CN105586134A - Calcium-based lubricating grease composition with excellent antifriction property and preparation method therefor - Google Patents
Calcium-based lubricating grease composition with excellent antifriction property and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a calcium-based lubricating grease composition with excellent antifriction property. The lubricating grease composition contains the following ingredients in percentage by weight: 65-95wt% of lubricating base oil, 5-35wt% of calcium-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 calcium-based lubricating grease composition with excellent antifriction property. The calcium-based lubricating grease composition disclosed by the invention contains the multipurpose additive, so that the antifriction capability and oxidation resistance of lubricating grease are greatly improved, and meanwhile, the influence on other properties of the calcium-based lubricating grease is low; and the high-temperature resistance, colloid stability and bearing capacity are still excellent, so that the lubricating grease composition can be adequate to harsh working conditions, such as high-temperature, high-speed, high-load and watery.
Description
Technical field
The present invention relates to lubricating grease field, particularly, relate to a kind of Wear vesistance that contains special additiveExcellent calcium base grease composition and preparation method thereof.
Background technology
China produces calcium-base grease since the forties in 20th century, due to its production technology and equipment letterSingle, raw material is easy to get, and low cost product, is subject to the producer and user's welcome deeply. Calcium-base grease toolHave good water-resistance, be difficult for emulsification, there is to good adhesiveness metal surface, colloid stability alsoGood, in storage process, do not analyse oil, but because it contains a certain amount of constitution water, when serviceability temperature exceedes100 DEG C time, the easy evaporation loss of water, causes the structure of calcium-base grease to be destroyed, and loses lubricated workWith, thereby calcium-base grease is generally only used on the friction position that operating temperature is no more than 60 DEG C.
Complex calcium lubricating grease is a kind of complex-soap base grease developing the earliest, and it is with aliphatic acid calcium soap and lowThe moderately viscous mineral lubricating oil of calcium complex soap multiviscosisty or synthetic lubricant fluid that molecule acid calcium salt is made are madeGrease product, there is higher temperature tolerance, under high temperature, consistency change is very little; Have well simultaneouslyWater-resistance, mechanical stability, colloid stability and good extreme pressure property, serviceability temperature wider range, isA kind of broad-spectrum brand-name grease. But because complex calcium lubricating grease is in storage and use procedureThere is sclerosis problem, greatly limited its propagation and employment.
For improving the performance of complex calcium lubricating grease, have in formula and manufacturing process it is carried out in recent yearsImproved as CN1888036 and CN101935573A; Have by the sour and long chain organic acid kind to little moleculeThe selection of class and the adjustment of ratio, and select some little molecule acid (boric acid) and other adminicle (dioxiesChange titanium) improve the sclerosis problem of complex calcium lubricating grease, but the production time is oversize and sclerosis improvement degreeLimited; Also have by introduce polyurea grease its performance is carried out improved, as CN1493673,US5084193 and US4902435, mix complex calcium lubricating grease with polyurea based lubricating grease, but produceRaw material and technique are comparatively complicated.
Anhydrous calcium base grease is not moisture, and dropping point is higher than 140 DEG C, and maximum operation (service) temperature is than common calcium Ji RunConsistent lubricant exceeds more than 50 DEG C, and short-term can reach 120 DEG C; Water-resistance and mechanical stability are more lubricated than calcium mixture baseFat is good; Compare with complex calcium lubricating grease, anhydrous calcium base grease is not stored sclerosis and is subject to thermmohardeningProblem, and production technology is fairly simple, manufacturing cost is lower than complex calcium lubricating grease. Anhydrous calcium basePERFORMANCE OF GREASES is good, have good oxidation stability, resistance to water, colloid stability, wear resistence,Low temperature flow, rust-preventing characteristic and mechanical stability.
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 providedCalcium base grease composition 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 excellenceCalcium base grease composition, taking the weight of lubricant composition as benchmark, described lubricant composition comprisesFollowing component: the lubricating base oil of 65-95 % by weight, calcium 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 calcium 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 calcium base grease composition of Wear vesistance excellenceMethod, described method comprises:
(1) by part lubricating base oil, higher fatty acids, optional middle molecule acid and little molecule acid,Calcium hydroxide Hybrid Heating, carries out saponification;
(2) heat up 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 65-95 weight%, the calcium base multiviscosisty of being prepared by higher fatty acids, optional middle molecule acid and little molecule acid, calcium hydroxideThe consumption of agent is 5-35 % by weight, and the consumption of additive is 0.1-15 % by weight, and described additive contains formula(I) compound of structure shown in:
Preferably, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 70-90 is heavyAmount %, the calcium base of being prepared by higher fatty acids, optional middle molecule acid and little molecule acid, calcium hydroxide is thickThe consumption of agent is 8-30 % by weight, and 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.
Calcium base grease composition 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 calcium-base grease, still toolThere are splendid heat-resisting quantity, colloid stability and bearing capacity, this lubricant composition can be competent atIn 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 calcium base grease composition of Wear vesistance excellence, with lubricant compositionWeight be benchmark, lubricant composition comprises following component: the lubricating base oil of 65-95 % by weight,The calcium 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, calcium 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 calcium base grease compositionCompound and realize goal of the invention, even if calcium base grease composition has the property such as good anti-attrition is anti-oxidantEnergy. Therefore, for the selection of each conventional component in calcium-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 5-32mm2/ 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, calcium base thickening agent can be the conventional calcium base thickening agent in this area, for example, and Ke YiweiAcid generates with calcium hydroxide reaction, and acid comprises higher fatty acids, optional middle molecule acid and little molecule acid.
In the present invention, " optionally " refers to can be had also and can not have. " optional middle molecule acid and little moleculeAcid " refer to that middle molecule acid and little molecule acid are all optional components, can comprise this two kinds of components, alsoCan not comprise this two kinds of components, that is, calcium base thickening agent of the present invention can be by higher fatty acids and hydrogen-oxygenChange calcium reaction and generate, also can be by higher fatty acids, the acid of middle molecule and little molecule acid and calcium hydroxide reactionGenerate.
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, middle molecule acid is preferably the carboxylic acid of C6-C10, more preferably sad, benzoic acid, to benzeneAt least one in dioctyl phthalate, azelaic acid and decanedioic acid.
Wherein, little molecule acid is preferably acetic acid.
Above-mentioned calcium 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 content of antioxidant can account for the 0.01-5 weight of lubricant composition gross weight%, preferably 0.1-2.5 % by weight; Extreme pressure anti-wear additives can be two sulfo-Acidic phosphates zinc, two sulfo-s twoAlkyl amino formic acid molybdenum, two sulfo-dialkyl amido lead formates, molybdenum bisuphide, polytetrafluoroethylene (PTFE), two fourthsIn base antimony dithiocarbamate, tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxideAt least one, the content of extreme pressure anti-wear additives can account for the 0.5-12 % by weight of lubricant composition gross weight,Be preferably 0.5-5 % by weight; Antirust agent can be barium mahogany sulfonate, calcium mahogany sulfonate, benzothiazole,At least one in BTA, zinc naphthenate and alkenyl succinic acid, the content of antirust agent can account for profitThe 0.01-4.5 % by weight of consistent lubricant composition total 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 dead plaster 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, calcium carbonate, calcium 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 dead plasterIn 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 calcium base grease compositionShown 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 calcium-base greaseThe conventional method using, for example, second aspect, the present invention also provides a kind of calcium of Wear vesistance excellenceThe preparation method of base grease composition, the method comprises:
(1) by part lubricating base oil, higher fatty acids, optional middle molecule acid and little molecule acid,Calcium hydroxide Hybrid Heating, carries out saponification;
(2) heat up 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 65-95 weight%, the calcium base multiviscosisty of being prepared by higher fatty acids, optional middle molecule acid and little molecule acid, calcium hydroxideThe consumption of agent is 5-35 % by weight, and the consumption of additive is 0.1-15 % by weight, and additive contains formula (I)Shown in the compound of structure:
In the inventive method, preferably, taking the weight of lubricant composition as benchmark, lubricating base oilConsumption is 70-90 % by weight, by higher fatty acids, optional middle molecule acid and little molecule acid, hydroxideThe consumption of calcium base thickening agent prepared by calcium is 8-30 % by weight, and the consumption of additive is 0.5-10 % by weight.
In the inventive method, total amount and the hydrogen-oxygen of higher fatty acids and optional middle molecule acid and little molecule acidThe mol ratio of changing calcium is preferably stoichiometric proportion, and calcium hydroxide also can excessive 1-10 % by weight. OptionalThe acid of middle molecule is preferably 1:0.37-3.4 with the mol ratio of higher fatty acids, higher fatty acids and optional inThe mol ratio of the total amount of molecule acid and optional little molecule acid is preferably 1:0.9-4. Those skilled in the art shouldThis understanding, according to by higher fatty acids, optional middle molecule acid and the acid of little molecule and calcium hydroxide systemThe consumption of standby calcium base thickening agent, can instead release higher fatty acids, middle molecule acid, little molecule acid and hydrogenThe consumption of calcium oxide, 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 middle moleculeSour and little molecule acid " refer to that the acid of middle molecule and little molecule acid are all optional components, can comprise this twoPlant component, also can not comprise these two kinds of components. " higher fatty acids and optional middle molecule acid and little pointThe total amount of son acid is stoichiometric proportion with the mol ratio of calcium hydroxide " refer to ought not contain middle molecule acid withWhen little molecule acid, the mol ratio of higher fatty acids and calcium hydroxide is stoichiometric proportion, when containing middle moleculeWhen sour and little molecule acid, higher fatty acids and the acid of middle molecule and the total amount of little molecule acid and rubbing of calcium hydroxideYou are than being stoichiometric proportion. " optional middle molecule acid is 1:0.37-3.4 with the mol ratio of higher fatty acids,The mol ratio of the total amount of higher fatty acids and optional middle molecule acid and optional little molecule acid is 1:0.9-4 "Refer to that, in the time containing middle molecule acid and the acid of little molecule, middle molecule acid with the mol ratio of higher fatty acids is1:0.37-3.4, the total amount of higher fatty acids and middle molecule acid and the mol ratio of little molecule acid are 1:0.9-4. AlwaysIt, it will be understood by those skilled in the art that calcium base thickening agent of the present invention can be by higher fatty acidsGenerate with calcium hydroxide reaction, also can be by higher fatty acids, the acid of middle molecule and little molecule acid and hydroxideCalcium reaction generates.
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), in the time not containing middle molecule acid and the acid of little molecule, step (1)Preferably include: by part lubricating base oil and higher fatty acids Hybrid Heating, be warming up to 80-105 DEG C, morePreferably 80-95 DEG C, adds calcium hydroxide to carry out saponification, and the saponification time is 0.2-1.5h, more excellentElect 0.5-1h as; In the time containing middle molecule acid and the acid of little molecule, step (1) preferably includes: by partLubricating base oil and calcium hydroxide mix, and at 15-50 DEG C, add little molecule acid to carry out the first saponification anti-Should, be then warming up to 80-100 DEG C, add higher fatty acids to carry out the second saponification, in then addingThe 3rd saponification is carried out in molecule acid, the first saponification, the second saponification, the 3rd saponificationTime is 10-60min, more preferably 20-40min.
In the inventive method step (2), in the time not containing middle molecule acid and the acid of little molecule, step (2)In, being preferably warming up to 140-160 DEG C and refining, the time of refining is preferably 5-15min; In containingWhen molecule acid and the acid of little molecule, in step (2), be preferably warming up to 180-220 DEG C, more preferably 190-210DEG C refine, the time of refining is preferably 5-15min.
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, middle molecule acid, little molecule acid, calcium hydroxide, additive asBefore described in, do not repeat them here.
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 dead plaster 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 acidCalcium 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 calcium base grease composition of the present invention and preparation method thereof.
(1) by 54kg150BS base oil, (100 DEG C of viscosity are 30mm2/ s, lower same) and 6kg12-Hydroxy stearic acid adds in fat still processed, and agitating heating under 180rpm, is warming up to 85 DEG C, adds 0.76kgThe mixture of calcium hydroxide and 4kg water, carries out saponification 0.5h;
(2) be warming up to 140 DEG C, refining 15min;
(3) add 18kg150BS base oil, stir and be cooled to 120 DEG C, add 1.6kgS1,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 calcium 8 % by weight; Lubricating base oil 90 % by weight; S12 % by weight.
Embodiment 2
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by 25kg500SN base oil, (100 DEG C of viscosity are 10mm2/ s, lower same) and 13.6kgStearic acid adds in fat still processed, and agitating heating under 200rpm, is warming up to 80 DEG C, adds 1.83kg hydrogenThe mixture of calcium oxide and 2kg water, carries out saponification 1h;
(2) be warming up to 145 DEG C, refining 8min;
(3) add 10kg500SN base oil, stir and be cooled to 105 DEG C, add 0.5kgS1,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: calcium stearate 29% by weight; Lubricating base oil 70 % by weight; S11 % by weight.
Embodiment 3
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by 22kgPAO6 synthetic hydrocarbon oil, (100 DEG C of viscosity are 5.8mm2/ s, lower same) and 10.9kgStearic acid adds in fat still processed, and agitating heating under 300rpm, is warming up to 95 DEG C, adds 1.5kg hydrogenThe mixture of calcium oxide and 4kg water, carries out saponification 0.8h;
(2) be warming up to 160 DEG C, refining 5min;
(3) add 21.5kgPAO6 synthetic hydrocarbon oil, stir and be cooled to 130 DEG C, add 2.9kgS1,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: calcium stearate 20% by weight; Lubricating base oil 75 % by weight; S15 % by weight.
Embodiment 4
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 40kg500SN and 150BS, (100 DEG C of viscosity are 16mm2/ s, lower same)Add in fat still processed with 11.3kg12-hydroxy stearic acid, agitating heating under 230rpm, is warming up to 90DEG C, add the mixture of 1.45kg calcium hydroxide and 2.8kg water, carry out saponification 0.6h;
(2) be warming up to 150 DEG C, refining 10min;
(3) add the miscella of 25.6kg500SN and 150BS, stir and be cooled to 100 DEG C, add2.4kgS1, under 230rpm, 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 calcium 15 % by weight; Lubricating base oil 82 % by weight; S13 % by weight.
Comparative example 1
Method according to embodiment 4 is prepared calcium-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 calcium 15.5 % by weight, lubricating base oil 84.5 % by weight.
Embodiment 5
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by 64.1kg500SN base oil, (100 DEG C of viscosity are 10mm2/ s, lower same) and containing 2kgThe suspension (calcium hydroxide content is 8 % by weight) of calcium hydroxide adds in fat still processed, at 180rpmUnder be uniformly mixed, at 25 DEG C, add 1.6kg acetic acid, reaction 20min, be then warming up to 80 DEG C, addEnter the 12-hydroxy stearic acid of 2.3kg, reaction 30min, then adds 2.7kg sad, reaction 40min;
(2) be warming up to 190 DEG C, refining 15min;
(3) add 21.4kg500SN base oil, stir and be cooled to 120 DEG C, add 1.9kgS1,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 calcium 2.55 % by weight; Calcium octoate 3.25 % by weight; Calcium acetate 2.2 % by weight, lubricating base oil 90% by weight; S12 % by weight.
Embodiment 6
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by 13kg150BS base oil, (100 DEG C of viscosity are 30mm2/ s, lower same) and containing 3.9kgThe suspension (calcium hydroxide content is 10 % by weight) of calcium hydroxide adds in fat still processed, at 200rpmUnder be uniformly mixed, at 15 DEG C, add 4.5kg acetic acid, reaction 40min, be then warming up to 100 DEG C,Add the 12-hydroxy stearic acid of 2.8kg, reaction 20min, then adds 1.5kg terephthalic acid (TPA), anti-Answer 30min;
(2) be warming up to 210 DEG C, refining 5min;
(3) add 130kg150BS base oil, stir and be cooled to 100 DEG C, add 0.4kgS1,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: 12-hydroxyl is hardResin acid calcium 7.95 % by weight; Terephthalic acid (TPA) calcium 5.33 % by weight; Calcium acetate 15.72 % by weight; LubricatedBase oil 70 % by weight; S11 % by weight.
Embodiment 7
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by 10kgPAO6 synthetic hydrocarbon oil, (100 DEG C of viscosity are 5.8mm2/ s, lower same) and containing 1.1kgThe suspension (calcium hydroxide content is 12 % by weight) of calcium hydroxide adds in fat still processed, at 300rpmUnder be uniformly mixed, at 35 DEG C, add 0.73kg acetic acid, reaction 25min, be then warming up to 90 DEG C,Add the stearic acid of 2.9kg, reaction 40min, then adds 0.6kg decanedioic acid, reaction 20min;
(2) be warming up to 195 DEG C, refining 10min;
(3) add 8kgPAO6 synthetic hydrocarbon oil, stir and be cooled to 110 DEG C, add 1.2kgS1,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: calcium stearate12.99 % by weight; Decanedioic acid calcium 3.03 % by weight; Calcium acetate 3.98 % by weight; Lubricating base oil 75 weightsAmount %; S15 % by weight.
Embodiment 8
The present embodiment is used for illustrating calcium base grease composition of the present invention and preparation method thereof.
(1) by the miscella of 37.8kg500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, underWith) and add fat still processed containing the suspension (calcium hydroxide content is 16 % by weight) of 2.9kg calcium hydroxideIn, under 230rpm, be uniformly mixed, at 50 DEG C, add 3kg acetic acid, reaction 30min, then risesTemperature, to 95 DEG C, adds the stearic acid of 4.75kg, and reaction 25min, then adds 1.2kg sad, reaction35min；
(2) be warming up to 205 DEG C, refining 8min;
(3) add the miscella of 19kg500SN and 150BS, stir and be cooled to 130 DEG C, add 2.1kgS1 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: calcium stearate 7.32% by weight; Calcium octoate 1.97 % by weight; Calcium acetate 5.71 % by weight; Lubricating base oil 82 % by weight;S13 % by weight.
Comparative example 2
Method according to embodiment 8 is prepared calcium-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: calcium stearate 7.55% by weight; Calcium octoate 2.03 % by weight; Calcium acetate 5.89 % by weight; Lubricating base oil 84.53 % by weight.
Table 1
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; Coefficient of friction: SH/T0847.
Table 2
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Surface sclerosis value: GB/T269; Be oxidized initial temperatureDegree: ASTMD5483; Stencil oil-dividing: SH/T0324; Tetra-ball machine test PB, PD:SH/T0202; Coefficient of friction: SH/T0847;Copper corrosion: GB/T7326; Anticorrosive property: GB/T5018.
It will be understood by those skilled in the art that dropping point is higher, the resistance to elevated temperatures of lubricating grease is better;Drawing cone in-degree is less, and the multiviscosisty performance of grease thickener is better; Sclerosis value in surface is less, lubricating greaseResistance hardening can be better; Oxidation onset temperature is higher, and the oxidation resistance of lubricating grease is better; Steel mesh dividesOil value is less, and the colloid stability of lubricating grease is better; PB, PD value are larger, the bearing capacity of lubricating greaseBetter; Coefficient of friction is less, and the antifriction performance of lubricating grease 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 and antifriction performance.
Calcium base grease composition 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 calcium-base grease, still toolThere are splendid heat-resisting quantity, colloid stability and bearing capacity, this lubricant composition can be competent atIn 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 (20)
1. a calcium base grease composition 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 calcium 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 calcium 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 calcium base thickening agentFor acid and calcium hydroxide reaction generate, described acid comprises higher fatty acids, optional middle molecule acid and little pointSon acid.
7. lubricant composition according to claim 6, wherein, described higher fatty acids isThe aliphatic acid of C12-C25; Described middle molecule acid is the carboxylic acid of C6-C10; Described little molecule acid is acetic acid.
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 middle molecule acid is sad, benzoic acid, terephthalic acid (TPA), azelaic acid and the last of the ten Heavenly stemsAt least one in diacid.
9. 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.
10. lubricant composition according to claim 9, wherein, described antioxidant is arylamine classAntioxidant, is preferably at least one in diphenylamines, PA and di-iso-octyldiphenylamine, more excellentElect di-iso-octyldiphenylamine as.
11. lubricant compositions according to claim 9, wherein, described extreme pressure anti-wear additives is twoSulfo-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.
12. lubricant compositions according to claim 9, wherein, described antirust agent is oil sulphurIn acid barium, petroleum sodium sulfonate, benzothiazole, BTA, zinc naphthenate and alkenyl succinic acid extremelyFew a kind of.
The preparation method of the calcium base grease composition of 13. 1 kinds of Wear vesistance excellences, described method comprises:
(1) by part lubricating base oil, higher fatty acids, optional middle molecule acid and little molecule acid,Calcium hydroxide Hybrid Heating, carries out saponification;
(2) heat up 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 65-95 weight%, the calcium base multiviscosisty of being prepared by higher fatty acids, optional middle molecule acid and little molecule acid, calcium hydroxideThe consumption of agent is 5-35 % by weight, and the consumption of additive is 0.1-15 % by weight, it is characterized in that, described inThe compound that additive contains structure shown in formula (I):
14. methods according to claim 13, 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 middle molecule acid andThe consumption of calcium base thickening agent prepared by little molecule acid, calcium hydroxide is 8-30 % by weight, the consumption of additiveFor 0.5-10 % by weight.
15. according to the method described in claim 13 or 14, 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.
16. methods according to claim 15, 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.
17. according to the method described in claim 13 or 14, wherein, described part lubricating base oil withThe weight ratio of described residue lubricating base oil is 50-75:25-50.
18. according to the method described in claim 13 or 14, wherein, higher fatty acids and optional inMolecule acid and the total amount of little molecule acid and the mol ratio of calcium hydroxide are stoichiometric proportion; Optional middle moleculeAcid is 1:0.37-3.4 with the mol ratio of higher fatty acids, higher fatty acids and optional middle molecule acid totalMeasuring with the mol ratio of optional little molecule acid is 1:0.9-4.
19. according to the method described in claim 13 or 14, wherein,
In the time not containing middle molecule acid and the acid of little molecule, step (1) comprising: by part lubricating base oilWith higher fatty acids Hybrid Heating, be warming up to 80-105 DEG C, preferably 80-95 DEG C, adds calcium hydroxide to enterRow saponification, the saponification time is 0.2-1.5h, is preferably 0.5-1h;
In the time containing the acid of middle molecule and the acid of little molecule, step (1) comprising: by part lubricating base oil withCalcium hydroxide mixes, and at 15-50 DEG C, adds little molecule acid to carry out the first saponification, then heats upTo 80-100 DEG C, add higher fatty acids to carry out the second saponification, then add middle molecule acid to carry outThree saponifications, the time of the first saponification, the second saponification, the 3rd saponification is10-60min, is preferably 20-40min.
20. according to the method described in claim 13 or 14, wherein,
In the time not containing middle molecule acid and the acid of little molecule, in step (2), be warming up to 140-160 DEG C and carry outRefining, the time of refining is 5-15min;
In the time containing middle molecule acid and the acid of little molecule, in step (2), be warming up to 180-220 DEG C, preferablyRefine for 190-210 DEG C, the time of refining is 5-15min.
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