CN102066537A - Polyalkylene glycol-based wind turbine lubricant compositions - Google Patents

Abstract

A lubricant composition that is especially useful under extreme conditions, such as in wind turbine gearboxes, comprises a mixed feed glycol; a polyol ester; two particular antioxidants; a phosphorus-based extreme pressure additive; a yellow metal passivator; and at least one specified corrosion inhibitor. The composition passes testing according to ASTM D665B even at 168 hours from initiation, and/or the SKF-Emcor Test Method DIN 51802:1990.

Description

Wind turbine lubricant compositions based on polyalkylene glycol

Cross reference to related application

This application is to require the U.S. Provisional Patent Application in submission on April 28th, 2008, the non-provisional application that name is called the right of priority of " based on the wind turbine lubricant compositions of polyalkylene glycol ", the instruction of this provisional application is combined in herein by reference, as it is replicated in hereinafter in full.

This invention design lubricant compositions.More specifically, the present invention relates to polyalkylene glycol (PAG) the series lubricant agent composition that can under extreme environment and mechanical conditions, use, as be used for those lubricant compositions of wind turbine wheel casing.

Though known thousands of year, along with coal and oil are the cost that the energy goes up, wind turbine obtained the concern that increases day by day now.(OPEC) since bulletin causes oil embargo that oil price significantly improves first, it is especially strong that this concern has become from twentieth century Organization of the Petroleum Exporting Countries's seventies (Organization of Petroleum-Exporting Countries).Now, some countries as Germany, Spain, Denmark and the U.S. efforts be made so that a big chunk that produces their institute's energy requirement with wind turbine more and more, in some areas, wind turbine provides a large amount of generatings that are equal to mutually with the nuclear power plant under the situation with minimum relatively environmental influence.

Typical wind turbine comprises parts such as wheel casing, and described wheel casing holds the gear that slow-speed shaft is connected with high speed shaft.These axles make rotating speed change to 1 from 40 rpms of (rpm)-60rpm, 500rpm-1, and 800rpm, the scope of back is represented the rotating speed that most of generator for electricity generation are required.Though wind turbine has impressive record of reliability, when breaking down, they are often traced back to the box bearing fault.These bearings must bear high load, and the performance requirement that often changes.For example, under the certain operations condition, bearing need bear medium load with low speed, and bearing then need bear much lower load with much higher speed elsewhere.In addition, gentle breeze needs bearing to bear high capacity with low speed.These conditions that often change in wheel casing and rigorous environment condition usually as high temperature, water, oxygen with cause bearing corrosion and the salt of wearing and tearing combines, and produce undesired result.Perhaps lubricant destroys, and promptly kinetic viscosity (KV) reduces and the contact fatigue failure generation; Perhaps system needs the oil draining period of unfavorable weak point, means that turbine consumes the stop time of unacceptable amount.

Usually, the lubricant formulations that is used for wind turbine gearbox now comprises synthetic oil but not natural oil.Synthetic oil uses the combination and the polyalkylene glycol of ester class, poly-alpha olefins (PAO), PAO and ester class usually.PAO often provides high viscosity index (HVI) (VI) and low pour point, and this supports the operating temperature of wide region.PAG provides anti-little spot corrosion (micropitting) property of improvement, but may be incompatible with coating and/or sealing material in some cases.Solution for described problem can comprise following content recently.

Disclosed a kind of solution is to comprise following lubricant compositions in U.S. Patent application publication (United States Patent (USP) (USPAP)) 2005/009409 of Devlin etc.: sulfocompound, P contained compound, alkylene amine modified antifriction compound, the compound dispersing agent that contains basic nitrogen, and thinner or base oil (base oil).

Disclosed another kind of solution is to comprise the lubricant compositions of (〉=) two kinds of basic raw materials at least in the United States Patent (USP) 2006/0276355 of Cary etc., described basic raw material is preferably synthetic basic raw material, wherein a kind of basic raw material 100 degrees centigrade (℃) have greater than (＞) 100 centistokes (cSt) kinetic viscosity (Kv100 ℃) (centistokes), and second kind of basic raw material has Kv100 ℃ less than (＜) 10cSt.Composition can comprise various additives, as can be used for those additives in the various commercial gear oil suits.

Or the United States Patent (USP) 2005/0090410 of Devlin etc. discloses the lubricant compositions that is described to be applicable in the wind turbine gearbox.Described composition comprises sulfocompound, alkylamine compound, thiophosphoric acid alkyl ester compound, friction modified immunomodulator compounds and thinner or base oil.

Though described technology has pointed out that for the effort that meets the wind turbine application demand performance expection does not still realize by the product on the market routinely.Oil draining period still is shorter than the oil draining period of expectation, and this is the particular problem that offshore wind turbine is faced.Burn into wearing and tearing and viscosity destroy continue to this highly grow up, the industry of fast development challenges.

On the one hand, the present invention is a kind of lubricant compositions, described lubricant compositions comprises the following of significant quantity: (1) based on the PAG of oxyethane (EO) and propylene oxide (PO), wherein the described PAG of at least 30 weight % (weight percent) is the EO unit; (2) polyol ester; (3) N-phenyl-1,1,3,3-tetramethyl butyl naphthalene-1-amine, it is as first antioxidant; (4) by N-phenyl-aniline and 2,4, the alkylated diphenylamine that the reaction product of 4-2,4,4-Trimethyl-1-pentene or blended octyl groupization and butylation pentanoic form, it is as second antioxidant; (5) phosphorus base extreme pressure additive; (6) yellow metal passivator; (7) at least a being selected from: (a) amine salt of aliphatic phosphate by the inhibiter in the following group of forming; (b) alkenyl succinic acid half ester in the mineral oil; (c) be combined with the amine salt of the alkylphosphonic acid carboxylic acid of phosphorodithioic acid derivative; (d) combination of dinonyl naphthalene sulfonate barium and dinonyl naphthalene monocarboxylic acid barium in the hydrotreated naphthenic oil; (e) their combination.

In related fields, the present invention comprises following lubricant compositions:

(1) 80 weight % based on the random of oxyethane and propylene oxide or segmented copolymer polyalkylene glycol, wherein 60 weight % are ethylene oxide units, and 40 weight % are propylene oxide units, and described have an ISO viscosity grade of 460 based on the random of oxyethane and propylene oxide or segmented copolymer polyalkylene glycol;

The pentaerythritol ester of the paraffinic acid of (2) 15 weight %;

The N-phenyl-1,1,3 of (3) 1 weight %, 3-tetramethyl butyl naphthalene-1-amine, it is as first antioxidant;

(4) 1.3 weight % by N-phenyl-aniline and 2,4, the alkylated diphenylamine that the reaction product of 4-2,4,4-Trimethyl-1-pentene forms, it is as second antioxidant;

The isopropylation triaryl phosphate that is combined with monododecyl phosphte and triphenylphosphate of (5) 1.5 weight %, it is as extreme pressure additive;

The tolyl-triazole of (6) 0.1 weight %, it is as yellow metal passivator; With

At least a amine salt of the aliphatic phosphate of (7) 0.6 weight %, it is as inhibiter.

Lubricant compositions demonstrates based on land with in based on the purposes of ocean and in various extreme environment and the practicality in the mechanical conditions.Such application comprises, for example wind turbine gearbox, seabed hydraulic efficiency system, compressor, and viscosity, rust inhibition, anti-attrition and long-life purposes that other especially need be stable.For example, lubricant compositions preferably passes through to use the SKF-Emcor testing method DIN 51802:1990 (ISO 11 007) of distilled water and use salt solution (0.5 weight % sodium-chlor is based on the brinish gross weight) with 0 grade.For by such test, composition must have and not be higher than 1 grade.After lubricant also preferably begins by ASTM D665B at least 168 hours.

In the embodiment of some indefinitenesses, the PAG that is applicable to above lubricant compositions is selected from the random and segmented copolymer glycol based on blended EO and PO raw material.Because their pour point, the random copolymers glycol can be applicable to this paper especially.Can use one or more PAG, but be based on the PAG gross weight, preferably in the scope of 30 weight % to 95 weight %, all the other are the PO unit to EO unit total content.Based on the PAG gross weight, EO unit content is more preferably in the scope of 50 weight % to 85 weight %, and more preferably in the scope of 60 weight % to 70 weight %, all the other are the PO unit.PAG can be monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol, more high-grade polyfunctional alcohol, perhaps their combination.In some nonrestrictive embodiments, can select dibasic alcohol.

As an example the explanation and without limitation, the preparation of suitable PAG can be undertaken by any means well known by persons skilled in the art or method.For example, using for example rare acid potassium permanganate or perosmic anhydride, can be EO and PO with ethene and propylene selective oxidation.At conversion of olefines is in the reaction of alkoxide, can alternatively use hydrogen peroxide.Subsequently can be by in initiator such as ethylene glycol or propylene glycol, adding EO and PO simultaneously, and for example use basic catalyst such as potassium hydroxide to promote polymerization, thus make EO and PO polymerization to form random PAG multipolymer.

People can change into and buy PAG multipolymer basis fluid (base fluid).For example, SYNALOX ^TMAnd UCON ^TMLubricant fluid can be available from Dow Chemical (The Dow Chemical Company).In some nonrestrictive embodiments, viscosity 22 to 1000 (promptly, 22cSt to 1 in the time of 40 ℃, the KV of 000cSt) fluid in the ISO range of viscosities may be effective especially, although the viscosity can be chosen in 40 ℃ for some application the time in the scope of 220cSt to 680cSt.In some concrete and nonrestrictive embodiments, can select 320 ISO viscosity grade.What may also suit is to select water miscible rather than non-water-soluble multipolymer basis fluid, because water miscible base fluids can provide the friction control of improvement in specific application.

Polyol ester can pass through polyvalent alcohol (for example, neopentyl glycol; Tetramethylolmethane, TriMethylolPropane(TMP)) and sour reaction formation.Normally used acid comprises having 5 carbon atom (C ₅) to 18 carbon atom (C ₁₈) monoprotic acid, as C ₅(valeric acid), C ₁₀(capric acid) and C ₁₈(oleic acid), and binary-and triprotic acid.Ronald Shubkin edits Synthetic lubricant and functional liquid (Synthetic Lubricants ﹠amp; Functional Fluids)The instruction that comprises the synthetic lipid of polyol ester about preparation is provided.Polyol ester is preferably the pentaerythritol ester of paraffinic acid.

Can adopt alkylene oxide polymer and and their interpretation that passes through esterification modification and derivative with terminal hydroxy group replace in the above polyol ester some or all.These example can be singly-or polycarboxylate, for example, acetic ester, blended C ₃-C ₈Fatty acid ester, from the acid anhydrides ester that forms of maleic anhydride and succinyl oxide reaction for example, and their combination.

Also can be used in some nonrestrictive embodiment of the present invention be dicarboxylic acid (for example, phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, alkenyl propanedioic acid etc.) with the ester of various alcohol (for example, butanols, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol monoalkyl ethers of diethylene glycol, propylene glycol etc.).The specific examples of these esters comprises the complex ester of the 2 ethyl hexanoic acid reaction formation of the 2-ethylhexyl diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, fumaric acid dihexyl, sebacic acid dibutyl ester, nonane diacid Diisooctyl, nonane diacid two isodecyl fat, o-phthalic acid dibutyl ester, phthalic acid dodecyl ester, sebacic acid two (eicosyl) ester (sebacate dicicosyl), linoleic acid dimer, the sebacic acid by 1 mole and 2 moles Tetraglycol 99 and 2 moles, or the like.

The available ester comprises by C in addition ₅To C ₁₂The ester that monocarboxylic acid, polyvalent alcohol and polyol ethers are made, described polyvalent alcohol and polyol ethers such as have neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and tripentaerythritol, polytetrahydrofuran, they combination, or the like.Also comprise polyol ester and di-esters, two of alkyl carboxylic acid-aliphatic dibasic acid esters for example, as be described in United States Patent (USP) 4,859, in 352 can be with the trade mark EMERY of Emery Chemicals ^TM2960 di(2-ethylhexyl)azelates that are purchased, hexanodioic acid two-isodecyl ester and hexanodioic acid two-tridecyl ester.Other polyol ester that is fit to is produced by Exxon-Mobil Chemicals.The polyol ester P-43, the NP343 that contain the Exxon-Mobil Chemical of two kinds of alcohol, and M-045, and the HATCO of Hatco Corporation ^TM2939 can be used for some nonrestrictive embodiments.

Can select di-esters, aliphatic dibasic acid esters as dicarboxylic acid, perhaps alkyl dicarboxylic aid's dialkyl group aliphatic diester is as di(2-ethylhexyl)azelate, two different decayl esters of azelaic acid, nonane diacid two-tridecyl ester, hexanodioic acid two-isodecyl ester, hexanodioic acid two-tridecyl ester.For example, di(2-ethylhexyl)azelate can be with trade mark EMERY ^TM2958 are purchased the Chemicals from Emery.

The EMERY that describes in polyol ester such as the United States Patent (USP) 5,344,579 from Cognis ^TM2935,2936 and 2939, and from the HATCO of Hatco Corporation ^TM2352,2962,2925,2938,2939,2970,3178 and 4322 polyol esters; With MOBIL from Exxon-Mobil Chemical ^TMEster P 24 also is an available.Can use Exxon-Mobil ester class, for example ester by dicarboxylic acid, two pure and mild monocarboxylic acids or monohydroxy-alcohol reaction are made.In some concrete and nonrestrictive embodiment, be used for herein polyol ester and can have-100 ℃ with down to-20 ℃ pour point, and in the time of 100 ℃ the viscosity below the 10cSt.

The ester of selecting can be aliphatic series or aromatics in itself, and can comprise, for example, and di-esters, phthalic ester, benzenetricarboxylic acid ester, pyromellitic ester, dimeric dibasic acid ester, polyvalent alcohol and heavy wool acid esters.In concrete nonrestrictive embodiment, ester is pentaerythritol ester (for example, the HERCOLUBE of paraffinic acid ^TMJ can be available from Hercules Incorporated).In other nonrestrictive embodiment, ester is usually by making carboxylic acid and chemical formula C ((CH at some ₂) _nOH) ₄Polyol reaction and the hydrophobic ester that obtains, wherein n be comprise end points based on the integer between 1 to 3.These polyvalent alcohols are called as the tetramethylolmethane homologue in this article.

Can be by any way, as United States Patent (USP) 2 by McNeil, 961,406 method prepares ester, described in this United States Patent (USP) by one or more paraffinic acids with single-and the compound of two-PEOH between prepared in reaction list-tetramethylolmethane (PEOH) four esters with pair-PEOH six esters.The suitable acid of Miao Shuing comprises acetate, propionic acid, butyric acid, 2 Methylpropionic acid, valeric acid, caproic acid, enanthic acid, sad, 2 ethyl hexanoic acid and n-nonanoic acid (nonanonic acid) there.

For McNeil alternative be, can make mixture and for example batch-wise list of paraffinic acid or acid-and two-PEOH reaction, four esters and six esters with many batches of gained mix subsequently.In addition, use the McNe of paraffinic acid to be more typically than instruction, the mixture of described acid or acid can be selected from carboxylic acid; These acid can be straight or branched, saturated or undersaturated, aliphatic series or aromatics, perhaps their arbitrary combination.

Available list-comprise alkyl (alkyl that comprises straight chain and side chain), saturated and unsaturated alkyl and their combination with two-PEOH ester.Alkyl comprises aliphatic series, alicyclic and aromatic group, such as alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl.Alkyl also comprises the alkyl of unsubstituted alkyl and replacement, and the latter is meant and also has other substituent hydrocarbyl portion except carbon and hydrogen; Correspondingly, aliphatic, alicyclic and aromatic group is understood to include unsubstituted aliphatic series, alicyclic and aromatic group, and the aliphatic series, the alicyclic and aromatic group that replace, and the latter is meant also has other substituent aliphatic series, alicyclic and aromatics part except carbon and hydrogen.

Alkyl can comprise the heteroatom group of at least one hydrolysis-stable, and the group of hydrolysis does not take place in the presence of aqueous medium " hydrolysis-stable " expression group.The heteroatom group of suitable hydrolysis-stable comprises that ether, ester, acid amides, thioether, sulfone and tertiary amine are connected, and halo alkyl (for example, chlorination or fluor alkaline).

The PEOH ester can comprise the substituting group of arbitrary combination, and condition is that the mixture of gained PEOH ester is hydrophobic.Substituting group preferably includes hydrogen or C independently ₁-C ₂₂Alkyl or alkyl more preferably comprise hydrogen or C ₁-C ₁₄Alkyl or alkyl also more preferably comprise C ₄-C ₉Alkyl or alkyl, and be more preferably and comprise saturated C ₄-C ₉Alkyl (that is C, ₅-C ₁₀Monobasic saturated acid, preferred monobasic C ₅-C ₁₀The mixture of linear saturated fatty acids, list-and two-PEOH ester).

Can include but not limited to the example of the acid of polyol reaction: formic acid, acetate, propionic acid, vinylformic acid, butyric acid, isopropylformic acid, propanedioic acid, valeric acid, pentanedioic acid, caproic acid, hexanodioic acid, sad, capric acid, sebacic acid, palmitinic acid, dodecanedioic acid, Zoomeric acid, stearic acid, oleic acid, linolenic acid, docosoic and erucic acid.

Available PEOH ester comprises can be from Hercules Incorporated as HERCOLUBE ^TMAnd HERCOFLEX ^TMThe ester that synthetic ester is purchased.These synthetic PEOH esters are essentially C ₅-C ₁₀The list of lipid acid-and two-pentaerythritol ester.The ester that also can have three-PEOH ester and more senior PEOH oligopolymer.Preferably,＜1 the PEOH ester of weight % comprises impurity.Specific product comprises all can be available from the HERCOLUBE of Hercules Incorporated ^TMF, HERCOLUBE ^TMJ, HERCOLUBE ^TM202 and HERCOFLEX ^TM707A.Alternative commercially available ester comprises SYNATIVE ^TMES TMP and TMTC unsaturation and saturated TMP ester, and from the saturated NPG/PE ester of Cognis.

Out of Memory can be at Kirk-Othmer Encyclopaedia of Chemical Technology, and (the 4th edition, 1994), the 9th volume finds in the 781-812 page or leaf, and it is combined in herein by quoting in full.

Lubricant compositions comprises N-phenyl-1,1,3, and 3-tetramethyl butyl-naphthalene-1-amine is as first antioxidant.First antioxidant can IRGANOX ^TML06 is purchased the Corporation from Ciba Chemicals.

Lubricant compositions comprises alkylated diphenylamine as second antioxidant.Alkylated diphenylamine can be N-phenylaniline and 2,4, the reaction product of 4-2,4,4-Trimethyl-1-pentene, the mixture of octyl groupization and butylation pentanoic, perhaps their combination.N-phenylaniline and 2,4, the commercial examples of the reaction product of 4-2,4,4-Trimethyl-1-pentene are can be available from the IRGANOX of Ciba Chemicals Corporation ^TML57.The commercial examples of blended octyl groupization and butylation pentanoic is can be available from RT.Vanderbilt Company, the VANLUBE of Inc ^TM961.

Lubricant compositions also wraps the phosphorous-containigroups groups extreme pressure additive, and the example of described phosphorus base extreme pressure additive comprises the triaryl phosphate class of isopropylation, phosphoric acid amine (amine-phosphates); Group thiophosphate (phosphor-thionates), acid phosphate class, alkyl phosphate class (for example, monododecyl phosphte), and their combination.Commercially available DURAD from Chemtura ^TM310M is the combination of triaryl phosphate and a spot of monododecyl phosphte and the triphenylphosphate of isopropylation.Other extreme pressure additive comprises the Company from RT.Vanderbilt, the VANLUBE of Inc ^TM719,7611,727 and 9123.

Lubricant compositions further comprises yellow metal passivator.As using " yellow metal " to be meant a kind of metallurgy classification in this article, it comprises brass and bell metal, xantal, phosphor bronze, copper, cupronickel and beryllium copper.Typical yellow metal passivator comprises, for example, and the mixture of benzotriazole, Methylbenzotriazole (tolutriazole), tolyl-triazole (tolyltriazole), Methylbenzotriazole sodium and tolyl-triazole, and their combination.In a concrete and nonrestrictive embodiment, select to contain the compound of tolyl-triazole.The yellow metal passivator of typical commodity comprises can be available from the IRGAMET of Ciba Chemicals Corporation ^TM-30 and IRGAMET ^TM-42, and can be available from RT.Vanderbilt Company, the VANLUBE of Inc ^TM601 and 704, with CUVAN ^TM303 and 484.

Lubricant compositions also further comprises at least a following inhibiter that is selected from: the amine salt of (1) aliphatic phosphate (for example, can be available from the NA-LUBE of King Industries ^TM6110); (2) alkenyl succinic acid half ester in the mineral oil (for example, can be available from the IRGACOR of Ciba Chemicals Corporation ^TML12); (3) being combined with the amine salt of the alkylphosphonic acid carboxylic acid of phosphorodithioic acid derivative (for example, can be available from the NA-LUBE of King Industries ^TM6330); (4) combination of dinonyl naphthalene sulfonate barium and dinonyl naphthalene monocarboxylic acid barium (for example, can be available from the NA-SUL of King Industries in the hydrotreated naphthenic oil ^TMBSN); (5) their combination.

Other possible inhibiter comprises the IRGACOR from Ciba Chemicals Corporation ^TML17, IRGACOR ^TMDSSG, IRGALUBE ^TM349 and SARKOSYL ^TMO, and from RT.Vanderbilt Company, the VANLUBE of Inc ^TM601,601E, 704,692 and 719.

Lubricant compositions comprises the component of every kind of regulation, but such component can change in the corresponding proportional range when the total lubricant compositions with suitable character is provided each other.PAG preferably in the scope of 50 weight % to 99 weight %, preferred 〉=70 weight %, more preferably 〉=＞80 weight %.Polyol ester is preferably in the scope of 10 weight % to 20 weight %, and more preferably 15 weight %.First antioxidant preferably in the scope of 0.1 weight % to 5.0 weight %, more preferably 〉=0.5 weight % and more preferably 〉=1.0 weight %.Second antioxidant in the scope of 0.5 weight % to 5.0 weight %, more preferably 〉=1.0 weight % and being more preferably 〉=1.3 weight %.Extreme pressure additive preferably in the scope of 0.1 weight % to 3 weight %, more preferably 〉=1.5 weight % and being more preferably 〉=2 weight %.Yellow metal passivator preferably at 0.01 weight % to 0.5 weight %, more preferably in the scope of 0.05 weight % to 0.1 weight %.Inhibiter preferably at 0.1 weight % to 1.0 weight %, more preferably at 0.2 weight % to 0.75 weight % and be more preferably in the scope of 0.5 weight % to 0.6 weight %.Each weight % in this section is based on the lubricant compositions gross weight.

Lubricant compositions can also comprise the traditional lubrication agent addition agent of one or more components that are different from afore mentioned rules.Such additive (for example comprises defoamer such as polymethyl siloxane, emulsion splitter, antioxidant, phenol antioxidant, hindered phenol anti-oxidants, the olefine sulfide that adds in addition, aromatic amine antioxidant, amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, and their mixture), copper inhibitor, rust-preventive agent, pour point depressant, washing composition, dyestuff, metal passivator, additional friction modifiers, thinner, their combination etc.The traditional lubrication agent addition agent under situation about existing, based on the lubricant compositions gross weight, typically from 100 1,000,000 weight parts (ppm) that account for lubricant compositions weight to the scope of 2 weight %.

Lubricant compositions can prepare by any method known to those skilled in the art.For example, typical mixing device comprises paddle blade type mixer, cylindrical blender, oar formula and plough formula mixing machine, and list or double-shaft mixer.The common regulation of scheme is at first loaded base fluids, is the combination of PAG and polyol ester in this article; The component of using with relative small proportion with the random order filling is antioxidant, extreme pressure additive, yellow metal passivator, one or more inhibiter and any other additive of having selected in this article subsequently.

Though it seems that the potential application of lubricant compositions be unrestricted, they are particularly useful for extreme condition, for example comprise extreme environment and mechanical conditions.U.S. test and materials association (American Society for Test and Materials) (ASTM) are tested the D665B of method to(for) such applicating evaluating lubricant compositions are provided.The lubricant compositions of Miao Shuing can pass through this test like a bomb in this article, under many circumstances, even does not also demonstrate significant failure sign in back 168 hours in beginning.

Example and all respects or the embodiment of unrestricted this invention are more than described and example subsequently.

Unless by opposite explanation, " comprising " can comprise any other additive, auxiliary material or polymerization or non-polymeric compound.Otherwise, " basically by ... form " in any scope of enumerating subsequently, get rid of any other component, step or program, except the requisite content of operability." by ... form " eliminating any component that does not specifically describe or enumerate, step or program.Except as otherwise noted, " or " be meant individually and with arbitrary combination the member that enumerates.

Finish test in accordance with following standard according to hereinafter embodiment and comparative example.

Carry out antirust test according to ASTM D665, that is, in the presence of water, suppress the standard method of test of the rust-preventing characteristic of mineral oil.ASTM D665A tests with distilled water, and ASTM D665B tests with salt solution.Steel test rod or pin are immersed in the beaker that contains oil and 10 weight % water at 140 ℉.After 24 hours, depend on spot corrosion and corrosive degree, estimate rod or pin and with the result be reported as by or failure.In embodiment and comparative example subsequently, test is extended to 168 hours, with about 24 hours gap report result.

By mixing following preparation lubricant compositions, this lubricant compositions is called " reference composition ": 60/40 ethylene oxide/propylene oxide (w/w) parallel feeding glycol (SYNALOX of 81.1 weight % ^TM40D300, Dow Chemical (The Dow Chemical Company)), the N-phenyl-1,1,3 of conduct first antioxidant of 1 weight %, 3-tetramethyl butyl naphthalene-1-amine (IRGANOX ^TML06, Ciba Corporation), conduct second antioxidant of 1.3 weight % in N-phenyl-aniline and 2,4, the reaction product (IRGANOX between the 4-2,4,4-Trimethyl-1-pentene ^TML57, Ciba Corporation), the pentaerythritol ester (HERCOLUBE of the paraffinic acid of 15 weight % ^TMJ, Hercules Incorporated), 1.5 weight %) as the triaryl phosphate (DURAD of the isopropylation of wear preventive additive ^TM310M, the tolyl-triazole of the yellow metal passivator of the conduct of Chemtura and 0.1 weight % is that each weight % is based on composition weight and add up to 100 weight %.Based on the above-mentioned reference composition of 100pbw, this reference composition also comprises the polydimethylsiloxane of 0.002pbw as defoamer.See Table 1 for the reference composition composition.

Use stirring rod on mixed plate, to mix reference composition, simultaneously 60 ℃ temperature heating 60 minutes.Test reference composition according to ASTM D665B, and the result is summarised in the table 2.

Embodiment 1

Repeat the preparation of reference composition, but with the amine salt mixture (NA-LUBE of the aliphatic phosphate of 0.6 weight % ^TM6110, King Industries) replaces the parallel feeding glycol of equivalent as inhibiter.This prescription is presented in the table 1, and test result is presented in the table 2.Embodiment 1 has also passed through use distilled water and has used the test according to SKF-Emcor testing method DIN 51802:1990 (ISO 11 007) of salt solution (0.5 weight %NaCl), is to have 0 grade in 1 the described test allowing greatest level by test.

Embodiment 2

Repeat the preparation of reference composition, but with the mineral oil solution (IRGACOR of the alkenyl succinic acid half ester of 0.25 weight % ^TML12) replace the parallel feeding glycol of equivalent as inhibiter.

Embodiment 3

Repeat the preparation of reference composition, still with the alkylphosphonic acid carboxylic acid of 1 weight % and the amine salt (NA-LUBE of phosphorodithioic acid derivative ^TM6330, King Industries) replaces the parallel feeding glycol of equivalent as inhibiter.

Embodiment 4

Repeat the preparation of reference composition, but with the dinonyl naphthalene sulfonate barium in hydrotreated cycloalkyl thinning oil/dinonyl naphthalene monocarboxylic acid barium (NA-SUL of 0.5 weight % ^TMBSN, King Industries) replaces the parallel feeding glycol of equivalent as inhibiter.

Embodiment 5 (comparison)

Repeat the preparation of reference composition, but the phosphamide and the Hete rocyclic derivatives chemical (NA-LUBE that prepare with the patent of 1 weight % ^TM6220, King Industries) replaces the parallel feeding glycol of equivalent as inhibiter.Comparing embodiment 5 is not by test in 24 hours.

Embodiment 6 (comparison)

Repeat the preparation of reference composition, but with dodecyl dimethyl bicarbonate of ammonia/dodecyl dimethyl volatile salt (CARBOSHIELD of 0.2 weight % ^TM1000, Lonza Inc.) replaces balanced mix charging glycol as inhibiter.Comparing embodiment 6 is not by test in 24 hours.

Embodiment 7 (comparison)

Repeat the preparation of reference composition, but than the pentaerythritol ester (HERCOLUBE that uses paraffinic acid ^TMJ), equivalent increases the parallel feeding glycol remedying untapped material, and the parallel feeding glycol is become SYNALOX ^TM40D220 (Dow Chemical) is to lack HER

Implement

1 SYNALOX 40D220 is the random 60/40 EO/PO multipolymer that has the typical kinetic viscosity of 320cSt in the time of 40 ℃.

2 SYNALOX 40D300 are the random 60/40 EO/PO multipolymers that have the typical kinetic viscosity of 460cSt in the time of 40 ℃.

3 DCF200-12500 are polymethyl siloxane defoamers, can be available from Dow Corning Corporation.

Table 2

1P represents the D665B by ASTM.

2F represents not by ASTM D665B.

3n/a represents inapplicable, and test stops with failure.

4N represents can't see muddiness.

The muddy expression of 5Y-can be seen yellow/white opacity.

Claims (8)

1. lubricant compositions, described lubricant compositions comprises the following of significant quantity:

(1) based on the random of oxyethane and propylene oxide or segmented copolymer polyalkylene glycol, wherein the described polyalkylene glycol of at least 30 weight % is an ethylene oxide unit;

(2) polyol ester;

(3) N-phenyl-1,1,3,3-tetramethyl butyl naphthalene-1-amine, it is as first antioxidant;

(4) by N-phenyl-aniline and 2,4, the reaction product of 4-2,4,4-Trimethyl-1-pentene, or the alkylated diphenylamine of blended octyl groupization and the formation of butylated pentanoic, it is as second antioxidant;

(5) phosphorus base extreme pressure additive;

(6) yellow metal passivator; And

(7) at least a being selected from: (a) amine salt of aliphatic phosphate by the inhibiter in the following group of forming; (b) alkenyl succinic acid half ester in the mineral oil; (c) be combined with the amine salt of the alkylphosphonic acid carboxylic acid of phosphorodithioic acid derivative; (d) combination of dinonyl naphthalene sulfonate barium in hydrotreated naphthenic oil and dinonyl naphthalene monocarboxylic acid barium; (e) their combination.

2. lubricant compositions according to claim 1, wherein said random or segmented copolymer polyalkylene glycol contains the ethylene oxide unit of 50 weight % to 85 weight %, and all the other are propylene oxide units.

3. lubricant compositions according to claim 1, wherein said polyol ester are the pentaerythritol esters of paraffinic acid.

4. lubricant compositions according to claim 1, wherein said phosphorus base extreme pressure additive is selected from the group of being made up of following: the triaryl phosphate class of isopropylation; The phosphoric acid amine; Group thiophosphate; The acid phosphate class; The alkyl phosphate class; With their combination.

5. lubricant compositions according to claim 1, wherein said yellow metal passivator is selected from the group of being made up of following: the mixture of benzotriazole, tolyl-triazole, Methylbenzotriazole, tolyl-triazole sodium and Methylbenzotriazole sodium, and their combination.

6. at least 168 hours ASTM D665B after lubricant compositions according to claim 1, wherein said composition pass through to begin.

7. according to each described lubricant compositions among the claim 1-6, the SKF-Emcor testing method DIN 51802:1990 (ISO 11 007) that wherein said composition passes through to use distilled water and uses salt solution (0.5 weight % sodium-chlor is based on the brinish gross weight) with 0 grade.

8. lubricant compositions, described lubricant compositions comprises:

(1) 80 weight % based on the random of oxyethane and propylene oxide or segmented copolymer polyalkylene glycol, wherein 60 weight % are that ethylene oxide unit and 40 weight % are propylene oxide units, and described have an ISO viscosity grade of 460 based on the random of oxyethane and propylene oxide or segmented copolymer polyalkylene glycol;

The pentaerythritol ester of the paraffinic acid of (2) 15 weight %;

The N-phenyl-1,1,3 of (3) 1 weight %, 3-tetramethyl butyl naphthalene-1-amine, it is as first antioxidant;

(4) 1.3 weight % by N-phenyl-aniline and 2,4, the alkylated diphenylamine that the reaction product of 4-2,4,4-Trimethyl-1-pentene forms, it is as second antioxidant;

The triaryl phosphate of the isopropylation that is combined with monododecyl phosphte and triphenylphosphate of (5) 1.5 weight %, it is as extreme pressure additive;

The tolyl-triazole of (6) 0.1 weight %, it is as yellow metal passivator; With

At least a amine salt of the aliphatic phosphate of (7) 0.6 weight %, it is as inhibiter.