CN106883911A - A kind of high temperature oxidation resisting methyl alcohol machine oil and preparation method thereof - Google Patents

A kind of high temperature oxidation resisting methyl alcohol machine oil and preparation method thereof Download PDF

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Publication number
CN106883911A
CN106883911A CN201710051132.0A CN201710051132A CN106883911A CN 106883911 A CN106883911 A CN 106883911A CN 201710051132 A CN201710051132 A CN 201710051132A CN 106883911 A CN106883911 A CN 106883911A
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China
Prior art keywords
methyl alcohol
machine oil
high temperature
temperature oxidation
oxidation resisting
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CN201710051132.0A
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Chinese (zh)
Inventor
金海玲
金先扬
陶劲峰
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Zhejiang Geely Holding Group Co Ltd
Hunan Geely Automobile Parts Co Ltd
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Zhejiang Geely Holding Group Co Ltd
Hunan Geely Automobile Parts Co Ltd
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Priority to CN201710051132.0A priority Critical patent/CN106883911A/en
Publication of CN106883911A publication Critical patent/CN106883911A/en
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    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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Abstract

The present invention provides a kind of high temperature oxidation resisting methyl alcohol machine oil, in terms of the weight of methyl alcohol machine oil, the base oil comprising 80 90wt% and surplus additive, it is characterised in that：The base oil includes poly alpha olefin and straight chain polyalcohols ester, and the poly alpha olefin is 2 with the weight ratio of straight chain polyalcohols ester:7~3:1, the additive includes the friction improver of the amine type antioxidant, the viscosity index improver of 2 6wt% and 0.5 1wt% of 1 3wt%.The present invention also provides a kind of preparation method of the high temperature oxidation resisting methyl alcohol machine oil.Methyl alcohol machine oil of the invention has emulsion resistance, fire-resistant oxidation resistant, wear-resistant premium properties.

Description

A kind of high temperature oxidation resisting methyl alcohol machine oil and preparation method thereof
Technical field
The present invention relates to technical field of methanol fuel, more particularly to high temperature oxidation resisting methyl alcohol machine oil and preparation method thereof, should Methyl alcohol machine oil is mainly used in methyl alcohol car engine lubricating system.
Background technology
It is short and non-renewable due to petroleum resources, and for the purpose of environmental protection, major automobile factorys of the world are all The automotive fuel of alternative oil is actively being researched and developed, methyl alcohol is the most promising substitute fuel of internal combustion engine, it is main excellent Put and be：Methyl alcohol can reach the discharge lower than HC fuel, reduce atmosphere pollution；There is succession with traditional engine technology Property, it is not required to do engine structure and significantly changes；Other its octane number is high, during as spark-ignition engine fuel, can be used for Compression ratio engine higher, improves the thermal efficiency of engine.Therefore, start to the methanol vehicle eighties in 20th century formal in city Field sale." machine oil " used by methanol vehicle as engine " blood ", the quality of its performance directly influences methyl alcohol and starts The dynamic property of machine, safety and reliability, the performance requirement of methyl alcohol machine oil is concentrated mainly on methyl alcohol machine oil wear resistance, Demulsification performance, high temperature oxidation resistance and how to adapt to cold starting.
However, the latent heat of vaporization of methyl alcohol is big, vaporization is difficult, is also easy to scurry into cylinder because vaporization is bad.Scurry into cylinder Methyl alcohol, due to itself being good organic solvent, the lubricating oil being attached on cylinder wall can be washed down, thus bring three Big consequence：First, the lubricating oil film of cylinder rubbing surface is diluted or serious aging, abrasion is caused；Second, methyl alcohol with wash down Lubricating oil mixing, be easily collectively forming emulsion with machine oil in low temperature；Third, the antioxygen antiwear additive ZDDP commonly used in machine oil (zinc dialkyl dithiophosphate) easily reacts with alcohols, loses antioxygen antiwear characteristics.
Therefore it provides a kind of emulsion resistance for methanol vehicle, fire-resistant oxidation resistant, wear-resistant methyl alcohol machine oil just seem It is most important.
The content of the invention
In view of more than, the invention provides a kind of high temperature oxidation resisting methyl alcohol machine oil, in terms of the weight of methyl alcohol machine oil, comprising The base oil and surplus additive of 80-90wt%, it is characterised in that：The base oil includes that poly alpha olefin and straight chain are polynary Alcohol ester, the poly alpha olefin is 2 with the weight ratio of straight chain polyalcohols ester:7~3:1, the additive includes that the amine type of 1-3wt% resists The friction improver of oxygen agent, the viscosity index improver of 2-6wt% and 0.5-1wt%.
According to one embodiment of present invention, the amine type antioxidant is in dialkyl diphenylamine, diphenylamines or p-phenylenediamine One or two kinds of more than.
According to one embodiment of present invention, the viscosity index improver is common selected from polymethacrylates, ethylene, propylene One or more in polymers, polyisobutene, hy drogenated styrene-diene copolymer.
According to one embodiment of present invention, the friction improver is using organic-molybdenum salt and the compound of nano material.Should Organic-molybdenum salt be selected from D2EHDTPA molybdenum, molybdenum dialkyldithiocarbamacompositions (MoDTC), dialkyl dithio phosphoramidic acid molybdenum, One or more in organic-molybdenum mixture etc., the nano material is selected from the nano metal hydroxide containing Na, Mg, K or Ca Thing.
The present invention also provides a kind of preparation method of high temperature oxidation resisting methyl alcohol machine oil, comprises the following steps：By 80-90wt% Poly alpha olefin and straight chain polyalcohols ester add boiling flask, heat 2-12 hours under magnetic stirring, be sufficiently mixed Solution, the wherein weight ratio of poly alpha olefin and straight chain polyalcohols ester is 2:7~3:1；The viscosity index (VI) of 2-6wt% is added to change Enter agent, heated 10-15 hours under magnetic agitation, make it be completely dissolved to form homogeneous phase solution；Add the amine type antioxygen of 1-3wt% Agent, the friction improver of 0.5-1wt%, after being sufficiently stirred for and being heated for a period of hours, are completely dissolved it and form homogeneous phase solution；Stop Only heat, standing is cooled to normal temperature, obtains required methyl alcohol machine oil.
Using the solution of the present invention, the methyl alcohol machine oil of preparation has very excellent pyro-oxidation resistance, of the invention Base oil PAO+ polyol esters have excellent compatibility, and antioxidant, friction improver and other additions with encapsulant Agent has good compatibility, while reducing the greasy filth that machine oil is produced by oxidation, nitrification, extends the drain period of machine oil；It is also true Protecting the methyl alcohol machine oil for preparing has good low temperature flow, fuel economy and excellent wear resistance.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention, And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the invention can Become apparent, below especially exemplified by preferred embodiment, and coordinate accompanying drawing, describe in detail as follows.
Brief description of the drawings
Fig. 1 is preparation facilities schematic diagram of the present invention.
Fig. 2 is the automotive engine component using methyl alcohol machine oil of the invention through the photo after experiment.
Fig. 3 is the automotive engine component using conventional methyl alcohol machine oil through the photo after experiment.
Specific embodiment
Further to illustrate the present invention to reach technological means and effect that predetermined goal of the invention is taken, below in conjunction with Accompanying drawing and preferred embodiment, it is as follows to the detailed description of the invention.
High temperature oxidation resisting methyl alcohol machine oil (that is, methanol-fueled engine lubricating oil) of the invention is used in the hair of methanol vehicle Motivation lubricating system, for lubricating engine, to improve the wear resistance of engine, reduces the wear extent of engine cylinder-body.
The present invention provides a kind of high temperature oxidation resisting methyl alcohol engine oil base oil, with the gross weight meter of methyl alcohol engine oil base oil, should Methyl alcohol engine oil base oil includes the base oil of 80-90wt% and the additive of surplus.Wherein, the base oil includes poly- α-alkene Hydrocarbon and straight chain polyalcohols ester, the poly alpha olefin are 2 with the weight ratio of straight chain polyalcohols ester:7~3:1.The additive includes 1- The friction of the amine type antioxidant of 3wt%, the viscosity index improver (abbreviation viscosity index improver) of 2-6wt% and 0.5-1wt% is improved Agent (abbreviation anti-friction agent).
Poly alpha olefin abbreviation PAO, is referred to as the 4th class base oil.The present invention uses PAO+ straight chain polyalcohols ester conducts Base oil, the lubricity of obtained machine oil product is improved using straight chain polyalcohols ester favorable lubricating property in itself；It is simultaneously logical Cross and oil based on straight chain polyalcohols ester is added in PAO, it is possible to reduce coefficient of friction.Because, PAO does not allow readily soluble in itself Solution additive, and straight chain polyalcohols ester can be dissolved in PAO, while can also solubilising additive, dissolved this makes it possible to help PAO Additive.Meanwhile, esters pole tropism in itself causes that oil film molecule sticks to metal surface, so as to reduce the abrasion of metalwork. In addition, straight chain polyalcohols ester also have good low temperature flow and viscosity so that both composition base oil have compared with Viscosity index (VI) and excellent oxidation-stabilized performance high, can effectively reduce the greasy filth that machine oil is produced by oxidative nitration, extend machine oil Drain period.
In the present invention, the PAO can be using PAO products, the PAO of British Petroleum Company of commercially available Mobil Oil Corporation Product.
So-called polyol ester (polyolester) system by aliphatic carboxylic acid or aromatic carboxylic acid with it is two or more The ester of hydroxy fatty alcohols (polyalcohol) generation.Carboxylic acid has aliphatic carboxylic acid, aromatic series benzene first carboxylic acid and phthalic acid.Polyalcohol There are ethylene glycol, propane diols, polyethylene glycol, glycerine, pentaerythrite, sucrose and D-sorbite.Straight chain polyalcohols ester is to be by fat Race's carboxylic acid or aromatic carboxylic acid and the ester that two or more hydroxy fatty alcohols (polyalcohol) are generated are straight chain type.The straight chain Polyol ester is using the big Priolube 3970 of Britain's standing grain.
The amine type antioxidant prevents or suppresses by catching peroxy radical chain initiation reaction and chain increases also known as hindered amine Reaction long, so as to terminate free chain reaction, reaches antioxidation.In the present invention, the amine type antioxidant is dialkyl group Diphenylamines, diphenylamines, p-phenylenediamine etc..The amine type antioxidant overcomes antioxygen antiwear additive ZDDP in the prior art to be occurred instead with alcohol The possibility answered, while effectively inhibiting the phosphorism in three-way catalyst.
In one embodiment of the invention, alternatively, the amine type antioxidant and age resister phenylpropyl alcohol azole, benzophenone The collaboration such as class is used, and can be obtained than more preferable effect is used alone.
The viscosity index improver is selected from polymethacrylates (PMMA), ethylene propylene copolymer (OCP), polyisobutene (PIB), in hy drogenated styrene-diene copolymer (HSD) one or more.In one embodiment of the invention, this glues Degree index improver uses the PMMA of pectinate texture, and it has excellent viscosity temperature characteristic and HTHS values (High higher Temperature High Shear, high temperature high shear).HTHS is that fluid is tested at 150 DEG C by capillary viscosity The apparent viscosity for arriving, that is, dynamic viscosity, are to simulate the survey done under the conditions of cylinder of internal-combustion engine operating temperature and high speed shear The fuel economy of lubrication and lubricating oil between examination, reflection cylinder liner piston ring.Because between cam and push rod, piston and cylinder it Between, between axle and bearing shell all exist very big normal pressure (compression, non-shear stress), oil film can be squeezed and broken, and HTHS is exactly anti- The oiliness improver for having reflected between piston and cylinder, having been added in the adhesive ability of lubricating oil between axle and bearing shell, with lubricating oil Or polar agent is relevant, film strength is called.
Thus, the use of viscosity index improver so that machine oil has good low temperature flow and fuel economy, together Shi Youxiao overcomes causes the abrasion of cylinder wall because methanol fuel scurries into crankcase.With the oil product for being not added with viscosity index improver Compare, lubrication oil consumption can reduce by 27%, and fuel oil consumption can reduce 3-5%.
The friction improver can obviously reduce the coefficient of friction of machine oil using organic-molybdenum salt and the compound of nano material, Improve the fuel economy of engine, increasing service life of engine.Both compounds also have excellent antioxygenic property, The formation of high temperature deposition thing is reduced, effectively suppresses machine oil oxidation, while impaired friction surface can be repaired.Of the invention one In individual embodiment, the organic-molybdenum salt is selected from D2EHDTPA molybdenum, molybdenum dialkyldithiocarbamacompositions (MoDTC), dialkyl disulfides For one or more in phosphoramidic acid molybdenum, organic-molybdenum mixture etc., the nano material is selected from receiving containing Na, Mg, K or Ca Rice metal hydroxides.The action principle of organic-molybdenum salt is probably that molybdenum penetrates into coarse galling face, and forms the two of poly- state Molybdenum sulfide.And the presence of nano level metal hydroxides, impaired galling face can be filled and led up so that galling face becomes It is smooth, while the poly- state material that organic-molybdenum salt is formed forms one layer of oxide-film of densification on wear surface top layer, so as to improve metal The wearability on part surface.
In one embodiment of the invention, the friction improver also includes C2-C20Aliphatic acid, using C2-C20Fat Fat acid is modified the friction improver, nano grain surface is formed the chemical modification layer of stabilization, and this modification can The reunion of nano particle is controlled, it is dispersed in lubricating oil.
Preferably, in one embodiment of the invention, the high temperature oxidation resisting methyl alcohol machine oil also includes detergent-dispersant additive, clearly Net dispersant includes detersive and dispersant, and Main Function is engine interior is kept cleaning, makes the insoluble substance of generation In colloidal suspension state, it is unlikely to further to form carbon deposit, paint film or greasy filth.
Specifically, the detersive uses SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, with the weight of the high temperature oxidation resisting methyl alcohol machine oil Meter, the detersive is 2wt%-3.5wt% relative to the percentage by weight of the methyl alcohol machine oil.It can be with neutral lubrication oil oxidation life Into organic acid and inorganic acid, prevent its further condensation cause paint film to reduce, while can also prevent these acidic materials to hair The corrosion of motivation part.The dispersant uses diene base succimide, in terms of the weight of the high temperature oxidation resisting methyl alcohol machine oil, should Dispersant is 1wt%-2wt% relative to the percentage by weight of the methyl alcohol machine oil.It can be originally undissolvable solid in oil Body or liquid substance are solubilized into the micella center of multiple diene base succimide set, form colloid, prevent further Oxidation and condensation, reduce the formation of harmful deposits and aggregation on engine components.
The detersive and the dispersant can also adsorb the solid granules such as the carbon deposit and the paint film that have generated, make one Plant colloidal solution state to be dispersed in oil, prevent the further coacervating large particle of these materials and stick on parts, or deposition It is greasy filth.It can also the paint film and carbon deposit that will adsorb in parts surface are washed, it is dispersed in oil, makes engine Keep cleaning with metal surface.
Preferably, in another embodiment of the present invention, the high temperature oxidation resisting methyl alcohol machine oil also includes with methyl alcohol machine oil Weight meter, the matal deactivator of 0.5wt%-1wt%, the matal deactivator is using benzotriazole derivative or the sub- water of N, N'- bis- Yankee propane diamine.It can suppress influence of the metal to oil product, improve the stability of oil product, extend shelf life.
Preferably, in another embodiment of the present invention, the high temperature oxidation resisting methyl alcohol machine oil also includes antirust agent, and this is prevented Rust agent uses alkenyl succinic acid half ester.In terms of the weight of the high temperature oxidation resisting methyl alcohol machine oil, the antirust agent is relative to the Methanol Engine The percentage by weight of oil is 0.25wt%-0.5wt%.It can be strongly penetrated into iron rust, erosion, greasy dirt so as to easily remove Fall the rusty stain and erosion of metal surface, and can be formed on parts surface and store one layer of lubricating film, suppress moisture and other The corrosion that chemical analysis is caused.
Preferably, the high temperature oxidation resisting methyl alcohol machine oil also includes pour-point depressant, and the pour-point depressant uses polyacrylate, resistance to this The weight meter of high-temperature oxydation methyl alcohol machine oil, the pour-point depressant is 0.25wt%- relative to the percentage by weight of the methyl alcohol machine oil 0.5wt%.A small amount of significant apparent viscosity and yield value freezing point for reducing oil product of addition energy, so as to improve low temperature flow.
Preferably, the high temperature oxidation resisting methyl alcohol machine oil also includes anti-foaming agent, and the anti-foaming agent is being total to for polyacrylate and ether Polymers.In the present invention, the anti-foaming agent is commercially available.In terms of the weight of the high temperature oxidation resisting methyl alcohol machine oil, the anti-bubble Agent is 0.25wt%-0.5wt% relative to the percentage by weight of the methyl alcohol machine oil.
In another embodiment of the present invention, the high temperature resistant methyl alcohol machine oil also includes demulsifier, and the demulsifier is using more Effect demulsifier DL-32, it is polyethers macromolecular compound demulsifier, is also purchased from market, for example, had by the specialization work of Jinzhou hundred Limit company produces.In terms of the weight of the high temperature oxidation resisting methyl alcohol machine oil, weight percent of the demulsifier relative to the methyl alcohol machine oil Than being 0.5wt%.
High temperature oxidation resisting methyl alcohol machine oil of the invention has advantages below：First, being made using fully synthetic PAO+ polyol esters Based on oil, make preparation methyl alcohol machine oil have very excellent pyro-oxidation resistance.Second, using amine type antioxidant for example Dialkyl diphenylamine, overcomes the possibility that antioxygen antiwear additive ZDDP reacts with alcohol, while effectively inhibiting three-element catalytic Phosphorism in agent.Third, using the PMMA viscosity index improvers of pectinate texture, effectively overcoming because methanol fuel scurries into song Axle box and cause the abrasion of cylinder wall.Fourth, using the compound of organic-molybdenum salt and nano material as friction improver, can have Effect reduces the generation of high temperature deposition thing.
The present invention also provides a kind of preparation method of high temperature oxidation resisting methyl alcohol machine oil, and it comprises the following steps：First, will The PAO of 80-90wt% is added in boiling flask with straight chain polyalcohols ester, is heated 2-12 hours under magnetic stirring, is obtained fully The solution of mixing, wherein PAO are 2 with the weight ratio of straight chain polyalcohols ester:7~3:1.Then, the viscosity index (VI) of 2-6wt% is added Modifier, heats 10-15 hours under magnetic agitation, makes it be completely dissolved to form homogeneous phase solution.Then, the amine of 1-3wt% is added The friction improver of type antioxidant, 0.5-1wt%, after being sufficiently stirred for and being heated for a period of hours, is completely dissolved it and forms homogeneous Solution.Stop heating, standing is cooled to normal temperature, the machine oil after observation cooling is appropriate if having with the presence or absence of being layered, whetheing there is precipitation Increase the consumption of base oil, be again stirring for heating for dissolving, form it into homogeneous phase solution；If nothing, experiment is completed, and sealing preserve is prepared Good methyl alcohol machine oil.
Alternatively, detersive, the 1wt%- of 2wt%-3.5wt% are added in the methyl alcohol machine oil that can also be configured at this The dispersant of 2wt%, the matal deactivator of 0.5wt%-1wt%, the antirust agent of 0.25wt%-0.5wt%, 0.25wt%- In the demulsifier of the pour-point depressant of 0.5wt%, the anti-foaming agent of 0.25wt%-0.5wt% or 0.5wt% one or two with On.After being sufficiently stirred for and being heated for a period of hours, it is completely dissolved it and forms homogeneous phase solution.
Below by taking embodiment 1 as an example, and the device combined shown in Fig. 1 illustrates high temperature oxidation resisting Methanol Engine of the invention The preparation technology of oil：
3-5 zeolite and magnetic stirring apparatus are put into the boiling flask of 2000mL first, weigh up respectively 600g PAO and 200g straight chain polyalcohols esters, are poured into boiling flask, and flask is placed on the heater with magnetic force induction.It is flat to prevent Flask is burst, and an asbestos gauge is placed between boiling flask and heater.It is heated for a period of hours and obtains well-mixed solution.
Then, add in 60g polymethacrylates to above-mentioned solution, magnetic agitation is simultaneously heated 10~15 hours, makes it It is completely dissolved and is formed homogeneous phase solution.
35g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBERs and 20g succimides are separately added into, magnetic agitation is simultaneously heated 1 hour, makes it It is completely dissolved and is formed homogeneous phase solution.
Successively toward addition 20g dialkyl diphenylamines, 10g D2EHDTPAs molybdenum and nano metal hydroxide in boiling flask Mixture, 10g benzotriazoles derivative, 10g alkenyl succinic acids half ester, 20g polyacrylate, 5g composite anti-foam agents and 10g are more Effect demulsifier DL-32, after being sufficiently stirred for and being heated for a period of hours, is completely dissolved it and forms homogeneous phase solution.
Stopping heating, standing is cooled to normal temperature, and the machine oil after observation cooling whether there is layering, precipitation be whether there is, if having The appropriate consumption for increasing base oil, is again stirring for heating for dissolving, forms it into homogeneous phase solution；If nothing, experiment is completed, sealing preserve The methyl alcohol machine oil for preparing.
Methyl alcohol machine oil is prepared with similar approach, the formula of embodiment 1-3 is as shown in table 1.To methyl alcohol obtained in embodiment 1-3 Machine oil product tests following physicochemical data respectively：
(1) 100 DEG C and 40 DEG C of kinematic viscosity (K inetic viscosity, KV), shows a kind of fluid-resistance flowing Or perhaps the metric of the ability of internal friction.Kinematic viscosity can be varied with temperature and changed, thus kinematic viscosity numerical value Need to indicate test temperature.Its detecting instrument be kinematic viscosity detector, determine kinematic viscosity standard method for GB/T 265, GB/T 11137, i.e., under a certain stationary temperature, the liquid of certain volume flows through a glass fiber demarcated under gravity The time of tubule.The capillary constant of viscosimeter and the kinematic viscosity that the product of flowing time is exactly liquid at this temperature.
(2) viscosity index (VI) VI, represents one of oil product viscosity temperature characteristic about quantitative values, and viscosity index (VI) is high, represents the viscous of oil product Degree is small with temperature change, and the viscosity temperature characteristic of oil product is good.Vice versa.So-called viscosity temperature characteristic, i.e., oil body is with temperature The property of change.The computational methods of viscosity index (VI) are in the GB/T 1995 of China or ASTM D 2270, the German DIN in the U.S. 51564th, it is discussed in detail in the standard such as ISO 2902, JIS K 2284 of Japan.Viscosity index (VI) can also be obtained with look-up table Arrive, the GB/T 2541 of China.
(3) the anti-shearing viscosity coefficient HTHS of high temperature, oil film high temperature anti-shear ability and oil film rotating speed condition of high temperature protection high Ability is relevant.The meaning of the anti-shearing viscosity coefficient of high temperature is the oil-film stabilization degree under machine oil high temperature.HTHS is higher, and machine oil can be It is supplied to the protection of engine better under high temperature.HTHS is lower, represents diluter during oil film high temperature, easily causes the abrasion of engine. HTHS needs that the abrasion of engine could be lowered more than 2.6.
(4) temperature pumping viscosity MRV, is that under conditions of ultralow temperature, it is normal that machine oil can also be pumped into engine interior During flowing, the critical numerical value of its viscosity.
(5) low-temperature dynamic viscosity CCS, is the measured internal friction size under the conditions of low temperature, high-rate of shear of oil product Measure, can be used as the indication viscosity index that can smoothly start under cryogenic of engine.Under same cryogenic conditions, The k value measured is smaller, illustrates that the cold starting performance of machine oil is better.
(6) total base number (Total base number, TBN), refers under prescribed conditions, neutralization is present in 1g oil samples complete Amount required for portion's alkaline constituents (highly basic and weak base), is converted into the alkali number of equivalent, represented with mgKOH/g.TBN representatives higher The acid that machine oil can be neutralized is more.
(7) ash content, oil product sample residue remaining after burning under prescribed conditions referred to as ash content, ash content is mainly profit The metallic salt and metal oxide that lubricating oil is generated after burning completely are constituted.Lubricating oil ash is excessive, is easily sent out on parts The hard carbon deposit of life, causes the abrasion of machine components.The measure of ash content is determined using the standard methods of GB/T 2433.
(8) amount that evaporation loss, i.e. oil product are lost by evaporation under certain condition, is represented with mass fraction.Evaporation Loss is directly proportional to the volatility of oil product.Evaporation loss is bigger, and the oil consumption in practical application is bigger.Lubricating oil is using process Middle evaporation, lubricants capacity is gradually decreased, it is necessary to supplement, viscosity increase influences fuel feeding in causing lubricating system.China determines lubrication The method of oily evaporation loss is the lubricating oil of GB/T 7325 and grease evaporation loss determination method and the evaporation of the lubricating oil of SH/T 0055 Injury test method (Angelika Noack method).The present invention is using the methods of SH/T 0055, i.e. sample in the instrument of regulation, in the temperature of regulation 1h is heated under degree and pressure, the oil vapour for evaporating is carried away by air stream.Difference according to sample size before and after heating determines profit The evaporation loss of lubricating oil.
(9) gel index, is measured using Fu Lande FDH-8808 lubricating oil gel index analyzers.
(10) high temperature deposition thing, is detected, it is intended to evaluate according to petroleum chemicals professional standard NB/SH/T0834-2010 Cleaning effect of the different product to automobile engine.Lubricating oil is deposited on in-engine material after and is commonly called as greasy filth, if The heat endurance of lubricating oil is poor, by engine repeatedly high-temperature heating and cooling after, it is easy to aged deterioration.Greasy filth is in hair Long-term accumulation inside motivation, can damage engine part, or even the service life for shortening engine.
The test of above-mentioned listed physicochemical property parameter, the tool for measuring are not carried out to Methanol Engine oil obtained in embodiment 1-3 Body numerical value is as shown in table 1.
Carry out engine pedestal long duration test in 100 hours respectively to the oil product obtained by embodiment 1-3 and vehicle road 10,000 is public In test, such as table 2 below is the physicochemical datas through long duration test in 100 hours and the used machine oil of 10,000 kilometers of vehicle road experiment.
The physicochemical data of the used machine oil of table 2
With the Data Comparison of table 1, it can be seen that kinematic viscosity somewhat decreases, amplitude very little, substantially 20% with It is interior, illustrate by after above-mentioned durable test, oil product kinematic viscosity is still in tolerance interval.According to GB/7607 standards, total base number Reduction reaches criteria for changing oil more than 50%, according to the data of total base number TBN in Tables 1 and 2, show that total base number is averagely reduced 35% or so, still not up to criteria for changing oil, that is, can also continue to use.Oxidizability, the degree of nitration are typically with fresh oil as base Standard, the numerical value of table 2 is also all in tolerance interval.Data above explanation oil product has pyro-oxidation resistance higher.
The wear condition that the content of iron and copper can reflect in process of the test in experiment oil sample, iron content increase, it may be possible to because For the abrasion increase of camshaft, rocking arm, cylinder sleeve causes iron content to raise, therefore, iron content increase may cause greasy filth to increase. Iron content is essentially a constant, unless connecting rod bearing shell is weightless too many.According to relevant criterion, the tenor in oil sample is less than 70ppm is tolerance interval, and the data of table 2 are far smaller than 70ppm, that is to say, that wear extent is smaller, still in tolerance interval.
Above analytic explanation, methyl alcohol machine oil of the invention has excellent high temperature oxidation resisting function and wear resistance.
In order to be compared with conventional commercial methanol machine oil, the applicant uses vehicle condition, brand identical vehicle, same warp 10,000 kilometers of experiments of long duration test in 100 hours and vehicle road are crossed, except that, the conventional city that this contrast test is used Sell methyl alcohol machine oil.Now, by using the automobile of methyl alcohol machine oil of the invention, and the above-mentioned vapour with conventional commercial methanol machine oil Car, after 10,000 kilometers of experiments of long duration test in 100 hours and vehicle road, the photo of the engine components that the machine of tearing open is obtained Respectively as shown in Figures 2 and 3, wherein Fig. 2 is the automotive engine component using methyl alcohol machine oil of the invention through the photograph after experiment Piece, Fig. 3 is the automotive engine component using conventional methyl alcohol machine oil through the photo after experiment.From photo as can be seen that using The engine components metal covering of methyl alcohol machine oil of the invention does not almost wear and tear, and paint film is uniformly peace and quiet, is not adhered to metal watch Face；Meanwhile, carbon deposit is little.And conversely, using the engine components metal covering then serious wear of conventional methyl alcohol machine oil, paint film glues Metal surface is attached to, carbon deposit is serious.
After through above-mentioned test, tear open machine evaluate two kinds of pyro-oxidation resistances of methyl alcohol machine oil (carbon deposit, greasy filth and paint film) with And wear resistance, result of the test is as shown in table 3 below.
From table 3 it can be seen that using methyl alcohol machine oil of the invention, bearing shell is weightless, cam wear is smaller, generation is started Machine oil mud is less, piston deposit is less, paint film it is nonadherent in engine metal surface, oil filter screen also not by Severe blockage. Relatively, using conventional methanol machine oil, bearing shell is weightless, cam wear is very serious, and metal deposit forms thick greasy filth, piston Deposit and paint film, oil filter screen is by Severe blockage.
Table 3 tears the high-temperature oxidation and abrasion resistance that machine evaluates methyl alcohol machine oil open
Parameter Using methyl alcohol machine oil of the present invention Using conventional methanol machine oil
Bearing shell weightlessness/mg 10 50
Average cam wear/μm 50 152
Engine sludge average score 9.8 7.2
Piston deposit scores 8.9 5.0
Engine paint film average score 9.5 6.0
Oil filter screen is blocked, % 2% 25%
Further to verify the effect of the methyl alcohol machine oil of different compositions of the invention, the present invention also provides following implementation Example, and comparative example 1 is provided.
Embodiment 4：
Similar to Example 1, it is diphenylamines that difference is antioxidant, and friction improver is using D2EHDTPA molybdenum+receive Rice magnesium hydroxide.
Embodiment 5：
Similar to Example 1, difference is that antioxidant uses p-phenylenediamine, friction improver to use dialkyl disulfides For carbamic acid molybdenum+nanometer NaOH, matal deactivator uses N, the salicylidene propane diamine of N '-two.
Embodiment 6：
Similar to Example 1, difference is that antioxidant uses diphenylamines+benzophenone, friction improver to use two Alkyl dithiophosphoramidic molybdenum+nanometer potassium hydroxide.
Comparative example 1：
Similar to Example 1, difference is that base oil uses hydrogenation mineral base oil.
Comparative example 2：
Similar to Example 1, difference is that antioxidant is not to use amine antioxidants, but the phenols antioxygen for using Agent, i.e., four (β-(3,5- tributyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters.
By above-described embodiment 4-6 and obtained in comparative example 1-2, methyl alcohol machine oil carries out the physics and chemistry of fresh oil with the method as table 1 Performance test.And these machine oil are also passed through into long duration test in 100 hours and the experiment of 10,000 kilometers of vehicle road, then re-test The physicochemical data of used machine oil is shown in Table 4.
From table 4 knowable to the contrast of comparative example 1 and embodiment 1, using oil based on traditional hydrogenation mineral base oil, Light stability is poor, and poor to the dissolubility of additive.Comparatively, methyl alcohol machine oil of the invention uses PAO+ polyol esters Based on oil, obtained methyl alcohol machine oil has excellent light stability, inoxidizability, good high and low temperature performance and low waves Hair property.
To find out its cause, because PAO good stabilities, although PAO oxidation stabilities in itself are not highests, but it is right The sensitivity of antioxidant is very good, adds a small amount of amine antioxidants, and PAO shows excellent oxidation stability.PAO and polyalcohol Ester is shared, and viscosity temperature characteristic, greasy property, the dissolubility to additive have significant increase.
Add nano material in friction improver, the particle size of nano material in 1-100nm, in cluster and macroscopic view The transitional region that object has a common boundary.Because the ratio between the surface atom number of nano material and total atom number increase as size diminishes, The crystal field environment of surface atom and combination can be different from interior atoms, electronics lacked around surface atom, therefore have many sky rails Road, makes it have unsaturation, produces " skin effect ".When the size of material is close with the wavelength of electronics conduction or more hour, Periodic boundary condition is destroyed, and the property such as magnetic, light adsorptivity, thermal resistance of material occurs great variety, produces so-called " bulk effect ".Scantling it is small to certain value when, can produce " quantum size effect ", therefore nanoscale friction improver has Skin effect, quantum size effect, bulk effect, four kinds of essential characteristics of macroscopic quantum tunneling.Add nano friction modifier not Only it is effectively reduced friction, reducing energy consumption, increasing service life of engine, moreover it is possible to repair damaged friction surface.
Amine antioxidants for the phenolic antioxidant of comparative example 2, with more preferable effect, the inoxidizability of machine oil Can be higher.
In addition, embodiment 6 is cooperateed with using amine type antioxidant with age resister benzophenone using, cooperative effect is produced, its Physicochemical property is significantly improved.
To sum up, using the solution of the present invention, the methyl alcohol machine oil of preparation has very excellent pyro-oxidation resistance, this hair Bright base oil PAO+ polyol esters and encapsulant have an excellent compatibility, and antioxidant, friction improver and other Additive has good compatibility, while reducing the greasy filth that machine oil is produced by oxidation, nitrification, extends the drain period of machine oil； Also assuring the methyl alcohol machine oil of preparation has good low temperature flow, fuel economy and excellent wear resistance.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, though So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people Member, without departing from the scope of the present invention, when making a little change or modification using the technology contents of the disclosure above It is the Equivalent embodiments of equivalent variations, as long as being without departing from technical solution of the present invention content, according to technical spirit pair of the invention Any simple modification, equivalent variations and modification that above example is made, still fall within the range of technical solution of the present invention.

Claims (16)

1. a kind of high temperature oxidation resisting methyl alcohol machine oil, in terms of the weight of methyl alcohol machine oil, base oil and surplus comprising 80-90wt% Additive, it is characterised in that：The base oil includes poly alpha olefin and straight chain polyalcohols ester, and the poly alpha olefin is polynary with straight chain The weight ratio of alcohol ester is 2:7~3:1, the additive includes the amine type antioxidant of 1-3wt%, the viscosity index (VI) of 2-6wt% is improved Agent and the friction improver of 0.5-1wt%.
2. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The amine type antioxidant is dialkyl group two It is more than the one or two kinds of in aniline, diphenylamines or p-phenylenediamine.
3. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The amine type antioxidant and phenylpropyl alcohol azoles Class, benzophenone collaboration are used.
4. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The viscosity index improver is selected from poly- One or more in methacrylate, ethylene propylene copolymer, polyisobutene, hy drogenated styrene-diene copolymer.
5. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The friction improver uses organic-molybdenum The compound of salt and nano material.
6. high temperature oxidation resisting methyl alcohol machine oil according to claim 5, it is characterised in that：The organic-molybdenum salt is selected from D2EHDTPA One or two in molybdenum, molybdenum dialkyldithiocarbamacompositions, dialkyl dithio phosphoramidic acid molybdenum, organic-molybdenum mixture etc. More than, the nano material is selected from the nano metal hydroxide containing Na, Mg, K or Ca.
7. high temperature oxidation resisting methyl alcohol machine oil according to claim 5, it is characterised in that：The friction improver also includes C2- C20Aliphatic acid.
8. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The high temperature oxidation resisting methyl alcohol machine oil is also Comprising detergent-dispersant additive, the detergent-dispersant additive is included in terms of Methanol Engine weight of oil, the detersive and 1wt%- of 2wt%-3.5wt% The dispersant of 2wt%, the detersive is SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, and the dispersant is diene base succimide.
9. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The high temperature oxidation resisting methyl alcohol machine oil is also Comprising in terms of Methanol Engine weight of oil, the matal deactivator of 0.5wt%-1wt%, the matal deactivator be selected from benzotriazole derivative or The salicylidene propane diamine of person N, N'- bis-.
10. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The high temperature oxidation resisting methyl alcohol machine oil Also include in terms of Methanol Engine weight of oil, the antirust agent of 0.25wt%-0.5wt%, the antirust agent is alkenyl succinic acid half ester.
11. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The high temperature oxidation resisting methyl alcohol machine oil Also include in terms of Methanol Engine weight of oil, the pour-point depressant of 0.25wt%-0.5wt%, the pour-point depressant is polyacrylate.
12. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The high temperature oxidation resisting methyl alcohol machine oil Also include in terms of Methanol Engine weight of oil, the anti-foaming agent of 0.25wt%-0.5wt%, the anti-foaming agent is being total to for polyacrylate and ether Polymers.
13. high temperature oxidation resisting methyl alcohol machine oil according to claim 1, it is characterised in that：The high temperature oxidation resisting methyl alcohol machine oil Also include in terms of Methanol Engine weight of oil, the demulsifier of 0.5wt%, the demulsifier is multiple-effect demulsifier DL-32.
A kind of 14. preparation methods of high temperature oxidation resisting methyl alcohol machine oil, comprise the following steps：
By in the poly alpha olefin of 80-90wt% and straight chain polyalcohols ester addition boiling flask, 2-12 is heated under magnetic stirring small When, well-mixed solution is obtained, wherein poly alpha olefin and the weight ratio of straight chain polyalcohols ester is 2:7~3:1；
The viscosity index improver of 2-6wt% is added, is heated 10-15 hours under magnetic agitation, make it be completely dissolved to form homogeneous Solution；
Amine type antioxidant, the friction improver of 0.5-1wt% of 1-3wt% are added, after being sufficiently stirred for and being heated for a period of hours, makes it It is completely dissolved and is formed homogeneous phase solution；
Stop heating, standing is cooled to normal temperature, obtains required methyl alcohol machine oil.
The preparation method of 15. high temperature oxidation resisting methyl alcohol machine oil according to claim 14, it is characterised in that：Observation stands cold But with the presence or absence of being layered, whetheing there is precipitation, the appropriate consumption for increasing base oil, is again stirring for heating molten to the methyl alcohol machine oil after if having Solution, forms it into homogeneous phase solution；If nothing, experiment is completed, the methyl alcohol machine oil that sealing preserve is prepared.
The preparation method of 16. high temperature oxidation resisting methyl alcohol machine oil according to claim 14, it is characterised in that：Configured at this Methyl alcohol machine oil in be optionally added into detersive, the dispersant of 1wt%-2wt%, the 0.5wt%-1wt% of 2wt%-3.5wt% Matal deactivator, the antirust agent of 0.25wt%-0.5wt%, the pour-point depressant of 0.25wt%-0.5wt%, 0.25wt%- More than the one or two kinds of in the anti-foaming agent of 0.5wt% or the demulsifier of 0.5wt%, it is sufficiently stirred for and is heated for a period of hours Afterwards, it is completely dissolved it and forms homogeneous phase solution.
CN201710051132.0A 2017-01-23 2017-01-23 A kind of high temperature oxidation resisting methyl alcohol machine oil and preparation method thereof Pending CN106883911A (en)

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CN110724583A (en) * 2019-10-28 2020-01-24 浙江吉利新能源商用车集团有限公司 Methanol engine lubricating oil composition and preparation method thereof
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CN111548849A (en) * 2020-06-03 2020-08-18 北京一元驭宝贸易有限公司 Lubricating oil with burning prevention function
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CN109913300A (en) * 2019-03-28 2019-06-21 王琰 A kind of biodegradable environment protective lubricant and preparation method thereof
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