CN102625827A

CN102625827A - Lubricating compositions

Info

Publication number: CN102625827A
Application number: CN2010800476770A
Authority: CN
Inventors: C·S·特里德盖特
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2009-09-07
Filing date: 2010-09-07
Publication date: 2012-08-01
Anticipated expiration: 2030-09-07
Also published as: RU2012113710A; JP2013503957A; WO2011026990A1; RU2555703C2; EP2475753A1; BR112012005155A2; JP5680648B2; US20120178658A1; BR112012005155B1; CN102625827B

Abstract

A lubricating composition comprising: (i) from 50% to 99% by weight of base oil; (ii) from 0.01% to 5% by weight of ionic liquid; and (iii) from 0.01% to 10% by weight of additive; wherein the lubricating composition has a pour point of at most -54 DEG C, a flashpoint of at least 246 DEG C and a kinematic viscosity at 100 DEG C in the range of from 4.9 to 5.4 mm2/s. The lubricating compositions according to the present invention are suitable for use in turbine engine oils and are useful for reducing the build up of sludge and for reducing coking in the lubricating composition.

Description

Lubricating composition

Technical field

The present invention relates to lubricating composition, particularly as the oily lubricating composition of aero-turbine.

Background technology

Aero-turbine oil (TEO) need show fabulous performance in wide TR, to satisfy the dual-use product specification of these products, i.e. MIL-PRF-23699 and SAE-AS-5780 respectively.Particularly, said two kinds of specifications all the product of regulation approval must satisfy some viscosity, pour point and flash-point requirement.

Along with the development of modern turbine engine, aero-turbine oil is exposed to aggressiveness day by day in the enhanced environmental, comprises strong heat and oxidation stress.This can cause undesired consequences, particularly unacceptable accumulation of sludge and unacceptable coking degree in oil system for turbine engine oil.The carbonaceous sediment that coke forms on Engine Surface when being considered to oil degradation usually.If these settlings form in aircraft engine, they just possibly stop up oil circuit and strainer and cause to conduct heat and descend.Aircraft industry has been developed coking tendency that hydrothermal solution processing simulation device (HLPS) test (SAE ARP 5996) estimates aero-turbine oil and this is the key request of civil and military specification.Therefore hope the turbine engine oil that a kind of wherein accumulation of sludge of preparation reduces and the coking degree reduces.

Known ion liquid is used for some lubricating composition.WO2008/154998 discloses and has used ionic liquid to improve the performance of lubricating composition.But in the document, do not mention Application of ion liquid in turbine engine oil.In the document, do not mention the accumulation of sludge that reduces in the lubricating composition yet or reduce coking.

WO2008/075016 discloses a kind of non-aqueous lubricating oil composition; It comprises the base oil and the minor amounts of additives of main amount; Said additive exists as the solution in the base oil and said additive is non-halide, non-aromatics ionic liquid, and this ionic liquid is general formula C ⁺A ^-Salt, positively charged ion C wherein ⁺Comprise heteroatomic season for having four alkyl and choosing wantonly

Or quaternary ammonium ion, wherein said alkyl needn't all have identical carbonatoms, and at least one long chain hydrocarbon groups has greater than 4 carbon atoms and at least one short-chain hydrocarbon group and has than each long chain hydrocarbon groups carbon atom and negatively charged ion A wherein still less ^-Comprise at least one Sauerstoffatom and have the ion head group that links to each other with at least one alkyl or alicyclic alkyl, said alkyl or alicyclic alkyl have four carbon atom and optional heteroatoms at least.Said ionic liquid can be used as wear resistant components and the friction modifier in the lubricating oil composition.Said lubricating oil composition can be used for ignition type engine.But in the document, do not mention and in turbine engine oil, use said ionic liquid.In the document, do not mention the accumulation of sludge that reduces in the lubricating composition yet or reduce coking.

The inventor it has surprisingly been found that now that when ionic liquid being joined in the turbine engine oil accumulation of sludge in the engine oil reduces and coking reduces.Advantageously, in the physicals that keeps the desired lubricating composition of dual-use specification, realize these benefits.

Summary of the invention

According to the present invention, a kind of lubricating composition is provided, it comprises:

(i) base oil of 50-99wt%;

The (ii) ionic liquid of 0.01-5wt%; With

The (iii) additive of 0.01-10wt%;

The pour point of wherein said lubricating composition at the most-54 ℃, flash-point is 4.9-5.4mm at least 246 ℃ and the kinematic viscosity under 100 ℃ ²/ s.

It has surprisingly been found that the part base oil through replacing with ionic liquid in turbine engine, using, the sludge content that observes by testing method FTD-STD-791-5308.7 obviously reduces.

Therefore, the purposes that the present invention also provides ionic liquid to reduce accumulation of sludge in the lubricating composition, wherein said lubricating composition comprises (i) base oil, (ii) ionic liquid and (iii) one or more additives.

It has surprisingly been found that the part base oil through replacing with ionic liquid in turbine engine oil, using, the coking degree obviously reduces.

Therefore, according to another aspect of the present invention, the purposes that provides ionic liquid to reduce the coking in the lubricating composition, wherein said lubricating composition comprises (i) base oil, (ii) ionic liquid and (iii) one or more additives.

Find also that in addition lubricating composition of the present invention has reduced the viscosity increase, reduced the TAN increase and reduced the vaporization losses that during testing method FTD-STD-791-5308.7, is observed.

Embodiment

Lubricating composition of the present invention is particularly useful as turbine engine oil.The turbine engine oil require meets some physicalies of stipulating among dual-use product specification MIL-PRF-23699 and the SAE-AS-5780 respectively.

The kinematic viscosity (press ASTM DIN455 measure) of lubricating composition of the present invention under 100 ℃ is 4.9-5.4mm ²/ s is preferably 4.9-5.1mm ²/ s.

The pour point of lubricating composition of the present invention (press ASTM D97 measure) is preferably at the most-57 ℃ at the most-54 ℃.

The flash-point of lubricating composition of the present invention (pressing ASTM D92 measures) is at least 246 ℃, is preferably at least 250 ℃.

The kinematic viscosity of lubricating composition of the present invention under-40 ℃ (measuring by ASTM DIN455) is preferably at the most 13,000mm ²/ s, more preferably at the most 11,500mm ²/ s.

The kinematic viscosity (by ASTM DIN455 measure) of lubricating composition of the present invention under 40 ℃ is preferably 23mm at least ²/ s is preferably 25mm at least ²/ s.

Said lubricating composition comprises base oil as main ingredient.

By the weight of lubricating composition, the amount of said base oil is 50-99wt%, is preferably 70-99wt%, more preferably 80-97wt%.

Can use any base oil that is applicable to turbine engine oil here.

Preferably, the kinematic viscosity of base oil under 40 ℃ is 20-30mm ²/ s, more preferably 22-25mm ²/ s, the kinematic viscosity under 100 ℃ is 4-6mm ²/ s, more preferably 4.85-5.15mm ²/ s, the kinematic viscosity under-40 ℃ is 7,000-13,000mm ²/ s, more preferably 8,000-10,000mm ²/ s, pour point are-50 ℃ to-65 ℃, more preferably-55 to-60 ℃ and flash-point be 230-260 ℃, more preferably 250-260 ℃.

Said base oil preferably comprises the synthetic ester base base-material, particularly polyol ester based base oil.The synthetic ester base base oil is known in the art and for example in GB-A-2384245, states.Heat and oxidative stability that ester group base oil (with selected additive-package) works in wide TR and shows.

Can use the known and familiar ordinary method of those skilled in the art is prepared ester and should preparation itself do not constituted a part of the present invention by alcohol and carboxylic acid with technology.Usually, choose wantonly in the presence of catalyzer, alcohol as industrial tetramethylolmethane are heated with needed mixture of carboxylic acids.Usually using excessive a little acid to order about reaction accomplishes.During reaction remove water, gas proposes excessive acid arbitrarily from reaction mixture then.For example the ester of industrial tetramethylolmethane can be without being further purified use for ester, perhaps can use conventional art such as distillation is further purified.

The further information of relevant synthetic ester base base oil can be with reference to GB-A-2384245, EP-A-0695797, EP-A-1323815, US-A-4826633 and US-A-5503761, and being taught in here wherein introduced as a reference.

Suitable synthesis for polyol ester base base oil can form through the esterification of aliphatic polyol and carboxylic acid.But aliphatic polyol preferably comprises 4-15 carbon atom and has 2-8 esterified hydroxy groups.Preferred examples is TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, NSC 6366, tripentaerythritol and their mixture.

The carboxylic acid reaction thing that is used to prepare the synthesis for polyol ester base oil can be selected from the mixture of mono carboxylic acid of aliphatic series or mono carboxylic acid of aliphatic series and aliphatic dicarboxylic acid suitably.Said carboxylic acid can comprise 2-20 carbon atom, is preferably 4-12 carbon atom, more preferably 5-10 carbon atom and comprise straight chain and the side chain aliphatic acid.Also can use the mixture of monocarboxylic acid.

Suitable polyol ester is by Chemtura; Middlebury, Connecticut, USA is with trade(brand)name Hatcol 2954, Hatcol 1754, Hatcol 1764, Hatcol 1765 and Hatcol 1760, by Croda; Snaith; UK is with trade(brand)name Priolube 3939 with by Cognis, Monheim, and Germany is purchased those materials of acquisition with trade(brand)name Synative ES 2939 and SynatiVe ES2931.

In addition, all base-materials of in EP-A-0518567 and EP-A-0695797, describing all are applicable in the lubricating composition of the present invention.

According to a preferred embodiment, said polyol ester base oil comprises the monopentaerythritol of 80wt% at least.

Suitably, said polyol ester base oil can be the mixture of the Dipentaerythritol of the monopentaerythritol of about 80-95wt% and 5-20wt%.This mixture is commonly called " industry " tetramethylolmethane and also can comprise some three with the four seasons penta tetrol, the latter forms as sub product at the production period of industrial tetramethylolmethane usually.

Even more preferably the polyol ester base oil comprises the monopentaerythritol greater than 90wt%, more preferably greater than the monopentaerythritol of 95wt%.Even more preferably the polyol ester base oil comprises the monopentaerythritol of about 100wt%.

Another main ingredient of lubricating composition of the present invention is an ionic liquid.

By the weight of lubricating composition, the ion liquid concentration that exists is 0.01-5%, is preferably 0.01-2%, more preferably 0.05-0.5%, particularly 0.1-0.3%.

Ionic liquid is at room temperature to be liquid melting salt, perhaps is defined as the melting salt that has less than 100 ℃ fusing point.They almost do not have vp and can show high thermostability.

Ionic liquid can be by general formula C ⁺A ^-Expression, wherein C ⁺Be suitable positively charged ion, and A ^-Be suitable negatively charged ion.

Suitable positively charged ion C ⁺Be selected from quaternary ammonium cation, phosphorus

Positively charged ion, imidazoles Positively charged ion, pyridine

Positively charged ion, pyrazoles Positively charged ion,

Azoles

Positively charged ion, tetramethyleneimine

Positively charged ion, piperidines

Positively charged ion, trialkyl sulfonium cation, thiazoline

Positively charged ion, guanidinesalt positively charged ion, morpholine positively charged ion, sulfonium cation and triazole

Positively charged ion.Preferred cation is selected from quaternary ammonium cation and phosphorus

positively charged ion.

Suitable negatively charged ion A ^-Be selected from [PF ₆] ^-, [BF ₄] ^-, [CF ₃CO ₂] ^-, [CF ₃SO ₃] ^-And its more higher homologue, [C ₄F ₉SO ₃] ^-Or [C ₈F ₁₇SO ₃] ^-More high-grade perfluoro alkyl sulfonic acid root, [(CF ₃SO ₂) ₂N] ^-, [(CF ₃SO ₂) (CF ₃COO) N] ^-, Cl ^-, Br ^-, I ^-, [C (CN) ₃] ^-, SCN ^-, [B (C ₂O ₄) ₂] ^-, [N (SO ₂CF ₃) ₂] ^-, [R ⁴SO ₃] ^-, [R ⁴OSO ₃] ^-, [R ⁴COO] ^-, [NO ₃] ^-, [N (CN) ₂] ^-, [HSO ₄] ^-, PF _6-XR ⁶ _XOr [R ⁴R ⁵PO ₄] ^-, R wherein ⁴And R ⁵Be independently selected from: hydrogen; Saturated or undersaturated aliphatic series or alicyclic alkyl with straight or branched of 1-20 carbon atom; Heteroaryl, in its assorted fragrant residue, has assorted virtue-C that 3-8 carbon atom and at least one heteroatoms are selected from N, O and S ₁-C ₆-alkyl, it can be selected from C by at least one ₁-C ₆The group of alkyl and/or halogen atom replaces; Aryl-aryl-the C that in its aromatic yl residue, has 5-12 carbon atom ₁-C ₆-alkyl, it can be by at least one C ₁-C ₆-alkyl replaces, R ⁶Can be for the perfluor ethyl or more high-grade perfluoroalkyl and x are the integer of 1-4.

Particularly preferably be and have highly fluorinated anion ion liquid, because these ions are normally highly heat-staple.In addition, these anionic water-retaining capacities obviously reduce owing to have two (trifluoromethyl sulfonyl) imide negatively charged ion.Another kind of preferred anionic surfactants is the trifluoroacetic acid root.

Examples of suitable ionic liquids include, but are not limited to butyl methyl pyrrolidine

- bis (trifluoromethylsulfonyl) imide (MBPimid), methyl-propyl-pyrrolidine

- double (trifluoromethylsulfonyl) imide (MPPimid), three - hexyl methyl imidazole

(perfluoro-ethylene) - trifluoro-phosphate (HMIMPFET), hexyl methyl imidazole

- double (trifluoromethylsulfonyl) imide (HMIMimid), hexyl methyl pyrrolidine - bis (trifluoromethylsulfonyl) imide (HMP), III - tetrabutylphosphonium

(perfluorinated ethylene) trifluoro-phosphate (BuPPFET), octyl methyl imidazole

hexafluorophosphate ( OMIM? PF6), hexyl pyridine

- bis (trifluoromethyl) sulfonyl imide (Hpyimid), methyl trioctyl ammonium - trifluoroacetate (MOAac), butyl-methyl-pyrrolidine

(pentafluoroethyl) three fluorophosphate (MBPPFET), three hexyl (tetradecyl) phosphorus

- bis (trifluoromethylsulfonyl) imide (HPDimid), hexyl methyl imidazole

- tetrafluoroborate (HMI? BF4), hexyl methylimidazole

hexafluorophosphate (HMI? PF6), 1 - ethyl-3 - methyl imidazole

diethyl phosphate (EMIM? DEP), 1 - ethyl-3 - methyl imidazole

methyl sulfate (EMIM ? DSU), 1 - ethyl-3 - methyl imidazole double [oxalate (2 -)-O, O +] borate (EMIM? BOB), and mixtures thereof.

These ionic liquids of listing above can be by Merck, Darmstadt, and Germany and Sigma Aldrich, St Louis, Missouri, the U.S. is purchased acquisition.By BASF, Ludwigshafen, Germany also is adapted at using here with the ionic liquid that trade(brand)name Basionics is purchased acquisition.

For use in the compositions of the invention preferred ionic liquid is selected from methyl trioctyl ammonium - trifluoroacetate (MOAac), trihexyl (tetradecyl) phosphonium

- double (trifluoromethylsulfonyl) acyl imine (HDPimid), hexyl methyl imidazole

tetrafluoroborate (HMI? BF4), six methyl imidazole fluorophosphate (HMI? PF6), 1 - ethyl-3 - methyl imidazole

diethyl phosphate (EMIM? DEP), 1 - ethyl-3 - methyl imidazole

methylsulfate (BMIM? DSU) and mixtures thereof.Here the application is particularly preferred ionic liquids TRIHEXYL (tetradecyl) phosphonium

- bis (trifluoromethylsulfonyl) imide (HDPimid), hexyl methyl imidazole

hexafluorophosphate (HMI? PF6) and mixtures thereof.

Said lubricating composition also comprises one or more additives of significant quantity (usually concentration be the 0.01-10wt% of lubricating composition), for example includes but not limited to metal and ashless inhibitor, metal and ashless dispersion agent, metal and ashless purification agent, sanitas and rust-preventive agent, metal passivator, metal and nonmetallic, low-ash phosphorous and without phosphorus, sulfur-bearing and does not have anti-wear agent, metal and nonmetallic, phosphorous and without phosphorus, the sulfur-bearing of sulphur and do not have extreme-pressure additive, anti-stuck dose, pour point reducer, wax regulator, viscosity modifier, sealing compatilizer, friction modifier, lubricity agent, anti-staining agent, chromogenic reagent, skimmer, emulsion splitter and other additive-package commonly used of sulphur.For the summary of many typical additives, can be with reference to the Lubricants and Related Products of D.Klamann, Verlag Chemie, DeerfieldBeach, FL; " the Lubricant Additives " of ISBN 0-89573-177-0 and M.W.Ranney, by Noyes Data Corporation of Parkridge, N.J. (1973) publishes.

Viscosity index improver (being also referred to as VI improving agent, viscosity modifier or viscosity modifier) provides high temperature and low temperature operability for lubricant.These additives are at high temperature given shear stability and are given acceptable viscosity at low temperatures.

The preferred anti-wear additive that is used for the present composition comprises triaryl phosphoric acid salt, as by Chemtura with trade(brand)name Reolube OMTI, Durad 310M, Durad 110, Durad 125, Durad 150B, Reolube TXP, Durad 220B, Durad 620B, Durad 110B, Fryquel 150 and Fryquel 220 be purchased acquisition those materials, be purchased those materials of acquisition with trade(brand)name Additin RC 3661, Additin RC 3760 and Additin RC 3680 and be purchased those materials of acquisition by Supresta with trade(brand)name SynOAd 8475, SynOAd8484, SynOAd 8485, SynOAd 8478, SynOAd 8477, SynOAd 8499 and SynOAd 9578 by Rhein Chemie.Be included in the Tocp hydrochlorate in addition in the term triaryl phosphoric acid salt, like those materials by specification TT-T-656 approval.

Other preferred anti-wear additive comprises the metal alkyl thiophosphate, more particularly is zinc dialkyl dithiophosphate.Other preferred anti-wear additive comprises without phosphorus anti-wear additive, like aliphatic series, araliphatic or the alicyclic olefin of sulfur-bearing.Other preferred anti-wear additive comprises the polysulfide and the thiophosphoryl based bisulfide of thiophosphoric acid and thiophosphatephosphorothioate.

Glyceryl ester can be used as anti-wear additive.For example, can advantageous applications single-, two-and trioleate, list-cetylate and list-myristinate.Usually, in the gross weight of lubricating composition, the consumption of anti-wear additive can be about 0.01-6wt%, is preferably about 0.01-4wt%.

Suitable inhibitor postpones lubricating composition oxidative degradation during use.This degraded possibly cause in the metallic surface formation settling, exist mud or fluid viscosity to increase.Multiple suitable inhibitor is known, for example at the Lubricants of Klamann, and for example at US-A-4, those that describe in 798,684 and US-A-5,084,197.

For lubricating composition of the present invention, preferred anti-oxidants comprises amine antioxidants.They comprise alkylation and non-alkylating arylamine, for example have the aromatic monoamine of aliphatic series, aromatics or replacement aromatic substituent at the nitrogen-atoms place.Typical arylamine class inhibitor has the alkyl substituent that contains at least about 6 carbon atoms.The example of aliphatic group comprises hexyl, heptyl, octyl group, nonyl and decyl.Usually, aliphatic group contains and is no more than about 14 carbon atoms.The general amine antioxidants that can be used in the present composition comprises pentanoic, nonox, thiodiphenylamine, imidazoles diphenyl-methyl and diphenyl-phenylene-diamine.Also can use the mixture of two kinds or more kinds of arylamine, for example the mixture of PA (PANA) type inhibitor and pentanoic (DPA) class inhibitor.Also can use the polymeric amines inhibitor, for example be purchased the Vanlube 9317 of acquisition by RT Vanderbilt.The specific examples that can be used for arylamine class inhibitor of the present invention comprises: p, p '-dioctyl diphenylamine, t-octyl phenyl-alpha-naphthylamine, PA and p-octyl phenyl-alpha-naphthylamine.

The Additin 7130 that commercially available PA (PANA) type inhibitor comprises the Irganox L06 that for example is purchased by Ciba, be purchased by Rhein Chemie, the Naugalube APAN and the Naugard PAN that are purchased by Chemtura.

Commercially available pentanoic (DPA) type inhibitor comprises the Vanlube 81 that for example is purchased by RT Vanderbilt, by Chemtura, the Naugalube AMS that Germany is purchased, Naugalube 438, Naugalube 635, Naugalube 640, Naugalube 680, the Additin 7001 that is purchased by Rhein Chemie, Addition 7005A, Additin 7135, Additin 10314A, the Hitec 4720 that is purchased by Afton, Hitec 4721, Hitec 4777, the Irganox L 57, the Irganox L67 that are purchased by Ciba.

Other useful inhibitor comprises hindered phenol.Phenol antioxidant can former state use or use with the amine combination.These phenol antioxidant can be the neutrality or the alkaline metal salts of ashless (not containing metal) phenolic cpd or some phenolic cpds.Typical phenol antioxidant compound is to contain the Hinered phenols of sterically hindered hydroxyl and comprise that hydroxyl wherein is positioned at the verivate of those dihydroxyl aryl compounds of o-or p-position each other.The example of this type aldehydes matter comprises the 2-tertiary butyl-4-heptyl phenol, the 2-tertiary butyl-4-octyl phenol, the 2-tertiary butyl-4-4-dodecylphenol, 2; 6-two-tertiary butyl-4-heptyl phenol, 2,6-two-tertiary butyl-4-4-dodecylphenol, 2-methyl-6-tert butyl-4-heptyl phenol and 2-methyl-6-tert butyl-4-4-dodecylphenol.Single phenol antioxidant that is obstructed that other is useful can comprise for example be obstructed 2,6-two-alkyl-phenols propanoate ester derivatives.

Two-phenol antioxidant also can be advantageously used in the lubricating composition.Sulfurized alkylphenol and its basic metal or alkaline earth salt also are useful inhibitors.Doctor negative peroxide breakdown thing also can be used as inhibitor.Another kind of suitable inhibitor is an oil-soluble copper compounds.The example of suitable copper antioxidant comprises the mantoquita of dialkyl-sulfo-or phosphorodithioic acid copper and carboxylic acid.Other suitable mantoquita comprises MGD, sulphonate, phenates and the acetylacetonate of copper.Derived from alkali formula, neutrality or the acid copper Cu (I) of alkenyl succinic acid or acid anhydrides and/or Cu (II) salt known be useful especially.These inhibitors can every type of independent use or combination use each other.The consumption of these additives can be about 0.01-5wt%, is preferably about 0.01-2wt%.

Purification agent as additive can be simple purification agent or heterozygosis or compound purification agent.Suitable purification agent comprises anionic compound, its contain molecule long-chain oleophilic moiety and molecule less negatively charged ion or hate oily part.The anionicsite of purification agent is derived from organic acid usually, like sulfuric acid, carboxylic acid, phosphoric acid, phenol or their mixture.Gegenion is generally earth alkali metal or basic metal.Preferred purification agent comprises vitriol, sulphonate, phenates, carboxylate salt, phosphoric acid salt and the salicylate of basic metal or earth alkali metal.Suitable alkylaryl sulfonate comprises about 9-80 or more a plurality of carbon atom usually, is more typically about 16-60 carbon atom.Preferably the Lubricants of Klamann and Related Products and preceding text quote by Lezius-Hiles Co.of Cleveland, C.V.Smallheer that Ohio (1967) publishes and the middle those disclosed material of " the Lubricant Additives " of R.K.Smith.The earth alkali metal phenates is another kind of useful purification agent.These purification agents are reaction product of alkaline earth metal hydroxides or oxide compound and alkylphenol or sulfurized alkylphenol.Useful alkyl comprises the C of straight or branched ₁-C ₃₀Alkyl is preferably C ₄-C ₂₀The instance of suitable phenol comprises isobutyl-phenol, 2-ethylhexyl phenol, NP, 1-ethyl decyl phenol and analogue.The metal-salt of carboxylic acid also can be used as purification agent.Another kind of preferred purification agent is the earth alkali metal salicylate, comprises monoalkyl to tetraalkyl salicylates, and wherein alkyl has 1-30 carbon atom.Earth alkali metal is preferably calcium, magnesium or barium, and calcium is most preferred.Another kind of useful purification agent comprises alkali earth metal phosphate.Usually, in whole lubricating composition, total purification agent concentration is about 0.01-6wt%, is preferably about 0.1-4wt%.In addition, non-ionic detergents can be preferred in the lubricating composition.This non-ionic detergents can be ashless or low grey compound, and can comprise discrete molecular compound and oligomeric and/or polymeric compounds.

Additive can also comprise dispersion agent.Suitable dispersion agent comprises the polar group that is connected on the relative high-molecular weight hydrocarbon chain usually.Said polar group comprises at least a element in nitrogen, oxygen or the phosphorus usually.Typical hydrocarbon chain comprises about 50-400 carbon atom.Suitable dispersion agent comprise phenates, sulphonate, sulfuration phenates, salicylate, naphthenate, stearate, carbaminate and thiocarbamate.Useful especially one type of dispersion agent is the alkenyl succinic verivate, and wherein said alkenyl chain constitutes the oleophilic moiety of molecule, makes it in oil, have solubleness.Said alkenyl chain can be polyisobutenyl, those that for example in following document, describe: US-A-3,172,892, US-A-3,2145,707, US-A-3; 219,666, US-A-3,316,177, US-A-3,341,542, US-A-3; 454,607, US-A-3,541,012, US-A-3,630,904, US-A-3; 632,511, US-A-3,787,374 and US-A-4,234,435.

The suitable dispersant of other type is being stated in following document: US-A-3,036,003, US-A-3,200,107, US-A-3,254,025, US-A-3,275,554, US-A-3; 438,757, US-A-3,454,555, US-A-3,565,804, US-A-3,413,347, US-A-3,697; 574, US-A-3,725,277, US-A-3,725,480, US-A-3,726,882, US-A-4,454,059, US-A-3; 329,658, US-A-3,449,250, US-A-3,519,565, US-A-3,666,730, US-A-3; 687,849, US-A-3,702,300, US-A-4,100,082, US-A-5,705,458 and EP-A-471071.

Other suitable dispersion agent comprises the hydrocarbyl substituted succinic compound, is useful especially like succinimide, succinate or succinate acid amides (the substituted succsinic acid of hydrocarbon and at least one normal alkylene amines reaction through preferably in hydrocarbon substituent, having at least 50 carbon atoms prepare).

Material or compound that friction modifier promptly can change the fluid friction coefficient can use with the base oil component combination effectively.Suitable friction modifier can comprise metal-salt or metal ligand mixture, and wherein said metal can comprise basic metal, earth alkali metal or magnesium-yttrium-transition metal, those as in WO2004/053030, describing.

Other useful additive comprises pour point reducer, is used to reduce the minimum temperature that lubricating composition flows and maybe can topple over.The instance of suitable pour point reducer comprises the terpolymer of condensed products, vinyl carboxylic acid ester polymer and dialkyl group fumarate, vinyl fat acid esters and the allyl vinyl ether of Rohm tech inc, polyacrylic ester, aramid, halogenated alkane chloroflo and aromatic substance, those that for example in WO2004/053030, mention.

Suitable sealing compatilizer comprises organophosphate, aromatic ester, aromatic hydrocarbons, ester (for example phthalic acid butylbenzene-methyl esters) and polybutylene-based succinyl oxide.

The consumption of these additives can be about 0.01-3wt%.

Can advantageously in lubricating composition, add skimmer.These reagent will postpone the formation of stable foam.Siloxanes and organic polymer are typical skimmer, for example ZGK 5.Skimmer is commercially available, the DCF 200/12500 that for example is purchased, DCF200/500, DCF 200/30000, DCF 200/1000 by Dow Corning, and can using with other additive such as emulsion splitter in a small amount with routine.The combination consumption of these additives is usually less than 1wt%.

Suitable sanitas is those that mention among the Klamann that quotes of preceding text.The instance of suitable sanitas comprises thiadiazoles, benzotriazole, tolytriazole, zinc dithiophosphate, metal phenates, basic metal sulphonate, lipid acid, carboxylic acid and amine.The consumption of these additives can be about 0.01-5wt%, is preferably about 0.01-1.5wt%, more preferably about 0.01-1wt%.Suitable examples of preservatives can be at for example US-A-2, finds in 719,125, US-A-2,719,126 and US-A-3,087,932.The instance of suitable sanitas for be purchased with trade(brand)name Irgamet 39, Irgamet TTA and Irgamet 42 by Ciba those and be purchased with trade(brand)name Vanlube 887 and Vanlube 887E by Vanderbilt those.The further example of suitable sanitas is a dicarboxylicacid, those that for example are purchased with trade(brand)name Emerox1144 and Emerox1110 by Cognis.

The addition type additive that can further be attached in the lubricating composition of the present invention can comprise one or more additives, like emulsion splitter, solubilizing agent, flowing agent, tinting material, chromogenic reagent and analogue.Every kind of additive can comprise independent additive or their mixture.

The following embodiment of following reference describes the present invention:

Embodiment 1-18 and comparative example A

Turbine engine oil through the base oil shown in the blend following table 1-3 and additive preparation embodiment 1-18 and comparative example A.

Amount among the table 1-3 is represented with wt% based on the gross weight of the prescription of preparing fully.

The base oil used is the pentaerythritol ester of 5cSt in the prescription of table 1-3, further comprise Tocp hydrochlorate anti-wear additive, tolytriazole sanitas, dicarboxylicacid sanitas, dioctyl diphenylamine (DODPA) and diaryl pentanoic as pentanoic (DPA) type antioxidant ingredients, uncle p--octyl phenyl-alpha-naphthylamine as phenyl-α-naphthalene (PANA) class antioxidant ingredients and polysiloxane defoamers.The viscosity of pentaerythritol ester under 100 ℃ is 5mm ²/ s and the peak viscosity under-40 ℃ are 13,000mm ²/ s.In addition, pentaerythritol ester has-54 ℃ maximum pour point and 246 ℃ minimum flash point.

Table 1

	The comparative example A	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
								Base oil+additive-package	100	99.8	99.5	99.0	99.8	99.5	99.0
MOAac <sup>1</sup>	0	0.2	0.5	1.0	0	0	0
								HDPimid <sup>2</sup>	0	0	0	0	0.2	0.5	1.0

1. methyl trioctylammonium trifluoroacetate

2. three hexyls (tetradecyl) phosphorus

two (trifluoromethyl sulfonyl) imide

Table 2

	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12
							Base oil+additive-package	99.8	99.5	99.0	99.8	99.5	99.0
HMI?BF4 <sup>3</sup>	0.2	0.5	1.0	0	0	0
							HMI?PF6 <sup>4</sup>	0	0	0	0.2	0.5	1.0

3. hexyl methyl imidazoles

a tetrafluoro borate

4. hexyl methyl imidazoles

hexafluorophosphate

Table 3

	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17	Embodiment 18
							Base oil+additive-package	99.8	99.5	99.0	99.8	99.5	99.0
EMIM?DEP <sup>5</sup>	0.2	0.5	1.0	0	0	0
							EMIM?DSU <sup>6</sup>	0	0	0	0.2	0.5	1.0

5.1-ethyl-3-Methylimidazole diethyl phosphate

6.1-ethyl-3-Methylimidazole

Methylsulfate

The measurement of physicals

Through making lubricating composition experience various standard method of test (shown in following table 4), confirm the various physicalies of embodiment 1-18 and comparative example A's lubricating composition.Measured performance is shown in the following table 4.

Viscosity increases, TAN increases and the measurement of vaporization losses

In order to verify the various benefits of turbine engine oil of the present invention; Make embodiment 1,4 and 16 (containing 0.2%MOAac, 0.2%HDPimid and 0.2%EMIM MSU respectively) and comparative example A experience specified test in FED-STD-791-5308.7, increase and vaporization losses with viscosity increase, the TAN that measures at test period.Said test moves 72 hours down at 218 ℃.The result is shown in the following table 5.

Table 5

Embodiment	Viscosity changes, %	TAN changes, mgKOH/l	Vaporization losses, %	Mud content, mg
					A <sup>#</sup>	60.44	9.71	4.56	1.0
1(0.2％MOAac) <sup>##</sup>	39.10	5.61	3.72	0.1
					4(0.2％HDPimid) <sup>##</sup>	46.85	6.62	3.72	＜0.1
16(0.2％EMIM?MSU)	48.87	7.53	3.91	0.4

# result is 8 MVs of measuring

## result is the MV of twice measurement

The measurement of coking behavior

In order to measure the coking behavior of lubricating composition of the present invention, make embodiment 1 and 4 (comprising 0.2wt%MOAac and 0.2wt%HDPimid respectively) and comparative example A experience HPLS standard method of test SAE ARP 5996.After 20 hours the amount of coke that forms on the stainless steel tube weighed and write down the outward appearance of pipe.The result is shown in the following table 6.

Table 6

The measurement of carrying capacity

For carrying capacity and the wear resisting property of measuring lubricating composition of the present invention, make embodiment 7-12 and comparative example A experience the maximum weld load (each load stage continued for 10 seconds) of four balls tests (IP 239) and each institute's test sample article.The result is shown in the following table 7.

Table 7

Discuss

Result shown in the table 4 shows, the ionic liquid of in turbine engine oil, introducing lower concentration can not cause the physicals of turbine engine oil harmful effect (respectively such as dual-use specification be MIL-PRF-23699 and SAE-AS-5780 requirement).

Can find out by table 5, compare that the lubricating composition of embodiment 1 (containing 0.2% MOAa c), embodiment 4 (containing 0.2%HDPimid) and embodiment 16 (containing 0.2%EMIM MSU) shows accumulation of sludge to be reduced with comparative example A's (not containing ionic liquid).

Can find out from table 6, compare that the lubricating composition of embodiment 1 (containing 0.2%MOAac) and embodiment 4 (containing 0.2%HDPimid) shows coking to be reduced with comparative example A's (not containing ionic liquid).Embodiment 4 (containing 0.2%HDPimid) shows bigger coking than embodiment 1 (containing 0.2%MOAac) to be reduced.

Can find out from table 7, compare that the lubricating composition of embodiment 7-12 shows the increase of weld load and suitable grinding defect diameter with the comparative example A.

Claims

1. lubricating composition, it comprises: (i) base oil of 50-99wt%; The (ii) ionic liquid of 0.01-5wt%; The (iii) additive of 0.01-10wt%; It is 4.9-5.4mm greater than 246 ℃ and kinematic viscosity under 100 ℃ that the pour point of wherein said lubricating composition is lower than-54 ℃, flash-point ²/ s.

2. the lubricating composition of claim 1, it comprises the ionic liquid of 0.01-1wt%.

3. claim 1 or 2 lubricating composition, it comprises the ionic liquid of 0.05-0.5wt%.

4. lubricating composition, wherein ionic liquid is general formula C ⁺A ^-Salt, positively charged ion C wherein ⁺Be selected from quaternary ammonium cation, phosphorus

Positively charged ion, imidazoles

Positively charged ion, pyridine

Positively charged ion, pyrazoles

Positively charged ion,

Azoles

Positively charged ion, tetramethyleneimine

Positively charged ion, piperidines

Positively charged ion, trialkyl sulfonium cation, thiazoline Positively charged ion, guanidinesalt positively charged ion, morpholine positively charged ion, sulfonium cation and triazole

Positively charged ion and negatively charged ion A wherein ^-Be selected from [PF ₆] ^-, [BF ₄] ^-, [CF ₃CO ₂] ^-, [CF ₃SO ₃] ^-And its more higher homologue, [C ₄F ₉SO ₃] ^-Or [C ₈F ₁₇SO ₃] ^-More high-grade perfluoro alkyl sulfonic acid root, [(CF ₃SO ₂) ₂N] ^-, [(CF ₃SO ₂) (CF ₃COO) N] ^-, Cl ^-, Br ^-, I ^-, [C (CN) ₃] ^-, SCN ^-, [B (C ₂O ₄) ₂] ^-, [N (SO ₂CF ₃) ₂] ^-, [R ⁴SO ₃] ^-, [R ⁴OSO ₃] ^-, [R ⁴COO] ^-, [NO ₃] ^-, [N (CN) ₂] ^-, [HSO ₄] ^-, PF _6-XR ⁶ _XOr [R ⁴R ⁵PO ₄] ^-, R wherein ⁴And R ⁵Be independently selected from: hydrogen, have the saturated or undersaturated aliphatic series or the alicyclic alkyl of the straight or branched of 1-20 carbon atom; Heteroaryl, in its assorted fragrant residue, has assorted virtue-C that 3-8 carbon atom and at least one heteroatoms are selected from N, O and S ₁-C ₆-alkyl, it can be selected from C by at least one ₁-C ₆The group of alkyl and/or halogen atom replaces; Aryl-aryl-the C that in its aromatic yl residue, has 5-12 carbon atom ₁-C ₆-alkyl, it can be by at least one C ₁-C ₆-alkyl replaces, R ⁶Can be for the perfluor ethyl or more high-grade perfluoroalkyl and x are the integer of 1-4.

5 to any one of claims 1 to 4 lubricating composition, wherein said ionic liquid is selected from butyl methyl pyrrolidine

- double (trifluoromethylsulfonyl) imide, methyl propyl pyrrole alkyl

- bis (trifluoromethylsulfonyl) imide, III - hexyl methyl imidazole

(perfluorinated ethylene) - trifluoro-phosphate, hexyl methyl imidazole

- bis (trifluoromethylsulfonyl) imide, hexyl methyl pyrrolidine

- double (trifluoromethylsulfonyl) imide, three - four-butyl phosphate

(perfluoro-ethylene) trifluoro phosphate, octyl methyl imidazole

hexafluorophosphate, hexyl pyridine

- bis (trifluoromethyl) imide, A octyl trimethyl ammonium - trifluoroacetate, butyl methyl pyrrolidine

three (pentafluoroethyl) trifluoro-phosphate, tri-hexyl (tetradecyl) phosphorus

- double ( trifluoromethylsulfonyl) imide, hexyl methyl imidazole - tetrafluoroborate, hexyl methyl imidazole - hexafluorophosphate, 1 - ethyl-3 - A imidazole

diethyl phosphate, 1 - ethyl-3 - methyl-imidazolium

methyl sulfate, 1 - ethyl-3 - methyl imidazole

double [ oxalate (2 -)-O, O +] borate, and mixtures thereof.

6. each lubricating composition of claim 1-5, wherein said ionic liquid is selected from methyl trioctylammonium trifluoroacetate and three hexyls (tetradecyl) phosphorus

-two (trifluoromethyl sulfonyl) imide, hexyl methyl imidazoles

a tetrafluoro borate, hexyl methyl imidazoles

hexafluorophosphate, 1-ethyl-3-Methylimidazole

diethyl phosphate, 1-ethyl-3-Methylimidazole

Methylsulfate and their mixture.

7. each lubricating composition of claim 1-6, wherein said ionic liquid is selected from three hexyls (tetradecyl) phosphorus

-two (trifluoromethyl sulfonyl) imide, hexyl methyl imidazoles fluorophosphate and their mixture.

8. each lubricating composition of claim 1-7, wherein said base oil are for through the synthetic ester of polyvalent alcohol with the carboxylic acid reaction formation of general formula R COOH, and wherein R is the straight or branched alkyl with 5-10 carbon atom.

9. each lubricating composition of claim 1-8 is used for the purposes of lubricated turbine engine.

10. ionic liquid is used to reduce the purposes of the sludge content of lubricating composition, and said lubricating composition comprises (i) base oil, (ii) ionic liquid and (iii) one or more additives.

11. ionic liquid is used to reduce the purposes of the coking of lubricating composition, said lubricating composition comprises (i) base oil, (ii) ionic liquid and (iii) one or more additives.