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.