CN102105571A - Antiwear hydraulic fluid composition with useful emulsifying and rust prevention properties - Google Patents

Antiwear hydraulic fluid composition with useful emulsifying and rust prevention properties Download PDF

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Publication number
CN102105571A
CN102105571A CN2009801290600A CN200980129060A CN102105571A CN 102105571 A CN102105571 A CN 102105571A CN 2009801290600 A CN2009801290600 A CN 2009801290600A CN 200980129060 A CN200980129060 A CN 200980129060A CN 102105571 A CN102105571 A CN 102105571A
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hydraulic fluid
fluid composition
antiwear hydraulic
salt
alkyl
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CN102105571B (en
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R·H·小弗雷泽
P·哈梅尔
N·德尼奥尔
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Chevron Oronite SAS
Chevron Oronite Co LLC
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Chevron Oronite Co 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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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
    • C10M2201/18—Ammonia
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
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    • C10M2207/028—Overbased salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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    • 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
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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
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10M2223/045—Metal containing thio derivatives
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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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
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Abstract

Disclosed are antiwear hydraulic fluid compositions comprising (a) a major amount of a base oil of lubricating viscosity and (b) a minor amount of at least one oil soluble detergent additive comprising a salt of an alkyl-substituted hydroxybenzoic acid or a sulfurized derivative thereof, wherein said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts or substituted ammonium salts, and further wherein said antiwear hydraulic fluid compositions have a Carboxylate Index of greater than levels disclosed herein.

Description

Have the useful emulsification and the antiwear hydraulic fluid of rustless property
Invention field
The present invention relates to be used for the purification agent of antiwear hydraulic fluid composition.Specifically, the present invention relates to can be used for the antiwear hydraulic fluid composition of some mobile equipment purposes (for example, Architectural Equipment hydraulic liquid).
Background of invention
The hydraulic liquid equipment non-corrosive that needs protection.For realizing this point, they will be furnished with rust-preventive agent.Typical rust-preventive agent is metal sulfonate or succinic acid derivative.Hydraulic liquid generally also is designed to be easy to and water sepn (breakdown of emulsion).Usually, metal species rust-preventive agent plays the effect that improves hydraulic liquid breakdown of emulsion characteristic.
Japanese Unexamined Patent Publication No JP1999311187A has described the salicylic alkaline earth salt and (D) composition of 0.001-0.5wt% water sepn agent of zinc dithiophosphate, (C) 0.2-1wt% of the basal liquid that contains (A) sulphur content and be up to 100ppm, (B) 0.2-1wt%.
International application no WO0063325 has described the hydraulic liquid that comprises lube base liquid, 0.001-5wt% magnesium salicylate and 0.01-8wt% zinc dithiophosphate.Described hydraulic composition also comprises rust-preventive agent.This publication document also discloses the combination of calcium salicylate, zinc dithiophosphate and rust-preventive agent.
Above-mentioned open file has been described the composition of introducing alkylated salicylamide acid metal salt, zinc dithiophosphate and rust-preventive agent.General such combination comprises that also emulsion splitter is to promote water and described liquid separation.Yet, need the hydraulic liquid that makes emulsifying water rather than make the water deemulsification in some cases.These hydraulic liquids that comprise liquid with enhanced purification agent and dispersion agent characteristic (as being called HLPD and HVLPD liquid by what define in the German DIN51502 standard) and be used for some mobile equipment purposes (as are used for Caterpillar equipment, building machinery, excavator, hydrauliccrane, lifting gantry, the hydraulic liquid of punch press etc.), wherein may fully not remove and cause lubricated very poor with the water of liquid separation.Generally provide an approach of these emulsification properties with the engine liquid of a large amount of dispersion agent preparations.The hydraulic liquid that contains a certain amount of sulfonate detergent also can have these characteristics.
Summary of the invention
One aspect of the present invention is the antiwear hydraulic fluid composition that comprises main amount lubricant viscosity basal liquid and at least a oil soluble detergent additive of minor amount.This detergent additive comprises salt or its sulphurated derivatives of the hydroxy-benzoic acid of alkyl replacement, and wherein said salt is selected from an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, and the alkyl at least 90% of the hydroxy-benzoic acid of wherein said alkyl replacement is C 14Or it is higher.And, in ASTM D1401 water separability test method, described antiwear hydraulic fluid composition can reach the emulsion 30 minutes of 0 milliliter of hydraulic liquid, 0ml water and 80ml emulsion (being abbreviated as 0-0-80) or above, preferred 40 minutes or more than, and the carboxylic acid index of antiwear hydraulic fluid composition is greater than 0.084.
Another aspect of the present invention is the antiwear hydraulic fluid composition that comprises main amount lubrication base liquid and at least a oil soluble detergent additive of minor amount.This detergent additive comprises salt or its sulphurated derivatives of the hydroxy-benzoic acid of alkyl replacement, and wherein said salt is selected from an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, and the alkyl at least 90% of the hydroxy-benzoic acid of wherein said alkyl replacement is C 14Or it is higher.And, in ASTM D665 rust prevention test method, described antiwear hydraulic fluid composition can reach " by " the result.And the carboxylic acid index of antiwear hydraulic fluid composition is greater than 0.034.
Surprisingly, we find that above-mentioned salt presents splendid emulsification and rust-preventing characteristic.Compare with other purification agent, this over-all properties is unexpected.An advantage of the invention is and reduce or deducted conventional rust-preventive agent such as metal naphthalenesulfonate (as NA-from King Industries
Figure BDA0000045305140000021
).
Detailed Description Of The Invention
Antiwear hydraulic fluid uses in hydraulic efficiency system to prevent the wearing and tearing of mechanical means in the hydraulic efficiency system, for example prevents that metal from moving the wearing and tearing that take place as iron and steel on the metallic surface on steel surface.Antiwear hydraulic fluid is applicable to and for example prevents various pumps, includes but not limited to the wearing and tearing of vane pump, piston pump and toothed gear pump commonly used in the hydraulic efficiency system.Antiwear hydraulic fluid also provides protection for other parts such as motor, driving mechanism and the piston of hydraulic efficiency system.Antiwear hydraulic fluid generally comprises wear preventive additive or extreme pressure agent zinc dialkyl dithiophosphate.
Antiwear hydraulic fluid of the present invention presents several performance characteristics, particularly emulsification and the corrosion protection performance except that wear-resistant protection.In addition, antiwear hydraulic fluid of the present invention presents good oxidative stability, good filterableness, good thermostability, low internal friction and good stability to hydrolysis.
The lubricant viscosity base oil
Being used for lubricant viscosity base oil of the present invention can be mineral oil or synthetic oil.40 ℃ of viscosity are at least 10cSt (mm 2/ s) being lower than 20 ℃ with pour point, the base oil that preferably is equal to or less than 0 ℃ is wished.Base oil can be from synthetic or natural origin.The mineral oil that is used as base oil among the present invention comprises for example paraffinic oils, naphthenic oil and is usually used in other liquid of lubricating oil composition.Synthetic oil comprises for example having the hydrocarbon synthetic oil of wishing viscosity, synthetic ester and their mixture.The hydrocarbon synthetic oil can comprise the liquid polymers with proper viscosity that for example made by ethene or high alpha-olefin polymerization (poly-alpha olefins or claim PAO) or by the oil of hydrocarbon synthesis process as preparing that uses carbon monoxide and hydrogen in fischer-tropsch process.That especially be suitable for is C 6-C 12The hydrogenated liquid oligopolymer of alpha-olefin such as 1-decene tripolymer.Equally, can use alkylbenzene such as two dodecylbenzene of proper viscosity.The synthesizing ester that is suitable for comprises the ester of monocarboxylic acid and polycarboxylic acid and the ester of monohydroxy alkanol and polyvalent alcohol.Typical example be the two dodecane alcohol esters of hexanodioic acid, tetramethylolmethane four capronates, hexanodioic acid two-2-ethylhexyl, the two dodecane alcohol esters of sebacic acid or the like.The complex ester of being made by the mixture of monobasic and di-carboxylic acid and monobasic and dibasic alcohol also is suitable for.The mixed oil of mineral oil and synthetic oil also is suitable for.For example, the mixed oil of 150SUS (100F) mineral oil of the hydrogenation 1-decene tripolymer of 10-25wt% and 75-90wt% is made fabulous lube base liquid.
Base oil of the present invention is to exist with " main amount ".The lubricating oil viscosity base oil of " main amount " is meant in concentration oily described in the hydraulic composition at least about 40wt%.In some embodiments, the lubricating oil viscosity base oil of " main amount " is meant in the concentration of oil described in the hydraulic composition at least about 50wt%, at least about 60%, at least about 70wt%, at least about 80wt% or at least about 90wt%.
Detergent additive
As previously mentioned, be used for antiwear hydraulic fluid composition of the present invention and comprise at least a suitable oil soluble detergent additive.Such detergent additive comprises any suitable carboxylate-containing purification agent, comprises hydroxy benzoate and sulphurated derivatives thereof that alkyl replaces, and wherein the total basicnumber of detergent additive (" TBN ") is generally less than 200mgKOH/g, preferably less than 160mgKOH/g.During term " total basicnumber " or " TBN " are meant and the required KOH milligramequivalent number of 1g product.Therefore, high TBN reflects strong parlkaline product, therefore has higher alkalescence deposit to be used for neutralizing acid.The TBN of product can measure by ASTM standard D 2896 or equivalent method.Overbased detergent can be by making any purification agent of additive TBN raising such as adding alkali source (as lime) and acid parlkaline compound (as carbonic acid gas).
(as at least 80%, at least 85%, have 90%, at least 95% or at least 99% at least) is C in the preferred purification agent at least 75% of contained alkyl (as the alkyl of carboxylate-containing purification agent or alkyl substituted hydroxy-benzoic acid) 14Or it is higher as C 14-C 40, C 14-C 35, C 14-C 30Or C 14-C 25In some embodiments, in the purification agent at least 75% of contained alkyl (as at least 80%, at least 85%, have 90%, at least 95% or at least 99% at least), the rest part of contained alkyl in the purification agent (even as 25% or still less, about 20% or still less, 15% or still less, 10% or still less, 5% or still less 1% or still less) be C 8Or it is higher (as C 8-C 14, C 10-C 14Even, C 12-C 14).In a preferred embodiment, purification agent comprises the salt derived from the hydroxy-benzoic acid of the alkyl replacement of the hydroxy-benzoic acid of alkyl replacement, and wherein said alkyl is to contain 90%C at least 20Or the residue of the positive structure alpha-olefin of higher positive structure alpha-olefin.
In another embodiment, purification agent comprises the hydroxy benzoate (for example overbased salt) of carboxylate salt such as alkyl replacement, or even basic metal or alkaline earth salt, or the ammonium salt or the substituted ammonium salt of the hydroxy-benzoic acid of alkyl replacement.In another embodiment, purification agent comprises the hydroxy-benzoic acid of alkyl replacement and the overbased salt (as the over-based alkaline erath metal salt) of fortified phenol mixture.In another embodiment, purification agent comprises the overbased salt of the hydroxy-benzoic acid that alkyl replaces and/or the overbased salt of alkyl-substituted phenols, is used in combination or the use that is mixed of the non-overbased salt of the hydroxy-benzoic acid that replaces with one or more alkyl and alkyl substituted phenol.In another embodiment, the antiwear hydraulic fluid composition comprises one or more hydroxy-benzoic acid overbased salt that comprises that alkyl replaces and the purification agent of non-other overbased salt (not being the salt of purification agent).In this respect, detergent additive can comprise the negatively charged ion (as organic negatively charged ion) of any proper concn that is associated with carboxylate salt (or hydroxy benzoate of alkyl replacement).
Some non-limiting examples of other suitable purification agent that can be used in combination with the hydroxy benzoate that alkyl replaces comprise the alkyl or alkenyl aromatic sulphonate, boration sulfonate, the sulfuration of polyhydroxy alkyl or alkenyl aromatic compound or unvulcanized metal-salt, alkyl or alkenyl hydroxyaromatic sulfonate, sulfuration or unvulcanized alkyl or alkenyl naphthenate, the metal-salt of paraffinic acid, the metal-salt of alkyl or alkenyl polyacid and their chemistry and physical mixture.Other non-limiting example of the detergent additive that is suitable for comprises metal sulfonate, metal salicylate salt, metal phosphinate hydrochlorate, metal thio-phosphonates and combination thereof.Metal can be any metal that is fit to preparation sulfonate, salicylate or phosphonate purification agent.The non-limiting example of suitable metal comprises basic metal, alkaline-earth metal and transition metal.In some embodiments, metal is Ca, mG, Ba, Sr, K, Na, Li etc.
The detergent additive that is used for the present invention characterizes normally oil-soluble by following test method: with 600N oil with by the centrifugation and continue 30 minutes under 60 ℃ of temperature of the mixture of the additive of mixture total weight amount 10wt% concentration, described centrifugation operation is to carry out (should be understood that the centrifugation operation is promptly not carry out under the condition of solubilizing agent in not diluted) under the standard A STMD2273 defined terms, centrifugation, measure formed volume of sediment at once, if settling is less than 0.05%v/v (volume of sediment is with respect to the value of volume of mixture), can think that then this product is an oil soluble.
The total basicnumber of above-mentioned oil soluble detergent additive generally is lower than 200mgKOH/g and preferably is lower than 160mg KOH/g in the antiwear hydraulic fluid composition of the present invention.In antiwear hydraulic fluid composition of the present invention, based on hydraulic composition gross weight meter, the concentration of oil soluble detergent additive itself arrives about 0.3wt% and preferred about scope of 0.07% to about 0.25wt% at about 0.05wt% usually.In other words, detergent additive of the present invention exists with " minor amount "." minor amount " detergent additive is meant that the concentration of detergent additive in the hydraulic composition is less than about 60wt%.In some embodiments, " minor amount " detergent additive is meant that detergent additive concentration is less than about 50wt%, less than about 30wt%, less than about 10wt%, less than about 1wt% or less than about 0.5wt% in the hydraulic composition.
Generally speaking, purification agent keeps the colloidal suspension state to help to control lacquer deposit, ring district's settling and corrosion by making insoluble particles.Containing metal (or becoming grey purification agent) has simultaneously as purification agent controls settling and as the effect of acid neutralizing agent or rust-preventive agent, thereby reduces wear and corrode and prolong service life of equipment.The peace and quiet polarity head end that has long hydrophobic tail end that generally includes, the polarity head end comprises the metal-salt of acid organometallic compound.Described salt can comprise substantially and is the metal of stoichiometric number, and in this case, they are described to normal or neutral salt usually.
The hydroxy-benzoic acid detergent additive component that alkyl replaces
Detergent additive can be characterized when the number in potassium hydroxide by the amount of alkyl substituted hydroxy-benzoic acid salt in the purification agent (being also referred to as the salt of the hydroxy-benzoic acid that alkyl replaces here) or its sulphurated derivatives etc. in the antiwear hydraulic fluid composition of the present invention, represents and be called carboxylic acid index (CI) with the mgKOH/g purification agent.Therefore, the CI with detergent additive of 56mgKOH equivalent hydroxy benzoate/g purification agent is 56, and is called the hydroxy benzoate that the 56CI alkyl replaces.The carboxylic acid assessment of indices method of detergent additive and antiwear hydraulic fluid composition
The hydroxy benzoate detergent additive that alkyl is replaced is dissolved in the organic solvent also with isopyknic rare strong acid solution washing 3 times.Collect water layer.Water layer organic solvent washing after the merging.Remove water layer, organic layer is used distilled water wash after merging.Pour out water layer.The acidifying extract is handled with pyridine and with the standard base (SB) titration of diluting.
Then, the carboxylic acid index (CI) of detergent additive can be calculated by following formula:
CI＝(V 1×C×MW KOH)/W
In the formula
V1 arrives the required volume of titration curve first terminal point;
C is the concentration of the standard base (SB) of dilution;
MW KOHIt is the molecular weight of KOH; With
W is the weight of the hydroxy benzoate detergent additive of alkyl replacement.
In case calculate the CI of detergent additive, the amount that then is easy to the hydroxy benzoate detergent additive that replaced by the alkyl that exists in the composition is determined the CI of antiwear hydraulic fluid, and this can be represented by the formula:
The CI of the hydroxy benzoate purification agent that the CI=alkyl of antiwear hydraulic fluid composition replaces * (wt% of the hydroxy benzoate purification agent that alkyl replaces in the hydraulic liquid)
In one embodiment of the invention, the CI of antiwear hydraulic fluid composition greater than 0.084, be preferably greater than 0.1 and more preferably greater than 0.12.In another embodiment of the invention, the CI of antiwear hydraulic fluid composition is greater than 0.034 and more preferably greater than 0.04.
Concentrated liquid prescription
Oil soluble detergent additive of the present invention can the concentrated solution form use, and described concentrated solution generally contains capacity organic liquid diluent and the used oil soluble detergent additive of the present invention.Concentrated solution contains the capacity organic liquid diluent so that they are easy to handle when shipping and storage.Usually, described concentrated solution comprises from about 10-90wt%, preferably about 20-70wt% and the compatible organic liquid diluent of 20-35wt% more preferably from about.The organic liquid diluent that is suitable for comprise the paraffinic base oils that for example is refined to 100N as the 100N of Cit-Con 100N and hydrogenation as Chevron100N, or the like.100 ℃ of about 1-20cSt of viscosity of preferred organic liquid diluent.About 10-90wt%, preferably the concentrated solution of about 30-80wt% is a used oil soluble additives among the present invention.
Other binder component
Following binder component is some examples that are applicable to component of the present invention.The example of these additives provides for illustrating the present invention, and they are not to limit the present invention:
1. dispersion agent: alkenyl succinimide, alkenyl succinate, with the alkenyl succinimide of other organic compound modification, with the alkenyl succinimide of ethylene carbonate or boric acid aftertreatment, tetramethylolmethane, phenates-salicylate and their aftertreatment analogue, basic metal or blended basic metal, alkaline earth metal borate, the dispersion liquid of Hydrated Alkali Metals Borates, polymeric amide ashless dispersant, or the like and these dispersion agents mixture.
2. oxidation inhibitor: antioxidant can reduce the trend of mineral oil deterioration between the usage period, can find out deterioration by the greasy filth on oxidation products such as the metallic surface and lacquer deposit and viscosity increase.Be applicable to that antioxidant example of the present invention includes but not limited to, phenols (phenolic aldehyde) oxidation inhibitor, as 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2-methyl-6-tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-butylidene-two (3 methy 6 tert butyl phenols), 4,4 '-isopropylidene-two (2, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene radical-two (4-methyl-6-nonyl phenol), 2,2 '-isobutylene-two (4,6 xylenols), 2,2 '-methylene radical-two (4-methyl-6-cyclohexylphenol), 2, the 6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethylphenol, 2,6 di t butyl phenol, 2,4-dimethyl-6-tert.-butyl phenol, 2,6-di-t-butyl-1-dimethylamino p-cresol, 2,6-di-t-butyl-4-(N, N '-dimethylamino-cresols), 4,4 '-thiobis (2-methyl-6-tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide and two (3,5-di-t-butyl-4 hydroxybenzyl).Other type oxidation inhibitor comprises alkylated diphenylamine (as the Irganox L-57 from Ciba-Geigy), dithiocarbamic acid metal-salt (as zinc dithiocarbamate) and methylene-bis (dibutyl and thiocarbamate).
3. anti-wear agent: as its name suggests, these reagent can reduce the wearing and tearing of moving metal parts.The example of this class reagent includes but not limited to phosphoric acid salt, phosphite, carbamate, ester, sulfocompound and molybdenum match.
4. emulsifying agent: the straight chain alcohol b-oxide comprises deriving from Dow Chemical Company's
Figure BDA0000045305140000081
15-S-3.
5. emulsion splitter: the adduct of alkylphenol and oxyethane, Voranol EP 2001 and polyoxyethylene sorbitan esters.
6. extreme pressure agent (EP reagent): zinc dialkyl dithiophosphate (primary alkyl, secondary alkyl and aryl type), vulcanized oil, diphenyl sulfide, three chloro methyl stearates, naphthalene chloride, fluoro-alkyl polysiloxane and lead naphthenate.Preferred EP reagent is zinc dialkyl dithiophosphate (ZnDTP), as one of common interpolation component of antiwear hydraulic fluid of the present invention, shown in the following general formula:
Figure BDA0000045305140000082
In the formula, R 1And R 2Each naturally carbon number be 1 to 18 uncle or secondary alkyl, and can be identical or different.Carbon number shown in the top general formula is 1 to 18 R 1And R 2Uncle or secondary alkyl comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, 2-ethylhexyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.But the zinc dialkyl dithiophosphate that is preferred for antiwear hydraulic fluid composition of the present invention has the mixed alkyl that carbon number is 3 to 12 primary and secondary alkyl.It is 3 to 12 primary alkyl that the zinc dialkyl dithiophosphate that more preferably is used for antiwear hydraulic fluid composition of the present invention has carbon number.Dialkyl dithio dialkyl group zinc with mixed alkyl of primary and secondary alkyl can use separately or make up and be used for antiwear hydraulic fluid composition of the present invention.Zinc dialkyl dithiophosphate is introduced by the 0.01-0.50wt% of total composition, preferred 0.02-0.04wt% in phosphorus wherein.
7. friction improver: Fatty Alcohol(C12-C14 and C12-C18), lipid acid, fatty ester amine, boric acid ester and other ester.
8. multifunction additive: sulfuration oxygen molybdenum dithiocarbamate, sulfuration oxygen molybdenum organic disulfide substituted phosphate, oxygen molybdenum direactive glyceride, oxygen molybdenum diglycollic amide, the molybdenum match compound of amine-molybdenum match compound and sulfur-bearing.
9. viscosity index improver: polymethacrylic acid polymkeric substance, ethylene-propylene copolymer, styrene-isoprene multipolymer, hydrogenated styrene-isoprene copolymer, polyisobutene and dispersion agent class viscosity index improver.
10. pour point depressant: polymethacrylic acid polymkeric substance.
11. defoamer: methacrylate polymer and dimethyl organosilicon polymer.
Embodiment
Emulsifying property
Preparation benchmark prescription also is used to assess the performance of embodiment 1 purification agent in ASTM D 1401 water separabilities tests.Described benchmark prescription is to comprise 0.31wt% zinc dialkyl dithiophosphate, 0.15wt% hindered phenol antioxygen, 0.044wt% succinate dispersion agent, 0.044wt% fatty ester friction improver, the how pure emulsion splitter of 0.013wt% aryl and 0.008wt% suds suppressor in the basal liquid that contains the She11HVI base-material.All finished fluids among these embodiment all are the ISO VG46 that contains 8wt% polyalkyl methacrylate viscosity index improver.
Embodiment 1
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and calcium hydroxybenzoate purification agent that adds the replacement of 0.225wt% parlkaline alkyl and 0.06wt% succinate dispersion agent, at least 90% alkyl is C in the calcium hydroxybenzoate that described alkyl replaces 20Or it is higher.The calcium hydroxybenzoate that this parlkaline alkyl replaces prepare by Application No. 2007/0027043 embodiment 1 described method and calcium contents be 5.35wt%, TBN be 150 and CI be 56.
Embodiment 2
Press the formulation antiwear hydraulic fluid composition of embodiment 1, difference is to add 0.01wt% straight chain alcohol b-oxide emulsifying agent and 0.16wt% zinc dialkyl dithiophosphate.
Comparing embodiment 1
Preparation by the said reference prescription with add 0.041wt% and contain the antiwear hydraulic fluid composition that purification agent, 0.024wt% parlkaline phenol calcium, 0.027wt% naphthene sulfonic acid zinc salt rust-preventive agent and the 0.008wt% resol emulsion splitter of the hydroxy benzoate that the parlkaline alkyl monosulfide replaces constitute.The described purification agent that contains parlkaline sulfuration carboxylate salt prepare by Application No. 5808145 embodiment 16 described methods and calcium contents be 9.3wt%, sulphur content be 2.4wt%, TBN be 260 and CI be 28.
Comparing embodiment 2
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate that adds 0.075wt% embodiment 1 described 56CI parlkaline alkyl replacement.
Comparing embodiment 3
By the formulation antiwear hydraulic fluid composition of comparing embodiment 2, difference is to add 0.06wt% succinate dispersion agent.
Comparing embodiment 4
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate that adds 0.15wt% embodiment 1 described 56CI parlkaline alkyl replacement.
Comparing embodiment 5
By the formulation antiwear hydraulic fluid composition of comparing embodiment 4, difference is to add 0.06wt% succinate dispersion agent.
The emulsifying property test-results
The water separability of antiwear hydraulic fluid characterizes by ASTM D1401 test method.In this method, the specimen material of 40ml volume and the distilled water of 40ml volume were carried out emulsification in 5 minutes by 54 ℃ of following merging liquid that stir in being with graduated graduated cylinder.Stopping to stir afterwards by monitoring, the relative volume of corresponding hydraulic liquid, water and emulsion layer characterizes the performance that separation of emulsions becomes organic layer and water layer.The results are shown in following table 1, be respectively ml hydraulic liquid when stopping to stir some minutes-ml water-ml emulsion.
Table 1
Figure BDA0000045305140000111
1The CI=of antiwear hydraulic fluid composition (CI of the hydroxy benzoate purification agent that alkyl replaces) * (wt% of the hydroxy benzoate purification agent that alkyl replaces in the hydraulic liquid)
Rustless property
Preparation benchmark prescription also is used to assess the performance of various purification agents in ASTM D665 rust prevention test.Described benchmark prescription is to contain ExxonMobil AP/E
Figure BDA0000045305140000112
Comprise 0.31wt% zinc dialkyl dithiophosphate, 0.15wt% hindered phenol antioxygen, 0.044wt% succinate dispersion agent, 0.044wt% fatty ester friction improver, the how pure emulsion splitter of 0.013wt% aryl and 0.008wt% resol emulsion splitter in the basal liquid of base-material.All finished fluids among these embodiment all are ISO VG 68.
Embodiment 3
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate purification agent that adds 0.075wt% embodiment 1 described 56CI parlkaline alkyl replacement.
Comparing embodiment 6
Preparation by the said reference prescription with add 0.041wt% comparing embodiment 1 described 28CI and contain the antiwear hydraulic fluid composition that purification agent, 0.024wt% parlkaline calcium phenylate and the 0.027wt% naphthene sulfonic acid zinc salt rust-preventive agent of the hydroxy benzoate that the parlkaline alkyl monosulfide replaces constitute.
Comparing embodiment 7
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate purification agent that adds the replacement of 0.067wt% parlkaline alkyl, at least 90% alkyl of the calcium hydroxybenzoate that described alkyl replaces is C 14-C 18The TBN of purification agent be 168 and CI be 51.
Comparing embodiment 8
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate purification agent that adds the replacement of 0.049wt% parlkaline alkyl, the alkyl at least 90% of the calcium hydroxybenzoate that described alkyl replaces is C 20-C 28The TBN of purification agent be 230 and CI be 46.
Comparing embodiment 9
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate purification agent that adds the replacement of 0.035wt% parlkaline alkyl, the alkyl at least 90% of the calcium hydroxybenzoate that described alkyl replaces is C 20-C 28The TBN of this purification agent be 325 and CI be 36.
Comparing embodiment 10
The antiwear hydraulic fluid composition that preparation is made of said reference prescription and the calcium hydroxybenzoate purification agent that adds the replacement of 0.032wt% parlkaline alkyl, the alkyl at least 90% of the calcium hydroxybenzoate that described alkyl replaces is C 20Or it is higher.The calcium hydroxybenzoate purification agent that described parlkaline alkyl replaces prepare by U.S. Patent application 2007/0027043 embodiment 1 described method and calcium contents be 12.5wt%, TBN be 350 and CI be 37.
The test for rust preventing ability result
The rust-preventing characteristic of antiwear hydraulic fluid is measured with ASTM D 665 methods, and this test method is drawn and is reference.If ASTM D 665 is when being used for measuring water and mixing with hydraulic liquid, hydraulic liquid helps prevent the test method of the ability that the iron parts get rusty.For measuring rustless property of the present invention, adopt the method B of ASTMD 665.In this test, the 300ml experimental liquid of complete submergence cylindrical steel batten and the mixture of 30ml synthetic sea water were stirred 24 hours under 60 ℃ of temperature.The corrosion test result be reported as " by " or " by ".The results are shown in table 2.
Table 2
Figure BDA0000045305140000131
1. the CI=of antiwear hydraulic fluid composition (CI of the hydroxy benzoate purification agent that alkyl replaces) * (wt% of the hydroxy benzoate purification agent that alkyl replaces in the hydraulic liquid)
Compare with other carboxylate salt/salicylate purification agent (comparing embodiment 2-5), the hydroxy benzoate purification agent that the alkyl of embodiment 3 replaces has been showed beat all rustless property, compares with the prescription that contains rust-preventive agent (comparing embodiment 6) and has also showed beat all rustless property.Embodiment 3 prescriptions do not need fortunately for adding rust-preventive agent by this test.
As previously discussed, in some hydraulic liquid is used, use in the used hydraulic liquid and HLPD and HLVPD liquid, preferably make emulsifying water rather than make the water deemulsification as some mobile equipment.Because the hydroxy benzoate that the alkyl of embodiment 1 replaces has also represented good rust-preventing characteristic under without the condition of metal sulfonate rust-preventive agent and because it is known that metal sulfonate rust-preventive agent makes the water deemulsification, the hydroxy benzoate that embodiment 1 used alkyl replaces provides and helped making the other performance of hydraulic liquid emulsive.

Claims (22)

1. antiwear hydraulic fluid composition, comprise (a) and mainly measure lubricant viscosity base oil and (b) at least a oil soluble detergent additive of minor amount, described oil soluble detergent additive comprises salt or its sulphurated derivatives of the hydroxy-benzoic acid of alkyl replacement, wherein said salt is selected from an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, and the carboxylic acid index of described antiwear hydraulic fluid composition is greater than 0.084.
2. by the antiwear hydraulic fluid composition of claim 1, the hydroxy-benzoic acid that wherein said alkyl replaces comprises the alkyl group of straight chain or branching or the mixture of the alkyl group of straight chain and branching.
3. by the antiwear hydraulic fluid composition of claim 1, the alkyl at least 90% of the hydroxy-benzoic acid that wherein said alkyl replaces is C 14Or it is higher.
4. by the antiwear hydraulic fluid composition of claim 1, wherein in ASTM D1401 water separability test method, 0-0-80 emulsification when described antiwear hydraulic fluid composition can reach 40 minutes.
5. by the antiwear hydraulic fluid composition of claim 1, wherein said salt comprises calcium salt.
6. by the antiwear hydraulic fluid composition of claim 1, wherein said hydraulic composition does not conform to the rust-preventive agent that adds.
7. by the antiwear hydraulic fluid composition of claim 1, wherein said oil soluble detergent additive comprises the TBN less than 200mg KOH/g.
8. by the antiwear hydraulic fluid composition of claim 1, wherein said oil soluble detergent additive comprises the TBN less than 160mg KOH/g.
9. by the antiwear hydraulic fluid composition of claim 1, wherein said oil soluble detergent additive account for described antiwear hydraulic fluid composition total weight greater than 0.1wt%.
10. by the antiwear hydraulic fluid composition of claim 1, wherein said oil soluble detergent additive account for described antiwear hydraulic fluid composition total weight greater than 0.2wt%.
11., also comprise at least a following additive altogether: (a) ashless dispersant by the antiwear hydraulic fluid composition of claim 1; (b) oxidation inhibitor; (d) demulsifying agent; (e) extreme pressure agent; (f) friction improver; (g) multifunction additive; (h) viscosity index improver; (i) pour point depressant; (j) defoamer; (k) emulsifying agent.
12. antiwear hydraulic fluid composition, comprise (a) and mainly measure lubricant viscosity base oil and (b) at least a oil soluble detergent additive of minor amount, described oil soluble detergent additive comprises salt or its sulphurated derivatives of the hydroxy-benzoic acid of alkyl replacement, wherein said salt is selected from an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, and the carboxylic acid index of described antiwear hydraulic fluid composition is greater than 0.034.
13. by the antiwear hydraulic fluid composition of claim 12, the hydroxy-benzoic acid that wherein said alkyl replaces comprises the alkyl group of straight chain or branching or the mixture of the alkyl group of straight chain and branching.
14. by the antiwear hydraulic fluid composition of claim 12, the alkyl at least 90% of the hydroxy-benzoic acid that wherein said alkyl replaces is C 14Or it is higher.
15. by the antiwear hydraulic fluid composition of claim 12, wherein in ASTM D665 rust prevention test method, described antiwear hydraulic fluid composition can reach the result who passes through.
16. by the antiwear hydraulic fluid composition of claim 12, wherein said salt comprises calcium salt.
17. by the antiwear hydraulic fluid composition of claim 12, wherein said hydraulic composition does not contain the rust-preventive agent that adds.
18. by the antiwear hydraulic fluid composition of claim 12, wherein said oil soluble detergent additive comprises the TBN less than 200mg KOH/g.
19. by the antiwear hydraulic fluid composition of claim 12, wherein said oil soluble detergent additive comprises the TBN less than 160mg KOH/g.
20. by the antiwear hydraulic fluid composition of claim 12, wherein said oil soluble detergent additive account for described antiwear hydraulic fluid composition total weight greater than 0.05wt%.
21. by the antiwear hydraulic fluid composition of claim 12, wherein said oil soluble detergent additive account for described antiwear hydraulic fluid composition total weight greater than 0.07wt%.
22., also comprise at least a following additive altogether: (a) ashless dispersant by the antiwear hydraulic fluid composition of claim 12; (b) oxidation inhibitor; (d) demulsifying agent; (e) extreme pressure agent; (f) friction improver; (g) multifunction additive; (h) viscosity index improver; (i) pour point depressant; (j) defoamer; (k) emulsifying agent.
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CN1644665A (en) * 2003-12-22 2005-07-27 切夫里昂奥罗尼特有限责任公司 Lubricating oil composition containing an alkali metal salicylate detergent
US20070027043A1 (en) * 2005-07-29 2007-02-01 Chevron Oronite S.A. Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment

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CN110785477A (en) * 2017-06-30 2020-02-11 雪佛龙奥伦耐有限责任公司 Lubricating oil compositions containing detergent compounds
CN110785478A (en) * 2017-06-30 2020-02-11 雪佛龙奥伦耐有限责任公司 Magnesium detergent for lubricating oil and method of making and using same
CN110785478B (en) * 2017-06-30 2022-08-09 雪佛龙奥伦耐有限责任公司 Magnesium detergent for lubricating oil and method of making and using same
CN109370736A (en) * 2018-11-29 2019-02-22 郑州正赢石化有限公司 A kind of alkali resistance ashless hydraulic fluid
CN114075473A (en) * 2020-08-18 2022-02-22 中国石油化工股份有限公司 Emulsified hydraulic oil composition
CN114075473B (en) * 2020-08-18 2022-12-13 中国石油化工股份有限公司 Emulsified hydraulic oil composition

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