CN106221862A - Molybdenum modifiers dispersants, its preparation method and application - Google Patents

Molybdenum modifiers dispersants, its preparation method and application Download PDF

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Publication number
CN106221862A
CN106221862A CN201610682807.7A CN201610682807A CN106221862A CN 106221862 A CN106221862 A CN 106221862A CN 201610682807 A CN201610682807 A CN 201610682807A CN 106221862 A CN106221862 A CN 106221862A
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molybdenum
alkyl chain
preparation
add
acid
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CN106221862B (en
Inventor
刘烨
蔡涛
商旺吉
张云潇
孙俪文
夏骏远
曾红玲
王声培
刘丹
刘升高
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JIANGXI FUEL & LUBRAICANT ADDITIVE Co.,Ltd.
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Jiangxi Fuel & Lubraicant Additive Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M139/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54Fuel economy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a kind of molybdenum modifiers dispersants, its preparation method and application.Containing imines diethanol molybdic acid diglyceride group in this molybdenum modifiers dispersants, its preparation method includes: by alkyl chain succinic acid and/or alkyl chain succinic anhydrides, can select to add or without diluent, alcohol amine compound mixing carry out first stage reaction, remove the unreacted reactant that may remain afterwards, add molybdenum reagent and carry out second stage reaction, it is thus achieved that target product.The present invention not sulfur-bearing phosphorus, containing imines diethanol molybdic acid diglyceride group in each molecule, the molybdenum content being favorably improved in dispersant and raw material use the alkyl chain succinic acid of commercialization, cost can be substantially reduced, there is with alkylated diphenylamine class antioxidant in lubricating oil obvious high temperature and work in coordination with antioxidation, and with zinc dialkyl dithiophosphate, there is the most collaborative antiwear and antifriction effect, the dosage of similar additive during application, can be reduced, reduce phosphorus content, improve fuel economy.

Description

Molybdenum modifiers dispersants, its preparation method and application
Technical field
The present invention relates to a kind of molybdate compound lubriation material and preparation method thereof, particularly to a kind of molybdenum modification dispersion Agent, its preparation method and application.
Background technology
The development trend of automobile engine oil is to extend the drain period and improve fuel economy, and improves the master of fuel economy Wanting approach is to reduce oil viscosity and the frictional dissipation reduced between parts, and this just requires that lubricating oil has excellent antifriction antiwear Performance.
In order to improve the antifriction antiwear effect of lubricating oil, in lubricating oil, generally add a small amount of lube oil additive, pass The lube oil additive of system is sulfur, phosphorus and chlorine type, and this kind of material can have selectivity and corrosivity, particularly to surface of friction pair The lube oil additive of the elements such as sulfur-bearing, phosphorus or chlorine can discharge substantial amounts of waste water, waste gas and pollution during producing and using Thing, to environment.
Molybdate compound lubriation material, because of its excellent tribological property, occupies extremely important in numerous lubriation materials Status, be one of the focus of lube oil additive research both at home and abroad in recent years.Existing molybdate compound additive is predominantly Oil-soluble organo-molybdenum compound, after being added in lubricating oil, in greasing, organic molybdenum is thermal decomposited also Generating the ultra-fine or molybdenum bisuphide of approximation nanometer, this molybdenum bisuphide adheres to surface of friction pair, makes coarse surface " be filled out Flat " and become smooth.Therefore, oil-soluble organo-molybdenum compound is as extreme pressure anti-wear additives and friction improver, in lubricating oil and profit Consistent lubricant can reduce the friction and wear of slidingsurface, improve load-carrying ability, also there is fabulous collaborative oxidation resistance simultaneously, Capable of saving fuel 3% ~ 4%.
Common are machine molybdenum compound additive at present and be broadly divided into molybdenum dialkyl-dithiophosphate (MoDDP), dialkyl group Molybdenum dithiocarbamate (MoDTC), three core molybdenums and molybdenum amines etc., these products are mainly used in I. C. engine Among lubricating oil, gear oil, hydraulic oil, intermetallic composite coating and grease.Molybdenum dialkyl-dithiophosphate (MoDDP), dialkyl group two Thiocarbamic acid molybdenum (MoDTC) is although having been realized in now commercialization, but its dissolubility in base oil is poor, and And this compound still contains S, P, still can not meet the environmental requirement without sulfur phosphorus.
In recent years, CN104844656 discloses the branched alkyl imines diethanol molybdic acid diester of a kind of C1-C30, but should Organic molybdenum is poor with the compatibility of other additive, and high with dihydroxyalkyl amine for cost of material in production process.
Molybdenum modified succinimides dispersant is the molybdate compound lubriation material that a class that development in recent years is got up is novel. Such as, US8076275, USP20120190864, US20130261313 describe molybdenum modifiers dispersants, and it is mainly mono-/bis-and hangs Ashless butyl diimide dispersant is formed with the reaction such as molybdenum trioxide and water.But owing to this compound is to hang fourth two with mono-/bis- The active amino of acid imide ashless dispersant, as reaction site, builds the mesh that Mo-N key reaches to introduce in dispersant by molybdenum , thus the molybdenum content introduced is limited.
Summary of the invention
It is unable to reach the compatibility of environmental requirement, other additive for organic molybdenum additive in existing lubricating oil Difference, the deficiency that cost of material is high, present invention is primarily targeted at a kind of molybdenum modifiers dispersants of proposition and preparation method thereof.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
A kind of molybdenum modifiers dispersants, it is characterised in that: containing imines diethanol molybdic acid diglyceride group in this dispersant.
Preferably, described molybdenum modifiers dispersants has a following structural formula:
And/or
Wherein R is C2-C50Straight chained alkyl or the alkyl with side chain, m, n are the integer of 0-6, and dp is at least 1,2,3,4,5 Any one.
Present invention also offers the preparation method of a kind of molybdenum modifiers dispersants, comprising: by alkyl chain succinic acid and/or alkane Base chain succinic anhydrides, can select add or without diluent, alcohol amine compound mixing carry out first stage reaction, afterwards Removing the unreacted reactant that may remain, add molybdenum reagent and carry out second stage reaction, last post-treated acquisition target is produced Thing.
The preparation method of a kind of molybdenum modifiers dispersants is provided among some embodiments, comprising: by alkyl chain amber After amber acid and/or alkyl chain succinic anhydrides are sufficiently mixed uniformly with diluent, property adds or is dividedly in some parts alcohol amine compounds again Thing and can selecting add or without accelerator carry out first stage reaction, removing afterwards may the unreacted of residual Thing, property adds or is dividedly in some parts molybdenum reagent and carries out second stage reaction, last post-treated acquisition target product again.
Among some more preferred embodiment, described preparation method may include that polyisobutylene succinic acid Acid anhydride and/or high molecular weight polyisobutylene succinic anhydride are sufficiently mixed uniformly with diluent under conditions of temperature is 30 ~ 100 DEG C, Afterwards under conditions of temperature is 50 ~ 150 DEG C add alcohol amine compound and can select add or without accelerator, then Under conditions of temperature is 60 ~ 160 DEG C, reacts 0.2 ~ 8h, then removes the unreacted reactant that may remain, add molybdenum reagent Under conditions of temperature is 80 ~ 200 DEG C, constant temperature keeps 0.5 ~ 5h, last post-treated acquisition target product at reduced pressure conditions.
Another free-revving engine of the present invention is to provide the application of described molybdenum modifiers dispersants.
Such as, providing a kind of lubricant oil composite in some case study on implementation, it comprises described molybdenum modifiers dispersants.
Further, in certain embodiments, described lubricant oil composite also can comprise other multiple additives, such as dioxane Base diphenylamines, zinc dialkyl dithiophosphate.
Compared with prior art, the invention have the advantages that
(1) the molybdenum modifiers dispersants not sulfur-bearing phosphorus of the present invention, is a kind of real environment-friendly products;
(2) in the molybdenum modifiers dispersants of the present invention through alcohol amine compound modified and existing molybdenum modified succinimides phase Ratio, containing imines diethanol molybdic acid diglyceride group in each molecule, the molybdenum content being favorably improved in dispersant;
(3) the molybdenum modifiers dispersants raw material of the present invention uses alkyl chain succinic acid and/or alkyl chain succinic anhydrides, the energy of commercialization Be substantially reduced cost, with existing it has been reported that alkyl imino diethanol molybdic acid diester compared with, the dissolubility in base oil More preferably, and more preferable with the compatibility of other additive;
(4) the molybdenum modifiers dispersants of the present invention has obvious high temperature with alkylated diphenylamine class antioxidant in lubricating oil Collaborative antioxidation, and with zinc dialkyl dithiophosphate, there is the most collaborative antiwear and antifriction effect, therefore in application The dosage that adds of similar additive can be reduced time in lubricating oil, thus reduce the phosphorus content in lubricating oil product, be conducive to improving Overall fuel economy;
(5), in the preparation method of the present invention, by the screening of raw material and technological operation and the adjustment of process conditions, it is substantially improved Reaction rate, the response time foreshortens to 4 ~ 10h.
Hereafter technical scheme will be made the most detailed explanation.It is understood, however, that at model of the present invention In enclosing, can between above-mentioned each technical characteristic and each technical characteristic specifically described in below (eg embodiment) of the present invention It is combined with each other, thus constitutes new or preferred technical scheme.As space is limited, the most tired at this state.
Accompanying drawing explanation
Dispersant and the coefficient of friction of ZDDP compound use that the molybdenum of Fig. 1: different proportion is modified and the spot diameter curve that rubs.
Resisting of Fig. 2: under the conditions of 200 DEG C, the dispersant of the molybdenum modification of different proportion and the oil sample of diphenylamines compound use Oxygen results of property.
Detailed description of the invention
As it was previously stated, in view of many deficiencies of prior art, inventor is through long-term and in-depth study and a large amount of Practice, is proposed technical scheme, as detailed below.
One aspect of the present invention one molybdenum modifiers dispersants, it is characterised in that: containing imines diethanol in this dispersant Molybdic acid diglyceride group.
Preferably, described molybdenum modifiers dispersants has a following structural formula:
And/or
Wherein R is C2-C50Straight chained alkyl or the alkyl with side chain, m, n are the integer of 0-6, and dp is at least 1,2,3,4,5 Any one.
The molybdenum modifiers dispersants that the present invention provides is at room temperature blackish green thick liquid, has good oil-soluble.
Further, described molybdenum modifiers dispersants can be more than room temperature storage half a year, and without Precipitation.
Another aspect of the present invention provides the preparation method of a kind of molybdenum modifiers dispersants, comprising: by alkyl chain succinum Acid and/or alkyl chain succinic anhydrides, can select add or without diluent, alcohol amine compound mixing carry out the first stage Reaction, remove afterwards may the unreacted reactant of residual, add molybdenum reagent and carry out second stage reaction, the most post-treated obtain Obtain target product.
Specifically, this preparation method includes: by abundant with diluent to alkyl chain succinic acid and/or alkyl chain succinic anhydrides After mix homogeneously, again property add or be dividedly in some parts alcohol amine compound and can select add or without accelerator enter The row first stage reacts, remove afterwards may the unreacted reactant of residual, property adds or is dividedly in some parts molybdenum reagent and carries out again Second stage is reacted, last post-treated acquisition target product.
Among some more preferred embodiment, described preparation method may include that polyisobutylene succinic acid Acid anhydride and/or high molecular weight polyisobutylene succinic anhydride are sufficiently mixed uniformly with diluent under conditions of temperature is 30 ~ 100 DEG C, Afterwards under conditions of temperature is 50 ~ 150 DEG C add alcohol amine compound and can select add or without accelerator, then Under conditions of temperature is 60 ~ 160 DEG C, reacts 0.2 ~ 8h, then removes the unreacted reactant that may remain, add molybdenum reagent Under conditions of temperature is 80 ~ 200 DEG C, constant temperature keeps 0.5 ~ 5h, last post-treated acquisition target product at reduced pressure conditions.
Among some highly preferred embodiments, described preparation method may include that polyisobutylene succinic acid Acid anhydride and/or high molecular weight polyisobutylene succinic anhydride are sufficiently mixed uniformly with diluent under conditions of temperature is 30 ~ 100 DEG C, Afterwards under conditions of temperature is 50 ~ 120 DEG C add triethanolamine and can select add or without accelerator, then exist Temperature reacts 0.2 ~ 6h under conditions of being 90 ~ 160 DEG C, then remove the unreacted reactant that may remain, add molybdenum reagent and exist Under reduced pressure, under conditions of temperature is 80 ~ 180 DEG C, constant temperature keeps 1 ~ 4h, last post-treated acquisition target product.
It is further preferred that described reduced pressure refers to the condition of vacuum >=4KPa.
Such as, a kind of boron molybdenum integration modified succinimides dispersant in the more typical case study on implementation of the present invention one Synthesis route see following formula:
Such as, among a more typical concrete case, a kind of preparation method may include that the polyisobutylene fourth two of metering Anhydride and/or high molecular weight polyisobutylene succinic anhydride and solvent mix, and optimize the ratio of anhydride and alcohol amine compound, > 100 DEG C stirring 6h, then < 120 DEG C add metering molybdenum reagent and accelerator, mixture < 150 DEG C stir 0.5h, rise the most again Temperature back flow reaction < 10h, is filtered to remove the unreacted reactant that may remain, under conditions of vacuum >=4KPa, 200 DEG C of conditions of < Lower constant temperature keeps < 5h, removes solvent and water, i.e. can get target product.
The definition of heretofore described alkyl chain succinic acid, molybdenum reagent and accelerator be all those skilled in the art Through know.
More preferred, described alkyl chain succinic acid and/or alkyl chain succinic anhydrides are C2-C50Straight chained alkyl or band There are succinic acid and/or the alkyl chain succinic anhydrides of the alkyl of side chain.
Being more highly preferred to, described alkyl chain succinic acid and/or alkyl chain succinic anhydrides can be selected from, but not limited to, poly-isobutyl Alkene succinic acid, polyisobutylene butanedioic anhydride, high molecular weight polyisobutylene succinic acid, high molecular weight polyisobutylene succinic anhydride etc..
It is further preferred that in described polyisobutylene butanedioic anhydride the number-average molecular weight of polyisobutylene group be 500 ~ 5000。
More preferred, described alcohol amine compound can be selected from, but not limited to, methanol diethanol amine, triethanolamine, propanol two One or more in ethanolamine, butanol diethanolamine, amylalcohol diethanolamine, hexanol diethanolamine, enanthol diethanolamine Combination.
More preferred, the consumption of described alcohol amine compound and described alkyl chain succinic acid and/or alkyl chain succinic anhydrides The acid contained and/or the mol ratio of anhydride are 1:0.1 ~ 1:10.
More preferred, described molybdenum reagent can be selected from molybdate compound, such as preferably oneself but be not limited to titanium dioxide One or two in molybdenum, molybdenum trioxide, two water ten trithio ammonium molybdates, four thio ammonium molybdate, sodium molybdate, ammonium molybdate, molybdic acid Plant above combination.
More preferred, the consumption of described molybdenum reagent contains with described alkyl chain succinic acid and/or alkyl chain succinic anhydrides The mol ratio of some acid and/or anhydride is 1:0.1 ~ 1:10.
More preferred, described accelerator can be C1-C13Monohydric alcohol and/or polyhydric alcohol and deionized water in any One or more combination, it can accelerate two phase reaction speed.
Further, described alcohol preferably from but be not limited to methanol, ethanol, propanol, n-butyl alcohol, isobutanol, isoamyl alcohol, just Any one or multiple combination in capryl alcohol, isooctanol, ethylene glycol, Hexalin, cyclopentanol, the tert-butyl alcohol, sec-amyl alcohol.
It is further preferred that the mass ratio of described accelerator and described molybdenum reagent is 0.5~3:1.
More preferred, described diluent is selected from hydrocarbon solvent, lube base oil, many cerebrols, non-polar solven Any one or two or more combination.
Being more highly preferred to, described hydrocarbon solvent is selected from the low polar solvent that boiling range is 60 ~ 200 DEG C, and described hydrocarbon solvent includes Any one in toluene, dimethylbenzene, pentane, normal hexane, hexamethylene, normal heptane, normal octane, isobutyltrimethylmethane., n-decane, petroleum ether Kind or two or more combinations.
Being more highly preferred to, described non-polar solven includes glycol dimethyl ether, diethylene glycol dimethyl ether, N, N-dimethyl methyl Any one or two or more combination in amide, DMAC N,N' dimethyl acetamide, pyrrole network alkanone, oxolane.
Particularly preferably, described diluent includes normal hexane, petroleum ether, toluene, dimethylbenzene, glycol dimethyl ether, diethyl Any one in glycol dimethyl ether, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, lube base oil, many cerebrols Or two or more combinations.
It is further preferred that the consumption of described diluent is the reaction mass gross weight employed in this preparation method 0.1 ~ 3 times.
In the preparation process in accordance with the present invention, after the completion of reaction, unreacted raw material need to be removed, general conventional method Including but not limited to: methods such as filtration, centrifugal filtration, decant by unreacted solid material and impurity and required product It is separated.Filter aid such as kieselguhr (Celite) can be used, to improve separation efficiency.
Further, described post processing includes removing the water in obtained product and solvent, is typically steamed by normal pressure Evaporate or vacuum distilling removes solvent and water.
Another aspect of the invention provides the purposes of described molybdenum modifiers dispersants.
Such as, among some case study on implementation, described molybdenum modifiers dispersants can be compounded with multiple additives, allotment profit Sliding oil composition.
Thus, present invention also offers a kind of lubricant oil composite, it comprises described molybdenum modifiers dispersants.
Further, among some embodiments, described lubricant oil composite also can comprise other multiple additives.
Such as, described additive can be alkylated diphenylamine class antioxidant.Further, described molybdenum modifiers dispersants with Alkylated diphenylamine class antioxidant has the most collaborative antioxidation.
Such as, described additive can be zinc dialkyl dithiophosphate.Further, described molybdenum modifiers dispersants and dioxane Base zinc dithiophosphate has the most collaborative antiwear and antifriction effect, and its immediate cause is probably and defines two sulfur in contact surface Change molybdenum.
Further, described lubricant oil composite also can comprise one or more in following component, such as, lubricate oil base Plinth oil, detersive, antiwear additive, viscosity index improver, pour-point depressant, corrosion inhibitor, antirust agent, anti-foaming agent, supplement rub Wipe modifier or its mixture.
In conjunction with some embodiments, technical scheme will be described in detail as follows, but these embodiments will be to pass through Expand invention rather than limit what the mode invented proposed.
The preparation technology of some molybdenum modifiers dispersants is relate to, the various reactions employed in it among below embodiment Participate in thing and process conditions are all more typical examples, but verify through inventor's lot of experiments, in listed above Other type of reaction partner and other process conditions be the most all applicable, and also all the skill claimed invented by attainable cost Art effect.If not it addition, special instruction, " % " that address in below embodiment is " wt% ".
Embodiment 1
Weigh polyisobutylene butanedioic anhydride 10.0g(PIBSA, 0.01mol) it is directly added in 250ml there-necked flask, add three second Hydramine (TEA) 3.8g(0.025mol), xylene solvent 50ml is in this flask.Oil bath is heated, and temperature rises to 110 DEG C ~ 130 DEG C, use N2Extract the water byproduct reaction 6h generated.Weigh ammonium molybdate 4.0g(0.02mol), it is dissolved in 10ml water, obtains breast White or colourless solution, adds in there-necked flask, reacts 6h at 130 DEG C, and solution colour is blackish green, and oil bath is heated, and is warming up to 160 DEG C, magnetic agitation, dimethylbenzene or refluxing toluene, with the water in water knockout drum separation system, react 6h, to the most anhydrous steam the most anti- Should terminate, product is dark green solution, after reaction terminates, carries out sucking filtration separation while hot, and after separation, solution presents blackish green Color, filter paper presents dark green solid, containing a certain amount of green colored residue on there-necked flask wall.The solution obtained utilizes rotary evaporation Device steams xylene solvent.Rotating speed is 200 revs/min, and temperature is 85 DEG C, and pressure is 20bar, finally obtains bottle green oily liquid Body (code name is M1).
Embodiment 2
Weigh polyisobutylene butanedioic anhydride 10.0g(PIBSA, 0.01mol) it is directly added in 250ml there-necked flask, add diethyl Hydramine (DEA) 2.7g(0.025mol), toluene solvant 50ml is in this flask.Oil bath is heated, and temperature rises to 110 DEG C ~ 130 DEG C, Use N2Extract the water byproduct reaction 6h generated.Weigh molybdenum trioxide 2.9g(0.02mol), it is dissolved in 10ml water, obtains breast White or colourless solution, adds in there-necked flask, reacts 6h at 130 DEG C, and solution colour is blackish green, and oil bath is heated, and is warming up to 160 DEG C, magnetic agitation, dimethylbenzene or refluxing toluene, with the water in water knockout drum separation system, react 6h, to the most anhydrous steam the most anti- Should terminate, product is dark green solution, after reaction terminates, carries out sucking filtration separation while hot, and after separation, solution presents blackish green Color, filter paper presents dark green solid, containing a certain amount of green colored residue on there-necked flask wall.The solution obtained utilizes rotary evaporation Device steams xylene solvent.Rotating speed is 200 revs/min, and temperature is 85 DEG C, and pressure is 20bar, finally obtains bottle green oily liquid Body (code name is M2).
Embodiment 3
Weigh polyisobutylene butanedioic anhydride 10.0g(PIBSA, 0.01mol) it is directly added in 250ml there-necked flask, add ethanol Amine 1.6g(0.025mol), xylene solvent 50ml is in this flask.Oil bath is heated, and temperature rises to 110 DEG C ~ 130 DEG C, uses N2Carry Take the water byproduct reaction 6h of generation.Weigh sodium molybdate 4.8g(0.02mol), it is dissolved in 10ml water, obtains milky or nothing The solution of color, adds in there-necked flask, reacts 6h at 130 DEG C, and solution colour is blackish green, and oil bath is heated, and is warming up to 160 DEG C, magnetic Power stirs, dimethylbenzene or refluxing toluene, with the water in water knockout drum separation system, reacts 6h, steams i.e. reaction terminate, instead to the most anhydrous Answering product is dark green solution, reaction terminate after, carry out sucking filtration separation while hot, after separation, solution presents blackish green, on filter paper in Existing dark green solid, containing a certain amount of green colored residue on there-necked flask wall.The solution obtained utilizes rotary evaporator to steam diformazan Benzene solvent.Rotating speed is 200 revs/min, and temperature is 85 DEG C, and pressure is 20bar, and (code name is to finally obtain bottle green oily liquids M3).
The performance of following also obtained to embodiment 1 molybdenum modifiers dispersants is tested, and the experiment oil sample wherein used is The additive sample of certain mass is dissolved in base oil 150N the oil sample configured.
Antiwear and antifriction test (four ball frictional testing machines): according to SH/T 0189-92 perform (rotating speed 1200rpm ± 60rpm, temperature 75 DEG C ± 2 DEG C, time 60min ± 1min), test result is shown in Fig. 1.
Antioxidation test (PDSC method): according to SH/T 0719-2002 perform (pressure 3.5 ± 0.2MPa, flow velocity 100 ± 10mL/min), test result is shown in Fig. 2.
In summary, the oil-soluble molybdenum modifiers dispersants of the present invention in lubricating oil with alkylated diphenylamine class antioxidant There is obvious high temperature and work in coordination with antioxidation, with zinc dialkyl dithiophosphate, there is the most collaborative antiwear and antifriction effect, After the ZDDP compound use that addition is 0.5%wtMo and 0.5%wt, coefficient of friction is 0.057, and the ZDDP phase of 0.5%wt Ratio, coefficient of friction can reduce by 52.1%, and the spot diameter that rubs is 0.438mm, compares with base oil 150N, and the spot diameter that rubs reduces 47.1%.So, the present invention uses the dosage that adds that can reduce similar additive in lubricating oil, thus reduces in lubricating oil product Phosphorus content, be conducive to improving overall fuel economy.
The above is only the part preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, under the premise without departing from the principles of the invention, it is also possible to make some variations in detail, these variations in detail also should be regarded as this Bright protection domain.

Claims (10)

1. a molybdenum modifiers dispersants, it is characterised in that: containing imines diethanol molybdic acid diglyceride group in this dispersant.
Molybdenum modifiers dispersants the most according to claim 1, it is characterised in that: this dispersant has a following structural formula:
And/or
Wherein R is C2-C50Straight chained alkyl or the alkyl with side chain, m, n are the integer of 0-6, and dp is at least 1,2,3,4,5 Any one.
3. the preparation method of the molybdenum modifiers dispersants according to any one of claim 1-2, it is characterised in that including: by alkyl chain Succinic acid and/or alkyl chain succinic anhydrides, can select to add or without diluent, alcohol amine compound mixing carry out first Elementary reaction, remove afterwards may the unreacted reactant of residual, add molybdenum reagent and carry out second stage reaction, after through after place Reason obtains target product.
The preparation method of molybdenum modifiers dispersants the most according to claim 3, it is characterised in that:
This preparation method includes: after alkyl chain succinic acid and/or alkyl chain succinic anhydrides being sufficiently mixed uniformly with diluent, then Disposably add or be dividedly in some parts alcohol amine compound and can selecting add or without accelerator to carry out the first stage anti- Should, remove afterwards may the unreacted reactant of residual, property adds or is dividedly in some parts molybdenum reagent and carries out second stage reaction again, Last post-treated acquisition target product;
Preferably, this preparation method includes: by polyisobutylene butanedioic anhydride and/or high molecular weight polyisobutylene succinic anhydride with dilute Release agent and be sufficiently mixed uniformly under conditions of temperature is 30 ~ 100 DEG C, under conditions of temperature is 50 ~ 150 DEG C, adds hydramine afterwards Compound and can select add or without accelerator, then under conditions of temperature is 60 ~ 160 DEG C react 0.2 ~ 8h, Then remove the unreacted reactant that may remain, add molybdenum reagent at reduced pressure conditions under conditions of temperature is 80 ~ 200 DEG C Constant temperature keeps 0.5 ~ 5h, last post-treated acquisition target product;
It is further preferred that this preparation method includes: by polyisobutylene butanedioic anhydride and/or high molecular weight polyisobutylene succinic acid Acid anhydride and diluent are sufficiently mixed uniformly under conditions of temperature is 30 ~ 100 DEG C, add afterwards under conditions of temperature is 50 ~ 120 DEG C Enter triethanolamine and can select add or without accelerator, then under conditions of temperature is 90 ~ 160 DEG C react 0.2 ~ 6h, then removes the unreacted reactant that may remain, adds molybdenum reagent at reduced pressure conditions in the bar that temperature is 80 ~ 180 DEG C Under part, constant temperature keeps 1 ~ 4h, last post-treated acquisition target product.
5. according to the preparation method of the molybdenum modifiers dispersants according to any one of claim 3-4, it is characterised in that:
Described alkyl chain succinic acid and/or alkyl chain succinic anhydrides are C2-C50Straight chained alkyl or with the alkyl of side chain Succinic acid and/or succinic anhydrides;
Preferably, described alkyl chain succinic acid and/or alkyl chain succinic anhydrides can be selected from, but not limited to, polyisobutylene succinic acid, One in polyisobutylene butanedioic anhydride, high molecular weight polyisobutylene succinic acid, high molecular weight polyisobutylene succinic anhydride or it Mixture;
It is further preferred that the equal molecule of number of polyisobutylene group in described alkyl chain succinic acid and/or alkyl chain succinic anhydrides Amount is 500 ~ 5000.
6. according to the preparation method of the molybdenum modifiers dispersants according to any one of claim 3-5, it is characterised in that:
Described alcohol amine compound can be selected from, but not limited to, methanol diethanol amine, triethanolamine, propanol diethanol amine, butanol diethyl One or more combination in hydramine, amylalcohol diethanolamine, hexanol diethanolamine, enanthol diethanolamine;
Preferably, the acid that the consumption of described alcohol amine compound contains with described alkyl chain succinic acid and/or alkyl chain succinic anhydrides The mol ratio of acid anhydride and/or acid is 1:0.1 ~ 1:10.
7. according to the preparation method of the molybdenum modifiers dispersants according to any one of claim 3-6, it is characterised in that:
Described molybdenum reagent can be selected from molybdate compound, such as preferably from but be not limited to molybdenum dioxide, molybdenum trioxide, two water One or more kinds of combinations in ten trithio ammonium molybdates, four thio ammonium molybdate, sodium molybdate, ammonium molybdate, molybdic acid;
More preferred, anhydride that the consumption of described molybdenum reagent contains with described alkyl chain succinic acid and/or the mol ratio of acid For 1:0.1 ~ 1:10.
8. according to the preparation method of the molybdenum modifiers dispersants according to any one of claim 3-7, it is characterised in that:
Described accelerator includes C1-C13Monohydric alcohol and/or polyhydric alcohol and deionized water in any one or two or more Combination, described alcohol includes methanol, ethanol, n-butyl alcohol, isoamyl alcohol, n-octyl alcohol, isooctanol, propanol, isobutanol, ethylene glycol, ring Any one or two or more combination in hexanol, cyclopentanol, the tert-butyl alcohol, sec-amyl alcohol;
Preferably, the consumption of described accelerator is 0.2 ~ 3 times of described molybdenum reagent gross mass.
9. according to the preparation method of the molybdenum modifiers dispersants according to any one of claim 3-8, it is characterised in that:
Any one or two kinds that described diluent is selected from hydrocarbon solvent, lube base oil, many cerebrols, non-polar solven with On combination;
Preferably, described hydrocarbon solvent is selected from the low polar solvent that boiling range is 60 ~ 200 DEG C, and described hydrocarbon solvent includes toluene, diformazan Any one or two kinds in benzene, pentane, normal hexane, hexamethylene, normal heptane, normal octane, isobutyltrimethylmethane., n-decane, petroleum ether Above combination;
Preferably, described non-polar solven includes glycol dimethyl ether, diethylene glycol dimethyl ether, DMF, N, Any one or two or more combination in N-dimethyl acetylamide, pyrrole network alkanone, oxolane;
Particularly preferably, described diluent includes normal hexane, petroleum ether, toluene, dimethylbenzene, glycol dimethyl ether, diethylene glycol In dimethyl ether, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, lube base oil, many cerebrols any one or Two or more combinations;
It is further preferred that the consumption of described diluent is the reaction mass gross weight employed in this preparation method 0.1 ~ 3 Times.
10. a lubricant oil composite, it is characterised in that comprise the molybdenum modifiers dispersants described in claim 1-2 or according to right Require molybdenum modifiers dispersants prepared by the method described in 3-9.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN107418251A (en) * 2017-08-30 2017-12-01 金堆城钼业股份有限公司 A kind of anti-oxidation treatment method of ultra-fine molybdenum disulfide
CN110982582A (en) * 2019-12-04 2020-04-10 重庆昆崧科技有限公司 Preparation method of lubricating oil antiwear agent
CN114507511A (en) * 2022-02-28 2022-05-17 扬州润达油田化学剂有限公司 Emulsion molybdenum lubricant for environment-friendly drilling fluid salt slurry system and preparation method thereof

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CN103249717A (en) * 2011-01-21 2013-08-14 雪佛龙奥伦耐有限责任公司 Improved process for preparation of high molecular weight molybdenum succinimide complexes
CN104844656A (en) * 2015-03-24 2015-08-19 上海交通大学 Non-sulfur and non-phosphorus organic molybdenum compound and preparation method and application thereof
CN105695048A (en) * 2016-01-13 2016-06-22 北京联飞翔科技股份有限公司 Lubricant additive and lubricant containing same

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JPS6239696A (en) * 1985-08-14 1987-02-20 Asahi Denka Kogyo Kk Molybdenum-containing lubricating composition
CN103249717A (en) * 2011-01-21 2013-08-14 雪佛龙奥伦耐有限责任公司 Improved process for preparation of high molecular weight molybdenum succinimide complexes
CN104844656A (en) * 2015-03-24 2015-08-19 上海交通大学 Non-sulfur and non-phosphorus organic molybdenum compound and preparation method and application thereof
CN105695048A (en) * 2016-01-13 2016-06-22 北京联飞翔科技股份有限公司 Lubricant additive and lubricant containing same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107418251A (en) * 2017-08-30 2017-12-01 金堆城钼业股份有限公司 A kind of anti-oxidation treatment method of ultra-fine molybdenum disulfide
CN110982582A (en) * 2019-12-04 2020-04-10 重庆昆崧科技有限公司 Preparation method of lubricating oil antiwear agent
CN110982582B (en) * 2019-12-04 2022-05-13 重庆昆崧科技有限公司 Preparation method of lubricating oil antiwear agent
CN114507511A (en) * 2022-02-28 2022-05-17 扬州润达油田化学剂有限公司 Emulsion molybdenum lubricant for environment-friendly drilling fluid salt slurry system and preparation method thereof

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