CN101432405A - Stabilizing compositions for lubricants - Google Patents

Abstract

A lubricant composition is disclosed that comprises lubricating oil and a mixture of at least two antioxidants, the first antioxidant being a substituted diphenylamine and/or a heterocyclic amine and the second antioxidant being a substituted phenol. Also disclosed is a method of increasing the oxidation stability of a lubricating oil comprising adding thereto at least two antioxidants, the first antioxidant being a substituted diphenylamine and/or a heterocyclic amine and the second antioxidant being a substituted phenol.

Description

The stable composition that is used for lubricating oil

The autograph that the applicant requires on February 28th, 2006 to submit to according to United States Code § 119 the 35th chapter is U.S. provisional application number 60/776,934 rights and interests of " stable composition that is used for lubricating oil ".

Background of invention

1. invention field

The present invention relates to by improving lubricating oil, especially alkyl oxidation of lubricating oil stability to the combination that wherein adds at least two kinds of antioxidants.

2. description of Related Art

Those lubricating oil that lubricating oil for example is used for multiple machinery are in storage, transportation with between the usage period, particularly be subject to the influence of deterioration by oxidation effect when this lubricating oil is exposed to the high temperature that can greatly promote its oxidation and iron catalytic environment.If do not add control, this oxidation helps caustic acid product, sludge, varnish, resin and other to be insoluble to the formation of the product of oil, and can cause the regulation physics and the frictional property loss of energy of described lubricating oil.Therefore, in lubricating oil, comprise antioxidant usually and come anti-at least to a certain extent oxidation, thereby prolong their work-ing life.The known in the art lubricating oil composition that comprises different diarylamines or phenolic compound as antioxidant.

U.S. patent No.2,718,501 disclose the stabiliser system of being made up of the aromatic amine with at least two aromatic rings (comprising Ursol D) and organic aliphatic sulphur compound, it is said that this system is fit to be used for resistant mineral hydrocarbon lubricated oils, synthetic hydrocarbon oil class and poly-alkyl diol oils.

U.S. patent No.5,091,099 discloses a kind of lubricating oil composition that does not contain phosphorous acid ester, the mixture that it comprises mineral oil or synthetic oil or their mixture and contains at least a aromatic amine and at least a phenol.It is said that described lubricating oil composition has high-resistance to aging, and allegedly can prevent the formation of black sludge effectively.

U.S. patent No.5,229,442 disclose the heat treated stable composition of the process that is used for organic polymer, its mixture by at least a liquid phenol antioxidant and at least a amine antioxidants is formed, the stabilizing power that it is characterized in that them, this stabilizing power are higher than one-component or the stabilizing power of the mixture that is untreated accordingly significantly.These stabilized mixtures can be used for all areas that the one-component of described composition usually uses and the stabilization of the organic polymer that preferably can be used for usually being gone bad owing to oxidising process.

U.S. patent No.5,523,007 disclose the lubricating system that comprises diesel lubrication oil and have been used for stablize the purposes of ester of the thioester compound of diesel lubrication oil, and the ester of described diesel lubrication oil employing space hindered phenol compound is stablized.

WO 94/22988 discloses the fuel composition that allegedly improves the wear resistance and the viscosity controller performance of internal combustion (IC) engine lubricating oil during described running of an engine.A spot of described fuel composition combines with described internal combustion (IC) engine lubricating oil during running of an engine, and this is combined into the enhancing that described lubricating oil provides oxidation-resistance.Preferably described fuel comprise the substituted bicyclic aromatic amine that does not contain the benzyl hydrogen atom that 57g/1000 at least rises (as single-and/or the alkylating phenylenediamine of two-alpha-methyl styrene) and/or hindered phenol (as the cresols or two C of single vinylbenzeneization list-isobutyl alkylene ₁₆Alkylphenol).It is said that synergistic effect confirms by the mixture of described aromatic amine and hindered phenol.

JP 53,051, and 206 disclose and are used for improving the ester that also comprises disulphide or the N as antioxidant of mineral oil based oxidation of lubricating oil stability, N '-2-naphthyl-p-phenylenediamine.

JP 59,020, and 392 disclose the N that comprises that is used for the pressure forming fuel tank, the lubricating oil composition of N '-two sec-butyls-Ursol D.Described lubricating oil composition also comprises hindered phenol anti-oxidants.

Aforementioned disclosure is all incorporated this paper by reference into.

The invention summary

Have now found that specific phenol/amine antioxidants blend when being used for lube basestocks and/or lubricating oil formulation, the synergy of uniqueness and the performance of improvement can be provided from the oxidation-resistance angle.

" antioxidant blend " is meant the blend that is used to handle industry and motor vehicle lubricating oil, its comprise the combination of amine and phenol antioxidant additive and as if may exist they back-add and/or back-heating by product, pre--blend that described by product may be by described antioxidant and/or pre--heating produce owing to the effect/reaction of described antioxidant and/or owing to the effect/reaction of described antioxidant in lube basestocks and/or lubricating oil formulation produces.

" lube basestocks " is meant lubricating oil, for example is selected from the mineral and the synthetic base oil of I class, II class, III class, IV class, and poly-alpha olefins (PAO) and natural and synthetic ester (comprising polyol ester).

In the Base Oil Interchangeability Guidelines of American Petroleum Institute (API) (API), broadly stipulated the base oil in the I-V class.Described five class base oils are described in the table 1.

Normally, basestocks is the lubricating oil that only has the mentioned kind of other minimum additive, and described additive comprises but is not limited to antioxidant, rust-preventive agent, metal passivator etc.

" synthetic ester " is meant the ester based on the reaction product of polynary alcohol and carboxylic acid.The typical examples of polyhydric alcohols that is used for preparing synthetic ester includes but not limited to neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane and Dipentaerythritol, its can with for example valeric acid, isovaleric acid, caproic acid, enanthic acid, reaction such as sad of carboxylic acid.The example of commercially available synthetic ester includes but not limited to polyol ester, trimellitate, adipic acid ester, oleic acid ester etc.

" lubricating oil formulation " is meant the aforesaid lube basestocks that adds other additive, and described additive comprises but is not limited to antioxidant, rust-preventive agent, metal passivator, ashless dispersant, wear preventive additive, extreme pressure (e.p.) additive, purification agent etc. and their by product.

" their by product " is meant between these components and the described lubricating oil formulation and the chemistry between these components and/or heat/heat effect/reaction and the potential that forms, theoretic and/or possible any by product, reaction product, degradation production etc. in described lubricating oil formulation.

More particularly, the present invention relates to lubricating oil composition, it comprises:

(A) be selected from least a lubricating oil in natural lubricating base oil and the synthetic lubricating base oil;

(B) be selected from following at least a first antioxidant

(1) pentanoic represented of following formula

R wherein ₁And R ₂Be independently selected from hydrogen, alkyl, styryl and alpha-alkyl phenylethylene base, condition is R ₁And R ₂In at least one be not hydrogen; With

(2) heterocyclic amine of following formula

Wherein n is the integer of 0-50; With

(C) be selected from least a second antioxidant in the phenols that following formula represents

R wherein ₃, R ₄, R ₅And R ₆Be independently selected from moieties and X be selected from sulphur, replacement or unsubstituted nitrogen, oxygen, alkylidene group, alkylidene group-S-alkylidene group, alkylidene group-O-alkylidene group and-S-S-.

On the other hand, the present invention relates to improve the method for oxidation of lubricating oil stability, described lubricating oil comprises adding wherein:

(A) be selected from following at least a first antioxidant:

(1) pentanoic represented of following formula

R wherein ₁And R ₂Be independently selected from hydrogen, alkyl, styryl and alpha-alkyl phenylethylene base, condition is R ₁And R ₂In at least one be not hydrogen; With

(2) heterocyclic amine of following formula

Wherein n is the integer of 0-50; With

(C) be selected from least a second antioxidant in the phenols that following formula represents

R wherein ₃, R ₄, R ₅And R ₆Be independently selected from moieties and X be selected from sulphur, replacement or unsubstituted nitrogen, oxygen, alkylidene group, alkylidene group-S-alkylidene group, alkylidene group-O-alkylidene group and-S-S-.

On the other hand, the present invention relates to improve the method for oxidation of lubricating oil stability, described lubricating oil comprises adding wherein:

(A) be selected from following at least a first antioxidant:

(1) pentanoic represented of following formula

R wherein ₁And R ₂Be independently selected from hydrogen, alkyl, styryl and alpha-alkyl phenylethylene base, condition is R ₁And R ₂In at least one be not hydrogen; With

(2) heterocyclic amine of following formula

Wherein n is the integer of 0-50; With

(C) be selected from least a second antioxidant in the phenols that following formula represents

R wherein ₃, R ₄, R ₅And R ₆Be independently selected from moieties and X be selected from sulphur, replacement or unsubstituted nitrogen, oxygen, alkylidene group, alkylidene group-S-alkylidene group, alkylidene group-O-alkylidene group and-S-S-.

The description of preferred implementation

As mentioned above, the described pentanoic that is used as first antioxidant in the invention process is expressed from the next

R wherein ₁And R ₂Be independently selected from hydrogen, alkyl, styryl and alpha-alkyl phenylethylene base, condition is R ₁And R ₂In at least one be not hydrogen.

Work as R ₁And/or R ₂During for alkyl, they preferably are independently selected from the alkyl of 1-12 carbon atom, it can be side chain or straight chain, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, the isomer of above-mentioned group, as the tertiary butyl, 2-ethylhexyl etc., and the mixture of above-mentioned group.

Work as R ₁And/or R ₂During for the alpha-alkyl phenylethylene base, described alkyl is preferably low alkyl group, as the alkyl of 1-4 carbon atom, and for example methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-or the tertiary butyl.More preferably methyl or ethyl, most preferable.

Those those skilled in the art can recognize that described pentanoic can comprise the mixture of the component of the component of alkylation/vinylbenzeneization and non-alkylation/vinylbenzeneization, and these components can be included in theory in the described alkylated diphenylamine compound non-alkylating and single-, two-and three-alkylating variant.

The pentanoic additive of this alkylation and/or vinylbenzeneization can substitute with the heterocyclic amine antioxidant blend of following formula or by it

Wherein number of repeat unit n is the integer of 0-50.The example that the commerce of this compound can get comprises Naugalube (NL) TMQ, Durad AX51 and Durad AX53.

Second antioxidant of the present invention is the phenols that following formula is represented

R wherein ₃, R ₄, R ₅And R ₆Be independently selected from moieties and X be selected from sulphur (S-), replacement or unsubstituted nitrogen, oxygen, alkylidene group, alkylidene group-S-alkylidene group, alkylidene group-O-alkylidene group and-S-S-." alkylidene group " is meant formula-C _nH _2n-hydrocarbon.Preferably n is the integer of 1-10, for example methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl, the isomer of above-mentioned group and their mixture.X is preferably sulphur.The moieties that is connected on the described phenol ring preferably has 1-10 carbon atom, for example the isomer of methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and above-mentioned group, for example tertiary butyl and 2-ethylhexyl.

More preferably, described first antioxidant of the present invention is alkylated diphenylamine, wherein R ₁And R ₂For having general formula C _nH _2n+1Alkyl, n=4-9 wherein, octyl groupization/butylation and/or nonylated diphenylamine and described second antioxidant be sulfur-bearing alkylating phenol, wherein R suitably ₃And R ₄For having general formula C _nH _2n+1Alkyl, n=1-4 wherein.The example that the commerce of this alkylated diphenylamine can get comprises Durad AX57 (n=4-8), Durad AX59 (n=9), Naugalube 438, Naugalube 438L and Naugalube 640.

Most preferably, the alkylated phenol components of the described sulfur-bearing of above-mentioned blend has formula

Or formula

The example that the commerce of this alkylating phenol can get comprises Durad AX16, Lowinox TBM6, Lowinox TBP6 and Durad AX18.

Normally, can directly handle lube basestocks and/or lubricating oil formulation with above-mentioned amine and phenol antioxidant component.

Preferably, to form the homogeneous liquid mixture, it is added in described lube basestocks and/or the described lubricating oil formulation conversely by pre--blend for described amine and phenol antioxidant additive.But described homogeneous liquid is pre--blended mixts be preferably complete miscibility and be used for minimum length in time, reaching the storage of 24 hours (so that handling easily) and keep the stable solid precipitation that to avoid when handling most suitably.

Usually, by pre--about 6 hours of about 0.5-of blend, this can promote the blend of viscous liquid and/or the performance of improving with regard to oxidation-resistance is provided described homogeneous liquid mixture under the temperature of the about 100 ℃ rising of about 50-.

The phenol antioxidant of the amine antioxidants of the above-mentioned type and following structure is carried out in advance-stabilizing power of the raising of lube basestocks is provided is known (seeing U.S. patent No.5,229,442) in the prior art in blend

Wherein R is C _nH _2n+1, and n=6-20.

Preferably, but described amine and phenol antioxidant additive can be spared matter and liquid blend complete miscibility to form with other component blend, it can keep the stable long time, preferred 24-168 hour, more preferably 168-336 hour, time of 336-1000 hour or longer prolongation most preferably from about.

Preferably, described other component can include but not limited to I class, II class, III class or IV class basestocks, triaryl phosphate and/or trialkylphosphate, alkyl acid phosphate list acid esters and alkyl acid phosphate two acid esters, alkyl phosphite and/or aryl phosphite, liquid phenol antioxidant, amine antioxidants, carboxylicesters, aromatic hydrocarbons and liquid glycol (for example ethylene glycol).

More preferably, above-mentioned other component is selected from carboxylicesters, for example trimellitate, adipic acid ester, phthalic ester and oleic acid ester, and/or phosphoric acid ester for example trialkylphosphate and/or triaryl phosphate and/or blended alkyl acid phosphate/aryl ester.

Most preferably, above-mentioned other component is selected from tricresyl phosphate isobutyl (TiBP), tributoxyethyl phosphate (TBEP), tricresyl phosphate octyl group ester (TOP) and alkylating Triphenyl phosphate (as the Triphenyl phosphate of butylation and/or propylated) and aforesaid mixture.

Can comprise lubricating oil by the lube basestocks that described antioxidant addn of the present invention improves its antioxidant property, for example be selected from the mineral and the synthetic base oil of I class, II class, III class, IV class, and PAO (poly-alpha-olefin), natural esters and synthetic ester (comprising polyol ester), more particularly be not limited to turning oil, engine oil, gear oil, lubricating grease, hydraulic efficiency oil, turbine oil and metal working fluid.

Lube basestocks and/or lubricating oil formulation can have its antioxidant property that changes in wide region.This can be by following acquisition:

1. in described lube basestocks and/or lubricating oil formulation, select to provide alone or in combination the amine and/or the phenol antioxidant of oxidation-resistance optimum performance suitably.

2. change the ratio of described antioxidant addn, the ratio of phenol antioxidant additive and described amine antioxidant addn as described, or

3. in the processing rate that changes antioxidant addn described in (improve or reduce) described basestocks, keep aforementioned proportion constant.

In other words, described component alone or in combination can be designed to be provided at needed performance characteristic with regard to oxidation-resistance in adhoc basis material and/or the lubricating oil formulation.

In the preparation of described lubricating oil composition of the present invention, can be with about 10 weight % of about 0.01-separately, preferred described first and second antioxidants of amount blend in described composition of the about 5 weight % of about 0.1-.In addition can be with about 10 weight % of about 0.01-altogether, preferred amount optional component of blend in described lubricating oil composition of the about 5 weight % of about 0.1-.Described first antioxidant that uses in lubricating oil composition of the present invention and the content of second antioxidant are than can be nearly all ratio.But preferred described ratio is at the 1:99-99:1 weight part, more preferably in the scope of 90:10-10:90 weight part.

As mentioned above, described antioxidant blends of the present invention can use with other additive and other antioxidant combination that are typically found in the lubricating oil.The described additive that is typically found in the lubricating oil for example is dispersion agent, purification agent, anti-wear agent, antioxidant, friction modifiers, sealed expander, demulsifying agent, VI (viscosity index) improving agent, pour point reducer, foam preventer, anticorrosive agent and metal passivator.Described additive is that those skilled in the art are known, and the type that is used for these additives of the present invention is not had specific restriction.Incorporate the U.S. patent No.5 of this paper by reference into, 498,809 disclose useful lubricating oil composition additive.

The example of dispersion agent comprises polyisobutenyl succinimide, polyisobutylene succinic acid ester, Mannich Base ashless dispersants etc.The example of purification agent comprises metal and ashless alkyl phenate, metal and ashless alkyl monosulfide phenates, metal and ashless alkylsulfonate, metal and ashless alkylsalicylate, metal and ashless salicin derivatives etc.

The example of the antioxidant that can be used in combination with described antioxidant blends of the present invention comprise dimethyl quinoline class, trimethyldihydroquinoline class and by its deutero-oligomeric composition, thiopropionate (salt), metal dithionite for carbaminate, oil-soluble copper compounds etc.Can comprise organic borate, organic phosphite, organophosphate, sulfur-containing organic compound, olefine sulfide, sulfurized fatty acid derivative (ester), clorafin, zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate, dialkyl dithiophosphate, diaryl phosphorodithioate, phosphosulfurized hydrocarbon etc. with the anti-wear agent example that described additive combination of the present invention uses.Below be such additive example and can be commercial available from The Lubrizol Corporation especially: Lubrizol 677A, Lubrizol 1095, Lubrizol 1097, Lubrizol 1360, Lubrizol 1395, Lubrizol 5139 and Lubrizol 5604; Available from CibaCorporation especially: Irgalube Irgalube 211, Irgalube 232, Irgalube 349, Irgalube 353, Irgalube TPPT, Irgafos OPH and especially: Weston available from Chemtura Corporation

Weston DLP, WestonTPP.

The example of friction modifiers comprises fatty acid ester and acid amides, organic molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum dialkyl-dithiophosphate, molybdenumdisulphide, dialkyldithiocarbamacompositions three molybdenums bunch, non-sulphur molybdenum compound etc.Below be molybdenum additives example and can be commercial available from R.T.Vanderbilt Company, Inc. especially: Molyvan A, MolyvanL, Molyvan 807, Molyvan 856B, Molyvan 822, Molyvan 855.Below be such additive example and can be commercial available from Asahi Denka Kogyo K.K. especially: SAKURA-LUBE 100, SAKURA-LUBE 165, SAKURA-LUBE 300, SAKURA-LUBE 310G, SAKURA-LUBE 321, SAKURA-LUBE 474, SAKURA-LUBE600, SAKURA-LUBE 700.Below still the example of such additive and can be commercial available from AkzoNobel Chemicals GmbH especially: Ketjen-Ox 77M, Ketjen-Ox 77TS.Naugalube MolyFM also is that the example of such additive also can be commercial available from ChemturaCorporation.

The example of VI improving agent comprises olefin copolymer and decentralized olefin copolymer etc.The example of pour point reducer is a polymethacrylate etc.The example of foam preventer is a polysiloxane etc.The example of rust-preventive agent is polyoxyalkylene polyol (polyoxyalkylene polyglycol), benzotriazole derivatives etc.The example of metal passivator comprises triazole, benzotriazole, 2-mercaptobenzothiazole, 2,5-dimercaptothiodiazole, tolyl-triazole derivative, N, N '-two salicylidenes-1 etc.The example that below is metal passivator also can be commercial available from CibaCorporation:Irgamet

, Irgamet 39 and Irgamet 42.

Composition when comprising these additives, usually can effectively provide the amount of their normal accompaniment functions to be blended into described base oil with wherein additive.The representative significant quantity of described additive is listed in the table 2.

When using other additive, although it is nonessential, but may wish that preparation comprises the concentrated solution of theme additive of the present invention (with above-mentioned concentrated amount) and one or more described other additives (described enriched material is called as additive-package at this paper when constituting additive agent mixture) or the multifunctional additive for lubricating oils of dispersion, some additives can be joined simultaneously thus in the described base oil and the formation lubricating oil composition.Promote the dissolving of described multifunctional additive for lubricating oils in lubricating oil by solvent with by the mixing of following mildly heating, but this operation is not essential.When the lubricating base oil of described additive-package and predetermined amount makes up, thereby can typically be comprised described additive with appropriate vol, in final formulation, to provide desirable concentration by described enriched material of preparation or additive-package.Therefore, theme additive of the present invention can be joined in a spot of base oil or other compatible solvents with other appropriate addn, the additive-package that comprises activeconstituents with formation, wherein said additive with suitable ratio adopt be generally the about 90 weight % of about 2.5-, preferably the about 75 weight % of about 15-, more preferably from about the collective of the about 60 weight % of 25-measures, surplus is a base oil.Described final formulation can use the described additive-package of about 1-20 weight % usually, and surplus is a base oil.

Here Biao Shi all wt percentage ratio (unless otherwise prescribed) is based on activeconstituents (AI) content of described additive, and/or based on the gross weight of any additives bag or formulation, it adds the summation of all oil or thinner weight for the AI weight of each additive.

Normally, described additive of the present invention can be used in the multiple lube basestocks.Described lube basestocks under 100 ℃, have the about 200cSt of about 2-, more preferably from about the about 150cSt of 3-, most preferably be any natural or ucon oil basestocks fraction of the dynamic viscosity of the about 100cSt of about 3-.

Described lube basestocks can be from natural lubricating oil, ucon oil or their mixture.Proper lubrication oil base plinth material package is drawn together the basestocks that the isomerization by synthetic wax and wax obtains, and the hydrocracking basestocks that produces of the hydrocracking (rather than solvent extraction) of aromatics by crude oil and polar compound.Natural lubricating oil comprises animal oil such as lard, butter, vegetables oil (for example mustard caul-fat, Viscotrol C, sunflower oil), oil, mineral oil and from the oil of coal or shale.

Synthetic oil comprises the hydrocarbon ils of hydrocarbon ils and halogen-replacement, natural gas synthetic oil (Gas to Liquid), alkylbenzene, polyphenyl, alkylation phenyl ether, alkylation diphenyl sulfide and their derivative that makes as polymeric and mutually poly-alkene, by fischer-tropsch process, analogue, homologue etc.Ucon oil also comprises alkylene oxide polymer, interpretation, multipolymer and their derivative, and wherein terminal hydroxyl is modified by esterification, etherificate etc.The ucon oil of other suitable species comprises the ester of dicarboxylic acid and different alcohol.The ester that can be used as synthetic oil also comprises from C ₅-C ₁₈Those esters that monocarboxylic acid and polyvalent alcohol and polyol ethers make.Other ester that can be used as synthetic oil comprises those esters that made by the multipolymer of the dicarboxylic acid of the pure esterification of short or medium chain and alpha-olefin.

The for example poly-alkyl of silicon-based oil-, poly-aryl-, poly-alkoxyl group-or poly-aryloxy-silicone oil and silicic acid ester oil constitute the ucon oil of another useful type.Other ucon oil comprises liquid ester, polytetrahydrofuran, poly-alpha olefins of phosphoric acid etc.

Described lubricating oil can be from unrefined oil, treated oil, rerefined oils or their mixture.Unrefined oil directly obtains from natural origin or synthetic source (for example coal, shale or pitch and pitch) under the situation that does not have further to purify or handle.The example of unrefined oil comprises from the direct shale oil that obtains of destructive distillation operation, from oil that distills direct acquisition or the ester oil that directly obtains from esterification technique, uses under the situation of its each leisure without further processing then.Except treated oil being carried out one or more purification step to improve one or more performances, treated oil is similar to unrefined oil.Suitable purification techniques comprises distillation, hydrotreatment, dewaxing, solvent extraction, acid or alkaline extraction, filtration, diafiltration etc., and all these are known for a person skilled in the art.Rerefined oils can be similar to those the art breading treated oil that is used for obtaining treated oil by employing and obtain.These again-treated oil is also referred to as recovered oil or reprocessed oils, and often carries out other processing by the technology that is used to remove inefficacy additive and oil decomposition product.

Also can make up the lube basestocks that uses the hydroisomerization that comes from wax separately or with above-mentioned natural and/or synthetic basestocks.Under hydroisomerisation catalysts, carry out hydroisomerization by natural or synthetic wax or their mixture and make this wax isomer oil.Natural wax generally is the slack wax that reclaims by the solvent dewaxing of mineral oil; Synthetic wax generally is the wax that makes by Fischer-Tropsch process.Usually gained isomer products product is carried out solvent dewaxing and fractionation have the particular viscosity scope with recovery different fractions.The feature of wax isomer also is to have very high viscosity index, have usually be at least 130, preferred at least 135 or higher VI and dewaxing after, have pact-20 ℃ or lower pour point.

Described additive of the present invention can be used as the component in the multiple different oils composition especially.Described additive can be included in the multiple oil with lubricant viscosity, and described oil comprises natural and ucon oil and composition thereof.Described additive can be included in the crankcase oil that is used for spark-igniting and compression-ignition oil engine.Described composition also can be used for gas engine lubricating oil, steam turbine and internal combustion turbine lubricating oil, automatic transmission fluid, gear grease, compressor lubricant oil, Metalworking lubricating oil, hydraulic efficiency oil and and other lubricating oil and grease composition in.Described additive also can be used to stablize motor fuel composite.

To show advantage of the present invention and key character in the following embodiments.

Embodiment

Embodiment 1

Table 3 has been listed the chemical property of selecting to be used for tested antioxidants.Depend on test procedure and lubricant formula, also used other additive such as anti-wear agent, purification agent, dispersion agent, pour point reducer, viscosity index improver, metal passivator, anticorrosive agent etc.

Table 3

The chemical name and the description of the antioxidant of in this research, selecting

Sign	Chemical name	Element
			Durad?AX18	2,2 '-thiobis (4-methyl-6-tert butyl-phenol)	8.5 weight %S
Naugalube-438L	The pentanoic of nonylated	3.5 weight %N
			Naugalube-640	The pentanoic of butylated, octyl groupization	4.2 weight %N
Naugalube-531	3,5-di-t-butyl-4-hydroxyl phenylpropionic acid, C 7-C 9Branched alkyl ester	-

The described base oil that selection is used for this research comprises the I class and the III class basestocks of APII of I class basestocks, the hydrocracking of the solvent-refined API that obtains from the different refineries of the U.S..

Prepared blend in about 15 minutes by in adhoc basis oil, adding additive and under nitrogen protection, carrying out mechanically mixing in 65 ℃.All blends are prepared fresh before using pressurization dsc (PDSC) and rotational pressure vessel oxidation test (RPVOT) device to carry out the promote the oxidation engine bench test.

Described PDSC has detected oil oxidation stability under the film oxidation condition.In the isothermal pattern of PDSC temperature maintenance, according to oxidation induction period (OIT) (corresponding to because the heat release that the oxidation of oil begins to cause) evaluation test oil oxidation stability in set(ting)value.It has been generally acknowledged that the oil that provides longer OIT is more can be oxidation resistant.In order to accelerate described PDSC test process, use 50ppm oil soluble iron that every kind of test oil is carried out pre-treatment from iron naphthenate.Use following instrument condition to every kind of blend test twice, and determine average OIT.In order to obtain reproducible result,, determine that best PDSC probe temperature is 185 ℃ and is defined as 200 ℃ for other blend that uses II class and III class basestocks for I class oil blend.

Isothermal temperature:	To I class oil blend is 185 ℃; To II class, III class oil blend is 200 ℃
		Temperature rise rate:	40℃/min
Pressure:	500psi
		The O2 flow:	100ml/min
Sample size:	～1.5mg
		Dish:	Aluminium opens wide
Catalyzer:	The iron naphthenate of 50ppm (8%, in mineral oil)

All RPVOT test is carried out according to ASTM D2272 standard test procedure and is reported the result (OIT) who obtains from the mean value of twice test.It has been generally acknowledged that the oil that provides longer oxidation induction period is more can be oxidation resistant.

Certainly the synergy of lubricating oil antioxidant is a kind of cooperative response that is caused by two kinds of difference in functionalitys in same molecular.As Durad AX18, have the antioxidant of the functional group that free radical scavenging function and hydroperoxide decomposition function are provided, under suitable oxidizing condition, can demonstrate from synergy, therefore produced superior performance.In described engine bench test of the first round, Durad AX18 and Naugalube 531 with par (1.0 weight %) in a series of fully the preparation bus engine oil (PCMO) and industrial R﹠amp; Compare in the O turbine oil (it has used I class, II class or the III class base oil of API respectively).In PDSC, test described engine oil blend, and in having the RPVOT of above-mentioned test condition, tested described turbine oil.Table 4 and 5 has shown separately for the described PDSC of all blends and RPVOT test result.

Table 4

For the PDSC result of Durad AX18 and Naugalube-531, in the PCMO formulation that uses I class, II class or III class basestocks, test with 1.0 weight %

AO	Base oil types	PDSC?T(℃)	PDSC OIT, test 1 (minute)	PDSC OIT, test 2 (minute)	Mean P DSC, (minute)
						AX18	The I class	185	22.02	22.28	22.15
NL-531	The I class	185	4.65	4.48	4.75
AX18	The II class	200	9.05	10.42	9.74
						NL-531	The II class	200	<1	<1	<1
						AX18	The III class	200	10.91	10.72	10.82
NL-531	The III class	200	<1	<1	<1

Table 5

For the RPVOT result of Durad AX18 and Naugalube-531, in the industrial turbine oil formulation that uses I class, II or III basestocks, test at 1.0 weight %

AO	Base oil types	RPVOT OIT (minute)
			AX18	The I class	251
NL-531	The I class	264
AX18	The II of family	416
			NL-531	The II class	200
			AX18	The III class	488
NL-531	The III class	300

Except in based on the turbine oil formulation of I class oil, AX18 is better than 531 significantly in most of formulations.Response in this oil loss is likely owing to the chemical property of described basestocks and institute use test method (RPVOT) cause.Nitrogenous, the sulphur of known trace and heterocycle and mercaptan (RSH), thioether (R-S-R) and the disulphide (R-S-S-R) of oxygen are the integral parts of the complex combination thing of described I class base oil.If the ratio of aromatic substances and sulphur remains on the optimum level, then the natural oil oxidation-resistance is changed most.May be because these naturally occurring materials, thereby the described Naugalube-531 that comprises I class turbine oil in RPVOT is better than similar II class oil.Also may be owing to the antioxidant of these Balance of nature, the performance benefit that obtains by further interpolation sulphur in described I class oil is restricted.By introducing excessive sulphur, not only changed the optimum sulphur/aromatic substances balance of I class oil, and sulphur described in the described RPVOT test environment may hydrolysis take place also and form known can promotes oxidn the sulfur acid material of effect.Because the II class and the III oil of described serious hydrocracking do not comprise appreciable sulphur, therefore the sulphur from AX18 has strong and positive effect to the overall of described antioxidant from synergy.

Proved that base oil sulphur has influence to the performance of AX18, described antioxidant of associating and Naugalube-438L further study in based on the lubricating oil formulation of II class and III class oil.With described two kinds of antioxidants altogether 1.0 weight % various combination with other additive blend with form respectively PDSC (

200 ℃) and RPVOT in the bus engine oil and the industrial R﹠amp that test; The O turbine oil.The gained test result is shown in table 6 and 7.

Table 6

With the various combination of Naugalube-438L in for the PDSC result of Durad AX18, in the PCMO formulation that uses II class or III class basestocks, test.

AX18, weight %	NL-531, weight %	NL-438L, weight %	The base oil kind	PDSC OIT, test 1 (minute)	PDSC OIT, test 2 (minute)	Mean P DSC,
									1.0	The II class	21.66	22.05	21.86
0.5		0.5	The II class	20.56	20.52	20.54
							0.25		0.75	The II class	23.34	24.74	24.04
	0.25	0.75	The II class	20.36	18.98	19.67
		1.0	The III class	21.22	21.34	21.28
							0.25		0.75	The III class	24.83	25.14	24.99
	0.25	0.75	The III class	20.45	21.47	20.96

Table 7

With the various combination of Naugalube-438L in for the RPVOT result of Durad AX18, in the turbine oil formulation that uses II class or III class basestocks, test.

AX18, weight %	NL-531, weight %	NL-438L, weight %	The base oil kind	RPVOT OIT, minute
							1.0	The II class	1270
0.5		0.5	The II class	1162
					0.25		0.75	The II class	1344
	0.25	0.75	The II class	1117
		1.0	The III class	1352
					0.5		0.5	The III class	1253
0.25		0.75	The III class	1723
						0.25	0.75	The III class	1388

Compare with the Naugalube-531 data with the AX18 in listing in table 4 and 5, longer oxidation induction period is better than described two class phenol antioxidant to Naugalube-438L by having produced obviously in PDSC and RPVOT independently.When mixing Naugalube-438L and AX18 with 3:1 ratio (w/w) and the total concn of described antioxidant remained on 1.0 weight % consistently, from the gained mixture, observe the cooperative response of uniqueness.At first this response is from respect to the correspondence that is used for two groups of PCMO longer PDSC inductive phase (24.04 of described mixture for the 438L blend only; 24.99 minute) obvious (table 6).Under this blending ratio, also improved the RPVOT performance of turbine oil significantly, and make oxidation induction period for II class innage in 1300 minutes and for III class innage in 1700 minutes (table 7).Do not consider prescription and testing method, take turns the non-S of the containing Naugalube-531 that is included as reference in the test at this and as if do not produce synergistic effect with Naugalube-438L.

The repetition Naugalube-438L/Durad AX18 synergistic effect of alkylated diphenylamine antioxidant Naugalube-640 by using other kind also is successful.As shown in table 8 and 9, when with the described two kinds of antioxidants of 3:1 ratio (w/w) blend, observe the synergistic effect of conspicuous level for Naugalube-640 and AX18 mixture.

Table 8

With the various combination of Naugalube-640 in for the PDSC result of Durad AX18, in the PCMO formulation that uses II class or III class basestocks, test.

AX18, weight %	NL-531, weight %	NL-640, weight %	The base oil kind	PDSC OIT, test 1 (minute)	PDSC OIT, test 2 (minute)	Mean P DSC, (minute)
									1.0	The II class	21.54	22.67	22.11
0.5		0.5	The II class	21.98	21.47	21.73
							0.25		0.75	The II class	25.26	25.62	25.44
	0.25	0.75	The II class	20.92	21.81	21.37
		1.0	The III class	22.64	23.7	23.17
							0.25		0.75	The III class	25.77	25.33	25.55
	0.25	0.75	The III class	21.33	21.21	21.27

Table 9

With the various combination of Naugalube-640 in for the RPVOT result of Durad AX18, in the turbine oil formulation that uses II class or III class basestocks, test.

AX18, weight %	NL-531, weight %	NL-640, weight %	The base oil kind	RPVOT OIT, minute
							1.0	The II class	1744
0.5		0.5	The II class	1650
					0.25		0.75	The II class	1863
	0.25	0.75	The II class	1554
		1.0	The III class	1779
					0.5		0.5	The III class	1353
0.25		0.75	The III class	1860
						0.25	0.75	The III class	1665

The synergistic effect that obtains from the AX18/ADPA mixture may respond owing to bonded, and described bonded responds the interaction by same synergistic mechanism (homosynergistic mechanism) of the synergy certainly of self-enhancement AX18 each other itself and activity hydroxy and Naugalube-438L thereof.This just blended synergy provides extra stabilizing power for the AX18/ADPA system in PDSC and RPVOT.As if the synergistic detection of the type is depended on the kind of base oil with size, the more specifically sulphur of described oil and aromatic content as previously explained, and the blending ratio of included described two class antioxidants.By ratio in PCMO and turbine oil is that the AX18 of 1:1 (w/w) and the poorer performance of ADPA illustrate the importance (table 4-7) that keeps the optimum ratio.

Embodiment 2

Table 10 has shown by add the relative oxidative stability result that specific amine and phenol antioxidant blend obtain in I class and III class basestocks.

Durad AX15 is two [3-(3, the 5-di-tert-butyl-hydroxy phenyl)] propionic acid 2,2 '-sulfo-diethylidene ester.

Durad AX16 is 4,4 '-thiobis (the 2-tertiary butyl-5-methylphenol).

Durad AX32 is tetramethylene (3, a 5-di-t-butyl-4-hydroxyl hydrogenated cinnamate) methane.

Durad AX55 is the pentanoic of octyl groupization/vinylbenzeneization.

Durad AX57 is the pentanoic of butylation/octyl groupization.

Described five kinds of antioxidants exist with 0.5% processing rate.

Determine the relative oxidative stability of described multiple lube basestocks by rotational pressure vessel oxidation test (RPVOT), ASTM testing method D2272.Estimate described oxidative stability with the life-span that is recorded as minute.

Also can determine the oxidative stability of this class formulation by differential thermal analysis (DTA) (variant of dsc (DSC)), ASTM testing method D5483.Estimate described oxidative stability with the usage period that is recorded as minute.

Table 11 has shown by add the relative oxidative stability result's that specific amine and phenol antioxidant blend obtain example in I class and III class basestocks.

The described five kinds of antioxidant blends that are shown in Table 11 exist with amine/phenol antioxidant ratio (w/w) of 0.5% total processing rate and 4:1.

The expectation result and the actual result that represent according to " expectation " result of the calculating of each component based on table 10 result have been shown simultaneously.

Presentation of results in the above-mentioned table 11 has been seen in the synergistic effect aspect the oxidation-resistance for blend 2 when joining blend 2 (Durad AX55+Durad AX32) in the III class lubricating oil basestocks, 647 minutes of estimating of 865 minutes actual vs. have exceeded 35% than what estimate.

Unexpectedly, when joining blend 4 (Durad AX57+Durad AX16) in the III class basestocks, seen in the remarkable synergistic effect aspect the oxidation-resistance that for blend 4 1037 minutes of estimating of 2580 minutes actual vs. have exceeded 150% than what estimate.

Other formulation that only has that wherein can be observed synergistic effect is blend 5 (DuradAX57+Durad AX32), and in the time of in it being joined I class lubricating oil basestocks, 280 minutes of estimating of 328 minutes actual vs. have exceeded 17% than what estimate.

In being shown in all other blend embodiment of table 11, the antioxidant property in I class and/or III class basestocks arrives in the scope of bigger by 6% than predicated value (blend 4 in I class basestocks) at littler by 60% than predicated value (blend 3 in III class basestocks).

Embodiment 3

Table 12 has shown the relative oxidative stability result who obtains in the industrial turbine oil that uses II class or III class basestocks by specific amine and phenol antioxidant blend are joined.Along with the difference of antioxidant type in the final formulation, other additive of all in described turbine oil (comprising that metal takes off agent alive, anticorrosive agent and foam preventer) keeps identical and remains on constant level.

Table 12

The relative oxidative stability result of the use II class and the turbine oil of III class basestocks (minute)

Durad AX18 is 2,2 '-thiobis (the 6-tertiary butyl-4-methylphenol)

Naugalube 531 is 3,5-two-tertiary butyl-4-hydroxy phenylpropionic acid, C ₇-C ₉Branched alkyl ester

Naugalube 438L is the pentanoic of nonylated

Naugalube 640 is the pentanoic of butylation, octyl groupization

Described four kinds of antioxidants exist with the processing rate of 1.0 weight %.Determine the relative oxidative stability of multiple lube basestocks by RPVOT, ASTM testing method D 2272.Estimate described oxidative stability with the life-span that is recorded as minute.

Table 13 has shown the relative oxidative stability result's who obtains by the industrial turbine oil that specific amine and phenol antioxidant blend is joined use II class and III class basestocks embodiment.

Table 13

The RPVOT life-span of antioxidant blend (minute)

The described four kinds of antioxidant blends that are shown in Table 13 exist with total processing rate of 1.0 weight %, and amine/phenol antioxidant ratio is 3:1 (w/w).The expectation result that " expectations " result of calculating according to each component based on the result of table 5 represents and the result of reality have been shown.

Presentation of results in the above-mentioned table 13 has been seen in the synergistic effect aspect the oxidation-resistance for the basestocks blend 6 (Naugalube 438L+Naugalube 531) that uses II class or III class.For II class oil, 1003 minutes of estimating of 1117 minutes actual vs. have exceeded 11%.And for III class oil, 1089 minutes of estimating of 1338 minutes actual vs. have exceeded 23%.

For the synergistic effect of also having seen the oxidation-resistance of similar level on the blend 7 (Naugalube 640+Naugalube 531) that uses II class or III class basestocks.For II class oil, 1358 minutes of estimating of 1554 minutes actual vs. have exceeded 14%.And for III class oil, 1409 minutes of estimating of 1665 minutes actual vs. have exceeded 18%.

Unexpectedly, seen the synergistic effect of significant oxidation-resistance for the blend 8 (Naugalube 438L+Durad AX18) that uses II class or III class basestocks.For II class oil, 1057 minutes of estimating of 1334 minutes actual vs. have exceeded 26%.And for III class oil, 1136 minutes of estimating of 1723 minutes actual vs. have exceeded 52%.

Seen the synergistic effect of the oxidation-resistance of similar level for the blend 9 (Naugalube 640+Durad AX18) that uses II class or III class basestocks.For II class oil, 1412 minutes of estimating of 1863 minutes actual vs. have exceeded 32%.And for III class oil, 1456 minutes of estimating of 1860 minutes actual vs. have exceeded 28%.

Consider multiple change and the conversion that to make under the principle of the present invention not breaking away from, can understand protection domain provided by the invention with reference to appending claims.

Claims (10)

1. lubricating oil composition, it comprises:

(A) be selected from least a lubricating oil in natural lubricating base oil and the synthetic lubricating base oil;

(B) be selected from following at least a first antioxidant:

(1) pentanoic represented of following formula

R wherein ₁And R ₂Be independently selected from hydrogen, alkyl, styryl and alpha-alkyl phenylethylene base, condition is R ₁And R ₂In at least one be not hydrogen; With

(2) heterocyclic amine of following formula

Wherein n is the integer of 0-50; With

(C) be selected from least a second antioxidant in the phenols that following formula represents

R wherein ₃, R ₄, R ₅And R ₆Be independently selected from moieties and X be selected from sulphur, replacement or unsubstituted nitrogen, oxygen, alkylidene group, alkylidene group-S-alkylidene group, alkylidene group-O-alkylidene group and-S-S-.

2. the composition of claim 1, wherein R ₁And R ₂In at least one be the alkyl of 1-12 carbon atom.

3. the composition of claim 1, wherein R ₁And R ₂In at least one be the alpha-alkyl phenylethylene base, wherein said alkyl has 1-4 carbon atom.

4. the composition of claim 1, wherein R ₁And R ₂In at least one be the alpha-alkyl phenylethylene base, wherein said alkyl is a methyl.

5. the composition of claim 1, the n in the wherein said heterocyclic amine is the integer of 1-10, methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, the isomer of inferior decyl and their mixture.

6. the composition of claim 1, the moieties in the wherein said phenol ring have 1-10 carbon atom and are the isomer of methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl.

7. the composition of claim 1, wherein said amine antioxidants additive and phenol antioxidant additive and other component blend, described other component are selected from I class basestocks, II class basestocks, III class basestocks, IV class basestocks, triaryl phosphate, trialkylphosphate, alkyl acid phosphate list acid esters, alkyl acid phosphate two acid esters, alkyl phosphite, aryl phosphite, liquid phenol antioxidant, amine antioxidants, carboxylicesters, aromatic hydrocarbons and liquid glycol.

8. lubricating oil composition, it comprises:

(A) be selected from least a lubricating oil in natural lubricating base oil and the synthetic lubricating base oil;

(B) be selected from following at least a first antioxidant:

(1) pentanoic represented of following formula

R wherein ₁And R ₂Be general formula C _nH _2n+1Alkyl, n=4-9 wherein,

The pentanoic of octyl groupization/butylation and/or nonylated suitably; With

(2) heterocyclic amine of following formula

Wherein n is the integer of 0-50; With

(C) at least a second antioxidant represented of following formula as the alkylating phenol of sulfur-bearing

R wherein ₃And R ₄Be general formula C _nH _2n+1Alkyl, n=1-4 wherein.

9. the composition of claim 8, the alkylated phenol components of wherein said sulfur-bearing is selected from:

10. improve the method for oxidation of lubricating oil stability, it comprises to wherein adding (A) and is selected from following at least a first antioxidant:

(1) pentanoic represented of following formula

R wherein ₁And R ₂Be independently selected from hydrogen, alkyl, styryl and alpha-alkyl phenylethylene base, condition is R ₁And R ₂In at least one be not hydrogen; With

(2) heterocyclic amine of following formula

Wherein n is the integer of 0-50; With

(B) be selected from least a second antioxidant in the phenols that following formula represents

R wherein ₃, R ₄, R ₅And R ₆Be independently selected from moieties and X be selected from sulphur, replacement or unsubstituted nitrogen, oxygen, alkylidene group, alkylidene group-S-alkylidene group, alkylidene group-O-alkylidene group and-S-S-.