CN105586115A - A lithium-based lubricating grease composition with excellent wear resistance and a preparing method thereof - Google Patents
A lithium-based lubricating grease composition with excellent wear resistance and a preparing method thereof Download PDFInfo
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Abstract
A lithium-based lubricating grease composition with excellent wear resistance is disclosed. Based on the weight of the composition, the composition comprises 65-95% by weight of lubricating base oil, 5-35% by weight of a lithium-based thickening agent and 0.1-15% by weight of an additive. The additive comprises a compound having a structure shown as a formula (I). A preparing method of the composition is also disclosed. The composition comprises the multiple-effect additive, and therefore oxidation resistance and wear resistance of the lubricating grease composition are largely improved, other properties of the lithium-based lubricating grease composition are not influenced, and the composition still has extremely good high-temperature resistance, colloid stability, carrying capacity and waterproofness, so that the composition can be qualified for severe work conditions, such as high temperature, high speeds, high loads and high water contents.
Description
Technical field
The present invention relates to lubricating grease field, particularly, relate to a kind of Wear vesistance that contains special additiveExcellent compound lithium base grease and preparation method thereof.
Background technology
Lithium base grease is that the forties in 20th century is with fastest developing speed so far, current output maximum, application neckA kind of multipurpose grease that territory is the widest. U.S.'s grease institute is by a national lithium base grease institute accountingExample is as the mark of weighing its lubricating grease industrial technology level. It is stable that lithium base grease has good colloidThe advantages such as property, mechanical stability, life cycle length, wide ranges are a kind of desirable multipurpose, longevityLife lubricating grease, but also there are some defects in lithium base grease: as poor in antioxygenic property, abrasion resistance is poor,Water repelling property is also poor.
The conventional production methods of lithium base grease is in base oil, to adopt 12-hydroxy stearic acid or stearic acidReact with lithium hydroxide, heating saponification obtains end product, as US3980572.
In order to improve the performance of lithium base grease, changing in various degree all carried out in its composition and engineering aspectEnter. As more shallow, anti-oxidant by preparation technology's improvement has been prepared to a kind of color in CN101126045AThe better lithium base grease of performance; CN1718702A selects high viscosity mineral oil to prepare a kind of high extreme pressureLithium base grease; CN101880581A has improved reaction temperature, has improved greatly product service lifeAnd water-resistance. US3681242, US3929651, US3711407, CN1052890, CN1052891,CN1055384, CN101705141A have reported composition and the preparation method of lithium base grease, adopt 12-Hydroxy lithium stearate and binary acid or boric acid, salicylic lithium salts two components are composited, and also have employingThree components are compound; CN101921650, by add surfactant in formula, makes itself and soap moleculeForm synergy, thereby and then improve the arrangement mode of soap molecule and the ability of curing base oil has improvedThe dropping point of lubricating grease; CN101993769A provides a kind of preparation side of lithium base grease of simple processMethod, has reduced production cost; CN101200670 provides a kind of combination property good lithium base greasePreparation method, especially damaged bearing is had to repair function; CN10148137 adopts lower refiningTemperature processed, has made the lithium base grease of high dropping point, has reduced oil ageing in preparation process,Improve the oxidation stability of lubricating grease.
In recent years along with the development of modern industry, bearing, automobile, printing and dyeing, mine, metallurgy, aerospace etc.Industrial department has proposed more and more harsher requirement to the quality of lubricating grease, and many lubricant housings are all onceProperty fill fat, in running, no longer supplement or change, so require higher to the abrasion resistance of fat.
Summary of the invention
The object of the invention is the high request in order to meet the abrasion resistance to lubricating grease, a kind of anti-attrition is providedCompound lithium base grease of excellent performance and preparation method thereof.
The present inventor finds under study for action, and the additive in lubricant composition contains formula (I)Shown in the multipurpose additive of structure:
Can make lubricant composition there is the performances such as good anti-attrition is anti-oxidant.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of Wear vesistance excellenceCompound lithium base grease, taking the weight of lubricant composition as benchmark, described lubricant composition comprisesFollowing component: the lubricating base oil of 65-95 % by weight, lithium base thickening agent and the 0.1-15 of 5-35 % by weightThe additive of % 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 70-90 % by weight, the lithium base thickening agent of 8-30 % by weight and 0.5-10 % by weightAdditive.
Preferably, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Content is 0.1-10 % by weight, more preferably 1-5 % by weight.
On the other hand, the invention provides a kind of preparation of compound lithium base grease of Wear vesistance excellenceMethod, described method comprises:
(1) by part lubricating base oil, higher fatty acids and optional little molecule acid Hybrid Heating, riseTemperature, to 80-105 DEG C, adds lithium source, carries out saponification;
(2) being warming up to 180-220 DEG C refines;
(3) add residue lubricating base oil, be cooled to 100-120 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 amount %, the lithium base thickening agent prepared by higher fatty acids, optional little molecule acid and lithium source is 5-35% by weight, the consumption of additive is 0.1-15 % by weight, described additive contains structure shown in formula (I)Compound:
Preferably, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 70-90 is heavyAmount %, the consumption of the lithium base thickening agent of being prepared by higher fatty acids, optional little molecule acid and lithium source is 8-30% by weight, the consumption of additive is 0.5-10 % by weight.
Preferably, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Consumption is 0.1-10 % by weight, more preferably 1-5 % by weight.
Compound lithium base grease of the present invention, owing to containing multipurpose additive, has greatly improved lubricatedAnti-attrition ability and the oxidation resistance of fat, simultaneously little to other performance impact of lithium base grease, still toolThere are splendid heat-resisting quantity, colloid stability, bearing capacity and water proofing property, make this lubricant compositionCan be competent in high temperature, at a high speed, the harsh working condition such as high load capacity, many water.
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 multipurpose additive.
Fig. 2 is the reaction equation of the step (b) of preparing multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of the multipurpose additive prepared of preparation example.
Fig. 4 is the carbon spectrum spectrogram of the multipurpose additive prepared of preparation example.
Fig. 5 is the mass spectrogram of the multipurpose additive 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 compound lithium base grease of Wear vesistance excellence, with lubricant compositionWeight be benchmark, lubricant composition comprises following component: the lubricating base oil of 65-95 % by weight,The lithium base thickening agent of 5-35 % by weight and the additive of 0.1-15 % by weight, additive contains shown in formula (I)The compound of structure:
In the present invention, what multipurpose additive 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 70-90 % by weight, lithium base thickening agent and the 0.5-10 of 8-30 % by weightThe additive of % 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 0.1-10 % by weight, more preferably 1-5 % by weight.
The present invention is intended to contain structure shown in formula (I) by the additive in compound lithium base greaseCompound and realize goal of the invention, even if compound lithium base grease has the property such as good anti-attrition is anti-oxidantEnergy. Therefore, for the selection of each conventional component in lithium base grease, all less than specific restriction.
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 4-60mm2/ s, more preferably 6-32mm2/ 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, lithium base thickening agent can be the conventional lithium base thickening agent in this area, for example, and Ke YiweiAcid is reacted generation with lithium source, and acid comprises higher fatty acids and optional little molecule acid.
In the present invention, " optionally " refers to can be had also and can not have. " optional little molecule acid " refers toLittle molecule acid is a kind of optional component, can comprise this component, also can not comprise this component, that is,Lithium base thickening agent of the present invention can react generation with lithium source by higher fatty acids, also can be by senior fatSour and little molecule acid is reacted generation with lithium source.
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 can be the carboxylic acid of C2-C11, be preferably acetic acid, propionic acid, ethanedioic acid,At least one in adipic acid, azelaic acid, decanedioic acid and terephthalic acid (TPA), more preferably decanedioic acid, the ninth of the ten Heavenly StemsAt least one in diacid, adipic acid and terephthalic acid (TPA).
Wherein, lithium source is preferably lithium hydroxide. It will be understood by those skilled in the art that actual and makeUsed time, generally adds lithium hydroxide aqueous solution, for the concentration of lithium hydroxide aqueous solution without particular/special requirement,It can be for example 5-30 % by weight.
Above-mentioned lithium base thickening agent can adopt the thinkable the whole bag of tricks of those skilled in the art institute to obtain.
In the present invention, because multipurpose additive and other additives of structure shown in formula (I) have betterCompatibility, therefore, according to the use needs of lubricating grease, additive of the present invention can also contain otherAntioxidant, extreme pressure anti-wear additives and antirust agent at least one.
In the present invention, for other the kind of antioxidant, extreme pressure anti-wear additives, antirust agent and content without spyDifferent requirement, can adopt kind and the content of this area routine. For example, antioxidant can be anti-for arylamine classOxygen agent, is preferably at least one in diphenylamines, PA and di-iso-octyldiphenylamine, more preferablyFor di-iso-octyldiphenylamine, the 0.01-5 that the content of antioxidant can account for lubricant composition gross weight is heavyAmount %, preferably 0.1-2.5 % by weight; Extreme pressure anti-wear additives can be two sulfo-Acidic phosphates zinc, two sulfo-sDialkyl amido formic acid molybdenum, two sulfo-dialkyl amido lead formates, molybdenum bisuphide, polytetrafluoroethylene (PTFE), twoButyl antimony dithiocarbamate, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxideIn at least one, the 0.5-12 that the content of extreme pressure anti-wear additives can account for lubricant composition gross weight is heavyAmount %, is preferably 0.5-5 % by weight; Antirust agent can be barium mahogany sulfonate, mahogany acid lithium, benzo thiopheneAt least one in azoles, BTA, zinc naphthenate and alkenyl succinic acid, the content of antirust agent canThe 0.01-4.5 % by weight that accounts for 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) aniline, sulfur chloride and 4-chloroaniline are reacted to the intermediate shown in production (II)M，
(b) intermediate M step (a) being obtained and dimercapto-1,3,4-thiadiazole are under alkali conditionCarry out nucleophilic substitution, the multipurpose additive shown in production (I),
In step of the present invention (a), the concrete mode that aniline, sulfur chloride and 4-chloroaniline are reactedPreferably include:
(i) under inert atmosphere, in the first solvent, by aniline and sulfur chloride at-20-0 DEG C fullyReact;
(ii) 4-chloroaniline is added in the reaction system of step (i), at 15-30 DEG C, react 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.
In step of the present invention (i), the first solvent be preferably selected from carrene, oxolane, toluene,At least one in dimethylbenzene and dioxane, more preferably carrene and/or oxolane, more enters oneStep is preferably carrene.
In step in the present invention (i), fully react and refer to and react completely, reaction raw materials is completeEntirely react. Can adopt the conventional method in this area to monitor reaction, react completely confirming,For example can adopt the methods such as TLC (TLC) or gas-chromatography to monitor.
In step of the present invention (ii), at 15-30 DEG C, react 1-3h, preferably fully anti-in step (i)Ying Hou, rises to 15-30 DEG C gradually by the temperature of reaction system, then adds 4-chloroaniline to react 1-3h.Under this preferable case, can further improve reaction yield.
In step of the present invention (ii), the mode that adds of 4-chloroaniline is preferably gradation and adds, and for example canDivide and add for 3-4 time. Under this preferable case, can further improve reaction yield. Add for gradationTime, each addition can be identical, also can be different, and for easy to operate, preferably each addingMeasure identical.
In step of the present invention (ii), reaction 1-3h, the mode that stops reaction can be art technology peopleThe thinkable variety of way of member, for example, can add quencher to carry out cancellation, and quencher can be thisThe quencher that field is conventional can be for example saturated aqueous common salt.
In the present invention, the consumption of aniline, sulfur chloride and 4-chloroaniline is essentially equimolar amounts, but anilineWith sulfur chloride can be suitably excessive. The mol ratio of aniline, sulfur chloride and 4-chloroaniline is preferably 0.9-1.5:0.9-1.5：0.8-1.2。
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 washesWash, be dried, removal of solvent under reduced pressure, for example, the reaction system after cancellation is used respectively to distilled water and saturatedSaline solution washing then adds the drier such as anhydrous calcium chloride or anhydrous slufuric acid lithium at 15-30 DEG C,Keep 10-60min. Remove by filter after drier, at 0.01-0.05MPa, 40-60 DEG C, remove desolventizing,To obtain intermediate M.
In step of the present invention (a), the reaction equation that aniline, sulfur chloride and 4-chloroaniline reactAs shown in Figure 1, in Fig. 1, what the first solvent adopted is carrene, only for purposes of illustration,Scope of the present invention is not construed as limiting.
In step of the present invention (b), the condition of nucleophilic substitution preferably includes: under inert atmosphere,In the second solvent, dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed at 15-30 DEG C10-30min, then adds intermediate M, fully reacts. Be that alkali condition is provided by alkaline reagent.
" inert atmosphere ", " fully reacting " as previously mentioned, do not repeat them here.
In the present invention, intermediate M preferably slowly adds, for example, can gradation add, and generally can divideAdd for 3-4 time. Under this preferable case, can further improve reaction yield. Add for gradation fashionable,Each addition can be identical, also can be different, and for easy to operate, preferably each addition phaseWith.
In the present invention, the second solvent is preferably selected from carrene, oxolane, toluene, dimethylbenzene, N, N-At least one in dimethyl formamide, more preferably carrene and/or DMF,Further be preferably DMF.
In the present invention, alkaline reagent is preferably selected from the inorganic bases such as potash, lithium carbonate, lithium methoxide extremelyFew a kind of.
In the present invention, catalyst is preferably potassium sulfate.
In step of the present invention (b), the use of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate MAmount is essentially equimolar amounts, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive. TwoSulfydryl-1, the mol ratio of 3,4-thiadiazoles, alkaline reagent and intermediate M is preferably 0.9-3.0:0.9-5.0:0.8-1.5。
In step of the present invention (b), the consumption of catalyst can be catalytic amount, with dimercapto-1, and 3,4-thiophene twoThe molal quantity of azoles is benchmark, and the consumption of catalyst is preferably 5-100 % by mole, and more preferably 10-50 rubsYou are %.
In step of the present invention (b), the reaction that dimercapto-1,3,4-thiadiazole and intermediate M reactAs shown in Figure 2, in Fig. 2, what alkaline reagent adopted is potash to equation, is only illustrational order, scope of the present invention is not construed as limiting.
It will be understood by those skilled in the art that in order to obtain purer end product, i.e. the present inventionMultipurpose additive, the method that the present invention prepares multipurpose additive preferably also comprises reacted system is enteredRow post processing, the mode of post processing can comprise washing, dry, removal of solvent under reduced pressure, for example, will fillDivide reacted system to pour in the ethyl acetate (or carrene) of 1-10 times of volume, respectively with steamingHeat up in a steamer water and saturated common salt water washing, then at 15-30 DEG C, add anhydrous calcium chloride or anhydrous slufuric acid lithiumIn drier, keep 10-60min. Remove by filter after drier, at 0.01-0.05MPa, 40-60 DEG CDown except desolventizing, to obtain end product.
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.
In the present invention, without particular/special requirement, can be that this area is normal for the amount of the first solvent and the second solventThe solvent load of rule, this is conventionally known to one of skill in the art, does not repeat them here.
As mentioned above, the present invention is intended to contain formula (I) by the additive in compound lithium base greaseShown in structure compound and realize goal of the invention, even if lubricant composition has good anti-attrition antioxygenThe performances such as change. Therefore, without particular/special requirement, can adopt this area for the preparation method of lithium base greaseThe conventional method using, for example, second aspect, the present invention also provides a kind of lithium of Wear vesistance excellenceThe preparation method of base grease composition, the method comprises:
(1) by part lubricating base oil, higher fatty acids and optional little molecule acid Hybrid Heating, riseTemperature, to 80-105 DEG C, adds lithium source, carries out saponification;
(2) being warming up to 180-220 DEG C refines;
(3) add residue lubricating base oil, be cooled to 100-120 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 heavyAmount %, the consumption of the lithium base thickening agent of being prepared by higher fatty acids, optional little molecule acid and lithium 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 oilConsumption is 70-90 % by weight, and the lithium base of being prepared by higher fatty acids, optional little molecule acid and lithium source is thickThe consumption of agent is 8-30 % by weight, and the consumption of additive is 0.5-10 % by weight.
In the inventive method, higher fatty acids and the optional total amount of little molecule acid and the mol ratio in lithium source are excellentElect stoichiometric proportion as, lithium source also can excessive 1-10 % by weight. Higher fatty acids and optional little moleculeThe mol ratio of acid is preferably 1:0.1-1. It will be understood by those skilled in the art that basis is by senior fatThe consumption of lithium base thickening agent prepared by sour, optional little molecule acid and lithium source, can instead release senior fatThe consumption in sour, little molecule acid and lithium source, this is conventionally known to one of skill in the art, does not repeat them here.
In the present invention, as previously mentioned, " optionally " refers to can be had also and can not have. " optional little moleculeAcid " refer to that little molecule acid is a kind of optional component, can comprise this component, also can not comprise thisComponent; " mol ratio of higher fatty acids and optional little molecule acid is 1:0.1-1 " refers to when containing littleWhen molecule acid, the mol ratio of higher fatty acids and little molecule acid is preferably 1:0.1-1. In a word, this area skillArt personnel it should be understood that lithium base thickening agent of the present invention can be reacted by higher fatty acids raw with lithium sourceBecome, also can react generation with lithium source by higher fatty acids and the acid of little molecule.
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 0.1-10 % by weight, more preferably 1-5 % by weight.
It will be understood by those skilled in the art that in the inventive method, the consumption of lubricating base oil is portionDivide the consumption sum of consumption with the residue lubricating base oil of lubricating base oil. Part lubricating base oil and residueThe weight ratio of lubricating base oil is preferably 50-75:25-50.
In the inventive method step (1), be preferably warming up to 80-95 DEG C, the saponification time is preferably0.2-1.5h, more preferably 0.5-1h.
In the inventive method step (2), be preferably warming up to 190-210 DEG C, the time of refining is preferably5-15min。
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 20-400rpm.
Lubricating base oil, higher fatty acids, little molecule acid, lithium 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 method that monitoring reacts completely: thin-layer chromatography chromatogram (TLC) fluorescence developing method.
Gross production rate=end product mole/aniline mole × 100%
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 300rpm), being filled with nitrogen protectsProtect, add the carrene of 150ml, then add the sulfur chloride of 0.2mol, abundant in ice-water bathAfter cooling, add the aniline of 0.2mol. Monitoring is removed ice-water bath after reacting completely, and is placed in 25 DEG C of chambersUnder temperature, question response system rises to after 25 DEG C gradually, divides and adds for 3 times 4-chloroaniline to react, eachAddition is identical, adds altogether 4-chloroaniline 0.15mol. Sustained response adds the saturated food of 30ml after 2 hoursSalt solution cancellation reaction, then proceeds to reaction system in separatory funnel, uses respectively 50ml distilled water and 50mlSaturated common salt water washing, and add 10g anhydrous slufuric acid lithium dry 20min at 25 DEG C. Filter after filtrationLiquid, at 40 DEG C, steams and desolventizes under 0.05MPa, obtains intermediate M1.
In the 500ml flask with electromagnetic agitation (mixing speed is 400rpm), being filled with nitrogen protectsProtect, add the DMF (DMF) of 150ml, then add 0.2mol dimercapto-1,3,4-The potash of thiadiazoles and 0.2mol, the potassium sulfate of 0.05mol, stir 20 minutes at 25 DEG C, and points 3Inferiorly add above-mentioned intermediate M1, each addition is identical, adds altogether intermediate M10.12mol. MonitoringTo reacting completely, then reaction system is added to 250ml ethyl acetate, and proceed in separatory funnel, pointDo not use 100ml distilled water (twice) and the water washing of 50ml saturated common salt, and add 15g anhydrous slufuric acidLithium is dry 20min at 25 DEG C. Filtrate after filtration is steamed and is desolventized under 40 DEG C, 0.03MPa, obtainsEnd product S1. Calculating gross production rate is 76%.
The physico-chemical analysis data of product are as follows: sulfur content, 41.3%; Nitrogen content, 13.9%.
S1 is carried out to structural characterization, obtain respectively hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectivelySee Fig. 3, Fig. 4 and Fig. 5.
Can find out from physico-chemical analysis data, Fig. 3, Fig. 4 and Fig. 5 of above-mentioned preparation example, S1 has formula(I) structure shown in.
Embodiment 1
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by 540kg150BS base oil, (100 DEG C of viscosity are 31mm2/ s, lower same) and 62.75kg12-hydroxy stearic acid adds in fat still processed, and agitating heating under 180rpm, is warming up to 95 DEG C, adds27.03kg lithium hydroxide aqueous solution (concentration is 16.7 % by weight), carries out saponification 0.5h;
(2) be warming up to 190 DEG C, refining 8min;
(3) add 180kg150BS base oil, stir and be cooled to 120 DEG C, add 16kgS1,Under 180rpm, stir;
(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: 12-hydroxyl is hardResin acid lithium 8 % by weight; Lubricating base oil 90 % by weight; S12 % by weight.
Embodiment 2
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by 153.5kg500SN base oil, (100 DEG C of viscosity are 10mm2/ s, lower same) and 102.83Kg stearic acid adds in fat still processed, and agitating heating under 200rpm, is warming up to 85 DEG C, adds 101.47kgLithium hydroxide aqueous solution (concentration is 30 % by weight), carries out saponification 1h;
(2) be warming up to 210 DEG C, refining 5min;
(3) add 100kg500SN base oil, stir and be cooled to 105 DEG C, add 3.6kgS1,Under 200rpm, stir;
(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: lithium stearate 29% by weight; Lubricating base oil 70 % by weight; S11 % by weight.
Embodiment 3
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by 170kgPAO6 synthetic hydrocarbon oil, (100 DEG C of viscosity are 5.8mm2/ s, lower same) and 88.14kgStearic acid adds in fat still processed, and agitating heating under 300rpm, is warming up to 80 DEG C, adds 41.3kg hydrogenThe lithia aqueous solution (concentration is 30 % by weight), carries out saponification 0.8h;
(2) be warming up to 195 DEG C, refining 15min;
(3) add 167.5kgPAO6 synthetic hydrocarbon oil, stir and be cooled to 100 DEG C, add 22.5kgS1,Under 300rpm, stir;
(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: lithium stearate 20% by weight; Lubricating base oil 75 % by weight; S15 % by weight.
Embodiment 4
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by the miscella of 400kg500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, lower same)Add in fat still processed with the 12-hydroxy stearic acid of 94.12kg, agitating heating under 230rpm, is warming up to90 DEG C, add 67.66kg lithium hydroxide aqueous solution (concentration is 20 % by weight), carry out saponification 0.6h;
(2) be warming up to 200 DEG C, refining 10min;
(3) add the miscella of 125kg500SN and 150BS, stir and be cooled to 120 DEG C, add19.2kgS1 stirs under 230rpm;
(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: 12-hydroxyl is hardResin acid lithium 15 % by weight; Lubricating base oil 82 % by weight; S13 % by weight.
Comparative example 1
Method according to embodiment 4 is prepared lithium base grease, different, does not add S1. ProductCan be as shown in table 1.
In the lubricating grease that this comparative example obtains, taking lubricating grease weight as benchmark, consist of: 12-hydroxyl is hardResin acid lithium 15.5 % by weight, lubricating base oil 84.5 % by weight.
Embodiment 5
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by 540kg500SN base oil, (100 DEG C of viscosity are 10mm2/ s, lower with), 37.95kg12-Hydroxy stearic acid and 23.77kg azelaic acid add in fat still processed, and agitating heating under 180rpm heats upTo 85 DEG C, add 163.76kg lithium hydroxide aqueous solution (concentration is 10 % by weight), carry out saponification anti-Answer 0.5h;
(2) be warming up to 200 DEG C, refining 5min;
(3) add 180kg500SN base oil, stir and be cooled to 120 DEG C, add 16kgS1,Under 180rpm, stir;
(4) grind 2 times by three-roller and become fat. Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: 12-hydroxyl is hardResin acid lithium 4.8 % by weight; Azelaic acid lithium 3.2 % by weight; Lubricating base oil 90 % by weight; S12 % by weight.
Embodiment 6
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by 95kg150BS base oil, (100 DEG C of viscosity are 30mm2/ s, lower with), 66.99kgStearic acid and 7.82kg terephthalic acid (TPA) add in fat still processed, and agitating heating under 200rpm, is warming up to80 DEG C, add 84.26kg lithium hydroxide aqueous solution (concentration is 16.9 % by weight), carry out saponification1h；
(2) be warming up to 190 DEG C, refining 15min;
(3) add 90kg150BS base oil, stir and be cooled to 110 DEG C, add 2.7kgS1,Under 200rpm, stir;
(4) grind 3 times by three-roller and become fat. Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: lithium stearate 25.8% by weight; Terephthalic acid (TPA) lithium 3.2 % by weight; Lubricating base oil 70 % by weight; S11 % by weight.
Embodiment 7
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by 260.5kgPAO6 synthetic hydrocarbon oil, (100 DEG C of viscosity are 5.8mm2/ s, lower with), 74.29kgStearic acid and 28.59kg adipic acid add in fat still processed, and agitating heating under 300rpm is warming up to 95 DEG C,Add 94.12kg lithium hydroxide aqueous solution (concentration is 30 % by weight), carry out saponification 0.8h;
(2) be warming up to 195 DEG C, refining 8min;
(3) add 240kgPAO6 synthetic hydrocarbon oil, stir and be cooled to 100 DEG C, add 26.7kgS1,Under 300rpm, stir;
(4) grind 4 times by three-roller and become fat. Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: lithium stearate 14.2% by weight; Lithium adipate 5.8 % by weight; Lubricating base oil 75 % by weight; S15 % by weight.
Embodiment 8
The present embodiment is used for illustrating compound lithium base grease of the present invention and preparation method thereof.
(1) by the miscella of 456kg500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, lower same),The 12-hydroxy stearic acid of 87.8kg and 29.34kg decanedioic acid add in fat still processed, under 230rpm, stirHeating, is warming up to 90 DEG C, adds 100.33kg lithium hydroxide aqueous solution (concentration is 25 % by weight),Carry out saponification 0.6h;
(2) be warming up to 210 DEG C, refining 10min;
(3) add the miscella of 200kg500SN and 150BS, stir and be cooled to 115 DEG C, add24kgS1 stirs under 230rpm;
(4) grind 2 times by three-roller and become fat. Properties of product are as shown in table 2.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: 12-hydroxyl is hardResin acid lithium 11.1 % by weight; Decanedioic acid lithium 3.9 % by weight; Lubricating base oil 82 % by weight; S13 % by weight.
Comparative example 2
Method according to embodiment 8 is prepared lithium base grease, different, does not add S1. ProductCan be as shown in table 2.
In the lubricating grease that this comparative example obtains, taking lubricating grease weight as benchmark, consist of: 12-hydroxyl is hardResin acid lithium 11.5 % by weight; Decanedioic acid lithium 4 % by weight; Lubricating base oil 84.5 % 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; Tetra-ball machine test PB, PD:SH/T0202; Copper corrosion: GB/T7326; Anticorrosive property: GB/T5018; Water drenchesNumber of dropouts: SH/T0109; Coefficient of friction: SH/T0847.
Table 2
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Oxidation onset temperature: ASTMD5483; Steel meshDivide oil: SH/T0324; Copper corrosion: GB/T7326; Anticorrosive property: GB/T5018; Water drenches number of dropouts: SH/T0109; Four-ball testerTest PB, PD:SH/T0202; Coefficient of friction: SH/T0847.
It will be understood by those skilled in the art that dropping point is higher, the heat-resisting quantity of lubricating grease is better; WorkMake cone penetration less, the multiviscosisty performance of grease thickener is better; Oxidation stability is less, lubricating greaseAntioxygenic property is better; Oxidation onset temperature is higher, and the oxidation resistance of lubricating grease is better; Stencil oil-dividingBe worth littlely, the colloid stability of lubricating grease is better; PB, PD value are larger, and the bearing capacity of lubricating grease moreGood; Water pouring number of dropouts is less, and the water resistance of lubricating grease is better; Coefficient of friction is less, the subtracting of lubricating greaseThe performance of rubbing is better.
Embodiment 4 is compared with comparative example 1, embodiment 8 is compared with comparative example 2, canTo find out, lubricating grease of the present invention has better heat-resisting quantity, non-oxidizability, colloid stability, holdsLoading capability, water proofing property and antifriction performance.
Compound lithium base grease of the present invention, owing to containing multipurpose additive, has greatly improved lubricatedAnti-attrition ability and the oxidation resistance of fat, simultaneously little to other performance impact of lithium base grease, still toolThere are splendid heat-resisting quantity, colloid stability, bearing capacity and water proofing property, make this lubricant compositionCan be competent in high temperature, at a high speed, the harsh working condition such as high load capacity, many water.
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 (21)
1. a compound lithium base grease for Wear vesistance excellence, taking the weight of lubricant composition asBenchmark, described lubricant composition comprises following component: the lubricating base oil of 65-95 % by weight, 5-35The lithium base thickening agent of % by weight and the additive of 0.1-15 % by weight, is characterized in that, described additive containsThere is the compound of 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 70-90 % by weight,The lithium base thickening agent of 8-30 % by weight and the additive of 0.5-10 % 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 0.1-10 % 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 1-5 % 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 lithium base thickening agentReact generation for acid with lithium source, described acid comprises higher fatty acids and optional 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 C2-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 be acetic acid, propionic acid, ethanedioic acid, adipic acid, azelaic acid,At least one in decanedioic acid and terephthalic acid (TPA), is preferably decanedioic acid, azelaic acid, adipic acid and to benzeneAt least one in dioctyl phthalate.
9. lubricant composition according to claim 6, wherein, described lithium source is lithium hydroxide.
10. lubricant composition according to claim 1 and 2, wherein, described additive also containsThere is at least one in other antioxidant, extreme pressure anti-wear additives and antirust agent.
11. lubricant compositions according to claim 10, wherein, described antioxidant is arylamineKind antioxidant, is preferably at least one in diphenylamines, PA and di-iso-octyldiphenylamine, moreBe preferably di-iso-octyldiphenylamine.
12. lubricant compositions according to claim 10, wherein, described extreme pressure anti-wear additives isTwo sulfo-Acidic phosphates zinc, two sulfo-dialkyl amido formic acid molybdenums, two sulfo-dialkyl amido lead formates,Molybdenum bisuphide, polytetrafluoroethylene (PTFE), dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide,At least one in fluorographite, calcium carbonate and zinc oxide.
13. lubricant compositions according to claim 10, wherein, described antirust agent is oilIn barium sulfonate, petroleum sodium sulfonate, benzothiazole, BTA, zinc naphthenate and alkenyl succinic acidAt least one.
The preparation method of the compound lithium base grease of 14. 1 kinds of Wear vesistance excellences, described method comprises:
(1) by part lubricating base oil, higher fatty acids and optional little molecule acid Hybrid Heating, riseTemperature, to 80-105 DEG C, adds lithium source, carries out saponification;
(2) being warming up to 180-220 DEG C refines;
(3) add residue lubricating base oil, be cooled to 100-120 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 heavyAmount %, the consumption of the lithium base thickening agent of being prepared by higher fatty acids, optional little molecule acid and lithium 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:
15. methods according to claim 14, wherein, taking the weight of lubricant composition as baseStandard, the consumption of lubricating base oil is 70-90 % by weight, by higher fatty acids, optional little molecule acid andThe consumption of lithium base thickening agent prepared by lithium source is 8-30 % by weight, and the consumption of additive is 0.5-10 % by weight.
16. according to the method described in claims 14 or 15, wherein, and with the weight of lubricant compositionFor benchmark, shown in formula (I), the consumption of the compound of structure is 0.1-10 % by weight.
17. methods according to claim 16, wherein, taking the weight of lubricant composition as baseStandard, shown in formula (I), the consumption of the compound of structure is 1-5 % by weight.
18. according to the method described in claims 14 or 15, wherein, described part lubricating base oil withThe weight ratio of described residue lubricating base oil is 50-75:25-50.
19. according to the method described in claims 14 or 15, wherein, and higher fatty acids and optional littleThe mol ratio in the total amount of molecule acid and lithium source is stoichiometric proportion; Higher fatty acids and optional little molecule acidMol ratio be 1:0.1-1.
20. according to the method described in claims 14 or 15, wherein, in step (1), is warming up to80-95 DEG C, the saponification time is 0.2-1.5h, is preferably 0.5-1h.
21. according to the method described in claims 14 or 15, wherein, in step (2), is warming up to190-210 DEG C, the time of described refining is 5-15min.
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