WO2025010987A1 - 一种耐醇型低黏度的润滑油组合物及其应用 - Google Patents

一种耐醇型低黏度的润滑油组合物及其应用 Download PDF

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Publication number
WO2025010987A1
WO2025010987A1 PCT/CN2024/072460 CN2024072460W WO2025010987A1 WO 2025010987 A1 WO2025010987 A1 WO 2025010987A1 CN 2024072460 W CN2024072460 W CN 2024072460W WO 2025010987 A1 WO2025010987 A1 WO 2025010987A1
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lubricating oil
oil composition
agent
composition according
antioxidant
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French (fr)
Inventor
金理力
徐瑞峰
金志良
吕会英
薛卫国
黄卿
刘玉峰
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to DE112024002902.7T priority Critical patent/DE112024002902T5/de
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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
    • 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
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    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • 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
    • C10M2209/084—Acrylate; Methacrylate
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    • 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
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    • 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
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
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    • 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—Overbased sulfonic acid salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/083—Dibenzyl sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/18—Anti-foaming property
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    • C10N2030/72—Extended drain
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the invention belongs to the technical field of lubricating oils, and in particular relates to a lubricating oil composition whose performance meets the lubrication requirements of an M100 methanol passenger car engine.
  • the viscosity level of M100 passenger car methanol oil is 5W-30.
  • the use of oil in cold areas in winter (-36°C) has caused poor cold start performance (no start within 5 seconds) and large start-up wear (the oil has poor fluidity and cannot reach the surface of the machine parts in time to play a lubricating effect).
  • higher requirements are placed on the anti-wear performance of oil products.
  • the object of the present invention is to provide an alcohol-resistant low-viscosity lubricating oil composition and its application, wherein the lubricating oil composition has excellent anti-wear durability and low-temperature cold starting performance.
  • the present invention has systematically studied various types of additives and different types of base oils in the lubricating oil composition, and has comprehensively and systematically studied the interactions and relationships between the various components. How to solve the anti-wear durability of the oil is one of the key goals to be overcome. By effectively combining base oils, extreme pressure anti-wear agents, antioxidants and metal deactivators, etc., the problems of reduced anti-wear performance of lubricating oil in the presence of methanol, formic acid and water and poor low-temperature cold starting performance of methanol engines have been successfully solved.
  • the present invention provides an alcohol-resistant low-viscosity lubricating oil composition, which comprises, based on the total mass of the lubricating oil composition being 100%, 0.6-1.0% of a metal detergent (component A), 6.0-10.0% of an ashless dispersant (component B), 0.5-2.0% of an antioxidant and anti-wear agent (component C), 1.0-2.0% of a metal deactivator (component D), 0.2-1.0% of an extreme pressure and anti-wear agent (component E), 3.0-5.0% of a viscosity index improver (component F, which may also be referred to as a viscosity index improver), 0.1-0.2% of a pour point depressant (component G), 0.001-0.010% of an anti-foaming agent (component H), 30.0-50.0% CTL base oil (component I), and the balance is API III base oil (component J); wherein the antioxidant and anti-wear agent includes alkaline zinc dithiophosphate, amine ashless antioxidant,
  • the alkaline zinc dithiophosphate is basic bis(octyl)alkyl zinc dithiophosphate.
  • the present invention has conducted a lot of research work on different types of antioxidants and anti-wear agents.
  • the antioxidant and anti-wear agent is a mixture of amine ashless antioxidants, phenol ashless antioxidants, and alkaline zinc dithiophosphate.
  • Zinc dithiophosphate has excellent antioxidant, anti-wear and corrosion resistance. It is generally believed that it plays an antioxidant role by capturing free radicals and decomposing hydroperoxides. Due to the characteristics of methanol fuel, the increase of water in the combustion product greatly affects the antioxidant and anti-wear properties of neutral ZDDP.
  • alkaline zinc dithiophosphate such as basic dioctyl alkyl zinc dithiophosphate
  • shows good system stability and wear resistance in the presence of water, alcohol and acid and has good synergistic effect with amine ashless antioxidants and phenol ashless antioxidants, and is particularly suitable for methanol fuel engine oil.
  • Ashless antioxidants can provide hydrogen atoms for peroxide free radicals, destroy or prevent chain growth, and generate low-energy stable free radicals. Ashless antioxidants also have synergistic effects. When phenolic antioxidants and amine antioxidants are used together, they have obvious synergistic effects because phenol helps the regeneration of aromatic amines.
  • the amount of antioxidant and anti-wear agent added in the present invention is limited to 0.5-2.0%, and the preferred suitable range is 0.5-1.8%.
  • the metal deactivator is a mixture of thiadiazole-type metal deactivators and methylbenzotriazole-type metal deactivators.
  • Benzotriazole is an inhibitor of non-ferrous metals copper and silver. It can form chelates with copper and is an effective metal deactivator, but it has poor oil solubility. In order to improve its oil solubility, a derivative of benzotriazole has been developed. It is used in combination with a phenolic antioxidant (2,6-di-tert-butyl-p-cresol) to have an outstanding synergistic effect.
  • Thiadiazole metal deactivators are copper corrosion inhibitors that have the function of trapping active sulfur, thereby playing a metal deactivation role.
  • the present invention limits the amount of metal deactivators to about 1.0-2.0% of the total weight of the lubricating oil composition.
  • sulfide olefin anti-wear agents have high anti-sintering load and good heat resistance, but poor anti-wear performance
  • chlorinated paraffin has good anti-wear and extreme pressure properties and strong activity, but poor stability, easy to cause corrosion, and toxicity
  • nanoparticles have poor solubility and poor stability.
  • the extreme pressure anti-wear agent in the present invention is a thioether type extreme pressure anti-wear agent (such as dibenzyl disulfide, etc.), and its sulfur content is 14.0-15.0%.
  • Sulfide-type organic carboxylic acid esters can also be used as the sulfide-type extreme pressure anti-wear agent of the present application. Since the ester oil molecules have a highly active polar group "ester group", it has a good adsorption effect on the electron-rich metal surface, which is conducive to the spreading and maintenance of the lubricating oil film, has outstanding anti-wear performance, good heat resistance, good thermal stability, and low corrosion, and can effectively solve the problem of traditional anti-wear agent failure caused by methanol, formic acid, and water.
  • the present invention limits the addition amount of the extreme pressure anti-wear agent to 0.2-1.0%, and its preferred suitable range is 0.2-0.8%.
  • the antioxidant and anti-wear agent comprises 40-60% alkaline zinc dithiophosphate, 20-30% amine ashless antioxidant, and 10-20% phenolic ashless antioxidant; among the metal deactivators, the mass ratio of the thiadiazole type metal deactivator to the methylbenzotriazole type metal deactivator is 1:2-2:1.
  • the composition of the lubricating oil composition includes: 0.7-1.0% metal detergent, 6.0-8.0% ashless dispersant, 0.5-1.8% antioxidant and antiwear agent, 1.0-2.0% metal deactivator, 0.2-0.8% extreme pressure antiwear agent, 3.0-5.0% viscosity index agent, 0.1-0.2% pour point depressant, 0.001-0.010% antifoaming agent, 30.0-40.0% CTL base oil, and the balance is API III base oil (preferably 30-60%).
  • the metal detergent includes calcium salt and magnesium salt.
  • the calcium salt includes calcium salicylate and/or calcium sulfonate
  • the magnesium salt includes magnesium salicylate and/or magnesium sulfonate.
  • Sulfonate is used in engine oil, which can neutralize the acidic oxides formed during the use of the engine, and inhibit the oxidation and deterioration of lubricating oil or reduce the generation of high-temperature deposits on the surface of the piston ring area under high temperature conditions, so that the inside of the engine remains clean, and at the same time, the non-oil-soluble colloid or oxide element generated by the oxidation of lubricating oil and incomplete combustion of fuel can be solubilized in the oil, thereby inhibiting the tendency of forming deposits such as paint film, carbon deposition, and sludge.
  • Alkyl salicylate is to introduce carboxyl groups on alkylphenols, and transfer the metal from the hydroxyl position to the carboxyl position. This conversion makes its molecular polarity extremely strong, and the high-temperature detergency is greatly improved. It has good high-temperature detergency, certain low-temperature dispersion, anti-oxidation and anti-corrosion, extreme pressure and anti-wear, and good synergy with other agents. The compounding of different types of detergents can bring into play the synergistic effect of additives. In addition to ensuring that the oil has a certain alkalinity to neutralize acidic substances, it can also have good detergency, rust resistance and low sulfate ash.
  • the metal detergent accounts for about 0.6-1.0% of the total weight of the composition, and its preferred suitable range is 0.7-1.0%. If the amount is too small, the detergency of the oil will decrease, the alkalinity will be low, and the service life of the lubricant will be shortened. If the amount is too large, the ash content of the lubricant will increase, the frequency of low-speed pre-ignition will increase, and the role of other functional additives will be affected, and there will be no other beneficial effects.
  • the ashless dispersant includes polyisobutylene succinimide, more preferably a high nitrogen high base number polymer polyisobutylene succinimide, whose nitrogen content is 1.8-2.2% and the base number is 46-55 mgKOH/g.
  • Ashless dispersant is a surfactant, which is mainly used to disperse pollutants generated in the engine to ensure that the oil can flow freely. The dispersibility of ashless dispersant can help keep the engine clean, and in some cases, it helps to maintain the cleanliness of the piston. Different types of dispersants have different dispersing effects on sludge and sediments.
  • High base number polymer dispersants generally have a better dispersing effect on sediments generated at high temperatures, while general molecular weight dispersants have a better dispersing effect on sludge generated at low temperatures.
  • the ashless dispersant of the present invention is selected from high nitrogen content and base number polymer polyisobutylene succinimide, which, in addition to having a better dispersing effect, can also assist in reducing the performance decay of ZDDP, cooperate with the anti-wear effect of extreme pressure anti-wear agents, and increase the base number inventory of engine oil.
  • the ashless dispersant accounts for about 6.0-10.0% of the total weight of the composition, and the preferred suitable range is 6.0-8.0%.
  • the amount is too small, the dispersibility of the oil will be reduced, the surface deposits of the engine parts will increase, and the sludge in the oil pan will be thicker. If the amount is too large, the additive will be wasted and the effect of other functional additives in the lubricating oil will be affected, and there will be no other beneficial effects.
  • the viscosity modifier includes ethylene propylene copolymer, such as RHY615, 9230F, etc.
  • the performance of the lubricating oil is closely related to the type and shear stability of the viscosity modifier.
  • the viscosity modifier of the present invention preferably uses an ethylene propylene copolymer with a shear index of 20.
  • the viscosity modifier of the present invention accounts for about 3.0-5.0% of the total weight of the composition. If the amount is too small, the viscosity will be low, the thickness and stability of the oil film will decrease, and the anti-wear performance of the oil will be reduced in actual use. If the amount is too large, the additive will be wasted, the viscosity of the oil will be too large, and the low temperature performance and cleaning performance will be reduced, and there will be no other beneficial effects.
  • the pour point depressant includes polymethacrylate.
  • the addition of the pour point depressant will reduce the pour point of the lubricating oil and improve the use effect of the oil product in a low temperature environment.
  • the present invention does not specifically limit the amount of the pour point depressant, which is usually 0.1-0.2% of the total mass of the lubricating oil composition. If the value is less than 0.1%, the amount is too small, which will cause the pour point of the lubricating oil to fail to meet the standard requirements and affect the fluidity in a low temperature environment.
  • the antifoaming agent includes dimethyl silicone oil.
  • the antifoaming agent can reduce the phenomenon of foaming of the lubricating oil due to mechanical stirring during actual use, and avoid the problem of oil film rupture and wear of engine parts caused by the generation of a large amount of foam during use.
  • the present invention does not specifically limit the amount of antifoaming agent, which is usually 0.001-0.010% of the total mass of the lubricating oil composition. If the value is lower than 0.001%, the amount is too little, which will cause a decrease in antifoaming properties. If the value is higher than 0.010%, the amount is too much, which will result in a waste of additives and no other beneficial effects.
  • the CTL base oil is a coal-derived synthetic oil having a kinematic viscosity at 100° C. of 3.8-4.2 mm 2 /s, more preferably 4 mm 2 /s.
  • the API III base oil is an API III hydrocracked base oil having a kinematic viscosity at 100° C. of 3.8-4.3 mm 2 /s, more preferably 4 mm 2 /s.
  • the lubricating oil composition has a sulfur content of 0.20-0.30wt%, a phosphorus content of 0.06-0.07wt%, an alkali number of 9.0-11.0mgKOH/g, a sulfated ash content of 0.4-0.6wt%, and a four-ball wear spot diameter of the lubricating oil composition after a 120-hour endurance test of an M100 methanol engine in accordance with NB/SH/T 0189 is less than 0.8mm, and the methanol engine can be started within 3.5 seconds at -36°C.
  • the base oils mentioned above are two high viscosity index base oil compositions whose performance meets the requirements of API Group III base oil standards.
  • the present invention also provides application of the lubricating oil composition in an M100 methanol passenger car engine.
  • the present invention based on the action mechanism of additives, systematically and complicatedly screens and optimizes compounding of additives of different types and additives of the same type but with different compositions through a variety of simulation test methods, finally solves the key technical problems through laboratory simulation tests and M100 methanol engine durability tests, improves the synergistic effect between additives by introducing and adjusting the types and proportions of additives, and has better anti-wear performance and low-temperature cold starting performance compared with existing commercial products, meets the lubrication requirements of the M100 methanol engine, shows better anti-wear durability in the M100 methanol engine durability test, has better low-temperature cold starting performance in severely cold areas, and solves the use requirements of low viscosity and long oil change period of methanol engine oil.
  • Figure 1 is a photo of the piston pressure surface
  • Figure 2 is a photo of the non-pressure bearing surface of the piston
  • Figure 3 is a photo of the oil pan.
  • the present invention uses PDSC (induction period), wear spot diameter, low temperature dynamic viscosity and other test methods in the laboratory to evaluate the oxidation stability, wear resistance and low temperature fluidity of the oil.
  • the simulation test conditions are: PDSC oxidation induction period setting temperature 210°C, template diameter 392N, low temperature dynamic viscosity test temperature -35°C.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a lubricating oil composition, the raw materials used for 100 kg of the lubricating oil composition and their masses are:
  • High molecular weight polyisobutylene succinimide (base value 46 mgKOH/g, nitrogen content 1.8%) 8.0 Kg;
  • Dibenzyl disulfide antiwear agent (sulfur content is 14%) 0.8Kg;
  • Ethylene-propylene copolymer viscosity modifier (RHY615) 4.0Kg;
  • Dimethyl silicone antifoaming agent 0.005Kg
  • API III hydrogenated base oil (100°C viscosity 3.8-4.3mm 2 /s) 42.195Kg;
  • the sulfur content of the lubricating oil composition of this embodiment is 0.28%, and the phosphorus content is 0.067%.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a lubricating oil composition, the raw materials used for 100 kg of the lubricating oil composition and their masses are:
  • High molecular weight polyisobutylene succinimide (base value 48 mgKOH/g, nitrogen content 1.8%) 10.0 Kg;
  • Dibenzyl disulfide antiwear agent (sulfur content is 14%) 0.5Kg;
  • Ethylene-propylene copolymer viscosity modifier (9230F) 4.0Kg;
  • Dimethyl silicone antifoaming agent 0.005Kg
  • API III hydrogenated base oil (100°C viscosity 3.8-4.3mm 2 /s) 40.395Kg;
  • the sulfur content of the lubricating oil composition of this embodiment is 0.27%, and the phosphorus content is 0.070%.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • This embodiment provides a lubricating oil composition, the raw materials used for 100 kg of the lubricating oil composition and their masses are:
  • the alkyl magnesium salicylate with a base number of 400 in the above Example 2 is replaced by magnesium sulfonate with a base number of 395-430, and the other components are of the same quality.
  • the sulfur content of the lubricating oil composition of this example is 0.30%, and the phosphorus content is 0.068%.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • This embodiment provides a lubricating oil composition, the raw materials used for 100 kg of the lubricating oil composition and their masses are:
  • High molecular weight polyisobutylene succinimide (base value 47 mgKOH/g, nitrogen content 2.1%) 6.0 Kg;
  • Dibenzyl disulfide antiwear agent (sulfur content is 14%) 0.6Kg;
  • Ethylene-propylene copolymer viscosity modifier (RHY615) 5.0Kg;
  • Dimethyl silicone antifoaming agent 0.006Kg
  • API III hydrogenated base oil (100°C viscosity 3.8-4.3mm 2 /s) 34.394Kg;
  • the sulfur content of the lubricating oil composition of this embodiment is 0.22%, and the phosphorus content is 0.066%.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • This embodiment provides a lubricating oil composition, the raw materials used for 100 kg of the lubricating oil composition and their masses are:
  • High molecular weight polyisobutylene succinimide (base value 46 mgKOH/g, nitrogen content 1.8%) 7.0 Kg;
  • Dibenzyl disulfide antiwear agent (sulfur content is 14%) 0.8Kg;
  • Ethylene-propylene copolymer viscosity modifier (9230F) 4.0Kg;
  • Dimethyl silicone antifoaming agent 0.005Kg
  • API III hydrogenated base oil (100°C viscosity 3.8-4.3mm 2 /s) 38.695Kg;
  • the sulfur content of the lubricating oil composition of this embodiment is 0.26%, and the phosphorus content is 0.071%.
  • This comparative example provides a lubricating oil composition, the raw materials used for 100 kg of which and their masses are:
  • Example 1 The basic bis-octyl zinc thiophosphate in Example 1 was replaced by secondary alkyl zinc thiophosphate with a sulfur-to-phosphorus ratio of 2.1, and the other components were of the same quality.
  • the sulfur content of the lubricating oil composition of this comparative example was 0.35%, and the phosphorus content was 0.080%.
  • This comparative example provides a lubricating oil composition, the raw materials used for 100 kg of which and their masses are:
  • Example 1 The basic bis-octyl zinc sulfide in Example 1 was replaced by secondary alkyl zinc sulfide with a sulfur-phosphorus ratio of 2.1, the high molecular weight polyisobutylene succinimide was replaced by a boronized succinimide dispersant with a base value of 16, and the other components were of the same quality.
  • the lubricating oil composition of this comparative example had a sulfur content of 0.33% and a phosphorus content of 0.081%.
  • This comparative example provides a lubricating oil composition, the raw materials used for 100 kg of which and their masses are:
  • the CTL base oil in the above Example 1 was replaced with API III hydrogenated base oil (100° C. viscosity 5.8-6.2 mm 2 /s), and the other components were of the same quality.
  • the sulfur content of the lubricating oil composition of this comparative example was 0.28%, and the phosphorus content was 0.070%.
  • the lubricating oil of the present invention has good antioxidant and wear resistance in the PDSC oxidation induction period and wear spot diameter simulation test evaluation.
  • the wear spot diameter of the engine oil is below 0.8 mm, which is better than the wear spot diameter result of the commercial methanol engine oil after 100 hours of endurance test.
  • the -35°C low-temperature dynamic viscosity test it showed excellent low-temperature fluidity.
  • Example 1 completed the low-temperature cold start test of methanol automobile within 5s at an outdoor temperature of -36°C, and achieved the use effect of starting within 3.5 seconds.
  • Comparative Examples 1 and Comparative Examples 2 did not use alkaline zinc dithiophosphate (basic dioctyl alkyl zinc salt of sulfur phosphorus), although the PDSC performance of the engine oil was similar, but the anti-wear performance of the engine oil was significantly reduced after mixing with water, methanol and formic acid, and in Comparative Example 2, when high nitrogen high base number polymer polyisobutylene succinimide was not used, the wear test even showed serious results of biting.
  • Comparative Example 3 does not use CTL4 base oil, resulting in a significant decrease in the low-temperature fluidity of the engine oil, and the excellent low-temperature fluidity effect of the present invention cannot be achieved.
  • the lubricating oil composition of the present invention exhibited excellent detergency, dispersibility and anti-wear properties in the methanol engine test.

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Abstract

一种耐醇型低黏度的润滑油组合物及其应用，其中润滑油组合物的组成包括：0.6-1.0％金属清净剂、6.0-10.0％无灰分散剂、0.5-2.0％抗氧抗磨剂、1.0-2.0％金属减活剂、0.2-1.0％极压抗磨剂、3.0-5.0％黏指剂、0.1-0.2％降凝剂、0.001-0.010％抗泡剂、30.0-50.0％CTL基础油、余量为APIⅢ类基础油。润滑油组合物具有优异的抗磨耐久性和低温冷启动性。

Description

一种耐醇型低黏度的润滑油组合物及其应用 技术领域
本发明属于润滑油技术领域，具体涉及一种性能满足M100甲醇乘用车发动机润滑要求的润滑油组合物。
背景技术
目前M100乘用车甲醇机油产品黏度级别是5W-30，随着甲醇机油推广面的扩大，在寒冷地区冬季(-36℃)用油出现了冷启动性差(5s内不启动)，启动磨损大的问题(机油流动性差，不能及时到达机件表面起到润滑效果)。同时，为满足机油换油里程进一步延长的需求，对油品的抗磨性能有了更高要求。
发明内容
为了解决上述问题，本发明的目的在于提供一种耐醇型低黏度的润滑油组合物及其应用，该润滑油组合物具有优异的抗磨耐久性和低温冷启动性。
为了达到上述目的，本发明对润滑油组合物中的各类型添加剂和不同类型基础油进行了系统研究，并对各组分间的相互作用和关系进行了全面系统地研究，把如何解决油品抗磨持久性作为重点攻克目标之一，通过有效组合基础油、极压抗磨剂、抗氧抗磨剂、金属减活剂等，成功解决了润滑油在甲醇、甲酸、水存在下的抗磨性能下降和甲醇发动机低温冷启动性差的问题。
本发明提供了一种耐醇型低黏度的润滑油组合物，以该润滑油组合物的总质量为100％计算，其组成包括：0.6-1.0％金属清净剂(组分A)、6.0-10.0％无灰分散剂(组分B)、0.5-2.0％抗氧抗磨剂(组分C)、1.0-2.0％金属减活剂(组分D)、0.2-1.0％极压抗磨剂(组分E)、3.0-5.0％黏指剂(组分F，也可称为黏度指数改进剂)、0.1-0.2％降凝剂(组分G)、0.001-0.010％抗泡剂(组分H)、30.0-50.0％CTL基础油(组分I)、余量为APIⅢ类基础油(组分J)；其中，所述抗氧抗磨剂包括碱性二硫代磷酸锌、胺类无灰抗氧剂、酚类无灰抗氧剂；所述金属减活剂包括噻二唑型金属减活剂和甲基苯三唑型金属减活剂；所述极压抗磨剂包括硫醚型极压抗磨剂；所述抗氧抗磨剂中，所述碱性二硫代磷酸锌的硫磷比为1.8-1.9，锌磷比为1.1-1.2；所述极压抗磨剂中，所述硫醚型极压抗磨剂的硫含量为14.0-15.0％。
根据本发明的具体实施方案，优选地，所述碱性二硫代磷酸锌为碱式硫磷双辛伯烷基锌盐。
本发明对不同类型的抗氧抗磨剂进行了大量的研究工作，抗氧抗磨剂为胺类无灰抗氧剂、酚类无灰抗氧剂、碱性二硫代磷酸锌的混合物。二硫代磷酸锌具有优良的抗氧、抗磨、抗腐蚀性能，一般认为是通过捕捉自由基和分解氢过氧化物来起到抗氧作用的，因甲醇燃料的特性，燃烧产物水的增多大大影响了中性ZDDP的抗氧抗磨性，经试验室研究，碱性二硫代磷酸锌例如碱式硫磷双辛伯烷基锌盐，在水、醇、酸存在下，表现出了较好的体系稳定性和抗磨损性，且与胺类无灰抗氧剂、酚类无灰抗氧剂有较好的协同效果，特别适用于甲醇燃料发动机油。无灰抗氧剂可以为过氧化物自由基提供氢原子，破坏或阻止链的增长，同时生成低能态稳定的自由基，无灰抗氧剂间也存在协同效应，其酚类抗氧剂与胺类抗氧剂共同使用时具有明显的协合效应，因为酚有助于芳胺的再生。本发明对抗氧抗磨剂的加量限定为0.5-2.0％，其优选的适宜范围为0.5-1.8％。
油品在使用过程中，由于有氧存在，受热、光的作用，使油品氧化变质，若润滑油中含有金属，如铜、铁等，这些金属特别是金属离子会加速油品的氧化速度，生成酸、油泥和沉淀，使金属部件产生腐蚀、磨损。为了避免金属离子对润滑油的自动氧化的催化加速作用，本发明对不同类型的金属减活剂进行了大量的筛选和复配工作，金属减活剂为噻二唑型金属减活剂和甲基苯三唑型金属减活剂的混合物。苯三唑是有色金属铜和银的抑制剂，它能与铜生成鳌合物，是有效的金属减活剂，但油溶性差，为了改善其油溶性，发展了苯三唑的衍生物，其与酚型抗氧剂(2,6-二叔丁基对甲酚)复合使用，有突出的增效作用。噻二唑型金属减活剂是铜的腐蚀抑制剂，具有捕集活性硫的作用，从而起到金属减活作用，含有二硫键，可在金属表面形成硫化膜，抑制金属对油品的氧化催化作用，大幅度提高氧化寿命，改善水解安定性。本发明对金属减活剂的加量限定约占润滑油组合物总重量的1.0-2.0％。
为使组合物具备优异的抗磨性能，不同类型的抗磨剂间如何取舍及加入比例的复配非常关键。例如硫化烯烃抗磨剂抗烧结负荷高，耐热性好，但抗磨性能差；氯化石蜡抗磨性、极压性好，活性强，但稳定性差，易引起腐蚀，有毒性；磷酸酯胺盐抗磨剂性能越好，但其热稳定性越差；纳米颗粒存在溶解性不佳，稳定性差的问题。本发明中极压抗磨剂为一种硫醚型极压抗磨剂(例如二苄基二硫醚等)，其硫含量在14.0-15.0％。硫醚型有机羧酸酯也可作为本申请的硫醚型极压抗磨剂，其由于酯类油分子中存在具有较高活性的极性基团“酯基”，它对富电子的金属表面有良好的吸附作用，有利于润滑油膜的铺展和保持，抗磨性能突出，耐热性好，热稳定性好，腐蚀性低，可有效解决因甲醇、甲酸、水带来的传统抗磨剂失效问题。本发明对极压抗磨剂的加量限定0.2-1.0％，其优选的适宜范围为0.2-0.8％。
根据本发明的具体实施方案，优选地，以所述抗氧抗磨剂质量为100％计算，所述抗氧抗磨剂包括40-60％碱性二硫代磷酸锌、20-30％胺类无灰抗氧剂、10-20％酚类无灰抗氧剂；所述金属减活剂中，噻二唑型金属减活剂和甲基苯三唑型金属减活剂的质量比为1:2-2:1。
根据本发明的具体实施方案，优选地，所述润滑油组合物的组成包括：0.7-1.0％金属清净剂、6.0-8.0％无灰分散剂、0.5-1.8％抗氧抗磨剂、1.0-2.0％金属减活剂、0.2-0.8％极压抗磨剂、3.0-5.0％黏指剂、0.1-0.2％降凝剂、0.001-0.010％抗泡剂、30.0-40.0％CTL基础油、余量为APIⅢ类基础油(优选为30-60％)。
根据本发明的具体实施方案，优选地，所述金属清净剂包括钙盐和镁盐。
根据本发明的具体实施方案，优选地，所述钙盐包括水杨酸钙和/或磺酸钙，所述镁盐包括水杨酸镁和/或磺酸镁。磺酸盐用于发动机油中，能够中和发动机使用过程形成的酸性氧化物，并在高温条件下抑制润滑油氧化变质或减少活塞环区表面高温沉积物的生成，使发动机内部保持清净，同时可使润滑油氧化及燃料不完全燃烧所生成的非油溶性胶质或氧化物单质增溶于油内，从而抑制生成漆膜、积碳、和油泥等沉积物的倾向。烷基水杨酸盐是在烷基酚上引入羧基，并将金属由羟基位置转到羧基位置，这种转变使得其分子极性极强，高温清净性大为提高，具有良好的高温清净性，一定的低温分散、抗氧化抗腐蚀、极压抗磨及与其它剂具有良好的协合作用等特点。不同种类的清净剂复配，可发挥添加剂协同效果，在保证油品具备一定的碱值来中和酸性物质外，还能具有较好的清净性、防锈性和低的硫酸盐灰分。本发明中金属清净剂约占组合物总重量的0.6-1.0％，其优选的适宜范围为0.7-1.0％。用量过少，会造成油品清净性能下降，碱值偏低，润滑油使用寿命缩短的后果，用量过多，会使润滑油灰分升高，增大低速早燃出现的频次，影响其他功能添加剂的作用发挥，且无其他有益效果。
根据本发明的具体实施方案，优选地，所述无灰分散剂包括聚异丁烯丁二酰亚胺，更优选为高氮高碱值高分子聚异丁烯丁二酰亚胺，其氮含量为1.8-2.2％，碱值为46-55mgKOH/g。无灰分散剂是一种表面活性剂，主要是用来分散发动机中产生的污染物，以确保油品能够自由地流动。无灰分散剂的分散性可以帮助发动机保持清洁，并且在某些情况下，有助于维持活塞的清洁。不同种类的分散剂对油泥和沉积物的分散效果各不相同，高碱值高分子类分散剂一般对高温下生成的沉积物具有较好的分散效果，而一般分子量的分散剂对低温下生成的油泥分散效果更好。本发明无灰分散剂选用的为较高氮含量和碱值的高分子聚异丁烯丁二酰亚胺，除了具有更好的分散效果外，也能辅助降低ZDDP的性能衰败，协同极压抗磨剂的抗磨效果，增大机油的碱值存量。无灰分散剂约占组合物总重量的6.0-10.0％，其优选的适宜范围为6.0-8.0％。用量过少，会造成油品分散性能下降，发动机机件表面沉积物增多，油底壳油泥较厚的后果，用量过多，会造成添加剂浪费，且影响到润滑油中其他功能添加剂的效果，且无其他有益效果。
根据本发明的具体实施方案，优选地，所述黏指剂包括乙烯丙烯共聚物，例如RHY615、9230F等。润滑油的性能与黏指剂的类型及剪切稳定性都息息相关，本发明的黏指剂优选选用剪切指数为20的乙烯丙烯共聚物。本发明黏指剂约占组合物总重量的3.0-5.0％。用量过少，会造成黏度较低，油膜厚度及稳定性能下降，在实际使用中油品抗磨性能降低的后果，用量过多，会造成添加剂浪费，使油品黏度偏大，造成低温性能和清净性能下降的后果，且无其他有益效果。
根据本发明的具体实施方案，优选地，所述降凝剂包括聚甲基丙烯酸酯。降凝剂的加入会降低润滑油的倾点，提高油品在低温环境下的使用效果。本发明对降凝剂的加量不作特别的限定，通常为润滑油组合物总质量的0.1-0.2％，如果该值低于0.1％，则用量过少，会造成润滑油倾点不满足标准要求，影响低温环境下的流动性。
根据本发明的具体实施方案，优选地，所述抗泡剂包括二甲基硅油。抗泡剂可降低润滑油在实际使用过程中因机械搅拌生成泡沫的现象，避免在使用中因生成大量泡沫造成发动机机件部分油膜破裂发生磨损的问题。本发明对抗泡剂的加量不作特别的限定，通常为润滑油组合物总质量的0.001-0.010％，如果该值低于0.001％，则用量过少，会造成抗泡性下降，如果该值高于0.010％，则用量过多，会造成添加剂浪费的后果，且无其他有益效果。
根据本发明的具体实施方案，优选地，所述CTL基础油为100℃运动黏度是3.8-4.2mm2/s的煤制合成油，更优选为4mm2/s。
根据本发明的具体实施方案，优选地，所述APIⅢ类基础油为100℃运动黏度是3.8-4.3mm2/s的APIⅢ类加氢裂化基础油，更优选为4mm2/s。
根据本发明的具体实施方案，优选地，所述润滑油组合物的硫含量为0.20-0.30wt％，磷含量为0.06-0.07wt％，碱值为9.0-11.0mgKOH/g，硫酸盐灰分为0.4-0.6wt％，在M100甲醇发动机依照NB/SH/T 0189进行120小时耐久试验结束后润滑油组合物的四球磨斑直径在0.8mm以下，在-36℃下3.5秒内启动甲醇发动机。
根据本发明的具体实施方案，优选地，以上涉及的基础油为性能满足APIⅢ类基础油标准要求的两种高黏度指数基础油组合物。
本发明还提供了上述润滑油组合物在M100甲醇乘用车发动机中的应用。
本发明在基于添加剂作用机理的基础上，通过多种模拟试验手段，对不同类型添加剂间及同种类型不同组成的添加剂间进行了系统繁杂的筛选和优化复配，通过实验室模拟试验、M100甲醇发动机耐久试验测试最终解决了关键技术难题，通过引入和调整添加剂类型及比例，提高了添加剂间的协同效应，与现有市售产品相比，具有更优的抗磨性能、低温冷启动性能，满足M100甲醇发动机润滑要求，在M100甲醇发动机耐久性试验中表现出了更优异的抗磨耐久性，在严寒地区的低温冷启动性更优，解决了甲醇机油低黏度和长换油期使用需求。
附图说明
图1为活塞承压面照片；
图2为活塞非承压面照片；
图3为油底壳照片。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
为了筛选基础油和添加剂组分，本发明在实验室采用了PDSC(诱导期)、磨斑直径、低温动力黏度等试验方法，分别评价油品的氧化安定性、抗磨损性和低温流动性。模拟试验条件分别是：PDSC氧化诱导期设定温度210℃，模板直径为392N、低温动力黏度测试温度-35℃。
实施例1：
本实施例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
碱值为265-295的水杨酸钙0.5Kg；
碱值为395-430的磺酸镁0.5Kg；
高分子聚异丁烯丁二酰亚胺(碱值46mgKOH/g，氮含量1.8％)8.0Kg；
碱式硫磷双辛伯烷基锌盐(硫磷比1.80，锌磷比1.1)0.9Kg；
对,对-二异辛基二苯胺和酯型受阻酚(VANLUBE BHC)的混合物(质量比1:1)1.0Kg；
N,N-二(2-乙基己基)-甲基-1H-苯并三唑-1-甲胺和2,5-二巯基-1,3,4-噻二唑的混合物(质量比1:1)1.8Kg；
二苄基二硫醚抗磨剂(硫含量为14％)0.8Kg；
乙丙共聚物黏指剂(RHY615)4.0Kg；
聚甲基丙烯酸酯0.2Kg；
二甲基硅油抗泡剂0.005Kg；
CTL基础油(100℃黏度3.8-4.2mm2/s)40.0Kg；
APIⅢ类加氢基础油(100℃黏度3.8-4.3mm2/s)42.195Kg；
本实施例润滑油组合物的硫含量为0.28％，磷含量为0.067％。
实施例2：
本实施例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
碱值为320-360的水杨酸钙0.5Kg；
碱值为400的烷基水杨酸镁0.4Kg；
高分子聚异丁烯丁二酰亚胺(碱值48mgKOH/g，氮含量1.8％)10.0Kg；
碱式硫磷双辛伯烷基锌盐(硫磷比1.9，锌磷比1.1)1.0Kg；
对,对-二异辛基二苯胺和酯型受阻酚(VANLUBE BHC)的混合物(质量比1:1)1.0Kg；
N,N-二(2-乙基己基)-甲基-1H-苯并三唑-1-甲胺和2,5-二巯基-1,3,4-噻二唑混合物(质量比1:1)2.0Kg；
二苄基二硫醚抗磨剂(硫含量为14％)0.5Kg；
乙丙共聚物黏指剂(9230F)4.0Kg；
聚甲基丙烯酸酯0.2Kg；
二甲基硅油抗泡剂0.005Kg；
CTL基础油(100℃黏度3.8-4.2mm2/s)40.0Kg；
APIⅢ类加氢基础油(100℃黏度3.8-4.3mm2/s)40.395Kg；
本实施例润滑油组合物的硫含量为0.27％，磷含量为0.070％。
实施例3：
本实施例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
将上述实施例2中的碱值为400的烷基水杨酸镁用碱值为395-430的磺酸镁替换，其它组分与质量相同。本实施例润滑油组合物的硫含量为0.30％，磷含量为0.068％。
实施例4：
本实施例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
碱值为265-295的水杨酸钙0.7Kg；
碱值为395-430的磺酸镁0.3Kg；
高分子聚异丁烯丁二酰亚胺(碱值47mgKOH/g，氮含量2.1％)6.0Kg；
碱式硫磷双辛伯烷基锌盐(硫磷比1.8，锌磷比1.1)1.0Kg；
对,对-二异辛基二苯胺和酯型受阻酚(VANLUBE BHC)的混合物(质量比1:1)0.8Kg；
N,N-二(2-乙基己基)-甲基-1H-苯并三唑-1-甲胺和2,5-二巯基-1,3,4-噻二唑的混合物(质量比1:1)1.0Kg；
二苄基二硫醚抗磨剂(硫含量为14％)0.6Kg；
乙丙共聚物黏指剂(RHY615)5.0Kg；
聚甲基丙烯酸酯0.2Kg；
二甲基硅油抗泡剂0.006Kg；
CTL基础油(100℃黏度3.8-4.2mm2/s)50.0Kg；
APIⅢ类加氢基础油(100℃黏度3.8-4.3mm2/s)34.394Kg；
本实施例润滑油组合物的硫含量为0.22％，磷含量为0.066％。
实施例5：
本实施例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
碱值为320-360的水杨酸钙0.3Kg；
碱值为400的烷基水杨酸镁0.6Kg；
高分子聚异丁烯丁二酰亚胺(碱值46mgKOH/g，氮含量1.8％)7.0Kg；
碱式硫磷双辛伯烷基锌盐(硫磷比1.8，锌磷比1.1)1.0Kg；
对,对-二异辛基二苯胺和酯型受阻酚(VANLUBE BHC)的混合物(质量比1:1)1.0Kg；
N,N-二(2-乙基己基)-甲基-1H-苯并三唑-1-甲胺和2,5-二巯基-1,3,4-噻二唑混合物(质量比1:1)1.5Kg；
二苄基二硫醚抗磨剂(硫含量为14％)0.8Kg；
乙丙共聚物黏指剂(9230F)4.0Kg；
聚甲基丙烯酸酯0.1Kg；
二甲基硅油抗泡剂0.005Kg；
CTL基础油(100℃黏度3.8-4.2mm2/s)45.0Kg；
APIⅢ类加氢基础油(100℃黏度3.8-4.3mm2/s)38.695Kg；
本实施例润滑油组合物的硫含量为0.26％，磷含量为0.071％。
对比例1：
本对比例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
将上述实施例1中的碱式硫磷双辛伯烷基锌盐用硫磷比为2.1的硫磷仲烷基锌盐替代，其它组分与质量相同。本对比例润滑油组合物的硫含量为0.35％，磷含量为0.080％。
对比例2：
本对比例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
将上述实施例1中的碱式硫磷双辛伯烷基锌盐用硫磷比为2.1的硫磷仲烷基锌盐替代，高分子聚异丁烯丁二酰亚胺替代为碱值为16的硼化丁二酰亚胺分散剂，其它组分与质量相同。本对比例润滑油组合物的硫含量为0.33％，磷含量为0.081％。
对比例3：
本对比例提供一种润滑油组合物，其100Kg所用的原料及其质量为：
将上述实施例1中的CTL基础油替换为APIⅢ类加氢基础油(100℃黏度5.8-6.2mm2/s)，其它组分与质量相同。本对比例润滑油组合物的硫含量为0.28％，磷含量为0.070％。
为验证本发明的效果，采用本发明实施例制备的发动机润滑油进行了实验室模拟性能评价和发动机台架试验，试验结果见表1：
1、润滑油组合物实验室性能评价
表1润滑油组合物性能评价结果

由表1数据可以看出，本发明润滑油在PDSC氧化诱导期、磨斑直径模拟试验评价中有较好的抗氧化性和抗磨损性，在120小时M100甲醇发动机耐久试验后，机油磨斑直径在0.8mm以下，优于市售甲醇机油100小时耐久试验后磨斑直径结果。在-35℃低温动力黏度测试中表现出了优异的低温流动性，实施例1完成了室外温度-36℃下甲醇汽车5s内低温冷启动试验，达到了3.5秒内启动的使用效果。对比例1和对比例2因没有使用碱性二硫代磷酸锌(碱式硫磷双辛伯烷基锌盐)，虽然机油PDSC性能相近，但在混入水、甲醇和甲酸后机油的抗磨性能均出现了明显下降，且在对比例2中不使用高氮高碱值高分子聚异丁烯丁二酰亚胺的情况下磨损试验甚至出现了卡咬的严重结果。对比例3没有使用CTL4基础油，导致机油低温流动性下降显著，不能达到本发明优异的低温流动性的效果。
2、实施例1润滑油组合物发动机台架试验后拆检情况
由发动机拆检后如图1-图3，本发明润滑油组合物在甲醇发动机试验中表现出了优异的清净分散、抗磨损性。

Claims (15)

  1. 一种耐醇型低黏度的润滑油组合物，以该润滑油组合物的总质量为100％计算，其组成包括：
    0.6-1.0％金属清净剂、6.0-10.0％无灰分散剂、0.5-2.0％抗氧抗磨剂、1.0-2.0％金属减活剂、0.2-1.0％极压抗磨剂、3.0-5.0％黏指剂、0.1-0.2％降凝剂、0.001-0.010％抗泡剂、30.0-50.0％CTL基础油、余量为APIⅢ类基础油；
    其中，所述抗氧抗磨剂包括碱性二硫代磷酸锌、胺类无灰抗氧剂、酚类无灰抗氧剂；
    所述金属减活剂包括噻二唑型金属减活剂和甲基苯三唑型金属减活剂；
    所述极压抗磨剂包括硫醚型极压抗磨剂；
    所述抗氧抗磨剂中，所述碱性二硫代磷酸锌的硫磷比为1.8-1.9，锌磷比为1.1-1.2；
    所述极压抗磨剂中，所述硫醚型极压抗磨剂的硫含量为14.0-15.0％。
  2. 根据权利要求1所述的润滑油组合物，其中，所述碱性二硫代磷酸锌为碱式硫磷双辛伯烷基锌盐。
  3. 根据权利要求1或2所述的润滑油组合物，其中，以所述抗氧抗磨剂质量为100％计算，所述抗氧抗磨剂包括40-60％碱性二硫代磷酸锌、20-30％胺类无灰抗氧剂、10-20％酚类无灰抗氧剂；
    所述金属减活剂中，噻二唑型金属减活剂和甲基苯三唑型金属减活剂的质量比为1:2-2:1。
  4. 根据权利要求1所述的润滑油组合物，其中，所述润滑油组合物的组成包括：
    0.7-1.0％金属清净剂、6.0-8.0％无灰分散剂、0.5-1.8％抗氧抗磨剂、1.0-2.0％金属减活剂、0.2-0.8％极压抗磨剂、3.0-5.0％黏指剂、0.1-0.2％降凝剂、0.001-0.010％抗泡剂、30.0-40.0％CTL基础油、余量为APIⅢ类基础油。
  5. 根据权利要求1所述的润滑油组合物，其中，所述金属清净剂包括钙盐和镁盐。
  6. 根据权利要求5所述的润滑油组合物，其中，所述钙盐包括水杨酸钙和/或磺酸钙，所述镁盐包括水杨酸镁和/或磺酸镁。
  7. 根据权利要求1所述的润滑油组合物，其中，所述无灰分散剂包括聚异丁烯丁二酰亚胺。
  8. 根据权利要求7所述的润滑油组合物，其中，所述聚异丁烯丁二酰亚胺的氮含量为1.8-2.2％，碱值为46-55mgKOH/g。
  9. 根据权利要求1所述的润滑油组合物，其中，所述黏指剂包括乙烯丙烯共聚物。
  10. 根据权利要求1所述的润滑油组合物，其中，所述降凝剂包括聚甲基丙烯酸酯。
  11. 根据权利要求1所述的润滑油组合物，其中，所述抗泡剂包括二甲基硅油。
  12. 根据权利要求1所述的润滑油组合物，其中，所述CTL基础油为100℃运动黏度是3.8-4.2mm2/s的煤制合成油。
  13. 根据权利要求1所述的润滑油组合物，其中，所述APIⅢ类基础油为100℃运动黏度是3.8-4.3mm2/s的APIⅢ类加氢裂化基础油。
  14. 根据权利要求1所述的润滑油组合物，其中，所述润滑油组合物的硫含量为0.20-0.30wt％，磷含量为0.06-0.07wt％，碱值为9.0-11.0mgKOH/g，硫酸盐灰分为0.4-0.6wt％，在M100甲醇发动机依照NB/SH/T 0189进行120小时耐久试验结束后润滑油组合物的四球磨斑直径在0.8mm以下，在-36℃下3.5秒内启动甲醇发动机。
  15. 权利要求1-14任一项所述的润滑油组合物在M100甲醇乘用车发动机中的应用。
PCT/CN2024/072460 2023-07-11 2024-01-16 一种耐醇型低黏度的润滑油组合物及其应用 Pending WO2025010987A1 (zh)

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