CN105623788B - Lubricant oil composite and the method for improving lubricating oil comprehensive performance - Google Patents

Abstract

The present invention proposes a kind of lubricant oil composite and the method for improving lubricating oil comprehensive performance.The composition of the present invention includes：Alkyl sulfide alcohol ester, demulsifier, detersive, antioxidant, dispersant and major amount of lubricating base oil.The lubricant oil composite of the present invention has excellent high temperature detergency, oxidation stability, antiwear and antifriction, especially there is excellent high temperature detergency and demulsification performance, divide water quick, thorough, suitable for the lubrication of marine diesel engine, crankcase lubrication, the lubrication of middling speed piston type diesel engine especially suitable for two-stroke low speed cross head marine diesel machine.

Description

Lubricant oil composite and the method for improving lubricating oil comprehensive performance

Technical field

The present invention relates to a kind of lubricant oil composite, more particularly to a kind of lubricating oil groups suitable for marine diesel engine Close object.

Background technology

With China's economic development, sea transport industry rapidly develops, and the demand of large ship bunker oil is continuously increased, oil Quality is continuously improved.These oil products mainly include two-stroke low speed cross-head type steam cylinder oil, system oil and four stroke middling speed cylinders Shape piston diesel engine oil etc..Wherein, although system oil and four stroke diesel engine oil with medium speed are not so good as marine cylinder oil work Make condition harshness, but the fuel being still related to is the higher diesel oil of sulfur content, has different areas of activity existing for water.Therefore, it is oily Product there are certain requirements for base number, generally require system oil in the range of 6~10mgKOH/g, middling speed machine oil require base number 6~ In the range of 40mgKOH/g.Generally speaking, it is desirable that system oil and middling speed machine oil have preferable high temperature detergency, inoxidizability, acid Neutralize performance, it is point aqueous can and demulsification performance, wherein high temperature detergency and aqueous energy and demulsification performance be divided to be two important Index.In recent years, also there are many research reports of middling speed machine oil and system oil.

CN 1203263《Crank axle for vessel case fluid composition containing demulsifier》A kind of crank axle for vessel case composition is described, is wrapped Include substantial amounts of mineral oil base oil, a small amount of alkyl monosulfide phenates, salicylate, polyisobutene succinimide, dialkyl group two Thiophosphate, epoxy second, propane block co-polyether, alcohols, dimethicone can modulate 3 according to requirement of the oil product to base number The crank axle for vessel case oil of~40mgKOH/g, to meet low speed crosshead engine of boat and ship crankcase system and medium speed trunk piston The lubricating requirement of engine.

CN 1253542《Lubricant oil composite》It describes one kind and lights ship hair for four stroke plunger type medium speed compressions The lubricant oil composite of motivation, it includes a kind of mixtures of following substance：(A) a kind of oil of lubricant viscosity, accounts for more amount； A kind of (B) oil-soluble overbased metal detergent additive, accounts for less amount, exists in the form of a kind of complex compound, Stablize detergent base stock with more than one surfactant in the complex compound；Said composition is substantially free of scattered Agent or the dispersant containing 1% based on composition quality or less than 1%, preferably less than 0.5%；And the TBN value of composition exists 3.5~100mgKOH/g, preferably in 8~100mgKOH/g.Said composition has excellent high temperature detergency and relatively low cost.

CN 1257255《Lubricant oil composite》, the lubricant oil composite of introduction is suitable for low speed, the work of 4 stroke cartridge type of middling speed Plug either 2 stroke crosshead engines lubrication, lubricant oil composite, including：The major amount of oil with lubricant viscosity, wherein Contain a small amount of fuel oil with slag fuel content：With mixed, a small amount of, at least one to have at least two be aromatics Residue moiety or by the oil-soluble of doubly linked adjacent substitutable carbon atom or the ashless organic compound of oily dispersibility, Described in carbon atom be respectively provided with oxygen-containing or oxygen-containing and nitrogen functional group, two kinds of groups are derived from carboxyl.Mainly solve cartridge type Piston engine (TPEO), marine cylinder oil (MDCL), fuel are mixed into the scattering problem of lubricating oil.

CN 1257256《Lubricate the method for four stroke medium speed compression ignition engine of boat and ship》、CN 1322797《Lubricating oil Composition》The lubricant oil composite of introduction includes, and the lubricating oil of (1) at least 60%, 100 dynamic viscosities are in 2~40mm2/s, (2) 2.55%~30% calcium salicylate, base number is in 100~450mgKOH/g, as unique overbased metal detersive, (3) 0.1%~1.5% dihydrocarbyl dithiophosphate trbasic zinc phosphate, composition are free of dispersant, and base number is in 25~100mgKOH/g, Said composition has excellent high temperature detergency.

CN 101570712《A kind of high-base-number ship cylinder lubricating oil》The lubricant oil composite of introduction, base oil are centre Base base oil, metal detergent are the 40TBN high-base-number ship cylinder lubricating oils peculiar to vessel of calcium naphthenate.Be by weight percentage by Calcium naphthenate 0.2%~25%, sulfurized alkylphenol calcium 0.2%~20%, succimide 0.2%~20%, tricresol phosphate Fat or benzotriazole fatty amine salt 0.05%~15%, carbaminate 0.1%~18%, alkylnaphthalene 0.1%~16%, dimethyl Silicon 0.0001%~0.1%, polyethers 0.01%~5% and base oil form for surplus, and there is excellent diffusivity, water resistant to divide water Property, the performances such as corrosion and wear resistance and detergency, be in a leading position level at home, bunker oil production similar with foreign big oil companies Quality is suitable, can meet the requirement of ocean and coastal waters large ship to bunker oil.

US 4358386《Crank axle for vessel case lubricating oil》Describe a kind of low speed bunker oil bent axle of base number in 3~10TBN Case oil has preferable antiwear and antifriction, breaking, point aqueous, including high base number alkyl phenol calcium 1%~5%, dialkyl group Dithiophosphates 0.1%~1%, oxiranylalkyl phenol 0.2%~0.4%, N alkyl glycines derivative 0.75%~ 2%.

US 5753598《Lubricant oil composite with improved point of aqueous energy》Describe a kind of point of water performance improvement Lubricant oil composite, demulsifier uses epoxyalkane and heterocyclic compound, such as dimercaptothiodiazole, with 0.1：1~0.5:1 Ratio is added in lubricating oil, is shown the demulsification effect of consonance and is preferably divided aqueous energy.

More than achievement in research can provide the ship lubricant oil of better performances or be four-stroke piston middling speed machine oil, It can meet the job requirement of engine in most of occasion.With the reduction of petroleum resources, diesel oil sulphur that bunker fuel oil uses Content is more and more, and this requires the high temperature detergency of oil product further improves.Meanwhile with the increase of engine power, oil The extension of product drain period, it is desirable that the properties of original oil product will also further improve, wherein dividing water and demulsibility It is required that it is also higher and higher, and divide water and demulsibility that cannot meet the requirements sometimes in existing formula, therefore, it is necessary to further It improves.

The content of the invention

The present invention proposes a kind of lubricant oil composite and the method for improving lubricating oil comprehensive performance.

The lubricant oil composite of the present invention includes：Alkyl sulfide alcohol ester, demulsifier, detersive, antioxidant, dispersant and main The lubricating base oil of amount.

The alkyl hydrosulfide and the esterification products of the alkyl carboxylic acid of C2~C20 that the alkyl sulfide alcohol ester is C2~C20, preferably The alkyl hydrosulfide and C2 of the esterification products of the alkyl hydrosulfide of C5~C20 and the alkyl carboxylic acid of C2~C15, most preferably C10~C18~ The esterification products of the alkyl carboxylic acid of C8.When preparing the alkyl sulfide alcohol ester, the alkyl hydrosulfide and C2 of the C2~C20~ The molar ratio of the alkyl carboxylic acid of C20 preferably 1：1~1.02, reaction temperature is 60~120 DEG C, when the reaction time is 2~4 small, two Person occurs to be preferably added to catalyst during esterification, and the addition of the catalyst is the 5%~10% of the two material gross mass, The preferred concentrated sulfuric acid of catalyst.

The alkyl sulfide alcohol ester accounts for the 0.01%~2% of lubricant oil composite gross mass, preferably 0.05%~1%, most It is preferred that 0.05%~0.5%.

The demulsifier is non-polyether class demulsifier and/or polyethers demulsifier.

The non-polyether class demulsifier is acrylate and the copolymer of α-olefin sulfonic acid.

The structure of the copolymer of the acrylate and α-olefin sulfonic acid is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5 ~C10 alkyl or its mixed alkyl；Wherein A1 be hydrogen or methyl, A2 be hydrogen or C1~C4 alkyl, preferably hydrogen, methyl, ethyl or Propyl, most preferably hydrogen, methyl or ethyl, x be 0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is During hydrogen, x is positive integer；M be 1~50 integer, preferably 5~50, most preferably 10~30, n be 1~50 integer, preferably 5~ 50, most preferably 10~20.

The molecular weight of the copolymer of the acrylate and α-olefin sulfonic acid between 1000~15000, preferably 1500~ 10000, most preferably 2000~8000.

The preparation method of the copolymer of the acrylate and α-olefin sulfonic acid is by alkyl acrylate and α-alkenyl sulphur Acid is copolymerized, and collects product.

The structure of the alkyl acrylate is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5 ~C10 alkyl or its mixed alkyl；A1 is hydrogen or methyl.

The alkyl acrylate is to be obtained by methacrylic acid or acrylic acid with alkylol by esterification, and esterification is anti- It is the acidic catalysts such as the concentrated sulfuric acid, acid-exchange resin to answer common catalyst.

The structure of the α-olefin sulfonic acid is：

Wherein A2 is hydrogen or C1~C4 alkyl, and preferably hydrogen, methyl, ethyl or propyl, most preferably hydrogen, methyl or ethyl, x is 0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is hydrogen, x is positive integer.

α-the olefin sulfonic acid is that alpha-olefin and sulfonating agent sulfonating reaction occur and obtains.The alpha-olefin is C3~C10 Alkene, such as the one or more in propylene, butylene, amylene, hexene, heptene, octene, nonene and decene can be selected, preferably C3~C8 alkene, most preferably C3~C6 alkene.The sulfonating agent can select oleum and/or sulfur trioxide.

When sulfonating reaction occurs for alpha-olefin and sulfonating agent, solvent, preferably varsol, the varsol can be added in It is preferred that C5~C10 alkane or its mixture.The 20%~200% of the preferred alpha-olefin quality of addition of the solvent, in sulfonation Solvent is removed after reaction.

The reaction pressure of sulfonating reaction occurs for the alpha-olefin and sulfonating agent preferably between 0.1~4MPa, and most preferably 0.3 ~3.0MPa, reaction temperature is preferably between 0~30 DEG C, and most preferably between 0~20 DEG C, the reaction time preferably 0.1~8 is small When, most preferably 0.3~5 it is small when.

The molar ratio of the alpha-olefin and sulfonating agent preferably 1：1~1.5, more preferable 1：1~1.2.

In the product of the sulfonating reaction alkyl acrylate is cannot participate in containing α-olefin sulfonic acid, sultone, sultone With the copolyreaction of α-olefin sulfonic acid.

Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1, preferably 1~10：10~ 1, most preferably 1~3：2~1.

The copolyreaction of the alkyl acrylate and α-olefin sulfonic acid preferably carries out in a solvent, and the solvent is preferably fragrant One or more in hydrocarbon solvent, such as benzene, toluene and dimethylbenzene；Preferably 20~200 DEG C of reaction temperature, more preferable 30~150 DEG C, most preferably 40~120 DEG C, when the time preferably 1~20 of polymerization is small, it is more preferable 2~15 it is small when, most preferably 3~10 it is small when.

The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized, addition is alkyl acrylate The 0.05%~5% of base ester and α-olefin sulfonic acid gross mass, preferably 0.05%~3%；The preferred azo compound of the initiator And/or peroxide, such as azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, peroxidating bay can be selected Acyl, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, perbenzoic acid uncle Butyl ester, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and mistake Aoxidize the one or more in two dicyclohexyl carbonates, preferably azo diisobutyl and/or benzoyl peroxide, most preferably azo Bis-isobutyronitrile.

Material is washed with water after copolyreaction between the alkyl acrylate and α-olefin sulfonic acid, is removed not The sultone and initiator of reaction；If adding solvent when being copolymerized, removing solvent is needed.

Neutral oil, the neutrality can be added in copolyreaction between the alkyl acrylate and α-olefin sulfonic acid The addition of oil is the 20%~100% of the polymer quality.The neutral oil preferred solvent refined oil and/or poly- α-alkene Hydrocarbon synthetic oil, such as HVI150, No. 6 hydrogenated oils, PAO4, PAO6 can be selected, 100 DEG C of dynamic viscosities of the neutral oil are 1 ~8mm²Between/s.

The polyethers demulsifier is sulfenyl phenolate and propylene oxide, the copolymer of ethylene oxide.

The sulfenyl phenolate and propylene oxide, the structure of copolymer of ethylene oxide are：

Wherein X group isA be 10~100 between integer, preferably 15~80, it is optimal Select 20~60, b be 5~100 between integer, preferably 5~60, most preferably 10~40；K be 1~10 between integer, preferably 1 ~6, most preferably 1~2；J is the integer between 1~10, and the j on each sulphur bridge can be the same or different, preferably 1~6, most It is preferred that 1~4；R2 is C1~C18 alkyl or its mixed alkyl, preferably C3~C15 alkyl or its mixed alkyl, most preferably C3~ C10 alkyl or its mixed alkyl.

The sulfenyl phenolate and propylene oxide, the preparation method of copolymer of ethylene oxide include：By sulfenyl phenolate First with Polymerization of Propylene Oxide, again with ethylene oxide polymerization, product is collected.

The sulfenyl phenolate is vulcanization C1~C18 alkyl phenols, preferably vulcanizes C3~C15 alkyl phenols, most preferably vulcanizes C3 ~C12 aligns alkyl phenol；The sulfenyl phenolate is obtained by the reaction by alkyl phenol and vulcanizing agent, and the vulcanizing agent can select sulphur One or more in sulphur, sulfur chloride and sulfur dichloride, the molar ratio of the alkyl phenol and the vulcanizing agent is 1~3：3~1. The temperature of vulcanization is room temperature to 200 DEG C.The sulfur content of sulfenyl phenolate obtained is 5%~20%.

The molar ratio of phenolic hydroxyl group and propylene oxide in the sulfenyl phenolate is 1：10~100, preferably 1：15~80, most It is preferred that 1：20~60；The molar ratio of phenolic hydroxyl group and ethylene oxide in the sulfenyl phenolate is 1：5~100, preferably 1：5~ 60, most preferably 1：10~40.

When preparing the copolymer of the sulfenyl phenolate and propylene oxide, ethylene oxide, solvent is preferably added to, it is described molten Agent preferred aromatic hydrocarbons solvent, most preferably dimethylbenzene and/or toluene, the mass ratio preferably 1 of the sulfenyl phenolate and the solvent： 0.1~50, more preferable 1：0.2~20.

When preparing the copolymer of the sulfenyl phenolate and propylene oxide, ethylene oxide, catalyst is preferably added to, it is described Catalyst preferred alkali metal hydroxide, most preferably potassium hydroxide and/or sodium hydroxide, the sulfenyl phenolate and the catalysis The molar ratio of agent preferably 1：1~20, more preferable 1：1~10, most preferably 1：3~8.

The sulfenyl phenolate and propylene oxide, the reaction pressure of ethylene oxide polymerization are 0.1~1MPa, preferably 0.1~ 0.8MPa, most preferably 0.2~0.6MPa；Reaction temperature be 80 DEG C~200 DEG C, preferably 100 DEG C~160 DEG C, most preferably 120 DEG C~ 140℃；Reaction time for 1~10 it is small when, preferably 2~8 it is small when, most preferably 2~4 it is small when.

The sulfenyl phenolate and propylene oxide, ethylene oxide polymerisation after, 60 are added in into reaction product ~90 DEG C of petroleum ethers, 10% sulfuric acid solution, neutralization reaction product to neutrality after dividing water, drying, add in neutral oil, steam molten Agent obtains sulfenyl phenolate propylene oxide ethylene oxide polymer.

The molecular weight of the sulfenyl phenolate and propylene oxide, the copolymer of ethylene oxide is 1000~30000, preferably 5000~20000, most preferably 10000~20000.

The copolymer of the acrylate and α-olefin sulfonic acid, sulfenyl phenolate propylene oxide ethylene oxide copolymer can be with It is used alone, can also be used in combination；During compound use, mass ratio preferably 1~3 therebetween：3~1.

The demulsifier preferably accounts for the 0.001%~0.1% of lubricant oil composite gross mass, most preferably 0.01%~ 0.1%.

The detersive is high-base-number detergent and/or low alkali value detersive, wherein the high-base-number detergent is selected from Base number is more than over base sulfosalt, high base number alkyl phenate and one kind or more in high base number salicylate of 300mgKOH/g Kind, preferably alkyl benzene calcium sulfonate of the base number between 300~400mgKOH/g, SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER are most preferably high-alkali It is worth sulfurized alkylphenol calcium, the alkyl of the sulfurized alkylphenol calcium is C₁₀~C₃₀, preferably C₁₀~C₂₀。

The low alkali value detersive includes low alkali value alkyl benzene calcium sulfonate, low alkali value of the base number in 20~150mgKOH/g One or more in Sulfonic Lithium, low alkali value alkyl sodium salicylate and low alkali value sulfurized alkylphenol calcium, preferably low alkali value alkylbenzene One or more in sulfoacid calcium, low alkali value Sulfonic Lithium and low alkali value alkyl sodium salicylate, most preferably low alkali value alkyl benzene sulphonate Calcium and/or low alkali value Sulfonic Lithium.

The detersive preferably accounts for the 0.1%~20% of lubricant oil composite gross mass, and more preferable 0.2%~15%, most It is preferred that 0.3%~10%.

The antioxidant is zinc dialkyl dithiophosphate, dialkyl dithiophosphoric acid copper, alkylated diphenylamine, two uncles Butyl paracresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines, sulfenyl phenolate, one kind in dialkyl dithio amino formate or It is a variety of, preferably in zinc dialkyl dithiophosphate, alkylated diphenylamine, dialkyl dithio amino formate and sulfenyl phenolate One or more, most preferably zinc dialkyl dithiophosphate and/or dialkyl dithio amino formate.The antioxidant accounts for The 0.1%~5% of lubricant oil composite gross mass, preferably 0.2%~4%, most preferably 0.3%~2.5%.

The preferred polyisobutene succinimide ashless dispersant of the dispersant can select mono butonediimide, double One or more in succimide and more succimides, the wherein number-average molecular weight of polyisobutene part 500~ Between 4000, preferably 1000~3000.The most preferably double succimides of the dispersant.The dispersant accounts for lubricant oil composite The 0.1%~10% of gross mass, preferably 0.2%~8%, most preferably 0.3%~5%.

The lubricating base oil can select the one or more in API I, II, III, IV, V class lubricating base oil, It is preferred that the one or more in API I, II, Group III oil.

The I class oil is the lubricating oil that fraction oil is obtained by clay-filtered, solvent refining, Viscosity Index 80~ Between 100,100 DEG C of dynamic viscosities are in 1~40mm²Between/s；The II class oil is distillate by lube oil hydrogenation Reason obtains, and Viscosity Index is between 100~120, and 100 DEG C of dynamic viscosities are in 1~40mm²Between/s；The Group III oil It is that distillate is obtained by hydroisomerizing, Viscosity Index is more than 120, and 100 DEG C of dynamic viscosities are in 1~40mm²Between/s； The IV classes oil is the synthetic oil of alpha-olefine polymerizing, and Viscosity Index is between 120~150, and 100 DEG C of dynamic viscosities are 1 ~40mm²Between/s；The V classes oil is Synthin oil or Esters oil, and Viscosity Index is between 120~150,100 DEG C dynamic viscosity is in 1~40mm²Between/s, such as adipic acid aliphatic ester, decanedioic acid aliphatic ester, pentaerythritol ester etc..

The present invention also provides a kind of methods for improving lubricating oil comprehensive performance, and this method is by above-mentioned alkyl hydrosulfide Ester, demulsifier, detersive, antioxidant, dispersant are added in lubricating base oil.

The lubricant oil composite of the present invention has excellent high temperature detergency, oxidation stability, antiwear and antifriction, especially has There are excellent high temperature detergency and demulsification performance, divide water quick, thoroughly, suitable for the lubrication of marine diesel engine, especially Crankcase lubrication, the lubrication of middling speed piston type diesel engine suitable for two-stroke low speed cross head marine diesel machine.

Specific embodiment

It further illustrates the present invention rather than limits the invention by the following examples.

The preparation of 1 tert-dodecylmercaotan capronate S-1 of embodiment

With motor agitators and reflux water-dividing, condense the 500mL three-necked flasks of facility, add in 80 grams No. 120 Industrial naptha, tert-dodecylmercaotan 100 grams (M=202.4,0.49mol) then add in 15 gram of 98% concentrated sulfuric acid, and control is anti- Temperature is answered as 90 DEG C, caproic acid 56.9 grams (M=116.2,0.49mol) is added dropwise with separatory funnel, when time for adding is 1 small, then When back flow reaction 3 is small, and the water in reaction is separated, when a point water reaches 8.7 grams (98.6%), stop reaction, cooling separates Then the concentrated sulfuric acid is washed with deionized oil reservoir after neutrality, solvent is evaporated off, obtains 146 grams of oily liquids, As tert-dodecylmercaotan capronate S-1, S content 10.2%.

The preparation of 2 tetradecyl mercaptan propionic ester S-2 of embodiment

With motor agitators and reflux water-dividing, condense the 500mL three-necked flasks of facility, add in 60 grams No. 120 Industrial naptha, tetradecyl mercaptan 90 grams (M=230.45,0.39mol) then add in 11 grams of the concentrated sulfuric acid, controlling reaction temperature For 95 DEG C, propionic acid 28.9 grams (M=74,0.39mol) is added dropwise with separatory funnel, when time for adding is 1.2 small, is then refluxed for reacting 4 it is small when, and separate reaction in water, when a point water reaches 6.9 grams (98.3%), stop reaction, cooling, separate water layer, so After oil reservoir is washed with deionized after neutrality, solvent is evaporated off, obtains 111.3 grams of oily liquids, be ten Tetraalkyl mercaptan propionic ester S-2, S content are 11.3%.

The preparation of 3 propene sulfonic acid mixture of embodiment

With stirring, heating, cryostat the corrosion-resistant autoclaves of 500mL in add in 80 grams of 30 DEG C~60 DEG C petroleum ethers, so Rear enclosed reaction kettle opens stirring, and is passed through cryostat and carries out temperature control, then squeezes into 40 grams of propylene into kettle with high-pressure pump (0.952mol), and be passed through high pure nitrogen, control reactor pressure between 0.8~1MPa, control the temperature of reaction kettle 0~ 10 DEG C, the steel cylinder for storing sulfur trioxide is heated, is placed in measuring on electronic scale, then heating temperature is controlled to cause three oxidations Sulphur steel cylinder pressure is more than autoclave pressure, and opens sulfur trioxide steel cylinder outlet valve, and gas is passed through to the snorkel of autoclave In, it then passes to and sulfonating reaction is carried out in the liquid phase of autoclave, sulfur trioxide intake is 77.7 grams (0.971mol), at this time Pressure in reaction kettle is controlled between 0.8~1.2MPa, when the reaction time is 3.2 small, after reaction, to continuously decrease reactor Pressure, after pressure reaches normal pressure, stop stirring, then solvent distillation, obtains 115.8 grams of propene sulfonic acid mixture, analysis It was found that；Containing 54% propene sulfonic acid in the product, 46% propene sultone, the acid value of mixture is 260.8mgKOH/g.

The preparation of 4 butylene azochlorosulfonate acid mixture of embodiment

With stirring, heating, 70 grams of n-hexanes of addition in the 500mL autoclaves of cryostat, then capping kettle, is opened Stirring, and be passed through cryostat and carry out temperature control, butylene 38 grams (0.679mol) is then squeezed into kettle with high-pressure pump, and is passed through High Purity Nitrogen Gas, control reactor pressure control the temperature of reaction kettle that will store sulfur trioxide at 0~10 DEG C between 0.8~1MPa Steel cylinder heats, and is placed in measuring on electronic scale, then controls heating temperature that sulfur trioxide steel cylinder pressure is caused to be more than autoclave pressure Power, and sulfur trioxide steel cylinder outlet valve is opened, gas is passed through in the snorkel of autoclave, then passes to the liquid of autoclave Sulfonating reaction is carried out in phase, sulfur trioxide intake is 54.88 grams (0.686mol), at this time control reaction kettle in pressure 0.8 Between~1.2MPa, when the reaction time is 2.8 small, after reaction, the pressure of reactor is continuously decreased, when pressure reaches normal pressure Afterwards, stirring is stopped, then solvent distillation obtains 91.3 grams of butylene azochlorosulfonate acid mixture, containing 53% butylene sulfonic acid in the product, 47% butene sultone, the acid value of mixture is 225.3mgKOH/g.

The synthesis of 5 acrylic acid C5 ester butylene sulfonic acid copolymers P1 of embodiment

In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70 DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, when polymerisation 1 is small, adds embodiment 4 64 grams of the butylene azochlorosulfonate acid mixture (containing 53% butylene sulfonic acid, 0.25mol, M=136) of preparation, 0.05 gram of two isobutyl of azo Nitrile, be gradually heating to 105 DEG C carry out copolyreaction 4 it is small when.Twice, then reaction product is washed respectively with 200 grams of distilled water 60 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company) are added in, material is warming up to 125 DEG C and is evaporated under reduced pressure, is obtained Acrylic acid C5 ester butylene sulfonic acid copolymer 157.6 grams (P1).Infrared analysis the result shows that：In 1721cm^-1、1160cm^-1Nearby have Strong absworption peak, and illustrate to contain ester type compound in product, 1184cm^-1、1053cm^-1、3650cm^-1Neighbouring spike shows have Sulfonic acid group exists, 1640cm^-1Nearby non-telescope vibration peak occurs, and does not have double bond presence in compound, illustrates that the compound is Acrylic acid C5 ester butylene sulfonic acid copolymers；Gpc analysis shows the number-average molecular weight of copolymer for 5130, wherein copolymer Content is 61.92%, and the content of flux oil is 38.02%, and the content of acrylic acid C5 esters is 65.47% in copolymer, butylene sulphur The content of acid is 34.53%.

The synthesis of 6 methacrylic acid C8 ester propene sulfonic acids copolymer p 2 of embodiment

In the 500mL three-necked flasks with motor agitators and condenser pipe, 100 grams of dimethylbenzene, 73.6 grams of first are added in Base acrylic acid C8 esters (0.38mol, M=196) add in 0.07 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and rise Temperature is to 75 DEG C, and observing response object has apparent heat release at this time, and controlling reaction temperature is 95 DEG C, when polymerisation 1.5 is small, is added 90.37 grams of propene sulfonic acid mixture (containing 54% propene sulfonic acid, 0.4mol, M=122) prepared by embodiment 3,0.06 gram of idol Nitrogen bis-isobutyronitrile, be gradually heating to 108 DEG C carry out copolyreaction 5 it is small when.Two are washed with 200 grams of distilled water respectively to reaction product It is secondary, 80 grams of HVI150N (production of Sinopec Shanghai Gaoqiao petrochemical industry branch company) are then added in, material is warming up to 125 DEG C of progress Vacuum distillation, obtains methacrylic acid C8 ester propene sulfonic acids copolymer 201 grams (P2).Infrared analysis the result shows that：In 1721cm^-1、1160cm^-1Nearby there is strong absworption peak, and illustrate to contain ester type compound in product, 1184cm^-1、1053cm^-1、3650cm^-1 The spike at place shows with the presence of sulfonic acid group, 1640cm^-1Locate non-telescope vibration peak to occur, there is no double bond presence in compound, say The bright compound is methacrylic acid C8 ester propene sulfonic acid copolymers；Gpc analysis shows that the number-average molecular weight of copolymer is 3860, the wherein content of copolymer is 60.2%, and the content of flux oil is 39.8%, and methacrylic acid C8 esters contains in copolymer Amount is 60.83%, and the content of propene sulfonic acid is 39.17%.

The synthesis of 7 sulfenyl phenolate A of embodiment

Nonyl phenol 100 grams (0.455mol), 100mL are added in the 500ml three-necked flasks with temperature control and water cooling, stirring N-decane adds in sulphur 35 grams (1.09mol), is then gradually heating to 160 DEG C, and reaction mass is protected with nitrogen, while will be anti- Tail gas is answered to be passed through 10% sodium hydroxide solution, with the hydrogen sulfide gas that absorbing reaction generates, nonyl phenol is by colourless gradual change at this time For dark brown, eventually become black liquor, when reaction 4 is small after, vacuum distillation controlled at 165 DEG C, obtains after steaming desolventizing Sulfenyl phenolate A measures sulfur content as 23.9%.It is measured with VPO methods, the average molecular weight of vulcanization nonyl phenol A is (equivalent for 881 Containing 3 alkyl phenols in each molecule, 3.5) average value of k 1, number of sulfur atoms j is.

The synthesis of 8 sulfenyl phenolate B of embodiment

Dodecylphenol 100 grams (0.382mol) is added in the 500ml three-necked flasks with temperature control and water cooling, stirring, 60~90 DEG C of petroleum ethers of 100ml, controlled at 25~35 DEG C, then be added dropwise sulfur monochloride 36 grams (0.267mol), then by 160 DEG C are gradually warming up to, reaction mass is protected with nitrogen, while reaction end gas is passed through 10% sodium hydroxide solution, it is anti-to absorb The hydrogen chloride gas that should be generated, at this time dodecylphenol gradually become dark brown by colourless, black liquor is eventually become, by 5 It is dripped off after hour, then heats to 100 DEG C, removed solvent, obtain sulfenyl phenolate B, measure sulfur content as 14.7%.Use VPO Method measure, the average molecular weight of vulcanization dodecylphenol B (are converted into each molecule containing 3 alkyl phenols, k 1, sulphur original for 912 2) subnumber j is.

The synthesis of 9 sulfenyl phenolate C of embodiment

Nonyl phenol 100 grams (0.455mol), 100mL are added in the 500ml three-necked flasks with temperature control and water cooling, stirring N-decane adds in sulfur dichloride 35.1 grams (0.34mol), is then gradually heating to 160 DEG C, protects reaction mass with nitrogen, together When reaction end gas is passed through 10% sodium hydroxide solution, with the hydrogen chloride gas that absorbing reaction generates, nonyl phenol is by colourless at this time Gradually become dark brown, eventually become black liquor, when reaction 4 is small after, vacuum distillation controlled at 165 DEG C, steams desolventizing After obtain sulfenyl phenolate C, measure sulfur content as 10.2%, measured with VPO methods, the average molecular weight of vulcanization nonyl phenol A is 970 It (converts into containing 4 alkyl phenols in each molecule, 1) k 2, number of sulfur atoms j is.

The preparation of 10 sulfenyl phenolate propylene oxide ethylene oxide polymer M1 of embodiment

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate A 3.4 is added in Gram (0.0039mol contains 0.012mol phenolic hydroxyl groups), 5 grams of dimethylbenzene, 1 gram of solid potassium hydroxide (0.0179mol), Ran Houyong Nitrogen displacement is warming up to 90 DEG C afterwards three times；30 grams of propylene oxide (0.517mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 122 DEG C, when reaction 2.5 is small；Ethylene oxide 12 grams (0.272mol), control are added dropwise into autoclave Reaction pressure 0.5MPa, reaction temperature is 125 DEG C, when reaction 2 is small；It transfers the material into 200ml beakers, adds after reaction Enter 60~90 DEG C of 30 grams of petroleum ethers, 50 milliliters of 10% sulfuric acid solution, remaining potassium hydroxide in neutralization reaction product, and spend Ion water washing, until reaction product is in neutrality；12 grams of HVI150 neutral oils are added in, the oil reservoir in material is put into vacuum distillation Device obtains 53.3 grams of product after steaming solvent, as vulcanizes nonyl phenol propylene oxide ethylene oxide polymer M1, infrared analysis The result shows that 723cm in product^-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm^-1、1249cm^-1Neighbouring peak corresponds to In aromatic ring and the stretching vibration peak of hydroxyl oxygen, in 1060~1150cm^-1Nearby there is the stretching vibration peak of alkyl ehter bond, 2900cm^-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, and the compound for showing generation is sulfenyl phenolate epoxy third Alkane ethylene oxide polymer, determination of elemental analysis sulfur content are 1.56%, and it is 11094 that by gpc analysis, it, which counts equal molecular mass,.

The preparation of 11 sulfenyl phenolate propylene oxide ethylene oxide polymer M2 of embodiment

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate B 4.25 is added in Gram (0.00467mol contains 0.014mol phenolic hydroxyl groups), 6 grams of dimethylbenzene, 1.2 grams of solid potassium hydroxides (0.0214mol), then 90 DEG C are warming up to afterwards three times with nitrogen displacement；28 grams of propylene oxide (0.483mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 122 DEG C, when reaction 2.5 is small；Ethylene oxide 17 grams (0.386mol), control are added dropwise into autoclave Reaction pressure 0.5MPa, reaction temperature is 125 DEG C, when reaction 3 is small；It transfers the material into 200ml beakers, adds after reaction Enter 60~90 DEG C of 40 grams of petroleum ethers, add in remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and It is washed with deionized, until reaction product is in neutrality；10 grams of 6# oil is added in, the oil reservoir in material is put into vacuum distillation dress It puts, 58.8 grams of thick liquid is obtained after steaming solvent, as vulcanization dodecylphenol propylene oxide ethylene oxide polymer M2, it is red Outer analysis the result shows that, 723cm in product^-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm^-1、1249cm^-1Near Peak corresponds to the stretching vibration peak of aromatic ring and hydroxyl oxygen, in 1060~1150cm^-1Nearby there is the stretching vibration peak of alkyl ehter bond, In 2900cm^-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, and the compound for showing generation is sulfenyl phenolate epoxy Propane ethylene oxide polymer, determination of elemental analysis sulfur content are 1.06%, and by gpc analysis, its equal molecular mass of number is 10366。

The preparation of 12 sulfenyl phenolate propylene oxide ethylene oxide polymer M3 of embodiment

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate C 3.0 is added in Gram (0.0031mol contains 0.0124mol phenolic hydroxyl groups) 5 grams of dimethylbenzene, 1.3 grams of solid potassium hydroxides (0.0232mol), then 90 DEG C are warming up to afterwards three times with nitrogen displacement；22 grams of propylene oxide (0.38mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 122 DEG C, when reaction 2.5 is small；Ethylene oxide 20 grams (0.455mol), control are added dropwise into autoclave Reaction pressure 0.5MPa, reaction temperature is 125 DEG C, when reaction 3 is small；It transfers the material into 200ml beakers, adds after reaction Enter 60~90 DEG C of 35 grams of petroleum ethers, add in remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and It is washed with deionized, until reaction product is in neutrality；9 grams of HVI150 oil is added in, the oil reservoir in material is put into vacuum distillation Device obtains 54.6 grams of thick liquid after steaming solvent, as vulcanization nonyl phenol propylene oxide ethylene oxide polymer M3, infrared Analysis result shows 723cm^-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm^-1、1249cm^-1Neighbouring peak corresponds to The stretching vibration peak of aromatic ring and hydroxyl oxygen, in 1060~1150cm^-1Between peak correspond to alkyl ehter bond stretching vibration peak, 2900cm^-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, and the compound for showing generation is sulfenyl phenolate epoxy third Alkane ethylene oxide polymer, determination of elemental analysis sulfur content are 0.57%, and it is 14353 that by gpc analysis, it, which counts equal molecular mass,.

The synthesis of 1 acrylic acid C5 ester acrylic copolymers D1 of comparative example

In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70 DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, when polymerisation 1 is small, adds acrylic acid 18 Gram (0.25mol, M=72), 0.05 gram of azodiisobutyronitrile, be gradually heating to 105 DEG C carry out copolyreaction 4 it is small when.To reaction Product is washed twice respectively with 200 grams of distilled water, and then adding in 52 grams and HVI150, (Sinopec Yanshan Petrochemical branch company gives birth to Production), material is warming up to 125 DEG C and is evaporated under reduced pressure, obtains acrylic acid C5 esters acrylic copolymer 135 grams (D1).Analysis knot Fruit shows：The number-average molecular weight of copolymer is 4938, and the wherein content of copolymer is 61.48%, and the content of flux oil is 38.52%, the content of acrylic acid C5 esters is 78.02% in copolymer, and the content of acrylic acid is 21.98%.

The synthesis of 2 alkyl phenol propylene oxide ethylene oxide polymer D2 of comparative example

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, 2.8 grams of nonyl phenol is added in (0.0127mol contains 0.0127mol phenolic hydroxyl groups), 1 gram of solid potassium hydroxide (0.0179mol), then with being risen after nitrogen displacement Temperature is to 92 DEG C；30 grams of propylene oxide (0.517mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 125 DEG C, when reaction 2.5 is small；Ethylene oxide 12 grams (0.272mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, instead Temperature is answered as 125 DEG C, when reaction 2 is small；It transfers the material into after reaction in 200ml beakers, adds in 60~90 DEG C of petroleum ethers 50 grams, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and be washed with deionized, until anti- Product is answered to be in neutrality；12 grams of HVI150 neutral oils are added in, the oil reservoir in material is put into vacuum distillation apparatus, are obtained after steaming solvent To 55.6 grams of thick liquid, infrared analysis the result shows that, 1500cm^-1、1249cm^-1Neighbouring peak corresponds to aromatic ring and hydroxyl oxygen Stretching vibration peak, 1060~1150cm^-1Between peak correspond to the stretching vibration peak of alkyl ehter bond, in 2900cm^-1Neighbouring peak corresponds to Methyl and methylene stretching vibration peak show that the compound of generation for nonyl phenol propylene oxide ethylene oxide polymer D2, passes through Its equal molecular mass of number of gpc analysis is 3561.

Test method and experiment raw material

Test method used by 1.

GB/T265 oil product kinematic viscosity measuring methods and dynamic viscosity calculating method

GB/T2541 oil products viscosity index (VI) calculates table

GB/T3535 petroleum products pour point measuring methods

GB/T7305 oil and Synthesis liquid resistance to emulsion pipette method

GB/T11143 inhibitings mineral oil test for rust preventing ability method in the presence of water

GB/T12579 lubricating oil spumescence measuring methods

GB/T3142 load carrying capacity of lubricant measuring method four ball methods

SH/T0251 oil product base numbers measuring method (perchloric acid potentiometric titration)

SH/T0619 oil-water separativeness measuring methods peculiar to vessel

SH/T0649 marine lubricant etching tests

High temperature detergency measuring method

The method of evaluation high temperature detergency is lacquering and QZX experiment, which tests in L-1 plate-type cokings device, into Burnt experimental condition is：Plate temperature/oil temperature=320 DEG C/100 DEG C, time 2 h stop/ETAD expected time of arrival and departure=45 second/15 second, lacquering test bar Part is：Plate temperature/oil temperature=300 DEG C/150 DEG C, time 2 h are carried out continuously.

Inoxidizability measuring method

The method of evaluation anti-oxidative stability is PDSC experiments, which is on 2910 thermal analyzers of TA 5000DSC It carries out, experimental condition：Heating rate is 100 DEG C/min, constant temperature 60min, 3.5MPa.

2. base oil used in experiment

The base oil of 1 experiment of table

3. test additive therefor

The additive of 2 experiment of table

According to tetra- stroke medium speed trunk piston machine oil of API40 viscosity level modulations 12TBN and No. 40 ship lubricant oils, wherein Reality is formed using alkyl sulfide alcohol ester, acrylate olefin sulfonic acid copolymer, sulfenyl phenolate propylene oxide ethylene oxide polymer Apply example 13~22, using common demulsifier T1001, DL-32, comparative example 1,2 demulsifiers, commercially available TBN12 middling speeds machine oil and No. 40 ship lubricant oils comparative example 3~14 together, formula composition are shown in Table 3,4 tables 7,8, test result is shown in Table 5,6, table 9,10.

The embodiment of 3 12TBN of table, tetra- stroke medium speed trunk piston machine oil

The comparative example of 4 12TBN of table, tetra- stroke medium speed trunk piston machine oil

The performance test of 5 12TBN of table, tetra- stroke middling speed piston oil embodiments

The performance test of 6 12TBN of table, tetra- stroke middling speed piston oil comparative examples

The embodiment of 7 No. 40 ship lubricant oils of table

The comparative example of 8 No. 40 ship lubricant oils of table

The performance test of 9 No. 40 ship lubricant oil embodiments of table

The performance test of 10 No. 40 ship lubricant oil comparative examples of table

It can be seen from the above result that using alkyl sulfide alcohol ester, acrylate olefin sulfonic acid copolymer and/or sulfenyl phenolate ring Ethylene Oxide ethylene oxide is the tetra- stroke medium speed trunk piston oils of TBN12 and No. 40 system oils of demulsifier allotment, is had preferable Wear resistence, inoxidizability divide water and demulsibility, anti-foaming property.Using oiliness improver, T1001 and DL32 demulsifiers, comparative example 1, It is the tetra- stroke medium speed trunk piston oils of TBN12 and the wear resistences of No. 40 system oils of the allotment of 2 demulsifiers, inoxidizability, breaking, anti- Bubble property is not so good as embodiment.The marine lubricant composition of the present invention has excellent high temperature detergency, inoxidizability, antiwear and antifriction Property divides water and breaking, anti-foaming property.

Claims (17)

1. a kind of lubricant oil composite, including：Alkyl sulfide alcohol ester, demulsifier, detersive, antioxidant, dispersant and major amount of Lubricating base oil；The demulsifier is non-polyether class demulsifier and/or polyethers demulsifier, and the non-polyether class demulsifier is The copolymer of acrylate and α-olefin sulfonic acid, the polyethers demulsifier are sulfenyl phenolate and propylene oxide, ethylene oxide Copolymer；

The structure of the copolymer of the acrylate and α-olefin sulfonic acid is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl, and A2 is hydrogen or C1~C4 alkyl, and x is 0~4 Integer；When A2 is hydrogen, x is positive integer；M is 1~50 integer, and n is 1~50 integer；

The sulfenyl phenolate and propylene oxide, the structure of copolymer of ethylene oxide are：

Wherein X group is

A is the integer between 10~100, and b is the integer between 5~100；K is the integer between 1~10；

J is the integer between 1~10, and the j on each sulphur bridge can be the same or different；R2 is C1~C18 alkyl or it is mixed Close alkyl.

2. composition described in accordance with the claim 1, which is characterized in that the alkyl sulfide alcohol ester is the alkyl sulfide of C2~C20 The esterification products of the alkyl carboxylic acid of alcohol and C2~C20.

3. composition described in accordance with the claim 1, which is characterized in that the alkyl sulfide alcohol ester accounts for the total matter of lubricant oil composite The 0.01%~2% of amount.

4. composition described in accordance with the claim 1, which is characterized in that point of the acrylate and α-olefin sulfonic acid copolymer Son amount is between 1000~15000.

5. composition described in accordance with the claim 1, which is characterized in that the copolymer of the acrylate and α-olefin sulfonic acid Preparation method is to be copolymerized alkyl acrylate and α-olefin sulfonic acid, collects product；The alkyl acrylate Structure is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl.

The structure of the α-olefin sulfonic acid is：

Wherein A2 is hydrogen or C1~C4 alkyl, and x is 0~4 integer；When A2 is hydrogen, x is positive integer；

Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1；

The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized.

6. according to the composition described in claim 5, which is characterized in that the copolymerization of the alkyl acrylate and α-olefin sulfonic acid The temperature of reaction is 20~200 DEG C, when the time of reaction is 1~20 small.

7. composition described in accordance with the claim 1, which is characterized in that the sulfenyl phenolate and propylene oxide, ethylene oxide Copolymer preparation method be by sulfenyl phenolate first with Polymerization of Propylene Oxide, again with ethylene oxide polymerization, collect product.

8. according to the composition described in claim 7, which is characterized in that the sulfenyl phenolate is vulcanization C1~C18 alkyl phenols.

9. according to the composition described in claim 7, which is characterized in that phenolic hydroxyl group and propylene oxide in the sulfenyl phenolate Molar ratio be 1：10~100；The molar ratio of phenolic hydroxyl group and ethylene oxide in the sulfenyl phenolate is 1：5~100.

10. according to the composition described in claim 7, which is characterized in that the sulfenyl phenolate and propylene oxide, ethylene oxide The reaction pressure of polymerization is 0.1~1MPa；Reaction temperature is 80 DEG C~200 DEG C；When reaction time is 1~10 small.

11. composition described in accordance with the claim 1, which is characterized in that the sulfenyl phenolate and propylene oxide, ethylene oxide Copolymer molecular weight be 1000~30000.

12. composition described in accordance with the claim 1, which is characterized in that the demulsifier accounts for lubricant oil composite gross mass 0.001%~0.1%.

13. composition described in accordance with the claim 1, which is characterized in that the detersive is high-base-number detergent and/or low Base number detersive, wherein the high-base-number detergent is selected from over base sulfosalt, the high base number alkane that base number is more than 300mgKOH/g One or more in base phenates and high base number salicylate；The low alkali value detersive include base number 20~ Low alkali value alkyl benzene calcium sulfonate, low alkali value Sulfonic Lithium, low alkali value alkyl sodium salicylate and the low alkali value vulcanization alkane of 150mgKOH/g One or more in base phenol calcium；The detersive accounts for the 0.1%~20% of lubricant oil composite gross mass.

14. composition described in accordance with the claim 1, which is characterized in that the antioxidant for zinc dialkyl dithiophosphate, Dialkyl dithiophosphoric acid copper, alkylated diphenylamine, di-tert-butyl p-cresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines, vulcanization alkane One or more in base phenol, dialkyl dithio amino formate account for the 0.1%~5% of lubricant oil composite gross mass.

15. composition described in accordance with the claim 1, which is characterized in that the dispersant is polyisobutene succinimide Ashless dispersant accounts for the 0.1%~10% of lubricant oil composite gross mass.

16. composition described in accordance with the claim 1, which is characterized in that the lubricating base oil be selected from API I, II, III, One or more in IV, V class lubricating base oil.

17. it is a kind of improve lubricating oil comprehensive performance method, be by described in one of claim 1-16 alkyl sulfide alcohol ester, demulsification Agent, detersive, antioxidant, dispersant are added in lubricating base oil.