weight of the total fluid composition.
  • the amount of glycol borate ester is preferably no greater than about 70 percent by weight of the total fluid composition, more preferably no greater than about 65 percent by weight of the total fluid composition, and most preferably no greater than about 60 percent by weight of the total fluid composition. In an especially preferred embodiment, the amount of glycol borate ester is no greater than about 56 percent by weight of the total fluid composition.
  • Borate esters useful in the functional fluid compositions of the present invention may be prepared by reacting boric acid with a suitable glycol component which is typically a selective mixture of glycols containing at least 90 percent by weight, and preferably 95 percent by weight, of the triethylene glycol species.
  • borate esters examples include those containing methoxy triethylene glycol borate ester, ethyl triethylene glycol borate ester, butyl triethylene glycol borate ester and mixtures thereof. Particularly good results have been obtained with a borate ester component containing greater than 90 percent methoxy triethylene glycol borate ester based on the total weight of all glycol borate ester components.
  • the functional fluids of the present disclosure also include an additive package which contains one or more corrosion inhibitors and one or more of the following: an antifoaming agent, a pH stabilizer, a chelating agent, and an antioxidant.
  • the corrosion inhibitors are preferably present in an amount that is at least about 0.3 percent by weight of the fluid formulation, more preferably at least about 1.0 percent by weight of the fluid formulation, and most preferably at least about 3.0 percent by weight of the fluid formulation.
  • the corrosion inhibitors are preferably present in an amount that is no greater than about 10 percent by weight of the fluid formulation, more preferably no greater than about 6.0 percent by weight of the fluid formulation, and most preferably no greater than about 4.0 percent by weight of the fluid formulation.
  • the corrosion inhibitors in the additive package preferably include compounds that inhibit the corrosion of tinned iron, steel, aluminum, cast iron, brass, and copper, each of which has a corrosion specification set forth in SAE J1704 and FMVSS 116.
  • the corrosion inhibitors also include one or more compounds that inhibit the corrosion of zinc.
  • the corrosion inhibitors preferably include at least one heterocyclic nitrogen-containing compound, for example, triazoles such as benzotriazole, tolytriazole, 1 ,2, 4 triazole, and mixtures thereof.
  • the triazole compounds are preferably present in an amount that is at least about 0.01 percent, more preferably at least about 0.05 percent, and most preferably at least about 0.1 percent by weight of the total fluid weight.
  • the triazole compounds are preferably present in an amount that is no greater than about 0.4 percent, more preferably no greater than about 0.3 percent, and most preferably no greater than about 0.25 percent by weight of the total fluid formulation.
  • triazole compounds such as benzotriazole, tolytriazole, and 1 , 2, 4 triazole are believed to be particularly effective for inhibiting copper corrosion.
  • the corrosion inhibitors also preferably include amine compounds other than triazoles, including alkyl amines (e.g., di n-butylamine and di n-amylamine), cyclohexylamine, piperazines (e.g., hydroxylethyl piperazine), and salts thereof.
  • alkyl amines e.g., di n-butylamine and di n-amylamine
  • piperazines e.g., hydroxylethyl piperazine
  • salts thereof e.g., hydroxylethyl piperazine
  • Non-triazole amine compounds which are particularly useful as corrosion inhibitors in the functional fluid compositions of the present disclosure include the alkanol amines, preferably those containing one to three alkanol groups with each alkanol group containing from one to six carbon atoms.
  • alkanol amines examples include mono-, di- and and trimethanolamine, mono-, di- and triethanolamine, mono-, di- and tripropanolamine and mono-, di- and triisopropanolamine.
  • Preferred alkanol amines include butyldiethanol amine and diisopropanolamine. Without wishing to be bound by any theory, the alkanolamines are believed to be effective for inhibiting the corrosion of ferrous compounds (e.g, iron, steel) and also act as a buffer.
  • the non-triazole amine compounds are preferably present in an amount that is at least about 0.01 percent, more preferably at least about 0.1 percent, and even more preferably, at least about 0.2 percent by weight of the fluid formulation.
  • the non-triazole amine compounds are preferably present in an amount that is no greater than about 4 percent, more preferably no greater than about 3.5 percent, and most preferably no greater than about 3.0 percent by weight of the total fluid formulation.
  • the corrosion inhibitors also include one or more alkenyl succinic anhydrides.
  • Preferred alkenyl succinic anhydrides include derivatives of maleic anhydride. Dodecenyl succinic anhydride is especially preferred.
  • the alkenyl succinic anhydrides are preferably present in an amount that is at least about 0.1 percent, more preferably at least about 0.12 percent, and most preferably at least about 0.14 percent by weight of the functional fluid composition.
  • the alkenyl succinic anhydrides are preferably present in an amount that is no greater than about 0.5 percent, more preferably no greater than about 0.3 percent, and most preferably no greater than about 0.2 percent by weight of the functional fluid composition.
  • the corrosion inhibitors also include one or more inorganic nitrates, preferably sodium nitrate.
  • the inorganic nitrates are preferably present in an amount that is at least about 0.01 percent, more preferably at least about 0.02 percent and most preferably at least about 0.04 percent by weight of the fluid formulation.
  • the inorganic nitrates are preferably present in an amount that is no greater than about 0.1 percent, more preferably no greater than about 0.08 percent, and most preferably no greater than about 0.06 percent by weight of the fluid formulation.
  • the inorganic nitrates are believed to be effective at inhibiting the corrosion of aluminum.
  • the corrosion inhibitors include one or more inorganic borates such as Sodium Tetraborate, commonly known as Borax.
  • the inorganic borates are preferably provided as solid hydrates.
  • An especially preferred inorganic borate is sodium tetraborate pentahydrate Na 2 B 4 O 7 -SH 2 O, also known as Borax 5 MoI.
  • Another exemplary inorganic borate is sodium tetraborate decahydrate (Na 2 B 4 O 7 -I OH 2 O).
  • the inorganic borate is preferably provided in an amount that is at least about 0.03 percent, more preferably at least about 0.05 percent, and most preferably at least about 0.07 percent by weight of the fluid formulation.
  • the inorganic borate is preferably provided in an amount that is no greater than about 0.1 percent, more preferably greater than about 0.09 percent, and most preferably no greater than about 0.08 percent by weight of the fluid formulation.
  • the corrosion inhibitors may include one or more silicone compounds such as silicate esters.
  • Preferred silicate esters include polymers of dialkoxysiloxanes, including without limitation poly(diethoxysiloxane) (e.g., PSI-21 ).
  • the silicone corrosion inhibitor is preferably provided in an amount that is at least about 0.001 percent, more preferably at least about 0.003 percent, and most preferably at least about 0.004 percent by weight of the fluid composition.
  • the silicone corrosion inhibitor is preferably provided in an amount that is no greater than about 0.008 percent, more preferably no greater than about 0.007 percent, and most preferably no greater than about 0.006 percent by weight of the fluid composition.
  • the silicone corrosion inhibitors are believed to inhibit the corrosion of brass and aluminum.
  • the functional fluid additive package may also include other additive compounds such as antifoaming agents, pH stabilizers, chelating agents, antioxidants, and the like.
  • Preferred antifoaming agents include poly(dimethylsiloxane) and silicone-based compounds such as SAG 100 Antifoam, a product of GE Advanced Materials.
  • the antifoaming agent is preferably provided in an amount that is no greater than about 0.00020 percent and more preferably no greater than about 0.00015 percent by weight of the fluid composition.
  • the antifoaming agent is preferably present in an amount that is at least about 0.00001 percent and more preferably at least about 0.00005 percent by weight of the fluid composition.
  • Suitable antioxidants include phenolic compounds and quinoline compounds.
  • Exemplary phenolic antioxidants include BHT (Butylated Hydroxytoluene); 2,6-di-tert-butyl-4-methyl phenol (which is supplied by Great Lakes Chemical Corporation under the name Lowinox ® 624); 2,6-di-tert-butyl-p- cresol); 2,6-di-tertiary-butyl-4-sec-butylphenol (which is supplied by the SI Group under the name Isonox ® 132); and bisphenol A.
  • Exemplary quinoline antioxidants include Agerite ® Resin D, a polymerized trimethyl dihydroquinoline compound supplied by the RT. Vanderbilt Company.
  • antioxidants are included in the additive package, they are preferably provided in an amount that is at least about 0.1 percent, more preferably at least about 0.2 percent, and most preferably at least about 0.3 percent by weight of the fluid composition.
  • the antioxidants are provided in an amount that is preferably no greater than about 1.0 percent, more preferably no greater than about 0.8 percent, and most preferably no greater than about 0.6 percent by weight of the fluid composition.
  • Suitable metal chelating agents include triocytlphosphine oxide, tributylphosphate, and dibutyl butyl phosphonate, DEHPA (Di (2-ethylhexyl) phosphoric acid) and propanediamine/xylene compositions such as Dupont Metal Deactivator (N, N' Disalicylidene-1 ,2-propanediamine and xylene).
  • the chelating agents are preferably present in an amount that is at least about 0.01 percent, more preferably at least about 0.05 percent, and most preferably at least about 0.08 percent by weight.
  • the chelating agents are preferably present in an amount that is no greater than about 0.2 percent, most preferably no greater than about 0.15 percent, and most preferably no greater than about 0.13 percent by weight of the fluid composition.
  • SAE Standard J1704 includes standards for borate ester based brake fluid certification which are similar to those of the DOT 4 standards set forth in FMVSS 116.
  • two sets of six specified metal corrosion test strips are polished, cleaned and weighed.
  • the six metal strips comprising each set are fastened together at one end.
  • Each strip is approximately 8 cm long, 1.3 cm wide, not more than 0.6 mm thick, and has a surface area of 25 ⁇ 5 cm 2 .
  • the specified metals are copper, brass, cast iron, aluminum, steel, and tinned iron.
  • SBR styrene-butadiene rubber
  • IRHD International Rubber Hardness Degree
  • the strips are each weighed to the nearest 0.1 mg and the change in weight is calculated for each strip.
  • the area of the strips is then determined, and the weight change per unit area in mg/cm 2 of surface area is calculated.
  • the diameter and IRHD values of the cups are then determined.
  • FMVSS 1 16 in order to be certified as a DOT 4 brake fluid, the weight change per unit surface area must not exceed the following specifications, which are identical to those of SAE JI 704:
  • the SBR cup specification of FMVSS 116 calls for an inner cup diameter increase of no more than 1.4mm and a hardness decrease of no more than 15 International Rubber Hardness Degrees.
  • the SAE J1704 specifications are identical, except that they call for an SBR Cup volume increase of no more than 16 percent instead of specifying a diameter increase.
  • the mixture when the functional fluids of the present disclosure are subjected to the J1704 corrosion test using a mixture of brake fluid with 5 percent water (by volume) and 25 ppm chloride ion, the mixture meets the J1704 and FMVSS 1 16 corrosion specifications for the maximum allowable weight change per surface area for tinned iron, steel, aluminum, cast iron, brass and copper. In a more preferred embodiment, the mixture meets the same specifications when the mixture of brake fluid and 5 percent (by volume) water includes 50 ppm chloride ion.
  • the fluid compositions of the present disclosure exhibit superior water stability and are able to maintain high boiling points and low viscosities at relatively high water levels.
  • the fluid compositions maintain an equilibrium reflux boiling point (ERBP) of no less than about 130°C, preferably no less than about 140 0 C, and more preferably no less than about 145 0 C at a water level of 5 percent by weight of the fluid composition.
  • ERBP equilibrium reflux boiling point
  • the fluids preferably have a -40 0 C kinematic viscosity of no more than about 1800 cSt, more preferably no more than about 1600 cSt, and most preferably no more than about 140O cSt.
  • Example 1 Corrosion Performance of Current DOT 4 Brake Fluids
  • DOT 4 brake fluids Four (4) commercially available DOT 4 brake fluids are subjected to an SAE J1704/FMVSS 1 16 corrosion test in which the brake fluid/ 5 percent water mixture includes 50 ppm chloride ion.
  • the tested brake fluids are DBF 460 and DBF 700, which are supplied by The Dow Chemical Company, a BASF DOT 4 brake fluid, and a Shell DOT 4 brake fluid.
  • Table 2 Table 2
  • Each of the tested brake fluids is certified to meet the J1704/FMVSS 1 16 corrosion standards. However, when the test is modified to include 50 ppm chloride ion in the brake fluid/water mixture, none of the brake fluids meet the tinned iron corrosion requirement of not more than 0.2 mg/cm 2 set forth in SAE J1704 and FMVSS 1 16.
  • Example 2 Exemplary Formulation of a DOT 4 Brake Fluid Capable of Meeting the Modified J1704/FMVSS 1 16 Corrosion Standard
  • a Dow Chemical Company DBF 700 brake fluid is modified to include an additive package in accordance with the present disclosure.
  • the unmodified and modified (“DBF 700a”) formulations are set forth below in Table 4: Table 4
  • Example 3 Water Stability of Functional Fluids of Present Disclosure
  • the DBF 700a fluid described above is mixed with varying degrees of water, and the boiling points and kinematic viscosities of the mixtures are determined.
  • the base formulation has a small amount of water (0.1416 percent by weight of the formulation) due to the moisture content of the various materials used to prepare it.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

La présente invention concerne des liquides fonctionnels à faible viscosité qui comprennent des esters de borate de glycols, des glycols, et un ensemble d’inhibiteurs de corrosion qui comprennent un ou plusieurs triazoles, amines, borates inorganiques, nitrates inorganiques, et un anhydride alcénylsuccinique. Les liquides sont particulièrement adaptés pour une utilisation en tant que liquides de frein DOT 4 et présentent des performances de corrosion robustes pendant une longue durée, de manière à réduire la fréquence à laquelle les liquides doivent être remplacés.
PCT/US2009/059181 2008-11-07 2009-10-01 Liquides fonctionnels à faible viscosité Ceased WO2010053639A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635825A (en) * 1967-07-14 1972-01-18 Olin Corp Water-insensitive hydraulic fluids containing bis-borate esters or bridged-borate esters
EP0454110A1 (fr) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Fluides pour freins inhibés contre la corrosion métallique à base de composés de glycols
EP0617116A1 (fr) * 1993-03-17 1994-09-28 BP Chemicals Limited Composition de fluide hydraulique
US6074992A (en) * 1999-02-02 2000-06-13 Union Carbide Chemicals & Plastics Technology Corporation Functional fluid compositions
WO2002038711A1 (fr) * 2000-11-10 2002-05-16 Union Carbide Chemicals & Plastics Technology Corporation Compositions de liquides fonctionnelles peu visqueuses
WO2009052024A1 (fr) * 2007-10-15 2009-04-23 Dow Global Technologies, Inc. Composition de fluides fonctionnels permettant d'améliorer la lubrification d'un système de freinage

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635825A (en) * 1967-07-14 1972-01-18 Olin Corp Water-insensitive hydraulic fluids containing bis-borate esters or bridged-borate esters
EP0454110A1 (fr) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Fluides pour freins inhibés contre la corrosion métallique à base de composés de glycols
EP0617116A1 (fr) * 1993-03-17 1994-09-28 BP Chemicals Limited Composition de fluide hydraulique
US6074992A (en) * 1999-02-02 2000-06-13 Union Carbide Chemicals & Plastics Technology Corporation Functional fluid compositions
WO2002038711A1 (fr) * 2000-11-10 2002-05-16 Union Carbide Chemicals & Plastics Technology Corporation Compositions de liquides fonctionnelles peu visqueuses
WO2009052024A1 (fr) * 2007-10-15 2009-04-23 Dow Global Technologies, Inc. Composition de fluides fonctionnels permettant d'améliorer la lubrification d'un système de freinage

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