US20070129264A1 - Hydraulic fluids with erosion resistance - Google Patents
Hydraulic fluids with erosion resistance Download PDFInfo
- Publication number
- US20070129264A1 US20070129264A1 US11/655,540 US65554007A US2007129264A1 US 20070129264 A1 US20070129264 A1 US 20070129264A1 US 65554007 A US65554007 A US 65554007A US 2007129264 A1 US2007129264 A1 US 2007129264A1
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- composition
- alkali metal
- weight
- perfluorophosphate
- carbon atoms
- 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.)
- Abandoned
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- 239000012530 fluid Substances 0.000 title claims abstract description 27
- 230000003628 erosive effect Effects 0.000 title abstract description 11
- -1 phosphate ester Chemical class 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 39
- 235000021317 phosphate Nutrition 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920001603 poly (alkyl acrylates) Polymers 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- FCRKQUHYNVKCST-UHFFFAOYSA-N CC(=O)C1CCC2OC2C1 Chemical compound CC(=O)C1CCC2OC2C1 FCRKQUHYNVKCST-UHFFFAOYSA-N 0.000 description 3
- 229910021135 KPF6 Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 0 *OC(C1CC2OC2CC1)=O Chemical compound *OC(C1CC2OC2CC1)=O 0.000 description 1
- FOUNRKRNEDRUPL-UHFFFAOYSA-N 2-octyl-n-(2-octylphenyl)aniline Chemical compound CCCCCCCCC1=CC=CC=C1NC1=CC=CC=C1CCCCCCCC FOUNRKRNEDRUPL-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- HDZSMFQGGFPQIM-UHFFFAOYSA-N 4-[3,5-bis(3,5-ditert-butyl-4-hydroxyphenyl)-2,4,6-trimethylphenyl]-2,6-ditert-butylphenol Chemical compound CC1=C(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 HDZSMFQGGFPQIM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017965 NH4 PF6 Inorganic materials 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BVEGNPSFKQMTQZ-UHFFFAOYSA-N calcium;1,2-di(nonyl)naphthalene Chemical compound [Ca].C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 BVEGNPSFKQMTQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SKSIDEOZXDVBGN-UHFFFAOYSA-N fluoro dihydrogen phosphate Chemical compound OP(O)(=O)OF SKSIDEOZXDVBGN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C10M2201/085—Phosphorus oxides, acids or salts
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/08—Aldehydes; Ketones
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- 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
- 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
- C10M2223/0405—Phosphate esters used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- the present invention is concerned with enhancing the anti-erosion properties of phosphate ester based fluids used in transmitting power in hydraulic systems.
- Hydraulic fluids are used in a wide variety of industrial applications, including control systems for jet turbines, steam turbines, aircraft and aerospace equipment.
- control systems for jet turbines, steam turbines, aircraft and aerospace equipment For example, in aircraft equipment they are used as the power transmitting medium in operating various moving parts of the aircraft, such as wing flaps, ailerons, rudders and landing gear.
- hydraulic fluids meet stringent performance requirements including thermal stability, fire resistance, hydrolytic stability and elastomer compatibility, to mention a few.
- Organic phosphate ester fluids have been recognized as a preferred base stock for use in hydraulic fluids. Indeed, in present commercial aircraft hydraulic fluids, phosphate esters are among the most commonly used base stocks.
- composition comprising:
- compositions of the present invention comprise a major amount of a phosphate ester base stock.
- the phosphate esters typically employed in such base stocks include trialkyl phosphates, dialkylaryl phosphates, and triaryl phosphates having alkyl groups of from 3 to 8 and preferably 4 to 5 carbon atoms.
- Such phosphate ester base stocks are the preferred base stocks of the instant invention.
- Particularly preferred phosphate esters are trialkyl phosphate esters and among these tri-n-butyl phosphate and tri-isobutyl phosphate are preferred.
- the amount of each type of phosphate ester comprising the base stock can vary depending upon the type of phosphate esters involved.
- the phosphate ester base stock used in the present invention comprises, based on the total weight of the base stock, (a) from about 10 wt % to about 100 wt %, and preferably from about 20 wt % to about 90 wt % of a trialkyl phosphate; (b) from 0 wt % to about 75 wt % and preferably from 0 wt % to about 50 wt % of a dialkylaryl phosphate; (c) from 0 wt % to about 3 wt %, and preferably from 0 wt % to 10 wt % of an alkyl diaryl phosphate; and (d) from 0 wt % to about 20 wt % and preferably from 0 wt % to about 15 wt % of a triaryl phosphate.
- composition of the present invention includes a minor but effective amount of both an alkali metal perfluoro phosphate and a mono epoxy cyclohexane carboxylate.
- the composition will include from about 0.01 wt % to about 0.5 wt % based on the weight of the composition, of an alkali metal perfluoro phosphate or mixtures of alkali metal perfluorophosphate.
- Alkali metals include lithium, sodium, potassium, rubidium and cesium.
- the alkali metal perfluorophosphate is potassium perfluoro phosphate.
- the composition of the present invention also will include a mono epoxycyclohexane carboxylate.
- the composition will include from about 1 wt % to about 10 wt % of a mono epoxide represented by the formula where R is selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms, and —(CH 2 ) n —OR 1 where R 1 is an alkyl group of 1 to 10 carbon atoms and n is an integer of from 1 to 3.
- R is a branched alkyl group of 4 to 8 carbon atoms and more preferably R is a 2-ethyl-1-hexyl group.
- the hydraulic fluid compositions of this invention further comprise an antioxidant or mixture of antioxidants in an amount effective to inhibit oxidation of the fluid or its components.
- Suitable antioxidants include polyphenols, trialkyl phenols and di(alkyl phenyl)amines.
- Representative examples include: bis(3,5-di-tert-butyl-4-hydroxy phenyl)methane (e.g., Hitec® 4702 from Ethyl Corp.); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy phenyl)benzene (e.g., Ethanox® 330 from Albemarle Corp.); tetrakis (methylene (3,5-di-tert-butyl-4-hydroxy hydrocinnamate) methane (e.g., Irganox® 1010 from Ciba Geigy); di(n-octylphenyl)amine (e.g., Vanlube 81 from Vanderbilt); and the like.
- bis(3,5-di-tert-butyl-4-hydroxy phenyl)methane e.g., Hitec® 4702 from Ethyl Corp.
- the antioxidants or mixture of antioxidants typically will be used in amounts ranging from about 0.5 wt % to about 3 wt % based on the total weight of the composition.
- compositions of this invention further comprise an effective amount of a rust inhibitor or a mixture of rust inhibitors.
- rust inhibitors include calcium dinonylnaphthalene, a Group I or Group II metal over based sulfurized phenate the like.
- the rust inhibitor or mixture thereof is employed at from about 0.001 wt % to about 1 wt % based on the weight of the composition.
- compositions further comprise a viscosity index improver (VII).
- VII viscosity index improver
- Especially preferred VII's are alkyl poly acrylates and alkyl polymethacrylate ester polymers in which at least 85% by weight have a molecular weight in the range of about 50,000 to about 100,000, and where the alkyl groups are preferably n-hexyl and isodecyl.
- composition of the invention can optionally contain further additives such as copper corrosion inhibitors, anti foaming agents, dyes and the like.
- a fluid composition was prepared by blending 66.8 wt % of tri-n-butyl phosphate, 12.1 wt % alkylated triphenyl phosphate; 6.2 wt % of a VI improver; 5.7 wt % of a mono epoxycyclohexane carboxylate; 0.05 wt % KPF 6 ; and the balance antioxidants, rust inhibitors dye and defoamer.
- the fluid was then tested in an electro-deposition test developed by Boeing Aircraft Company that simulates the tendency of deposit formation in aircraft components. The results are given in Table 1.
- Example 1 For comparative purposes a composition was prepared as in Example 1 but which contained as anti-erosion agent 0.05 wt % of a mixture of potassium perfluoro-octyl sulfonates (i.e., FC-98® from 3M) in lieu of KPF 6 . This fluid was also subjected to the electro-deposits test and the results are given in Table 1. TABLE 1 Properties Example 1 Comp.
- Example 1 and Comparative Example 1 were subjected to an erosion rig test according to AS1241. The tests were run at 225° F. and 275° F. and the pressure maintained at 3000 psi. The leakage rate was measured throughout the run. The results are shown in Table 2. TABLE 2 Initial Final Leakage, Leakage Delta Valve Test Flow, Flow, cc/ Run Fluid Positions Temp. cc/min cc/min min Hours Compar- 6&8 275° F. 400 355 65 524 ative 1 Example 1 5&7 225° F. 288 200 88 739
- a fluid composition was prepared containing: 78.7 wt % tributyl phosphate; 11.8 wt % isopropylated triphenyl phosphate; 6.2 wt % of a poly alkylacrylate VII; 2.3 wt % of a cyclo aliphatic diepoxide; 0.01 wt % of NH 4 PF 6 and the balance antioxidants, rust inhibitors, dye and defoamers.
- the composition was then subjected to the anti erosion rig test of Example 2 with the results set forth in Table 3. Included in Table 3 are the results of Example 2 using the fluid of Example 1. TABLE 3 Initial Final Leakage Leakage Test Flow, Flow, Delta Run Fluid Temp. cc/min cc/min cc/min Hours Comparative 3 225° F. 222 429 207 244 Example 1 225° F. 288 200 88 739
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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
The erosion resistance of phosphate ester based hydraulic fluids has been found to be enhanced by incorporating in the fluid a minor amount of an alkali metal perfluorophosphate and a mono epoxycyclohexane carboxylate.
Description
- Continuation-in-Part of U.S. Ser. No. 10/703,987 filed Nov. 7, 2003 which is based on Provisional Application 60/426,946 filed Nov. 15, 2002.
- The present invention is concerned with enhancing the anti-erosion properties of phosphate ester based fluids used in transmitting power in hydraulic systems.
- Hydraulic fluids are used in a wide variety of industrial applications, including control systems for jet turbines, steam turbines, aircraft and aerospace equipment. For example, in aircraft equipment they are used as the power transmitting medium in operating various moving parts of the aircraft, such as wing flaps, ailerons, rudders and landing gear.
- The proper functioning of such important control mechanisms dictate that the hydraulic fluids meet stringent performance requirements including thermal stability, fire resistance, hydrolytic stability and elastomer compatibility, to mention a few.
- Organic phosphate ester fluids have been recognized as a preferred base stock for use in hydraulic fluids. Indeed, in present commercial aircraft hydraulic fluids, phosphate esters are among the most commonly used base stocks.
- In order to meet the many performance criteria established for hydraulic fluids, and especially aircraft hydraulic fluids, it is common practice to incorporate various additives in: base stocks. For example, experience has shown that orifices in the servo control valves of aircraft hydraulic systems are subject to erosion which is attributed to streaming current induced by fluid flow. Valve orifice erosion, if extensive, can greatly impair the functioning of the valve as a precise control mechanism. Therefore, various additives have been used in hydraulic fluids as erosion inhibitors.
- Nonetheless there remains a need for increased choice of useful erosion inhibitors, especially for improved erosion inhibitors for phosphate ester based hydraulic fluids.
- It has now been discovered that by incorporating a minor amount of both an alkali metal perfluorophosphate and a mono epoxycyclohexane carboxylate into a major amount of a phosphate ester based hydraulic fluid the anti erosion properties of the composition are surprisingly enhanced. Thus, in one embodiment there is provided a composition comprising:
- a major amount of a phosphate ester base stock; and
- a minor amount of an alkali metal perfluoro phosphate and a mono epoxycyclohexane carboxylate.
- The compositions of the present invention comprise a major amount of a phosphate ester base stock. The phosphate esters typically employed in such base stocks include trialkyl phosphates, dialkylaryl phosphates, and triaryl phosphates having alkyl groups of from 3 to 8 and preferably 4 to 5 carbon atoms. Such phosphate ester base stocks are the preferred base stocks of the instant invention. Particularly preferred phosphate esters are trialkyl phosphate esters and among these tri-n-butyl phosphate and tri-isobutyl phosphate are preferred.
- The amount of each type of phosphate ester comprising the base stock can vary depending upon the type of phosphate esters involved. The phosphate ester base stock used in the present invention comprises, based on the total weight of the base stock, (a) from about 10 wt % to about 100 wt %, and preferably from about 20 wt % to about 90 wt % of a trialkyl phosphate; (b) from 0 wt % to about 75 wt % and preferably from 0 wt % to about 50 wt % of a dialkylaryl phosphate; (c) from 0 wt % to about 3 wt %, and preferably from 0 wt % to 10 wt % of an alkyl diaryl phosphate; and (d) from 0 wt % to about 20 wt % and preferably from 0 wt % to about 15 wt % of a triaryl phosphate.
- The composition of the present invention includes a minor but effective amount of both an alkali metal perfluoro phosphate and a mono epoxy cyclohexane carboxylate.
- Specifically the composition will include from about 0.01 wt % to about 0.5 wt % based on the weight of the composition, of an alkali metal perfluoro phosphate or mixtures of alkali metal perfluorophosphate. Alkali metals, of course, include lithium, sodium, potassium, rubidium and cesium. Preferably the alkali metal perfluorophosphate is potassium perfluoro phosphate.
- The composition of the present invention also will include a mono epoxycyclohexane carboxylate. Specifically the composition will include from about 1 wt % to about 10 wt % of a mono epoxide represented by the formula
where R is selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms, and —(CH2)n—OR1 where R1 is an alkyl group of 1 to 10 carbon atoms and n is an integer of from 1 to 3. Preferably R is a branched alkyl group of 4 to 8 carbon atoms and more preferably R is a 2-ethyl-1-hexyl group. - In a preferred embodiment the hydraulic fluid compositions of this invention further comprise an antioxidant or mixture of antioxidants in an amount effective to inhibit oxidation of the fluid or its components. Suitable antioxidants include polyphenols, trialkyl phenols and di(alkyl phenyl)amines. Representative examples include: bis(3,5-di-tert-butyl-4-hydroxy phenyl)methane (e.g., Hitec® 4702 from Ethyl Corp.); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy phenyl)benzene (e.g., Ethanox® 330 from Albemarle Corp.); tetrakis (methylene (3,5-di-tert-butyl-4-hydroxy hydrocinnamate) methane (e.g., Irganox® 1010 from Ciba Geigy); di(n-octylphenyl)amine (e.g., Vanlube 81 from Vanderbilt); and the like.
- The antioxidants or mixture of antioxidants typically will be used in amounts ranging from about 0.5 wt % to about 3 wt % based on the total weight of the composition.
- In another preferred embodiment the compositions of this invention further comprise an effective amount of a rust inhibitor or a mixture of rust inhibitors. Representative examples of rust inhibitors include calcium dinonylnaphthalene, a Group I or Group II metal over based sulfurized phenate the like. Typically the rust inhibitor or mixture thereof is employed at from about 0.001 wt % to about 1 wt % based on the weight of the composition.
- In yet another embodiment the compositions further comprise a viscosity index improver (VII). Especially preferred VII's are alkyl poly acrylates and alkyl polymethacrylate ester polymers in which at least 85% by weight have a molecular weight in the range of about 50,000 to about 100,000, and where the alkyl groups are preferably n-hexyl and isodecyl.
- The composition of the invention can optionally contain further additives such as copper corrosion inhibitors, anti foaming agents, dyes and the like.
- A fluid composition was prepared by blending 66.8 wt % of tri-n-butyl phosphate, 12.1 wt % alkylated triphenyl phosphate; 6.2 wt % of a VI improver; 5.7 wt % of a mono epoxycyclohexane carboxylate; 0.05 wt % KPF6; and the balance antioxidants, rust inhibitors dye and defoamer. The fluid was then tested in an electro-deposition test developed by Boeing Aircraft Company that simulates the tendency of deposit formation in aircraft components. The results are given in Table 1.
- For comparative purposes a composition was prepared as in Example 1 but which contained as anti-erosion agent 0.05 wt % of a mixture of potassium perfluoro-octyl sulfonates (i.e., FC-98® from 3M) in lieu of KPF6. This fluid was also subjected to the electro-deposits test and the results are given in Table 1.
TABLE 1 Properties Example 1 Comp. Example 1 Electrode appearance Clean Clean Electrode 2A 2C 2A 2C Metal wt loss, mg 0.70 18.80 1.50 5.20 Deposit wt, 1st rinse, mg 10.90 2.80 13.10 3.0 Deposits wt, 1st soak, mg 10.70 3.00 10.80 2.5 Deposit wt, 2nd soak, mg 9.90 2.40 10.40 2.50 Fluid appearance after test Purple Purple Brownish Brownish - The anti-erosion performance of Example 1 and Comparative Example 1 were subjected to an erosion rig test according to AS1241. The tests were run at 225° F. and 275° F. and the pressure maintained at 3000 psi. The leakage rate was measured throughout the run. The results are shown in Table 2.
TABLE 2 Initial Final Leakage, Leakage Delta Valve Test Flow, Flow, cc/ Run Fluid Positions Temp. cc/min cc/min min Hours Compar- 6&8 275° F. 400 355 65 524 ative 1 Example 1 5&7 225° F. 288 200 88 739 - A fluid composition was prepared containing: 78.7 wt % tributyl phosphate; 11.8 wt % isopropylated triphenyl phosphate; 6.2 wt % of a poly alkylacrylate VII; 2.3 wt % of a cyclo aliphatic diepoxide; 0.01 wt % of NH4 PF6 and the balance antioxidants, rust inhibitors, dye and defoamers. The composition was then subjected to the anti erosion rig test of Example 2 with the results set forth in Table 3. Included in Table 3 are the results of Example 2 using the fluid of Example 1.
TABLE 3 Initial Final Leakage Leakage Test Flow, Flow, Delta Run Fluid Temp. cc/min cc/min cc/min Hours Comparative 3 225° F. 222 429 207 244 Example 1 225° F. 288 200 88 739 - The data shows that the combination of KPF6 and a mono epoxy cyclohexane carboxylate provide surprisingly lower erosion as determined by the leakage flow.
Claims (7)
1. A fluid composition comprising:
a major amount of a phosphate ester base stock and a minor amount of an alkali metal perfluorophosphate or mixture of alkali metal perfluorophosphates and a mono epoxycyclohexane carboxylate.
2. The composition of claim 1 wherein the alkali metal perfluorophosphate or mixtures of alkali metal perfluorophosphates are present in an amount of from about 0.01 wt % to about 0.5 wt % based on the weight of the composition.
3. The composition of claim 2 wherein the mono epoxycyclohexane carboxylate is represented by the formula
where R is an alkyl group of 1 to 10 carbon atoms or —(CH2)n—OR, where n is an integer of 1 to 3 and R1 is an alkyl group of 1 to 10 and wherein said mono epoxycyclohexane carboxylate is present from about 1 wt % to about 10 wt % based on the weight of the composition.
4. A hydraulic fluid composition comprising:
(a) a major amount of a phosphate ester base stock comprising, based on the weight of base stock;
(i) from 10 to 100 wt % of trialkyl phosphate;
(ii) from 0 to 75 wt % of dialkyl aryl phosphates;
(iii) from 0 to 30 wt % of alkyldiaryl phosphates; and
(iv) from 0 to 20 wt % of alkylated triaryl phosphates, and wherein the alkyl groups of (i) to (iv) have from 3 to 8 carbon atoms; and
(b) both
(i) from about 0.01 wt % to about 0.5 wt %, based on the weight of the composition of an alkali metal perfluorophosphate or mixtures of alkali-metal perfluorophosphate; and
(ii) from about 1 wt % to about 10 wt %, based on the weight of the composition, of a compound having the formula
where R is an alkyl group of 1 to 10 carbon atoms or —(CH2)nOR, where n is an integer of 1 to 3 and R is an alkyl group of 1 to 10 carbon atoms.
5. The composition of claim 4 wherein the alkali metal of the perfluorophosphate is potassium and R is a branched alkyl group of 4 to 8 carbon atoms.
6. The composition of claim 5 including a poly(alkylacrylate) or poly(alkylmethacrylate) viscosity index improver (VII).
7. The composition of claim 6 wherein the VII is present at from about 3 wt % to about 10 wt % based on the weight of the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/655,540 US20070129264A1 (en) | 2002-11-15 | 2007-01-19 | Hydraulic fluids with erosion resistance |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42694602P | 2002-11-15 | 2002-11-15 | |
| US10/703,987 US20040127370A1 (en) | 2002-11-15 | 2003-11-07 | Hydraulic fluids with erosion resistance |
| US11/655,540 US20070129264A1 (en) | 2002-11-15 | 2007-01-19 | Hydraulic fluids with erosion resistance |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/703,987 Continuation-In-Part US20040127370A1 (en) | 2002-11-15 | 2003-11-07 | Hydraulic fluids with erosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20070129264A1 true US20070129264A1 (en) | 2007-06-07 |
Family
ID=46327083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/655,540 Abandoned US20070129264A1 (en) | 2002-11-15 | 2007-01-19 | Hydraulic fluids with erosion resistance |
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| Country | Link |
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| US (1) | US20070129264A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017099956A1 (en) * | 2015-12-07 | 2017-06-15 | Exxonmobil Research And Engineering Company | Functional fluid compositions containing erosion inhibitors |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983046A (en) * | 1973-09-24 | 1976-09-28 | Mcdonnell Douglas Corporation | Functional fluid compositions containing epoxy additives |
| US4132572A (en) * | 1976-04-21 | 1979-01-02 | The Diversey Corporation | Compositions for treatment of metallic surfaces by means of fluorophosphate salts |
| US5817606A (en) * | 1996-08-08 | 1998-10-06 | Rohm And Haas Company | Viscosity index improving additives for phosphate ester-containing hydraulic fluids |
| US6184187B1 (en) * | 1998-04-07 | 2001-02-06 | E. I. Dupont De Nemours And Company | Phosphorus compounds and their use as corrosion inhibitors for perfluoropolyethers |
-
2007
- 2007-01-19 US US11/655,540 patent/US20070129264A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983046A (en) * | 1973-09-24 | 1976-09-28 | Mcdonnell Douglas Corporation | Functional fluid compositions containing epoxy additives |
| US4132572A (en) * | 1976-04-21 | 1979-01-02 | The Diversey Corporation | Compositions for treatment of metallic surfaces by means of fluorophosphate salts |
| US5817606A (en) * | 1996-08-08 | 1998-10-06 | Rohm And Haas Company | Viscosity index improving additives for phosphate ester-containing hydraulic fluids |
| US6184187B1 (en) * | 1998-04-07 | 2001-02-06 | E. I. Dupont De Nemours And Company | Phosphorus compounds and their use as corrosion inhibitors for perfluoropolyethers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017099956A1 (en) * | 2015-12-07 | 2017-06-15 | Exxonmobil Research And Engineering Company | Functional fluid compositions containing erosion inhibitors |
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