CN107760419A - Lubricant composition for gasoline engine and preparation method thereof - Google Patents

Lubricant composition for gasoline engine and preparation method thereof Download PDF

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Publication number
CN107760419A
CN107760419A CN201610686069.3A CN201610686069A CN107760419A CN 107760419 A CN107760419 A CN 107760419A CN 201610686069 A CN201610686069 A CN 201610686069A CN 107760419 A CN107760419 A CN 107760419A
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China
Prior art keywords
oil
molybdenum
alkyl
scattered
proofness
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Chinese (zh)
Inventor
刘烨
曾红玲
蔡涛
夏骏远
刘升高
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Jiangxi Fuel & Lubraicant Additive Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Jiangxi Fuel & Lubraicant Additive Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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Priority to CN201610686069.3A priority Critical patent/CN107760419A/en
Publication of CN107760419A publication Critical patent/CN107760419A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy

Abstract

It is composed of the following components the invention discloses a kind of Lubricant composition for gasoline engine and preparation method thereof：（A）Ashless dispersant, the 6.0wt% of content 0.1；（B）Detersive, the 8.0wt% of content 0.1；（C）Oil-soluble or scattered oil-proofness boron-containing compound, the 1.5wt% of content 0.01；（D）Oil-soluble or scattered oil-proofness molybdate compound, the 0.5wt% of content 0.003；（E）Zinc dialkyl dithiophosphate, the 3.2wt% of content 0.02；（F）Antioxidant, the 3.0wt% of content 0.01；（F）Major amount of lube base oil, wherein described（C）Component with（D）The boron molybdenum mass ratio of component is 1:5‑10:1.Contain boron-containing compound, molybdate compound and zinc dialkyl dithiophosphate in the gasoline engine engine oil base oil that the present invention allocates simultaneously, the cooperative effect between additive is given full play to, the antioxygenic property, antiwear and friction reduction property and extreme pressure property of lubricant oil composite are improved, reduces ash content and sulphur phosphorus content in lubricant oil composite.

Description

Lubricant composition for gasoline engine and preparation method thereof
Technical field
The invention belongs to chemical field, and in particular to lubricant oil composite, more particularly to it is a kind of for petrol engine Lubricant oil composite.
Background technology
In recent years, with the getting worse of environmental pollution, particularly some extreme weathers frequently occur and haze It is seen everywhere, people generate to this greatly to be paid attention to.And the discharge of vehicle exhaust be the main reason for causing haze weather it One, therefore with the increasingly harshness of Abgasgesetz, the requirement to engine emission is also increasingly stricter, so as to engine lubrication The performance of oil it is also proposed higher requirement.
Current high-grade petrol engine lube product specification has been upgraded to International Lubricant standardization and certification committee member Meeting（ILSAC）And American Petroleum Institute (API)（API）SM/GF-4, SN/GF-5 rank of formulation, mainly to the anti-oxidant, living of oil product Fill in that peace and quiet, greasy filth is scattered, the performance such as wear-resistant proposes higher requirement.Such as：High-grade petrol engine lubricating oil is anti-oxidant The engine evaluation test of viscosity build was from 64 hours of program III E, develop into program III F 80 hours, to current journey 100 hours of sequence III G, and viscosity build requirement never exceeds 375% and is reduced to 275%, 150%, simulates piston high temperature deposition thing TEOST-MHT test requirements documents from the SL 35mg for being no more than 45mg, developing into SM, SN specification.Further, since phosphorus-containing catalyst Catalytic converter can be entered by exhaust gas recirculation or gas blowby process, and accumulated in active metal site, poison catalyst, so as to Reduce catalyst efficiency and shorten its service life, thus use phosphor-included additive as lubricating oil component by specification standards Limitation.Limitation in high-grade petrol engine lubricating oil standard to phosphorus content requires：The mass fraction of phosphorus content in SL oil products It is required that the mass fraction requirement less than phosphorus content in 0.1%, SM and SN rank oil products is less than 0.08%.
Strict limitation to phosphorus content in high-grade petrol engine lubricating oil so that the simple dialkyl group using regulation content Zinc dithiophosphate（ZDDP）It can not meet the requirement of oxidation stability, auxiliary antioxidant needed to use in lubricant formula.Seek More efficiently antioxidant additive is sought, is always the target that those skilled in the art make great efforts.
Because the lubricant formula of protosulfate ash content can effectively reduce coking and top land carbon deposit, valve system mill is reduced Damage, prevents that detonation is excessive with combustion chamber deposit, keeps spark plug clean.Other low ash content can reduce corrosive oxidation products, subtract Few engine component corrosion abrasion, extend safe operation cycle and the part service life of engine.Good engine lubrication Oily detergent power can extend filter life, reduce maintenance cost.Therefore low ash content is the development side of petrol engine lubricating oil To.
Content of ashes to reduce in lubricating oil keeps that the anti-oxidant of oil product, piston are peace and quiet, greasy filth is scattered, wear-resistant simultaneously Excellent performance, it must just reduce ZDDP usage amount and add the more excellent low grey or ashless additive of performance. CN103060059 discloses a kind of antioxidant composition with excellent antioxygen property and antiwear and friction reduction property, the antioxidant Composition includes arylamine kind antioxidant and organic molybdenum additive.
The content of the invention
Based on the deficiency of above-mentioned present situation, it is an object of the invention to provide low ash content, low-phosphorous and with excellent anti-oxidant, living Fill in that peace and quiet, greasy filth is scattered, the petrol engine lubricating oil composition of wear resistance.
To achieve the above object, each additive component in compositions of additives is selected meticulously.It is each except considering The component function additive performance of itself and it is prominent the advantages of outside, while using oxidation stability, heat endurance and wear resistence as One of top-priority condition.Therefore, only by additive each component performance also far from realizing above-mentioned purpose, it is necessary to group The performance between each additive component in compound is balanced investigation, and two or more is selected particular against oxygen agent, antiwear additive Different compounds, just allowing for and be easy to implement above-mentioned " balance ".
Lubricant composition for gasoline engine provided by the invention, including following components：
（A）Ashless dispersant, the ashless dispersant are selected from polyalkylene succimide, carboxylic acid amide, hydrocarbyl monoamine, alkyl Polyamines, Mannich base, the basic nitrogen compound of phosphonic amide and phosphamide and/or comprising with amine, acid amides, imines, acid imide, hydroxyl The copolymer of the carboxylate of the other polar functional group of one or more of base, carboxyl, contains（A）Component 0.1-6.0wt%；
（B）Detersive, the detersive are selected from alkylsulfonate, alkyl phenol calcium, sulfurized alkylphenol calcium, alkyl sodium salicylate, ring Combination more than one or both of alkanoic acid calcium, contains（B）Component 0.1-8.0wt%；
（C）Oil-soluble or scattered oil-proofness boron-containing compound, the oil-soluble or scattered oil-proofness boron-containing compound Friction modifiers, scattered alkali metal or the mixed alkali metal or alkaline-earth metal boric acid of dispersant, boration selected from boration Salt, the epoxides of boration, borate, the fatty amine of boration, the acid amides of boration, boration sulfonate in one kind Or two or more combinations, contain（C）Component 0.01-1.5wt%；
（D）Oil-soluble or scattered oil-proofness molybdate compound, the oil-soluble or scattered oil-proofness molybdate compound Selected from molybdenum dithiocarbamate, molybdenum dithiophosphate, scattered hydration molybdenum compound, acidic molybdenum compound or acid molybdenum chemical combination The salt of thing, the combination containing one or both of molybdenum complex above, contain（D）Component 0.003-0.5wt%；
（E）At least one zinc dialkyl dithiophosphate, contains（E）Component 0.02-3.2wt%；
（F）At least one antioxidant, contains（F）Component 0.01-3.0wt%；
（G）Major amount of lube base oil.
Oil-soluble or scattered oil-proofness boron-containing compound（C）With oil-soluble or scattered oil-proofness molybdate compound （D）Boron molybdenum mass ratio be 1:5-10:1.
Can also there are following other additives, such as antirust in the Lubricant composition for gasoline engine of the present invention Agent, pour-point depressant, viscosity index improver, anti-foaming agent etc..
（A）Ashless dispersant
Ashless dispersant includes but is not limited to polyalkylene succinic anhydride；The not nitrogen containing derivative of polyalkylene succinic anhydride；Choosing From the basic nitrogen chemical combination of succimide, carboxylic acid amide, hydrocarbyl monoamine, hydrocarbyl polyamine, Mannich base, phosphonic amide and phosphamide Thing；Triazole such as alkyl triazole and BTA；Comprising with one or more other polar functional groups（Including amine, acid amides, Asia Amine, acid imide, hydroxyl, carboxyl etc.）Carboxylate copolymer, such as by making chain alkyl acrylate or methacrylic acid The product that ester is prepared with the monomer copolymerization with above-mentioned functional group；And the like and their mixture.
The ashless dispersant is in polyisobutene succinimide, polyisobutene succinic carboxylic acid ester, Mannich base Combination more than one or both；
Preferably, polyisobutene succinimide may be selected from single polyisobutene succinimide, double hung in the ashless dispersant Combination more than one or both of polyisobutene succinimide, high molecular weight polyisobutylene succimide is hung, wherein The number-average molecular weight of polyisobutene part is 500-5000；
Preferably, polyisobutene succinic carboxylic acid ester may be selected from single polyisobutene succinic carboxylic acid ester, double hung in the ashless dispersant Hang one in polyisobutene succinic carboxylic acid ester, more extension polyisobutene succinic carboxylic acid esters, high molecular weight polyisobutylene succinic carboxylic acid ester Combination more than kind or both, the wherein number-average molecular weight of polyisobutene part is 500-5000.
（B）Detersive
Detersive includes but is not limited to alkylsulfonate, sulfoacid calcium, sulfonic acid magnesium such as C8-C30, C6-C40 alkyl phenol calcium, C6- C40 sulfurized alkylphenol calcium, salicylate, calcium salicylate, magnesium salicylate such as C8-C30, calcium naphthenate, and the like and Their mixture.
The detersive is selected from high base number alkyl sulfonic acid, middle basicity alkyl sulfonate, low alkali value alkylsulfonate, high base number Alkyl phenol calcium, SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, middle basicity alkyl phenol calcium, middle base number sulfurized alkylphenol calcium, high base number alkylated salicylamide Group more than one or both of sour calcium, middle basicity alkyl calcium salicylate, overbased calcium alkyl-salicylate, middle base number calcium naphthenate Close, the wherein base number of high base number is 200-450mgKOH/g, and the base number of middle base number is 100-200mgKOH/g, the base number of low alkali value For 10-100mgKOH/g.
（C）Oil-soluble or scattered oil-proofness boron-containing compound
At least one oil-soluble or scattered oil-proofness boracic chemical combination for Lubricant composition for gasoline engine of the present invention Thing includes the dispersant of boration；The friction modifiers of boration；Scattered alkali metal or mixed alkali metal or alkaline-earth metal boron Hydrochlorate, the epoxides of boration, borate, the fatty amine of boration, the acid amides of boration, sulfonate of boration etc., with And their mixture.
The dispersant of boration includes but is not limited to the polyalkenyl butanedioic acid of the ashless dispersant such as boration of boration Acid anhydride；The polyalkylene succinic anhydride of boration not nitrogen containing derivative；The basic nitrogen compound of boration, basic nitrogen compound choosing From succinimide, carboxylic acid amide, hydrocarbyl monoamine, hydrocarbyl polyamine, Mannich base, phosphonic amide, thio phosphonic amide and phosphamide, thiophene Azoles such as 2,5- dimercapto-1,3,4-thiadiazoles, mercaptobenzothiazoler and their derivative, triazole such as alkyl triazole and benzo Triazole, comprising with one or more other polar functional groups（Including amine, acid amides, imines, acid imide, hydroxyl, carboxyl etc.）'s The copolymer of carboxylate, such as by making chain alkyl acrylate or methacrylate and the monomer with above-mentioned functional group It is copolymerized the product prepared；And their analog and mixture.The dispersant of preferred boric acid is that the succimide of boron spreads out The polyisobutene succinimide of biology such as boration.
The friction modifiers of boration include but is not limited to the fat epoxide of boration, the alkoxylate fat of boration Fat amine, the glyceride of boration and their analog and mixture.
The epoxides of boration includes the reaction product by one or more boron compounds and at least one epoxides The epoxides of the boration of acquisition.Suitable boron compound includes boron oxide, boron oxide hydrate, and boron trioxide is borontrifluoride Boron, Boron tribromide, boron chloride, sour such as borinic acid, boric acid, tetraboric acid and the metaboric acid of boron, boron acid amides and boric acid it is each Kind ester.Epoxides is typically to have about 8-30 carbon atom, preferably from about 10-24 carbon atom and more preferably from about 12-20 carbon The aliphatic epoxide of atom.Suitable aliphatic epoxide includes Epoxydodecane, epoxyhexadecane and theirs is similar Thing and mixture.
Borate is included by making one or more above-disclosed boron compounds have appropriate oleophylic with one or more Property alcohol reaction obtain borate.Typically, the alcohol can contain about 6-30 carbon, preferably 8-24 carbon atom.
The fatty amine of boration is included by making one or more above-disclosed boron compounds and one or more fat The fatty amine for the boration that amine reaction of the amine for example with about 14-18 carbon atom obtains.The fatty amine of boration can pass through Make amine with boron compound in about 50-300oC, preferably from about 100-250oAt a temperature of C and with about 3:1-1:3 amine equivalent and boron It is prepared by the reaction of the ratio between compound equivalents.
The acid amides of boration is included by linear or side chain the saturation with about 8-22 carbon atom or unsaturated monovalence fat The acid amides and their analog for the boration that race's acid, urea and the reaction product of polyalkylene polyamine and boronic acid compounds obtain And mixture.
The sulfonate of boration includes the alkaline earth metal sulfonate of the boration by being obtained as below：（a）Deposited in hydrocarbon solvent Make under（i）Oil-soluble sulfonic acid or at least one of alkaline earth sulfonate or their mixture；（ii）At least one alkaline earth gold Category source；（iii）At least one boron source, and（iv）It is 1 anti-to the acid of the parlkaline in addition to boron source less than 10 moles of % relative to boron source Should；And（b）Will（a）The reaction product vapo(u)rizing temperature that is heated to above hydrocarbon solvent temperature it is molten to distill out hydrocarbon from reaction Agent and water.
（D）Oil-soluble or scattered oil-proofness molybdate compound
At least one oil-soluble or scattered oil-proofness chemical combination containing molybdenum for Lubricant composition for gasoline engine of the present invention The representative example of thing includes molybdenum dithiocarbamate；Molybdenum dithiophosphate；Scattered hydration molybdenum compound；Acid molybdenum chemical combination The salt of thing or acidic molybdenum compound；Containing molybdenum complex and their analog and mixture.
Scattered hydration molybdenum compound include scattered hydration polymolybdote, the more alkali metal molybdates of scattered hydration and Their analog and mixture.
Suitable molybdenum dithiocarbamates includes can be used as any dithiocarbamates first of the additive of lubricating oil Sour molybdenum.Suitable molybdenum dithiocarbamate compound includes but is not limited to molybdenum dithiocarbamate, vulcanizes Dipropyl disulfide is for carbamic acid molybdenum, butyl disulfide molybdenum dithiocarbamate, sulfuration diamyl dithiocarbamate molybdenum, Didecyl molybdenum dithiocarbamate, sulfuration dioctyl molybdenum dithiocarbamate, vulcanize didecyl dithiocarbamates first Sour molybdenum, double molybdenum didodecyl dithiophosphate carbamic acid molybdenum of sulfuration, vulcanize double tridecyl molybdenum dithiocarbamate, vulcanization two（Fourth Base phenyl）Molybdenum dithiocarbamate, vulcanization two（Nonyl phenyl）Molybdenum dithiocarbamate, made dithiocarbamates Formic acid oxygen molybdenum, vulcanization dipropyl disulfide butyl disulfide aminodithioformic acid oxygen molybdenum, vulcanize diamyl for carbamic acid oxygen molybdenum Aminodithioformic acid oxygen molybdenum, didecyl aminodithioformic acid oxygen molybdenum, vulcanize dioctyl aminodithioformic acid oxygen molybdenum, Vulcanize didecyl aminodithioformic acid oxygen molybdenum, vulcanize double molybdenum didodecyl dithiophosphate carbamic acid oxygen molybdenums, vulcanize double tridecyl Aminodithioformic acid oxygen molybdenum, vulcanization two（Butyl phenyl）Aminodithioformic acid oxygen molybdenum, vulcanization two（Nonyl phenyl）Two is thio Carbamic acid oxygen molybdenum, alkyl can be straight or branched among all of which, and their analog or mixture.
Suitable molybdenum dithiophosphate includes any molybdenum dithiophosphate that can be used as the additive of lubricating oil.Suitable two D2EHDTPA molybdenum includes dialkyl group or diaryldithiophosphate molybdenum phosphate such as diisopropyl disulfide for molybdenum phosphate, molybdenum two（2- ethyls Hexyl）Molybdenum dithiophosphate, two（Nonyl phenyl）Molybdenum dithiophosphate and their analog and mixture.
Feature containing molybdenum complex can be generally placed upon the molybdenum complex containing basic nitrogen compound or molybdenum/sulfide complex.This The complex compound containing molybdenum/nitrogen used in body is complexing that is as known in the art and being molybdic acid and the molten basic nitrogen compound of oil Thing.
（E）Zinc dialkyl dithiophosphate
Zinc dialkyl dithiophosphate include but is not limited to C2-C20 straight chained alkyl, C2-C20 the alkyl with side chain two One kind or their mixture in D2EHDTPA zinc, addition of the zinc dialkyl dithiophosphate in lubricating oil is with P elements Mass fraction calculate be less than 0.08%.
（F）Antioxidant
Antioxidant includes but is not limited to amine type antioxidant such as diphenylamines, phenyl-α-naphthylamine, N, N- bis-（Alkyl phenyl）Amine and alkyl Change phenylenediamine, phenolic antioxidant such as BHT, steric hindrance phenolic alkyl phenol such as 2,6- di-tert-butylphenols, 2,6- di-t-butyls are to first Phenol and 2,6- di-t-butyls -4-（2- octyl group -3- propionyl）Phenol, vulcanize phenolic ester type antioxidant, thioether-type antioxidant, phenothiazines Antioxidant and their mixture.
（G）Lube base oil
Lube base oil can be selected from mineral oil and synthetic lubricant fluid or their mixture.
The mineral oil in viscosity can from light fraction mineral oil to heavy distillat mineral oil, including saxol and plus Alkane, cycloalkanes and the mixing par-affinic-naphthenic types mineral lubricating oil that hydrogen is refined, solvent is treated, are generally divided into I, II, Group III Base oil, common trade names include I classes 150SN, 600SN, II class 100N, 150N, 500N, Yubase6, Group III 250N Deng.
Synthetic lubricant fluid includes polymerization hydrocarbon ils, alkyl benzene and its derivative, and polymerization hydrocarbon ils includes but is not limited to polybutene, gathered Propylene, propylene-isobutylene copolymers, the polybutene, poly- of chlorination（1- hexenes）, it is poly-（1- octenes）, it is poly-（1- decene）, common business For brand number including PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative includes but is not limited to detergent alkylate, 14 Alkylbenzene, dinonyl benzene, alkylation diphenyl ether and alkylation diphenyl sulfide and its derivative, analog and homologue.
Another suitable type of synthetic lubricant fluid is Esters oil, including dicarboxylic acids（Such as phthalic acid, butanedioic acid, alkyl amber Amber acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, Malonic acid, alkyl malonic acid, alkenyl malonic）With various alcohol（Such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohols, second Glycol, propane diols）The ester or complex ester of condensation reaction generation occurs.These esters include but is not limited to dibutyl adipate, the last of the ten Heavenly stems two Acid two（2- ethylhexyls）The just own ester of ester, fumaric acid two, di-n-octyl sebacate, diisooctyl azelate, azelaic acid two are different Last of the ten Heavenly stems ester, dioctyl phthalate, didecyl phthalate, decanedioic acid two（Eicosyl）The 2- of ester, linoleic acid dimer Ethylhexyl diester.
Another suitable type of synthetic lubricant fluid is fischer tropsch process synthetic hydrocarbon oil and different by being hydrogenated with to this synthetic hydrocarbon oil Structure, the lube base oil that PROCESS FOR TREATMENT obtains such as it is hydrocracked, dewaxes.
The base oil preferred viscosities index is more than 80, saturated hydrocarbon content mass fraction and is more than 90%, sulfur content mass fraction Lube base oil less than 0.03%.
There can also be following other additives in the Lubricant composition for gasoline engine of the present invention：
Antirust agentIt can use and be selected from non-ionic polyoxyalkylene polyalcohol and its ester, polyoxyalkylene phenol anionic alkyl group sulfonic acid, fat Fat race monoacid or polyacid etc., common example include dodecenylsuccinic acid, sorbitan monooleate, D-sorbite Monoleate of acid anhydride three etc..
Pour-point depressantOr make lube oil flow improvers, flow of fluid or the minimum temperature that can be toppled over can be reduced.Allusion quotation Type additive is that alkyl is C8-C18 dialkyl fumarate/vinyl acetate copolymer, poly- alkylmethacrylate etc., Common trade names have T803, VX385 etc..
Viscosity index improver
Suitable viscosity index improver is the copolymer of polyisobutene, ethene and propylene and high alpha-olefin, polymethyl Acid esters/salt, poly- alkylmethacrylate, methacrylate/salt copolymer, unsaturated dicarboxylic and vinyl compound Copolymer, the copolymer of styrene and acrylate, styrene/isoprene, phenylethylene/butadiene and isoprene/fourth two The partially hydrogenated homopolymer of the partially hydrogenated copolymer and butadiene and isoprene/divinylbenzene of alkene, it is common Trade names have LZ7070, LZ7065, LZ7067, LZ7077 of Lubrizol companies, SV260, SV261 of Infineum companies Deng they may be constructed the 0.01%-20% of lubricant oil composite gross mass.
Anti-foaming agentThe polymer of alkyl methacrylate can be selected；The polymer poly siloxanes such as silicon of dimethyl siloxane Oil or dimethyl silicone polymer, and their analog and mixture.
The method of the Lubricant composition for gasoline engine of the present invention prepares as follows：By dispersant, detersive, oil-soluble or Scattered oil-proofness boron-containing compound, oil-soluble or scattered oil-proofness molybdate compound, antioxidant, dialkyl dithio Trbasic zinc phosphate, antirust agent, pour-point depressant, anti-foaming agent and viscosity index improver are added separately in base oil, or additive is mixed Concentrate is made and is then added to heating mixing in base oil, mixing temperature is in 40-90oBetween C, incorporation time 1-6 hours it Between.
The beneficial effects of the invention are as follows：
（1）Contain boron-containing compound, molybdate compound and dialkyl group in the gasoline engine engine oil base oil that the present invention allocates simultaneously Zinc dithiophosphate, the cooperative effect between additive is given full play to, improved the antioxygenic property of lubricant oil composite, resist Antifriction performance and extreme pressure property are ground, so reduces the usage amount of zinc dialkyl dithiophosphate, so as to reduce lubricating oil group Ash content and sulphur phosphorus content in compound；
（2）The gasoline engine engine oil base oil that the present invention allocates has excellent antioxygen property, extends the drain period, has simultaneously Excellent cleansing performance, antiwear and friction reduction property and extreme pressure property；
（3）Production cost of the present invention is low, has good economic benefit and social benefit, and said composition allotment is convenient in addition, property Can be excellent, there is wide popularizing application prospect.
Brief description of the drawings
Fig. 1 is engine oil composition results of property schematic diagram.
Embodiment
Below in conjunction with some embodiments, the present invention is furture elucidated.These embodiments are merely to illustrate the present invention, and do not have to In limitation the scope of the present invention.
In order to screen additive component in lubricating oil, the present invention, which employs various test methods in laboratory and carries out simulation, to be commented It is fixed, wherein there is lubricating oil oxidation stability method of testing（PDSC methods）（SH/T 0719）, lubrication oil antiwear damage performance measurement method（Four Ball machine method）（SH/T 0189）, lubricating oil cleansing performance determination method（Coking tendency experiment）（SH/T 0300）, lubricating oil extreme pressure property Can method of testing（Four-ball tester method）（GB/T 12583）.
Embodiment 1
Lubricant composition for gasoline engine（I）, it includes：
Base oil：150N and 500N in mass ratio 1:The mixture 85.429% of 2 mixing
Dispersant：T154 and T161 in mass ratio 1:The mixture 2.5% of 1 mixing
Detersive：Calcium sulfonate with high base number and middle base number calcium salicylate in mass ratio 3:The mixture 1.8% of 1 mixing
Oil-soluble or scattered oil-proofness boron-containing compound：Boronation succimide 0.5%
Oil-soluble or scattered oil-proofness molybdate compound：Molybdenum succimide 0.3%
Zinc dialkyl dithiophosphate：T209 and T203 in mass ratio 3:The mixture 0.6% of 1 mixing
Antioxidant：Phenolic ester type antioxidant and alkylated diphenylamine in mass ratio 1:3 mixture 0.25%
Antirust agent：T706 0.1%
Pour-point depressant：T602 0.02%
Anti-foaming agent：T921 0.001%
Viscosity index improver：SV261 8.5%
Embodiment 2
Lubricant composition for gasoline engine（II）, it includes：
Base oil：150N and 250N in mass ratio 1:The mixture 85.929% of 4 mixing
Dispersant：T151 and T161 in mass ratio 1:The mixture 3.3% of 1 mixing
Detersive：Calcium sulfonate with high base number and middle base number sulfurized alkylphenol calcium in mass ratio 2:The mixture 1.6% of 1 mixing
Oil-soluble or scattered oil-proofness boron-containing compound：Boronation sulfoacid calcium 0.6%
Oil-soluble or scattered oil-proofness molybdate compound：Molybdenum succimide 0.3%
Zinc dialkyl dithiophosphate：T203 0.5%
Antioxidant：Phenolic ester type antioxidant and alkylated diphenylamine in mass ratio 1:3 mixture 0.25%
Antirust agent：T706 0.1%
Pour-point depressant：1-248 0.02%
Anti-foaming agent：T921 0.001%
Viscosity index improver：7067C 9.0%
Embodiment 3
Lubricant composition for gasoline engine（III）, it includes：
Base oil：150N and 500N in mass ratio 2:The mixture 85.629% of 3 mixing
Dispersant：T154 and T161 in mass ratio 1:The mixture 3.5% of 3 mixing
Detersive：Calcium sulfonate with high base number and middle base number calcium salicylate in mass ratio 2:The mixture 1.8% of 1 mixing
Oil-soluble or scattered oil-proofness boron-containing compound：Boronation succimide 0.6%
Oil-soluble or scattered oil-proofness molybdate compound：Molybdenum succimide 0.5%
Zinc dialkyl dithiophosphate：T209 and T203 in mass ratio 3:The mixture 0.6% of 1 mixing
Antioxidant：Phenolic ester type antioxidant and alkylated diphenylamine in mass ratio 1:3 mixture 0.25%
Antirust agent：T746 0.1%
Pour-point depressant：T602 0.02%
Anti-foaming agent：T921 0.001%
Viscosity index improver：SV260 7.0%
The preparation method of above-mentioned Lubricant composition for gasoline engine, step are as follows：
At room temperature, mixing speed 300rpm is controlled, viscosity index improver is added into base oil, after stirring, adjustment Rotating speed is to 500rpm, then by dispersant, detersive, oil-soluble or scattered oil-proofness boron-containing compound, oil-soluble or disperses Oil-proofness molybdate compound, antioxidant, zinc dialkyl dithiophosphate, antirust agent, pour-point depressant and anti-foaming agent add together, Continue to stir 3h, finished product is obtained after filtering.
The results of property of above-mentioned Lubricant composition for gasoline engine such as Fig. 1.
Described above is only the part preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, under the premise without departing from the principles of the invention, can also make some variations in detail, these variations in detail also should be regarded as this hair Bright protection domain.

Claims (10)

  1. A kind of 1. Lubricant composition for gasoline engine, it is characterised in that：Said composition includes following components：
    （A）Ashless dispersant, the ashless dispersant are selected from polyalkylene succimide, carboxylic acid amide, hydrocarbyl monoamine, alkyl Polyamines, Mannich base, the basic nitrogen compound of phosphonic amide and phosphamide and/or comprising with amine, acid amides, imines, acid imide, hydroxyl The copolymer of the carboxylate of the other polar functional group of one or more of base, carboxyl, contains（A）Component 0.1-6.0wt%；
    （B）Detersive, the detersive are selected from alkylsulfonate, alkyl phenol calcium, sulfurized alkylphenol calcium, alkyl sodium salicylate, ring Combination more than one or both of alkanoic acid calcium, contains（B）Component 0.1-8.0wt%；
    （C）Oil-soluble or scattered oil-proofness boron-containing compound, the oil-soluble or scattered oil-proofness boron-containing compound Friction modifiers, scattered alkali metal or the mixed alkali metal or alkaline-earth metal boric acid of dispersant, boration selected from boration Salt, the epoxides of boration, borate, the fatty amine of boration, the acid amides of boration, boration sulfonate in one kind Or two or more combinations, contain（C）Component 0.01-1.5wt%；
    （D）Oil-soluble or scattered oil-proofness molybdate compound, the oil-soluble or scattered oil-proofness molybdate compound Selected from molybdenum dithiocarbamate, molybdenum dithiophosphate, scattered hydration molybdenum compound, acidic molybdenum compound or acid molybdenum chemical combination The salt of thing, the combination containing one or both of molybdenum complex above, contain（D）Component 0.003-0.5wt%；
    （E）At least one zinc dialkyl dithiophosphate, contains（E）Component 0.02-3.2wt%；
    （F）At least one antioxidant, contains（F）Component 0.01-3.0wt%；
    （G）Major amount of lube base oil；
    The oil-soluble or scattered oil-proofness boron-containing compound and oil-soluble or scattered oil-proofness molybdate compound Boron molybdenum mass ratio is 1:5-10:1.
  2. 2. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The petrol engine lubrication There can also be group more than one or both of antirust agent, pour-point depressant, viscosity index improver, anti-foaming agent in fluid composition Close.
  3. 3. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The ashless dispersant is selected from Combination more than one or both of polyisobutene succinimide, polyisobutene succinic carboxylic acid ester, Mannich base；
    Preferably, polyisobutene succinimide may be selected from single polyisobutene succinimide, double hung in the ashless dispersant Combination more than one or both of polyisobutene succinimide, high molecular weight polyisobutylene succimide is hung, wherein The number-average molecular weight of polyisobutene part is 500-5000；
    Preferably, polyisobutene succinic carboxylic acid ester may be selected from single polyisobutene succinic carboxylic acid ester, double hung in the ashless dispersant Hang one in polyisobutene succinic carboxylic acid ester, more extension polyisobutene succinic carboxylic acid esters, high molecular weight polyisobutylene succinic carboxylic acid ester Combination more than kind or both, the wherein number-average molecular weight of polyisobutene part is 500-5000.
  4. 4. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The detersive is selected from high-alkali It is worth alkyl sulfonic acid, middle basicity alkyl sulfonate, low alkali value alkylsulfonate, high base number alkyl phenol calcium, high base number sulfenyl phenolate Calcium, middle basicity alkyl phenol calcium, middle base number sulfurized alkylphenol calcium, calcium alkyl salicylate with high base number, middle basicity alkyl calcium salicylate are high Combination more than one or both of base number calcium naphthenate, middle base number calcium naphthenate, the wherein base number of high base number is 200- 450mgKOH/g, the base number of middle base number is 100-200mgKOH/g, and the base number of low alkali value is 10-100mgKOH/g, alkyl C5- C40 straight chained alkyl, the C5-C40 alkyl with side chain；
    Preferably, the alkylsulfonate in the detersive is alkyl sulfonic acid calcium and/or alkyl sulfonic acid magnesium.
  5. 5. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The oil-soluble is scattered Oil-proofness boron-containing compound is selected from boration polyisobutene succinimide dispersant, middle base number boration sulfoacid calcium, middle alkali The combination being worth more than one or both of boration sulfonic acid magnesium.
  6. 6. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The oil-soluble is scattered Oil-proofness molybdate compound includes but is not limited to molybdenum dithiocarbamate, molybdenum dithiophosphate, scattered hydration molybdenum chemical combination Thing, the salt of acidic molybdenum compound or acidic molybdenum compound, containing molybdenum complex and their mixtures.
  7. 7. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The dialkyl dithio phosphorus Sour zinc include but is not limited to C2-C20 straight chained alkyl, C2-C20 the alkyl with side chain zinc dithiophosphate in one kind Or their mixture, addition of the zinc dialkyl dithiophosphate in lubricating oil is calculated with the mass fraction of P elements to be less than 0.08%。
  8. 8. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The antioxidant is included but not Be limited to amine type antioxidant, phenolic antioxidant, vulcanization phenolic ester type antioxidant, thioether-type antioxidant, phenothiazines antioxidant and they Mixture；
    Preferably, the antioxidant includes but is not limited to diphenylamines, phenyl-α-naphthylamine, N, N- bis-（Alkyl phenyl）Amine, alkylation Phenylenediamine, BHT, 2,6- di-tert-butylphenols, BHT, 2,6- di-t-butyls -4-（2- octyl group -3- propionyl） Phenol, vulcanization phenolic ester type antioxidant, thioether-type antioxidant, phenothiazines antioxidant and their mixture.
  9. 9. Lubricant composition for gasoline engine according to claim 1, it is characterised in that：The base oil can be selected from Mineral oil and synthetic lubricant fluid or their mixture.
  10. 10. a kind of preparation method of the Lubricant composition for gasoline engine described in any one of claim 1-9, its feature exist In：Dispersant, detersive, oil-soluble or scattered oil-proofness boron-containing compound, oil-soluble or scattered oil-proofness are contained Molybdenum compound, antioxidant, zinc dialkyl dithiophosphate, antirust agent, pour-point depressant, anti-foaming agent and viscosity index improver add respectively Enter into base oil, or additive is mixed and made into concentrate and is then added to heating mixing in base oil, mixing temperature is in 40- 90oBetween C, incorporation time filtering, that is, obtains Lubricant composition for gasoline engine between 1-6 hours.
CN201610686069.3A 2016-08-19 2016-08-19 Lubricant composition for gasoline engine and preparation method thereof Pending CN107760419A (en)

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CN113249160A (en) * 2020-02-13 2021-08-13 中国石油化工股份有限公司 Natural gas engine lubricating oil composition and preparation method thereof
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Application publication date: 20180306