CN105586137A - Complex aluminum-based lubricating grease composition with excellent oxidation resistance and preparation method therefor - Google Patents
Complex aluminum-based lubricating grease composition with excellent oxidation resistance and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a complex aluminum-based lubricating grease composition with excellent oxidation resistance. The lubricating grease composition contains the following ingredients in percentage by weight: 65-95wt% of lubricating base oil, 5-35wt% of complex aluminum-based thickener and 0.1-15wt% of additive, wherein the additive contains a compound with a structure represented by a formula (I) shown in the description. The invention further provides a preparation method for the complex aluminum-based lubricating grease composition with excellent oxidation resistance. The lubricating grease composition provided by the invention has good mechanical stability, water resistance and colloid stability, has obvious advantage in oxidation resistance and has good compatibility with other lubricating greases. Thus, grease can be adequate to lubricate various motors, power generators, air blowers and equipment of transportation industry, iron and steel enterprises and other various industries and is particularly applicable to the lubrication of friction parts of all kinds of mechanical equipment under relatively-high-temperature and wet conditions.
Description
Technical field
The present invention relates to lubricating grease field, particularly, relate to a kind of antioxygen property that contains special additiveExcellent composite aluminum base grease composition and method of making the same.
Background technology
The research of composite aluminum base grease starts from the 1950's, but until is just subject to the seventies heavilyDepending on, be mainly used in the concentrated for fat system of steel plant, in complex-soap base grease, output is only second to compound lithium baseLubricating grease occupies second. Composite aluminum base grease is a kind of high temperature multi-effect lubricating grease, has high dropping point and goodGood multiple-effect performance, as good colloid stability, oxidation stability, mechanical stability, water-resistance,Particularly there is good pump-conveying property, be applicable to central system. The people such as Li Laihong come with orthogonal design methodThe best proportioning of finding out stearic acid, benzoic acid and aluminium isopropoxide, has made the clad aluminum that meets professional standardBase grease; Cao Piye has studied the impact of solvent on composite aluminum base grease performance; Li Yeyu etc.The impact of the performance of the solvent that people has inquired into various base oils and fat on fat, has tentatively proposed compoundThe optimum formula of aluminium-base grease; CN102021067A has prepared one and has been applicable to the aluminium base profit of ships bariumConsistent lubricant; CN102021068A has prepared one and has been applicable to sodium aluminate soap grease for ship; CN1900244AIn composite aluminum base grease, introduced sulfoacid calcium, the composite aluminum base grease of preparation is not additivatedIn situation, water-resistance, rust-preventing characteristic, extreme pressure property, mechanical stability and high temperature colloid stability are improved.
The life-span of lubricating grease can shorten with the prolongation of serviceability temperature rising or lubrication time. From chemical propertyUpper theory is the major reason that causes lubricating grease oxidation deterioration as the metal soap of thickening agent. In order to suppressThe oxidation deterioration of lubricating grease, anti-oxidation product causes the corrosion of metal surface, add appropriate resistingOxygen additive. At present, conventional antioxidant is mainly divided into amine and phenols two classes. Phenolic antioxidant is generalComprise BHT, 2,6-di-tert-butylphenol etc., but its serviceability temperature is lower, generally existsIn 150 DEG C. Amine antioxidants is mainly alkylated diphenylamine, or alkylating phenyl-naphthylamines etc.
Summary of the invention
The object of the invention is the high request in order to meet the antioxygen property to lubricating grease, a kind of antioxygen is providedThe composite aluminum base grease composition and method of making the same of excellent performance.
The present inventor finds under study for action, and the additive in lubricant composition contains formula (I)Shown in the antioxidant of structure:
Can make lubricant composition there is the good performance such as anti-oxidant.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of antioxygen property excellenceComposite aluminum base grease composition, taking the weight of lubricant composition as benchmark, described lubricant compositionComprise following component: the lubricating base oil of 65-95 % by weight, the composite aluminum base thickening agent of 5-35 % by weightWith the additive of 0.1-15 % by weight, the compound that described additive contains structure shown in formula (I):
Preferably, taking the weight of lubricant composition as benchmark, described lubricant composition comprises following groupPoint: the lubricating base oil of 75-88 % by weight, the composite aluminum base thickening agent of 5-15 % by weight and 0.1-5 % by weightAdditive.
Preferably, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Content is 0.1-3 % by weight, more preferably 0.2-1 % by weight.
On the other hand, the invention provides a kind of composite aluminum base grease composition of antioxygen property excellencePreparation method, described method comprises:
(1) by the lubricating base oil of 1/5-2/5, higher fatty acids, that aluminium source heat temperature raising carries out saponification is anti-Should, then add the little molecule acid in the lubricating base oil that is dissolved in 1/10-1/5 to carry out recombination reaction;
(2) add water and lower the temperature, be then warming up to 200-220 DEG C and refine;
(3) add residue lubricating base oil, be cooled to 100-130 DEG C, then add additive;
(4) grind 2-4 time by three-roller;
Wherein, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 65-95 is heavyThe consumption of the composite aluminum base thickening agent of measure %, being prepared by higher fatty acids, little molecule acid and aluminium source is 5-35% by weight, the consumption of additive is 0.1-15 % by weight, it is characterized in that, described additive contains formula (I)Shown in the compound of structure:
Preferably, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 75-88 is heavyThe consumption of the composite aluminum base thickening agent of measure %, being prepared by higher fatty acids, little molecule acid and aluminium source is 5-15% by weight, the consumption of additive is 0.1-5 % by weight.
Preferably, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Consumption is 0.1-3 % by weight, more preferably 0.2-1 % by weight.
Lubricant composition provided by the invention, has good mechanical stability, water-resistance and colloid peaceQualitative, more on antioxygenic property, there is obvious advantage, and have good compatibility with other lubricating grease.Make this fat can be competent in various motors, generator, air blast, transportation, iron and steel enterprise andOther various industrial equipments lubricated, is specially adapted to plant equipment under various higher temperature wet conditionsLubricating of friction position.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Fig. 1 is the reaction equation of the step (a) of preparing antioxidant.
Fig. 2 is the reaction equation of the step (b) of preparing antioxidant.
Fig. 3 is the reaction equation of the step (c) of preparing antioxidant.
Fig. 4 is the hydrogen spectrum spectrogram of the antioxidant prepared of preparation example.
Fig. 5 is the carbon spectrum spectrogram of the antioxidant prepared of preparation example.
Fig. 6 is the mass spectrogram of the antioxidant prepared of preparation example.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of composite aluminum base grease composition of antioxygen property excellence, with lubricating grease groupThe weight of compound is benchmark, and lubricant composition comprises following component: the lubrication base of 65-95 % by weightOil, the composite aluminum base thickening agent of 5-35 % by weight and the additive of 0.1-15 % by weight, additive contains formula(I) compound of structure shown in:
In the present invention, what antioxidant referred to is the compound of structure shown in formula (I).
In the present invention, preferably, taking the weight of lubricant composition as benchmark, described lubricant compositionComprise following component: the lubricating base oil of 75-88 % by weight, the composite aluminum base thickening agent of 5-15 % by weightAdditive with 0.1-5 % by weight.
In the present invention, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Content be preferably 0.1-3 % by weight, more preferably 0.2-1 % by weight.
The present invention is intended to contain knot shown in formula (I) by the additive in composite aluminum base grease compositionThe compound of structure and realize goal of the invention, good anti-oxidant even if composite aluminum base grease composition hasEtc. performance. Therefore, for the selection of each conventional component in composite aluminum base grease, all less than specific limitSystem.
In the present invention, lubricating base oil can be the conventional lubricating base oil using in this area, for example canFor at least one in mineral oil, vegetable oil and artificial oil. 100 DEG C of kinematic viscosity of lubricating base oil are preferredFor 5-60mm2/ s, more preferably 10-30mm2/ s. Concrete for mineral oil, vegetable oil and artificial oilAlso there is no particular limitation for kind, can adopt the conventional mineral oil in this area, vegetable oil and artificial oil,For example, mineral oil can be selected paraffinic base, cycloalkyl series, vegetable oil can be castor oil, rapeseed oil,At least one in peanut oil and soybean wet goods, artificial oil can be poly-a-olefin oil (PAO), ester class oil,At least one in fluorocarbon oil and silicone oil etc.
In the present invention, composite aluminum base thickening agent can be the conventional composite aluminum base thickening agent in this area, for example,Can be that acid is reacted generation with aluminium source, acid comprises higher fatty acids and little molecule acid.
Wherein, higher fatty acids can be the aliphatic acid of C12-C25, be preferably laurate, palmitic acid,At least one in stearic acid and 12-hydroxy stearic acid, more preferably stearic acid and/or 12-hydroxyl tristearinAcid.
Wherein, little molecule acid is preferably the carboxylic acid of C4-C11, more preferably benzoic acid, terephthalic acid (TPA),At least one in azelaic acid and decanedioic acid.
Wherein, aluminium source is preferably aluminium isopropoxide and/or aluminium isopropoxide tripolymer.
Above-mentioned composite aluminum base thickening agent can adopt the thinkable the whole bag of tricks of those skilled in the art to obtain.
In the present invention, because having preferably, the antioxidant of structure shown in formula (I) and other additives joinWu Xing, therefore, according to the use needs of lubricating grease, additive of the present invention can also contain antirust agent.Without particular/special requirement, can adopt kind and the content of this area routine for the kind of antirust agent and content.For example, antirust agent can be at least one in barium mahogany sulfonate, dinonyl barium benzosulfonate and Lanolin Calcium SoapKind, the content of antirust agent can account for the 0.05-4.5 % by weight of lubricant composition gross weight, is preferably 0.1-2% by weight.
In the present invention, shown in formula (I), the preparation method of the compound of structure preferably includes:
(a) 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene are carried out to condensation reaction, shown in production (II)Intermediate M,
(b) intermediate M step (a) being obtained contacts with bromide reagent and carries out bromo-reaction, rawBromination product shown in an accepted way of doing sth (III),
(c) make the bromination product that step (b) obtains contact and carry out idol with the compound shown in formula (IV)Connection reaction, the antioxidant shown in production (I),
In step of the present invention (a), the condition of condensation reaction preferably includes: under inert atmosphere,In one solvent, under the existence of the first catalyst, by 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene at-20-0 DEG CAfter lower reaction 0.5-1.5h, rise to 15-30 DEG C, be then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the inert atmosphere of this area routine, for example can by nitrogen,The gases such as argon gas provide.
It will be understood by those skilled in the art that for stable reaction is carried out reaction at-20-0 DEG CAfter 0.5-1.5h, rise to 15-30 DEG C, should slowly be warming up to 15-30 DEG C, for example, can be by-20-0 DEG CSystem after lower reaction 0.5-1.5h is placed under the environment temperature of 15-30 DEG C, makes reaction system self slowBe warming up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from methyl alcohol, ethanol, DMF and acetonitrileAt least one, more preferably methyl alcohol and/or acetonitrile, is further preferably methyl alcohol.
In the present invention, the first catalyst can be inorganic acid or organic acid, is preferably selected from acetic acid, to methylAt least one in benzoic acid and benzene sulfonic acid, more preferably acetic acid.
In the present invention, the consumption of 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene is essentially equimolar amounts, butFormaldehyde and benzene can be suitably excessive. The mol ratio of 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene is preferably0.9-1.5:0.9-10:0.9-10。
In step of the present invention (a), the consumption of the first catalyst can be catalytic amount, with the tertiary fourth of 2,6-bis-The molal quantity of base phenol is benchmark, and the consumption of the first catalyst is preferably 5-100 % by mole, more preferably10-30 % by mole.
It will be understood by those skilled in the art that in step of the present invention (a), purer in order to obtainIntermediate M, also need reacted system to carry out post processing, the mode of post processing can comprise and subtractingPress except desolventizing, then through solvent dilution, washing, dry, decompression again except desolventizing, for example, will be anti-Should after system at 0.01-0.05MPa, 40-60 DEG C except desolventizing, then pour 1-10 times of volume intoIn ethyl acetate (or carrene), use respectively distilled water and saturated common salt water washing, then at 15-30 DEG CUnder add the drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keep 10-60min. Remove by filter dryAfter agent, at 0.01-0.05MPa, 40-60 DEG C, remove desolventizing, to obtain intermediate M.
In step of the present invention (a), 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction of condensation reactionAs shown in Figure 1, in Fig. 1, what the first solvent adopted is methyl alcohol to equation, and what the first catalyst adopted isAcetic acid, only for purposes of illustration, is not construed as limiting scope of the present invention.
In step of the present invention (b), the condition of bromo-reaction preferably includes: under inert atmosphere,In two solvents, under the existence of the second catalyst, under lucifuge condition, during step (a) is obtainedMesosome M reacts 1-2h with bromide reagent at 15-30 DEG C, then uses quencher cancellation.
" inert atmosphere " as previously mentioned, do not repeat them here.
To it will be understood by those skilled in the art that in order reacting more stably and to carry out, preferably to intermediateIn M, slowly add brominated reagent.
In the present invention, the second solvent is preferably selected from oxolane, carrene, chloroform and ether extremelyFew a kind of, more preferably oxolane.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azoAt least one in bis-isobutyronitrile (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more excellentElect NBS as.
In step of the present invention (b), carry out cancellation with quencher, quencher can be conventional for this areaQuencher can be for example saturated aqueous common salt.
In step of the present invention (b), the consumption of intermediate M and bromide reagent is essentially equimolar amounts,But bromide reagent generally can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate. Intermediate M withBromide reagent mol ratio is preferably 0.9-1.2:0.9-3.0.
In step of the present invention (b), the consumption of the second catalyst can be catalytic amount, with intermediate M'sMolal quantity is benchmark, and the consumption of the second catalyst is preferably 10-100 % by mole, and more preferably 40-60 rubsYou are %.
In the inventive method step (b), intermediate M contacts with bromide reagent and carries out the anti-of bromo-reactionAnswer equation as shown in Figure 2, in Fig. 2, that bromide reagent adopts is NBS, is only illustrational order, scope of the present invention is not construed as limiting.
In step of the present invention (b), except the bromination product shown in production (III), also has traceThe bromination product at ortho position generates, and between not having, the bromination product of position generates, but the amount of the bromination product at ortho position veryPettiness, does not have materially affect to subsequent reactions, negligible.
It will be understood by those skilled in the art that in step of the present invention (b), purer in order to obtainBromination product, also need the system after cancellation to carry out post processing, the mode of post processing can comprise waterWash, be dried, removal of solvent under reduced pressure, for example, the system after cancellation is washed with distilled water, then existAt 15-30 DEG C, add the drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keep 10-60min. FilterRemove after drier, at 0.01-0.05MPa, 40-60 DEG C, remove desolventizing, to obtain bromination product.
In step of the present invention (c), the condition of coupling reaction preferably includes: under inert atmosphere,In three solvents, under the existence of the 3rd catalyst, the bromination product that step (b) is obtained and formula (IV)Shown compound reacts 4-8h at 80-100 DEG C.
" inert atmosphere " as previously mentioned, do not repeat them here.
In the present invention, for stable reaction is carried out, be preferably warming up to gradually 80-100 DEG C, then existAt 80-100 DEG C, react 4-8h.
In the present invention, the 3rd solvent is preferably selected from carrene, chloroform, toluene and oxolane extremelyFew a kind of, more preferably carrene.
In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali. Palladium salt is preferably selected from palladiumAnd/or palladium-dibenzalacetone complex compound [Pd2(dba)3]; Part is preferably selected from tri-tert phosphorus, dinaphthol(BINAP) at least one and in two (diphenylphosphino) ferrocene (dppf); Alkali is preferably selected from uncleAt least one in sodium butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate.
In step of the present invention (c), the chemical combination shown in the bromination product that step (b) obtains and formula (IV)The consumption of thing is essentially equimolar amounts, but the compound shown in formula (IV) can be suitably excessive. Step(b) mol ratio of the compound shown in the bromination product obtaining and formula (IV) is preferably 0.9-1.5:0.9-2.5.
In step of the present invention (c), the consumption of catalyst can be catalytic amount, with bromination product moleNumber is benchmark, and the consumption of palladium salt is preferably 5-50 % by mole, and more preferably 5-20 % by mole more enters oneStep is preferably 5-10 % by mole; The consumption of part is preferably 5-50 % by mole, more preferably 10-30 % by mole;The consumption of alkali is preferably 5-50 % by mole, more preferably 10-30 % by mole.
In step of the present invention (c), the chemical combination shown in the bromination product that step (b) obtains and formula (IV)As shown in Figure 3, in Fig. 3, what palladium salt adopted is acetic acid to the reaction equation that coupling reaction is carried out in thing contactPalladium, only for purposes of illustration, is not construed as limiting scope of the present invention.
It will be understood by those skilled in the art that in order to obtain purer end product i.e. formula (I)Shown antioxidant, the inventive method preferably also comprises reacted system is carried out to post processing, post processingMode can comprise filtration, solvent dilution, washing, dry, removal of solvent under reduced pressure, for example, will be anti-Should after system filter after filtrate pour in the ethyl acetate (or carrene) of 1-10 times of volume,Then with distilled water washing, then at 15-30 DEG C, add anhydrous calcium chloride or anhydrous sodium sulfate etc. dryDrying prescription, keeps 10-60min. Remove by filter after drier, at 0.01-0.05MPa, 40-60 DEG C, removeDesolventizing, to obtain the antioxidant shown in formula (I).
Each step of the method for the compound of structure shown in preparation formula in the present invention (I) preferably under agitationCarrying out, without particular/special requirement, can be the mixing speed of this area routine for mixing speed, for example, stirsThe speed of mixing can be 100-800rpm.
Shown in preparation formula of the present invention (I) in the method for the compound of structure, for the first solvent, secondThe amount of solvent and the 3rd solvent, without particular/special requirement, can be the solvent load of this area routine, and this is abilityField technique personnel are known, do not repeat them here.
As mentioned above, the present invention is intended to contain formula by the additive in composite aluminum base grease composition(I) compound of structure shown in and realize goal of the invention, good anti-even if lubricant composition hasThe performances such as oxidation. Therefore,, can adopt without particular/special requirement for the preparation method of composite aluminum base greaseThe conventional method using in this area, for example, second aspect, the present invention also provides a kind of antioxygen property excellentThe preparation method of different composite aluminum base grease composition, the method comprises:
(1) by the lubricating base oil of 1/5-2/5, higher fatty acids, that aluminium source heat temperature raising carries out saponification is anti-Should, then add the little molecule acid in the lubricating base oil that is dissolved in 1/10-1/5 to carry out recombination reaction;
(2) add water and lower the temperature, be then warming up to 200-220 DEG C and refine;
(3) add residue lubricating base oil, be cooled to 100-130 DEG C, then add additive;
(4) grind 2-4 time by three-roller;
Wherein, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 65-95 is heavyThe consumption of the composite aluminum base thickening agent of measure %, being prepared by higher fatty acids, little molecule acid and aluminium source is 5-35% by weight, the consumption of additive is 0.1-15 % by weight, the chemical combination that additive contains structure shown in formula (I)Thing:
In the inventive method, preferably, taking the weight of lubricant composition as benchmark, lubricating base oilThe composite aluminum base multiviscosisty that consumption is 75-88 % by weight, prepared by higher fatty acids, little molecule acid and aluminium sourceThe consumption of agent is 5-15 % by weight, and the consumption of additive is 0.1-5 % by weight.
In the inventive method, the total amount of higher fatty acids and little molecule acid and being preferably of mol ratio in aluminium sourceLearn metering ratio, aluminium source also can excessive 1-10 % by weight. The mol ratio of higher fatty acids and little molecule acid is excellentElect 1:0.1-5 as, more preferably 1:0.3-2. It will be understood by those skilled in the art that basis is by seniorThe consumption of composite aluminum base thickening agent prepared by aliphatic acid, little molecule acid and aluminium source, can instead release senior fatThe consumption in fat acid, little molecule acid and aluminium source, this is conventionally known to one of skill in the art, does not repeat them here.
In the inventive method, taking the weight of lubricant composition as benchmark, the change of structure shown in formula (I)The consumption of compound is preferably 0.1-3 % by weight, more preferably 0.2-1 % by weight.
In the inventive method, the lubricating base oil of 1/5-2/5, the lubricating base oil of 1/10-1/5 refer to respectivelyAccount for 1/5-2/5, the 1/10-1/5 of lubricating base oil total amount.
In the inventive method step (1), be preferably heated to 90-120 DEG C, the saponification time is excellentElect 0.5-1.5h as, complex reaction time is preferably 0.5-1.5h.
In the inventive method step (2), the amount adding water preferably makes temperature be down to 70-90 DEG C, and preferably protectsTemperature 5-25min.
In the inventive method step (2), the time of refining is preferably 5-25min.
The each step of the inventive method is preferably under agitation carried out, for mixing speed without particular/special requirement, canFor the mixing speed of this area routine, for example, mixing speed can be 20-500rpm.
Lubricating base oil, higher fatty acids, little molecule acid, aluminium source, additive as previously mentioned, at this notRepeat again.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
The physico-chemical analysis method of product: by inductively coupled plasma emission of ions spectrographic determination elementContent.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen spectrum,13C carbon spectrum), high resolution mass spectrum.
Preparation example
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), being filled with nitrogen protectsProtect, add the methyl alcohol of 150ml and the acetic acid of 0.01mol, fully cooling in ice-water bath after, then divideDo not add 2 of 0.1mol, 6-DI-tert-butylphenol compounds, the formaldehyde of 0.2mol and the benzene of 0.3mol. Reaction 1After hour, remove ice-water bath, be heated to 75 DEG C after rising to 25 DEG C and stop reaction after continuing to reflux 2 hours,Reacted system is steamed to solvent at 0.03MPa, 50 DEG C, then adds 250ml ethyl acetate,And proceed in separatory funnel, use respectively 100ml distilled water (twice) and the water washing of 50ml saturated common salt,And adding 10g anhydrous calcium chloride dry 20min at 25 DEG C, the filtrate after filtration is at 40 DEG C, 0.03MPaLower steaming desolventizes, and obtains midbody product M1.
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), being filled with nitrogen protectsProtect, add the dry tetrahydrofuran of 150ml, then dissolve in midbody product M1, and add 0.05molAmmonium nitrate, under lucifuge condition, slowly add 0.1mol brominated reagent NBS. At 25 DEG C, stir anti-Answer 1.5h, then use saturated aqueous common salt cancellation, then use 100ml distilled water (twice) washing, and addEnter 10g anhydrous sodium sulfate dry 20min at 25 DEG C. Filtrate after filtration is at 40 DEG C, 0.03MPaLower steaming desolventizes, and obtains bromination product.
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), being filled with nitrogen protectsProtect, add the carrene of 150ml as solvent, add respectively above-mentioned bromination product and 0.12mol124 Triazole compound, adds the tri-tert phosphorus of 0.02mol subsequently, the sodium tert-butoxide of 0.02mol andThe Pd (OAc) of 0.005mol2. Be warming up to gradually 90 DEG C, continue to stir 6h. Then by reacted bodyFiltrate after system filters adds 250ml ethyl acetate, and proceeds in separatory funnel, uses 100ml distilled water(twice) washing, and add 10g anhydrous sodium sulfate dry 20min at 25 DEG C. Filtrate after filtrationUnder 40 DEG C, 0.03MPa, steam and desolventize, obtain end product S1.
The physico-chemical analysis data of S1 are as follows: nitrogen content, 11.2%.
S1 is carried out to structural characterization, obtain respectively hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectivelySee Fig. 4, Fig. 5 and Fig. 6.
Can find out from physico-chemical analysis data, Fig. 4, Fig. 5 and Fig. 6 of above-mentioned preparation example, S1 has formula(I) structure shown in.
Embodiment 1
The present embodiment is used for illustrating composite aluminum base grease composition and method of making the same of the present invention.
(1) by 135.8 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, lower with), 10.5Gram stearic acid and 7.2 grams of aluminum isopropylates add in fat still processed, under 200rpm stirs, are heated to110 DEG C, carry out saponification 1h, then by 4.5 grams of benzene that are dissolved in 45.2 grams of 500SN base oilsFormic acid adds in fat still processed and carries out recombination reaction 1h;
(2) add water and be cooled to 90 DEG C, keep 5min, continue stirring and be warming up to 210 DEG C, insulation refining5min；
(3) add 90.5 grams of 500SN base oils, treat that temperature is cooled to 110 DEG C, add 2 grams of S1,2.5 grams of barium mahogany sulfonates stir under 200rpm;
(4) grind 3 times by three-roller and become fat. Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: compound aluminium soap 7% by weight; Lubricating base oil 91 % by weight; S11 % by weight; Barium mahogany sulfonate 1 % by weight.
Embodiment 2
The present embodiment is used for illustrating composite aluminum base grease composition and method of making the same of the present invention.
(1) by 134 grams of 150BS base oils, (100 DEG C of viscosity are 30mm2/ s, lower with), 13.98 gramsStearic acid and 9.36 grams of aluminum isopropylates add in fat still processed, under 60rpm stirs, are heated to90 DEG C, carry out saponification 1.5h, then by 6 grams of benzene first that are dissolved in 42 grams of 150BS base oilsAcid adds in fat still processed carries out recombination reaction 1.5h;
(2) add water and be cooled to 70 DEG C, keep 25min, continue stirring and be warming up to 220 DEG C, insulation refining8min processed;
(3) add 88 grams of 150BS base oils, treat that temperature is cooled to 100 DEG C, add 2 grams of S1,2.5 grams of barium mahogany sulfonates stir under 60rpm;
(4) grind 4 times by three-roller and become fat. Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: compound aluminium soap 9% by weight; Lubricating base oil 89.5 % by weight; S10.7 % by weight; Barium mahogany sulfonate 0.8 % by weight.
Embodiment 3
The present embodiment is used for illustrating composite aluminum base grease composition and method of making the same of the present invention.
(1) by 145 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 10mm2/ s, lower with), 11.3Gram stearic acid and 5.9 grams of aluminum isopropylates add in fat still processed, under 300rpm stirs, are heated to100 DEG C, carry out saponification 1.2h, then by 4.9 grams that are dissolved in 35 grams of PAO6 synthetic hydrocarbon oilsBenzoic acid adds in fat still processed and carries out recombination reaction 1.2h;
(2) add water and be cooled to 80 DEG C, keep 15min, continue stirring and be warming up to 200 DEG C, insulation refining25min processed;
(3) add 88 grams of PAO6 synthetic hydrocarbon oils, treat that temperature is cooled to 105 DEG C, add 2 grams of S1,2.5 grams of barium mahogany sulfonates stir under 300rpm;
(4) grind 2 times by three-roller and become fat. Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: compound aluminium soap 7% by weight; Lubricating base oil 92 % by weight; S10.4 % by weight; Barium mahogany sulfonate 0.6 % by weight.
Embodiment 4
The present embodiment is used for illustrating composite aluminum base grease composition and method of making the same of the present invention.
(1) by the miscella of 146 grams of 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, underWith), 8.4 grams of stearic acid and 5.4 grams of aluminum isopropylates add in fat still processed, under 500rpm stirring, addHeat is warming up to 120 DEG C, carries out saponification 0.5h, then will be dissolved in 40 grams of 500SN and 150BSMiscella in 3.6 grams of benzoic acid add in fat still processed and carry out recombination reaction 0.5h;
(2) add water and be cooled to 85 DEG C, keep 10min, continue stirring and be warming up to 205 DEG C, insulation refining15min processed;
(3) add the miscella of 90 grams of 500SN and 150BS, treat that temperature is cooled to 130 DEG C, adds2 grams of S1,3 grams of barium mahogany sulfonates stir under 500rpm;
(4) grind 2 times by three-roller and become fat. Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: compound aluminium soap 6.5% by weight; Lubricating base oil 93 % by weight; S10.2 % by weight; Barium mahogany sulfonate 0.3 % by weight.
Comparative example 1
Method according to embodiment 4 is prepared composite aluminum base grease, different, S1 is replaced with etc.The diphenylamines of amount. Properties of product are as shown in table 1.
In the lubricating grease that this comparative example obtains, taking lubricating grease weight as benchmark, consist of: compound aluminium soap 6.5% by weight; Lubricating base oil 93 % by weight; Diphenylamines 0.2 % by weight; Barium mahogany sulfonate 0.3 % by weight.
Table 1
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Oxidation stability: SH/T0325; Stencil oil-dividing:SH/T0324; Anticorrosive property: GB/T5018; Water drenches number of dropouts: SH/T0109; Copper corrosion: GB/T7326.
It will be understood by those skilled in the art that Drawing cone in-degree is less, the multiviscosisty of grease thickenerPerformance is better; Oxidation stability is less, and the antioxygenic property of lubricating grease is better; Stencil oil-dividing value is less,The colloid stability of lubricating grease is better; Water pouring number of dropouts is less, and the water resistance of lubricating grease is better.
Embodiment 4 is compared and can be found out with comparative example 1, and lubricating grease of the present invention has betterNon-oxidizability, colloid stability and water proofing property.
Lubricant composition provided by the invention, has good mechanical stability, water-resistance and colloid peaceQualitative, more on antioxygenic property, there is obvious advantage, and have good compatibility with other lubricating grease.Make this fat can be competent in various motors, generator, air blast, transportation, iron and steel enterprise andOther various industrial equipments lubricated, is specially adapted to plant equipment under various higher temperature wet conditionsLubricating of friction position.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail, still, the present invention does not limitDetail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can be to the present inventionTechnical scheme carry out multiple simple variant, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode, for fear of needn'tThe repetition of wanting, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (19)
1. a composite aluminum base grease composition for antioxygen property excellence, with the weight of lubricant compositionAmount is for benchmark, and described lubricant composition comprises following component: the lubricating base oil of 65-95 % by weight,The composite aluminum base thickening agent of 5-35 % by weight and the additive of 0.1-15 % by weight, is characterized in that, described inThe compound that additive contains structure shown in formula (I):
2. lubricant composition according to claim 1, wherein, with the weight of lubricant compositionAmount is for benchmark, and described lubricant composition comprises following component: the lubricating base oil of 75-88 % by weight,The composite aluminum base thickening agent of 5-15 % by weight and the additive of 0.1-5 % by weight.
3. lubricant composition according to claim 1 and 2, wherein, with lubricant compositionWeight be benchmark, shown in formula (I), the content of the compound of structure is 0.1-3 % by weight.
4. lubricant composition according to claim 3, wherein, with the weight of lubricant compositionAmount is benchmark, and shown in formula (I), the content of the compound of structure is 0.2-1 % by weight.
5. lubricant composition according to claim 1 and 2, wherein, described lubricating base oilFor at least one in mineral oil, vegetable oil and artificial oil.
6. lubricant composition according to claim 1 and 2, wherein, described composite aluminum base is thickAgent is that acid is reacted generation with aluminium source, and described acid comprises higher fatty acids and little molecule acid.
7. lubricant composition according to claim 6, wherein, described higher fatty acids isThe aliphatic acid of C12-C25, described little molecule acid is the carboxylic acid of C4-C11.
8. lubricant composition according to claim 7, wherein, described higher fatty acids is the moonAt least one in cinnamic acid, palmitic acid, stearic acid and 12-hydroxy stearic acid, be preferably stearic acid and/or12-hydroxy stearic acid, described little molecule acid is in benzoic acid, terephthalic acid (TPA), azelaic acid and decanedioic acidAt least one.
9. lubricant composition according to claim 6, wherein, described aluminium source is aluminium isopropoxideAnd/or aluminium isopropoxide tripolymer.
10. lubricant composition according to claim 1 and 2, wherein, described additive also containsThere is antirust agent.
11. lubricant compositions according to claim 10, wherein, described antirust agent is oilAt least one in barium sulfonate, dinonyl barium benzosulfonate and Lanolin Calcium Soap.
The preparation method of the composite aluminum base grease composition of 12. 1 kinds of antioxygen property excellences, described methodComprise:
(1) by the lubricating base oil of 1/5-2/5, higher fatty acids, that aluminium source heat temperature raising carries out saponification is anti-Should, then add the little molecule acid in the lubricating base oil that is dissolved in 1/10-1/5 to carry out recombination reaction;
(2) add water and lower the temperature, be then warming up to 200-220 DEG C and refine;
(3) add residue lubricating base oil, be cooled to 100-130 DEG C, then add additive;
(4) grind 2-4 time by three-roller;
Wherein, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 65-95 is heavyThe consumption of the composite aluminum base thickening agent of measure %, being prepared by higher fatty acids, little molecule acid and aluminium source is 5-35% by weight, the consumption of additive is 0.1-15 % by weight, it is characterized in that, described additive contains formula (I)Shown in the compound of structure:
13. methods according to claim 12, wherein, taking the weight of lubricant composition as baseStandard, the consumption of lubricating base oil is 75-88 % by weight, by higher fatty acids, little molecule acid and aluminium source systemThe consumption of standby composite aluminum base thickening agent is 5-15 % by weight, and the consumption of additive is 0.1-5 % by weight.
14. according to the method described in claim 12 or 13, wherein, and with the weight of lubricant compositionFor benchmark, shown in formula (I), the consumption of the compound of structure is 0.1-3 % by weight.
15. methods according to claim 14, wherein, taking the weight of lubricant composition as baseStandard, shown in formula (I), the consumption of the compound of structure is 0.2-1 % by weight.
16. according to the method described in claim 12 or 13, wherein, and higher fatty acids and little molecule acidTotal amount and the mol ratio in aluminium source be stoichiometric proportion; The mol ratio of higher fatty acids and little molecule acid is1:0.1-5, be preferably 1:0.3-2.
17. according to the method described in claim 12 or 13, and wherein, in step (1), heating risesTemperature is to 90-120 DEG C, and the saponification time is 0.5-1.5h, and complex reaction time is 0.5-1.5h.
18. according to the method described in claim 12 or 13, wherein, in step (2), adds waterAmount makes temperature be down to 70-90 DEG C, and is incubated 5-25min.
19. according to the method described in claim 12 or 13, wherein, in step (2), described refiningThe time of system is 5-25min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106497643A (en) * | 2016-10-05 | 2017-03-15 | 中国石油化工股份有限公司 | Feed processing machinery food stage grease and preparation method and application |
| CN106701276A (en) * | 2016-12-11 | 2017-05-24 | 新乡市恒星科技有限责任公司 | Preparation method of reversible lubricating grease |
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| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| CN1160754A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Composite barium-base grease and its preparation |
| CN103013628A (en) * | 2012-12-27 | 2013-04-03 | 深圳市优宝惠新材料科技有限公司 | Complex aluminum-based grease composition and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5175224A (en) * | 1988-02-26 | 1992-12-29 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from bis-maleimide having azole ring |
| CN1160754A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Composite barium-base grease and its preparation |
| CN103013628A (en) * | 2012-12-27 | 2013-04-03 | 深圳市优宝惠新材料科技有限公司 | Complex aluminum-based grease composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106497643A (en) * | 2016-10-05 | 2017-03-15 | 中国石油化工股份有限公司 | Feed processing machinery food stage grease and preparation method and application |
| CN106701276A (en) * | 2016-12-11 | 2017-05-24 | 新乡市恒星科技有限责任公司 | Preparation method of reversible lubricating grease |
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