CN102105571B - 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
CN102105571B
CN102105571B CN200980129060.0A CN200980129060A CN102105571B CN 102105571 B CN102105571 B CN 102105571B CN 200980129060 A CN200980129060 A CN 200980129060A CN 102105571 B CN102105571 B CN 102105571B
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hydraulic fluid
alkyl
purposes
fluid composition
antiwear hydraulic
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CN102105571A (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
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • 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
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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
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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
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    • 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
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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
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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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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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/24—Emulsion properties
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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
    • C10N2030/40—Low content or no content 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

There is useful emulsification and the antiwear hydraulic fluid of rustless property
Invention field
The present invention relates to the purification agent for 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 is generally also designed to be easy to separated with water (breakdown of emulsion).Conventionally, metal species rust-preventive agent plays the effect that improves hydraulic liquid breakdown of emulsion characteristic.
Japanese Unexamined Patent Publication No JP1999311187A has described basal liquid, the zinc dithiophosphate of (B) 0.2-1wt%, the salicylic alkaline earth salt of (C) 0.2-1wt% and (D) composition of 0.001-0.5wt% water separating agent that contains (A) sulphur content and be up to 100ppm.
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 also comprises that emulsion splitter is to promote water and described liquid separation.Yet, need in some cases the hydraulic liquid that has the emulsifying water of making rather than make water deemulsification.These comprise and have the purification agent of enhancing and the liquid of dispersion agent characteristic (as what define, being called HLPD and HVLPD liquid in German DIN51502 standard) and for the hydraulic liquid of some mobile equipment purposes (as for Caterpillar equipment, building machinery, excavator, hydrauliccrane, lifting gantry, the hydraulic liquid of punch press etc.), wherein may fully not remove with the water of liquid separation and cause lubricated very poor.Generally with the engine liquid of a large amount of dispersion agent preparations, be to provide an approach of these emulsification properties.Hydraulic liquid containing 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 one oil soluble detergent additive of minor amount.Salt or its sulphurated derivatives of the hydroxy-benzoic acid that this detergent additive comprises alkyl replacement, 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 higher.And, in ASTM D1401 water separability test method, described antiwear hydraulic fluid composition can reach 0 milliliter of hydraulic liquid, 0ml water and 80ml emulsion (being abbreviated as 0-0-80) emulsion 30 minutes or above, preferably 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 one oil soluble detergent additive of minor amount.Salt or its sulphurated derivatives of the hydroxy-benzoic acid that this detergent additive comprises alkyl replacement, 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 higher.And, in ASTM D665 rust prevention test method, described antiwear hydraulic fluid composition can reach " by " 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 if metal naphthalenesulfonate is (as the NA-from King Industries ).
Detailed Description Of The Invention
Antiwear hydraulic fluid is used to prevent the wearing and tearing of mechanical means in hydraulic efficiency system in hydraulic efficiency system, for example prevent metal on metallic surface as iron and steel mobile wearing and tearing that occur on steel surface.Antiwear hydraulic fluid is applicable to for example prevent various pumps, includes but not limited to the wearing and tearing of vane pump conventional in hydraulic efficiency system, piston pump and toothed gear pump.Antiwear hydraulic fluid is also for other parts of hydraulic efficiency system provide protection as motor, driving mechanism and piston.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 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.
Lubricant viscosity base oil
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) and pour point lower than 20 ℃, the base oil that is preferably 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 in 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 wishes the hydrocarbon synthetic oil of viscosity, synthetic ester and their mixture.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 using the hydrocarbon synthesis process of carbon monoxide and hydrogen as the oil of preparing in fischer-tropsch process.That especially applicable is C 6-C 12the hydrogenated liquid oligopolymer of alpha-olefin is as 1-decene tripolymer.Equally, can use the alkylbenzene of proper viscosity as two dodecylbenzenes.Applicable synthesizing ester 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 etc.The complex ester of being made by the mixture of monobasic and di-carboxylic acid and monobasic and dibasic alcohol is also applicable.The mixed oil of mineral oil and synthetic oil is also applicable.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 " mainly amount ".The lubricating oil viscosity base oil of " mainly amount " refers in concentration oily described in hydraulic composition at least about 40wt%.In some embodiments, the lubricating oil viscosity base oil of " mainly amount " refers in the concentration of oil described in 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, for antiwear hydraulic fluid composition of the present invention, comprise at least one suitable oil soluble detergent additive.Such detergent additive comprises any suitable carboxylate-containing purification agent, comprise hydroxy benzoate and sulphurated derivatives thereof that alkyl replaces, wherein the total basicnumber of detergent additive (" TBN ") is generally less than 200mgKOH/g, is preferably less than 160mgKOH/g.During term " total basicnumber " or " TBN " refer to and the required KOH milligramequivalent number of 1g product.Therefore, high TBN reflects strong parlkaline product, therefore has higher alkalescence deposit for neutralizing acid.The TBN of product can measure by ASTM standard D 2896 or equivalent method.Overbased detergent can be by any purification agent such as adding alkali source (as lime) and acid parlkaline compound (as carbonic acid gas) that additive TBN is improved.
Preferably in purification agent at least 75% of contained alkyl (as the alkyl of carboxylate-containing purification agent or alkyl substituted hydroxy-benzoic acid) (as at least 80%, at least 85%, have 90%, at least 95% or at least 99% at least) is C 14or higher as C 14-C 40, C 14-C 35, C 14-C 30or C 14-C 25.In some embodiments, in 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 purification agent (even as 25% or still less, approximately 20% or still less, 15% or still less, 10% or still less, 5% or still less 1% or still less) be C 8or higher (as C 8-C 14, C 10-C 14even, C 12-C 14).In a preferred embodiment, the salt of the hydroxy-benzoic acid that the alkyl that purification agent comprises the hydroxy-benzoic acid replacing derived from alkyl replaces, wherein said alkyl is to contain at least 90%C 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) that carboxylate salt replaces as alkyl, or even basic metal or alkaline earth salt, or ammonium salt or the substituted ammonium salt of the hydroxy-benzoic acid of alkyl replacement.In another embodiment, the hydroxy-benzoic acid that purification agent comprises alkyl replacement and the overbased salt (as over-based alkaline erath metal salt) of fortified phenol mixture.In another embodiment, purification agent comprises the overbased salt of hydroxy-benzoic acid and/or the overbased salt of alkyl-substituted phenols that alkyl replaces, and 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, 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 anion) of any proper concn being associated with carboxylate salt (or hydroxy benzoate of alkyl replacement).
Some non-limiting examples of other applicable purification agent that can be used in combination with the hydroxy benzoate that alkyl replaces comprise 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 applicable detergent additive comprises metal sulfonate, metal salicylate salt, metal phosphinate hydrochlorate, metal thio-phosphonates and combination thereof.Metal can be any metal that is applicable to preparing 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.
Detergent additive for the present invention characterizes normally oil-soluble by following test method: by 600N oil with by the centrifugation at 60 ℃ of temperature of the mixture of the additive of mixture total weight amount 10wt% concentration, also continue 30 minutes, described centrifugation operation is under standard A STMD2273 defined terms, to carry out (should be understood that centrifugation operation is under the condition of solubilizing agent, not carry out in not diluted), centrifugation, measure at once formed volume of sediment, 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 this product is oil soluble.
In antiwear hydraulic fluid composition of the present invention, the total basicnumber of above-mentioned oil soluble detergent additive is generally lower than 200mgKOH/g and preferably lower than 160mg KOH/g.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 approximately 0.07% scope to about 0.25wt% at about 0.05wt% conventionally.In other words, detergent additive of the present invention exists with " minor amount "." minor amount " detergent additive refers to that in hydraulic composition, the concentration of detergent additive is less than about 60wt%.In some embodiments, " minor amount " detergent additive refers in hydraulic composition that detergent additive concentration is less than about 50wt%, is less than about 30wt%, is less than about 10wt%, is less than about 1wt% or is less than about 0.5wt%.
Generally speaking, purification agent is by making insoluble particles keep colloidal suspension state to contribute to control lacquer deposit ,Huan district's settling and corrosion.Containing metal (or becoming grey purification agent) has as purification agent simultaneously controls settling and as the effect of acid neutralizing agent or rust-preventive agent, thereby reduces wear and corrode and extension device work-ing life.The peace and quiet polarity head end generally including with long hydrophobic tail end, polarity head end comprises the metal-salt of acid organometallic compound.It is the metal of stoichiometric number that described salt can comprise substantially, and in this case, they are described to normal or neutral salt conventionally.
The hydroxy-benzoic acid detergent additive component that alkyl replaces
In antiwear hydraulic fluid composition of the present invention detergent additive can be in purification agent the amount etc. of alkyl substituted hydroxy-benzoic acid salt (salt of the hydroxy-benzoic acid replacing also referred to as alkyl here) or its sulphurated derivatives when the number in potassium hydroxide characterizes, with mgKOH/g purification agent, represent and be called carboxylic acid index (CI).Therefore, the CI with the detergent additive of 56mgKOH equivalent hydroxy benzoate/g purification agent is 56, and is called the hydroxy benzoate that 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 organic solvent and with isopyknic rare strong acid solution and washs 3 times.Collect water layer.Water layer organic solvent washing after merging.Remove water layer, organic layer is used distilled water wash after merging.Pour out water layer.The standard base (SB) titration of dilution is processed and used to acidifying extract with pyridine.
Then, the carboxylic acid index (CI) of detergent additive can be calculated by following formula:
CI＝(V 1×C×MW KOH)/W
In 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.
Once calculate the CI of detergent additive, the amount of the hydroxy benzoate detergent additive that the alkyl that is easy to exist in composition replaces 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 in hydraulic liquid, alkyl replaces)
In one embodiment of the invention, the CI of antiwear hydraulic fluid composition is 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 concentrated solution form be used, and described concentrated solution is generally containing enough organic liquid diluents and the present invention's oil soluble detergent additive used.Concentrated solution contains enough organic liquid diluents so that they are easy to process when shipping and storage.Conventionally, described concentrated solution comprises from about 10-90wt%, preferred about 20-70wt% and the compatible organic liquid diluent of 20-35wt% more preferably from about.Applicable organic liquid diluent comprises that the paraffinic base oils that is for example refined to 100N is as Cit-Con 100N, and the 100N of hydrogenation is as Chevron100N, etc.100 ℃ of about 1-20cSt of viscosity of preferred organic liquid diluent.The concentrated solution of about 10-90wt%, preferred about 30-80wt% is used oil soluble additives in 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, the basic metal of basic metal or mixing, alkaline earth metal borate, the dispersion liquid of Hydrated Alkali Metals Borates, polymeric amide ashless dispersant, etc., and these dispersion agents mixture.
2. oxidation inhibitor: antioxidant can reduce mineral oil deteriorated trend between the usage period, can find out deteriorated as the greasy filth on metallic surface and lacquer deposit and viscosity increase by oxidation products.Be applicable to antioxidant example of the present invention and include but not limited to, phenols (phenolic aldehyde) oxidation inhibitor, as 4，4'-methylene-bis(2，6-di-t-butyl phenol), 4,4 '-bis-(2,6 di t butyl phenols), 4,4 '-bis-(2-methyl-6-tert-butylphenols), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-butylidene-bis-(3 methy 6 tert butyl phenols), 4,4 '-isopropylidene-bis-(2,6 di t butyl phenols), 2,2 '-methylene radical-bis-(4-methyl-6-nonyl phenol), 2,2 '-isobutylene-bis-(4,6 xylenol), 2,2 '-methylene radical-bis-(4-methyl-6-cyclohexylphenol), 2,6 di tert butyl 4 methyl 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-butylphenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), 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: straight chain alcohol b-oxide, comprises and derive 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 following general formula:
In 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 general formula is 1 to 18 R above 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.More preferably for the zinc dialkyl dithiophosphate of antiwear hydraulic fluid composition of the present invention, having carbon number is 3 to 12 primary alkyl.The dialkyl dithio dialkyl group zinc with the mixed alkyl of primary and secondary alkyl can be used alone or combine 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, 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 copolymer, hydrogenated styrene-isoprene copolymer, polyisobutene and dispersion agent class viscosity index improver.
10. pour point depressant: polymethacrylic acid polymkeric substance.
11. defoamers: methacrylate polymer and dimethyl organosilicon polymer.
Embodiment
Emulsifying property
Prepare benchmark formula and in ASTM D 1401 water separabilities tests for assessment of the performance of embodiment 1 purification agent.Described benchmark formula is to comprise 0.31wt% zinc dialkyl dithiophosphate, 0.15wt% hindered phenol antioxygen, 0.044wt% succinate dispersion agent, 0.044wt% fatty ester friction improver, 0.013wt% aryl many alcohol emulsion splitter and 0.008wt% suds suppressor containing in the basal liquid of She11HVI base-material.All finished fluids in these embodiment are all the ISO VG46 containing 8wt% polyalkyl methacrylate viscosity index improver.
Embodiment 1
The antiwear hydraulic fluid composition that preparation consists of said reference formula and the calcium hydroxybenzoate purification agent that adds 0.225wt% parlkaline alkyl to replace and 0.06wt% succinate dispersion agent, in the calcium hydroxybenzoate that described alkyl replaces, at least 90% alkyl is C 20or higher.The calcium hydroxybenzoate that this parlkaline alkyl replaces by method described in U.S. Patent Application No. 2007/0027043 embodiment 1, prepare and calcium contents be 5.35wt%, TBN be 150 and CI be 56.
Embodiment 2
By the formula of embodiment 1, prepare antiwear hydraulic fluid composition, difference is to add 0.01wt% straight chain alcohol b-oxide emulsifying agent and 0.16wt% zinc dialkyl dithiophosphate.
Comparing embodiment 1
The antiwear hydraulic fluid composition that preparation consists of said reference formula and the purification agent, 0.024wt% parlkaline phenol calcium, 0.027wt% naphthene sulfonic acid zinc salt rust-preventive agent and the 0.008wt% resol emulsion splitter that add 0.041wt% to contain the hydroxy benzoate of parlkaline alkyl monosulfide replacement.The described purification agent containing parlkaline sulfuration carboxylate salt by method described in U.S. Patent Application No. 5808145 embodiment 16, prepare 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 the calcium hydroxybenzoate that preparation is replaced by said reference formula and the 56CI parlkaline alkyl adding described in 0.075wt% embodiment 1 forms.
Comparing embodiment 3
By the formula of comparing embodiment 2, prepare antiwear hydraulic fluid composition, difference is to add 0.06wt% succinate dispersion agent.
Comparing embodiment 4
The antiwear hydraulic fluid composition that the calcium hydroxybenzoate that preparation is replaced by said reference formula and the 56CI parlkaline alkyl adding described in 0.15wt% embodiment 1 forms.
Comparing embodiment 5
By the formula of comparing embodiment 4, prepare antiwear hydraulic fluid composition, difference is to add 0.06wt% succinate dispersion agent.
Emulsifying property test-results
The water separability of antiwear hydraulic fluid characterizes by ASTM D1401 test method.In this method, the distilled water of the specimen material of 40ml volume and 40ml volume is merged to liquid and within 5 minutes, carries out emulsification by stirring in the graduated cylinder with scale 54 ℃.The relative volume that stops the rear corresponding hydraulic liquid of stirring, water and emulsion layer by monitoring 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-ml water-ml emulsion while stopping stirring some minutes.
Table 1
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 in hydraulic liquid, alkyl replaces)
Rustless property
Prepare benchmark formula and in ASTM D665 rust prevention test for assessment of the performance of various purification agents.Described benchmark formula is to contain ExxonMobil AP/E
Figure BDA0000045305140000112
in the basal liquid of base-material, comprise 0.31wt% zinc dialkyl dithiophosphate, 0.15wt% hindered phenol antioxygen, 0.044wt% succinate dispersion agent, 0.044wt% fatty ester friction improver, 0.013wt% aryl many alcohol emulsion splitter and 0.008wt% resol emulsion splitter.All finished fluids in these embodiment are all ISO VG 68.
Embodiment 3
The antiwear hydraulic fluid composition that the calcium hydroxybenzoate purification agent that preparation is replaced by said reference formula and the 56CI parlkaline alkyl adding described in 0.075wt% embodiment 1 forms.
Comparing embodiment 6
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 preparation is replaced containing parlkaline alkyl monosulfide by said reference formula and the 28CI adding described in 0.041wt% comparing embodiment 1 forms.
Comparing embodiment 7
The antiwear hydraulic fluid composition that preparation consists of said reference formula and the calcium hydroxybenzoate purification agent that adds 0.067wt% parlkaline alkyl to replace, at least 90% alkyl of the calcium hydroxybenzoate that described alkyl replaces is C 14-C 18.The TBN of purification agent be 168 and CI be 51.
Comparing embodiment 8
The antiwear hydraulic fluid composition that preparation consists of said reference formula and the calcium hydroxybenzoate purification agent that adds 0.049wt% parlkaline alkyl to replace, the alkyl at least 90% of the calcium hydroxybenzoate that described alkyl replaces is C 20-C 28.The TBN of purification agent be 230 and CI be 46.
Comparing embodiment 9
The antiwear hydraulic fluid composition that preparation consists of said reference formula and the calcium hydroxybenzoate purification agent that adds 0.035wt% parlkaline alkyl to replace, the alkyl at least 90% of the calcium hydroxybenzoate that described alkyl replaces is C 20-C 28.The TBN of this purification agent be 325 and CI be 36.
Comparing embodiment 10
The antiwear hydraulic fluid composition that preparation consists of said reference formula and the calcium hydroxybenzoate purification agent that adds 0.032wt% parlkaline alkyl to replace, the alkyl at least 90% of the calcium hydroxybenzoate that described alkyl replaces is C 20or higher.The calcium hydroxybenzoate purification agent that described parlkaline alkyl replaces by method described in U.S. Patent application 2007/0027043 embodiment 1, prepare and calcium contents be 12.5wt%, TBN be 350 and CI be 37.
Test for rust preventing ability result
The rust-preventing characteristic of antiwear hydraulic fluid is measured by ASTM D 665 methods, and this test method is incorporated by reference.If ASTM D 665 is when measuring water and mix with hydraulic liquid, hydraulic liquid helps prevent the test method of the ability that iron parts get rusty.For measuring rustless property of the present invention, adopt the method B of ASTMD 665.In this test, the mixture of the 300ml experimental liquid of complete submergence cylindrical steel batten and 30ml synthetic sea water is stirred 24 hours at 60 ℃ of temperature.Corrosion test report the test be " 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 in hydraulic liquid, alkyl replaces)
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 shown beat all rustless property, compares and has also shown beat all rustless property with the formula (comparing embodiment 6) that contains rust-preventive agent.Embodiment 3 formulas do not need fortunately for adding rust-preventive agent by this test.
As previously discussed, in some hydraulic liquid application, as some mobile equipment, apply in hydraulic liquid used and HLPD and HLVPD liquid, preferably make emulsifying water rather than make water deemulsification.Because the hydroxy benzoate that the alkyl of embodiment 1 replaces has also represented good rust-preventing characteristic under the condition without metal sulfonate rust-preventive agent and because it is known that metal sulfonate rust-preventive agent makes water deemulsification, the hydroxy benzoate that embodiment 1 alkyl used replaces provides the other performance that is conducive to make hydraulic liquid emulsification.

Claims (22)

1. the salt of the hydroxy-benzoic acid that alkyl replaces is improving the emulsification of antiwear hydraulic fluid composition and the purposes in rustless property as oil soluble detergent additive, 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, wherein said carboxylic acid index is measured through the following steps (a) hydroxy benzoate of described alkyl replacement is dissolved in organic solvent and with isopyknic rare strong acid solution and is washed 3 times; (b) collect water layer; (c) with the water layer after organic solvent washing merging; (d) remove water layer; (e) merge organic layer and use distilled water wash; Pour out water layer; (f) with pyridine, process acidifying extract and use the standard base (SB) titration of diluting; (g) the carboxylic acid index (CI) of the hydroxy benzoate that described alkyl replaces can be calculated by following formula: CI=(V 1* C * MW kOH)/W, in formula, V1 arrives the required volume of titration curve First terminal point; C is the concentration of the standard base (SB) of described dilution; MW kOHit is the molecular weight of KOH; W is the weight of the hydroxy benzoate of alkyl replacement; (h) CI of antiwear hydraulic fluid composition calculates according to the following formula: the CI of the hydroxy benzoate that the CI=alkyl of antiwear hydraulic fluid composition replaces * (wt% of the hydroxy benzoate that in antiwear hydraulic fluid composition, alkyl replaces).
2. press the purposes of claim 1, the alkyl group that the hydroxy-benzoic acid that wherein said alkyl replaces comprises straight chain or branching or the mixture of the alkyl group of straight chain and branching.
3. by the purposes of claim 1, the alkyl at least 90% of the hydroxy-benzoic acid that wherein said alkyl replaces is C 14or higher.
4. by the purposes 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 purposes of claim 1, wherein said salt comprises calcium salt.
6. by the purposes of claim 1, wherein said hydraulic composition is not containing additional rust-preventive agent.
7. by the purposes of claim 1, wherein said oil soluble detergent additive comprises the TBN that is less than 200mg KOH/g.
8. by the purposes of claim 1, wherein said oil soluble detergent additive comprises the TBN that is less than 160mg KOH/g.
9. by the purposes of claim 1, wherein said oil soluble detergent additive accounts for the 0.1wt% that is greater than of described antiwear hydraulic fluid composition total weight.
10. by the purposes of claim 1, wherein said oil soluble detergent additive accounts for the 0.2wt% that is greater than of described antiwear hydraulic fluid composition total weight.
11. by the purposes of claim 1, and described antiwear hydraulic fluid composition also comprises at least one following additive altogether: (a) ashless dispersant; (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.
The salt of the hydroxy-benzoic acid that 12. alkyl replace is the purposes in the rustless property that improves antiwear hydraulic fluid composition as oil soluble detergent additive, 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, wherein said carboxylic acid index is measured through the following steps (a) hydroxy benzoate of described alkyl replacement is dissolved in organic solvent and with isopyknic rare strong acid solution and is washed 3 times; (b) collect water layer; (c) with the water layer after organic solvent washing merging; (d) remove water layer; (e) merge organic layer and use distilled water wash; Pour out water layer; (f) with pyridine, process acidifying extract and use the standard base (SB) titration of diluting; (g) the carboxylic acid index (CI) of the hydroxy benzoate that described alkyl replaces can be calculated by following formula: CI=(V 1* C * MW kOH)/W, in formula, V1 arrives the required volume of titration curve First terminal point; C is the concentration of the standard base (SB) of described dilution; MW kOHit is the molecular weight of KOH; W is the weight of the hydroxy benzoate of alkyl replacement; (h) CI of antiwear hydraulic fluid composition calculates according to the following formula: the CI of the hydroxy benzoate that the CI=alkyl of antiwear hydraulic fluid composition replaces * (wt% of the hydroxy benzoate that in antiwear hydraulic fluid composition, alkyl replaces).
13. by the purposes of claim 12, the alkyl group that the hydroxy-benzoic acid that wherein said alkyl replaces comprises straight chain or branching or the mixture of the alkyl group of straight chain and branching.
14. by the purposes of claim 12, and the alkyl at least 90% of the hydroxy-benzoic acid that wherein said alkyl replaces is C 14or higher.
15. by the purposes of claim 12, and wherein, in ASTM D665 rust prevention test method, described antiwear hydraulic fluid composition can reach the result of passing through.
16. by the purposes of claim 12, and wherein said salt comprises calcium salt.
17. by the purposes of claim 12, and wherein said hydraulic composition is not containing additional rust-preventive agent.
18. by the purposes of claim 12, and wherein said oil soluble detergent additive comprises the TBN that is less than 200mg KOH/g.
19. by the purposes of claim 12, and wherein said oil soluble detergent additive comprises the TBN that is less than 160mg KOH/g.
20. by the purposes of claim 12, and wherein said oil soluble detergent additive accounts for the 0.05wt% that is greater than of described antiwear hydraulic fluid composition total weight.
21. by the purposes of claim 12, and wherein said oil soluble detergent additive accounts for the 0.07wt% that is greater than of described antiwear hydraulic fluid composition total weight.
22. by the purposes of claim 12, and described antiwear hydraulic fluid composition also comprises at least one following additive altogether: (a) ashless dispersant; (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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