CN105586113A - Sodium-based lubricating grease composition with excellent oxidation resistance and preparation method therefor - Google Patents
Sodium-based lubricating grease composition with excellent oxidation resistance and preparation method therefor Download PDFInfo
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- CN105586113A CN105586113A CN201410573339.0A CN201410573339A CN105586113A CN 105586113 A CN105586113 A CN 105586113A CN 201410573339 A CN201410573339 A CN 201410573339A CN 105586113 A CN105586113 A CN 105586113A
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- IERZEVFTXXSUFS-UHFFFAOYSA-N CC(C)(C)c1cc(Cc(cc2)ccc2Nc2ccc(C[n]3nnc4c3cccc4)cc2)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(Cc(cc2)ccc2Nc2ccc(C[n]3nnc4c3cccc4)cc2)cc(C(C)(C)C)c1O IERZEVFTXXSUFS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a sodium-based lubricating grease composition with excellent oxidation resistance. The lubricating grease composition contains the following ingredients in percentage by weight: 65-95wt% of lubricating base oil, 4-30wt% of sodium-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 sodium-based lubricating grease composition with excellent oxidation resistance. The lubricating grease composition provided by the invention has good colloid stability, has obvious advantage in oxidation resistance and has good compatibility with other lubricating greases. Thus, grease can be adequate to lubricate various motors, power generators, air blowers and equipment of transportation industry, iron and steel enterprises and other various industries and is particularly applicable to the lubrication of various ball bearings such as high-speed ball bearings and medium-speed ball bearings.
Description
Technical field
The present invention relates to lubricating grease field, particularly, relate to a kind of antioxygen property that contains special additiveExcellent sodium base grease composition and method of making the same.
Background technology
Sodium base grease be generally by natural animal-plant grease soda soap or fatty acid sodium soap multiviscosisty mineral oil andMake, there is higher dropping point, good colloid stability, shear stability. Logical in process of productionCross change raw materials for production and preparation process condition, can make the product of different outward appearances and different performance.
CN102021546A has reported a kind of for the firm antirust aqueous rust preventive of product; CN101153236 willThe pressed powder that different-grain diameter distributes adds in lubricating grease, has not only strengthened the water repelling property of lubricating grease,Also improve extreme pressure anti-wear; CN1557922 has prepared and has contained by add clean water in sodium base greaseHave the moisture sodium base grease of 8-30% clean water, this fat is a kind of substantially pollution-free to environment, lubricated effectFruit is good, has thermal balance effect and the lubriation material that can be applicable to heavy load sliding bearing with low cost;CN102021068A has prepared a kind of sodium aluminate soap grease for ship, is applicable to marine propeller and waterborneCrane and dredger, dropping point more than 75 DEG C, has good water-resistance, protective and rust-preventing characteristic, bothThere is proper lubrication trace, have again corrosion-resisting function, and there is the function that lowers mechanicalness noise; US2468098In the lubricating grease that contains 5-35% fatty acid sodium soap, add 0.1-5% acrylic acid sodium salt, reduce soda soap at waterIn solubility; In US2591586 the people such as Morway find methacrylaldehyde and derivative thereof also can with high scoreSodium base grease is prepared in sub-acid.
The life-span of lubricating grease can shorten with the prolongation of serviceability temperature rising or lubrication time. From chemical propertyUpper theory is the major reason that causes lubricating grease oxidation deterioration as the metal soap of thickening agent. In order to suppressThe oxidation deterioration of lubricating grease, anti-oxidation product causes the corrosion of metal surface, add appropriate resistingOxygen additive. At present, conventional antioxidant is mainly divided into amine and phenols two classes. Phenolic antioxidant is generalComprise BHT, 2,6-di-tert-butylphenol etc., but its serviceability temperature is lower, generally existsIn 150 DEG C. Amine antioxidants is mainly alkylated diphenylamine, or alkylating phenyl-naphthylamines etc.
Summary of the invention
The object of the invention is the high request in order to meet the antioxygen property to lubricating grease, a kind of antioxygen is providedThe sodium base grease composition and method of making the same of excellent performance.
The present inventor finds under study for action, and the additive in lubricant composition contains formula (I)Shown in the antioxidant of structure:
Can make lubricant composition there is the good performance such as anti-oxidant.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of antioxygen property excellenceSodium 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, sodium base thickening agent and the 0.1-15 of 4-30 % 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 sodium base thickening agent of 4-28 % by weight and 1-10 % by weightAdditive.
Preferably, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Content is 0.1-3 % by weight, more preferably 0.2-1 % by weight.
On the other hand, the invention provides a kind of preparation of sodium base grease composition of antioxygen property excellenceMethod, described method comprises:
(1) by the lubricating base oil of 1/5-2/5 and higher fatty acids Hybrid Heating, be warming up to 70-90 DEG C,Add NaOH, carry out saponification, then optionally, add little molecule acid to carry out recombination reaction;
(2) be warming up to 100-120 DEG C, add the lubricating base oil of 1/5-2/5, be warming up to 180-220 DEG CRefine;
(3) add residue lubricating base oil, be cooled to 80-100 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 sodium base thickening agent of being prepared by higher fatty acids, optional little molecule acid and NaOHFor 4-30 % by weight, the consumption of additive is 0.1-15 % by weight, and described additive contains formula (I) instituteShow the compound of structure:
Preferably, taking the weight of lubricant composition as benchmark, the consumption of lubricating base oil is that 70-90 is heavyThe consumption of amount %, the sodium base thickening agent prepared by higher fatty acids, optional little molecule acid and NaOHFor 4-28 % by weight, the consumption of additive is 1-10 % by weight.
Preferably, taking the weight of lubricant composition as benchmark, the compound of structure shown in formula (I)Consumption is 0.1-3 % by weight, more preferably 0.2-1 % by weight.
Lubricant composition provided by the invention, has good colloid stability, more at antioxygenic propertyOn have obvious advantage, and have good compatibility with other lubricating grease. This fat can be competent in respectivelyPlant the profit of motor, generator, air blast, transportation, iron and steel enterprise and other various industrial equipmentsSliding, be specially adapted to the lubricated of the various ball bearings such as high speed, middling speed.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Fig. 1 is the reaction equation of the step (a) of preparing antioxidant.
Fig. 2 is the reaction equation of the step (b) of preparing antioxidant.
Fig. 3 is the reaction equation of the step (c) of preparing antioxidant.
Fig. 4 is the hydrogen spectrum spectrogram of the antioxidant prepared of preparation example.
Fig. 5 is the carbon spectrum spectrogram of the antioxidant prepared of preparation example.
Fig. 6 is the mass spectrogram of the antioxidant prepared of preparation example.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of sodium base grease composition of antioxygen property excellence, with lubricant compositionWeight be benchmark, lubricant composition comprises following component: the lubricating base oil of 65-95 % by weight,The sodium base thickening agent of 4-30 % 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 antioxidant referred to is the compound of structure shown in formula (I).
In the present invention, preferably, taking the weight of lubricant composition as benchmark, described lubricant compositionComprise following component: the lubricating base oil of 70-90 % by weight, sodium base thickening agent and the 1-10 of 4-28 % 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 0.1-3 % by weight, more preferably 0.2-1 % by weight.
The present invention is intended to contain structure shown in formula (I) by the additive in sodium base grease compositionCompound and realize goal of the invention, even if sodium base grease composition has the good performance such as anti-oxidant.Therefore, for the selection of each conventional component in sodium 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 5-60mm2/ s, more preferably 10-30mm2/ s. Concrete for mineral oil, vegetable oil and artificial oilAlso there is no particular limitation for kind, can adopt the conventional mineral oil in this area, vegetable oil and artificial oil,For example, mineral oil can be selected paraffinic base, cycloalkyl series, vegetable oil can be castor oil, rapeseed oil,At least one in peanut oil and soybean wet goods, artificial oil can be poly-a-olefin oil (PAO), ester class oil,At least one in fluorocarbon oil and silicone oil etc.
In the present invention, sodium base thickening agent can be the conventional sodium base thickening agent in this area, for example, and Ke YiweiGeneration is reacted in acid with NaOH, 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,Sodium base thickening agent of the present invention can be reacted by higher fatty acids generation with NaOH, also can be by seniorGeneration is reacted in aliphatic acid and the acid of little molecule with NaOH.
Wherein, higher fatty acids can be the aliphatic acid of C12-C25, be preferably laurate, palmitic acid,At least one in stearic acid and 12-hydroxy stearic acid, more preferably stearic acid and/or 12-hydroxyl tristearinAcid.
Wherein, little molecule acid is preferably the carboxylic acid of C4-C11, more preferably benzoic acid, terephthalic acid (TPA),At least one in azelaic acid and decanedioic acid.
It will be understood by those skilled in the art that in the time that reality is used, generally add NaOH water-solubleLiquid without particular/special requirement, for example, can be 1-30 % by weight for the concentration of sodium hydrate aqueous solution.
Above-mentioned sodium 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 having preferably, the antioxidant of structure shown in formula (I) and other additives joinWu Xing, therefore, according to the use needs of lubricating grease, additive of the present invention can also contain antirust agent.Without particular/special requirement, can adopt kind and the content of this area routine for the kind of antirust agent and content.For example, antirust agent can be at least one in barium mahogany sulfonate, dinonyl barium benzosulfonate and Lanolin Calcium SoapKind, the content of antirust agent can account for the 0.01-4.5 % by weight of lubricant composition gross weight, is preferably 0.1-2% by weight.
In the present invention, shown in formula (I), the preparation method of the compound of structure preferably includes:
(a) 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene are carried out to condensation reaction, shown in production (II)Intermediate M,
(b) intermediate M step (a) being obtained contacts with bromide reagent and carries out bromo-reaction, rawBromination product shown in an accepted way of doing sth (III),
(c) make the bromination product that step (b) obtains contact and carry out idol with the compound shown in formula (IV)Connection reaction, the antioxidant shown in production (I),
In step of the present invention (a), the condition of condensation reaction preferably includes: under inert atmosphere,In one solvent, under the existence of the first catalyst, by 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene at-20-0 DEG CAfter lower reaction 0.5-1.5h, rise to 15-30 DEG C, be then heated to 70-80 DEG C of reaction 1-3h.
In the present invention, inert atmosphere can be the inert atmosphere of this area routine, for example can by nitrogen,The gases such as argon gas provide.
It will be understood by those skilled in the art that for stable reaction is carried out reaction at-20-0 DEG CAfter 0.5-1.5h, rise to 15-30 DEG C, should slowly be warming up to 15-30 DEG C, for example, can be by-20-0 DEG CSystem after lower reaction 0.5-1.5h is placed under the environment temperature of 15-30 DEG C, makes reaction system self slowBe warming up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from methyl alcohol, ethanol, DMF and acetonitrileAt least one, more preferably methyl alcohol and/or acetonitrile, is further preferably methyl alcohol.
In the present invention, the first catalyst can be inorganic acid or organic acid, is preferably selected from acetic acid, to methylAt least one in benzoic acid and benzene sulfonic acid, more preferably acetic acid.
In the present invention, the consumption of 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene is essentially equimolar amounts, butFormaldehyde and benzene can be suitably excessive. The mol ratio of 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene is preferably0.9-1.5:0.9-10:0.9-10。
In step of the present invention (a), the consumption of the first catalyst can be catalytic amount, with the tertiary fourth of 2,6-bis-The molal quantity of base phenol is benchmark, and the consumption of the first catalyst is preferably 5-100 % by mole, more preferably10-30 % by mole.
It will be understood by those skilled in the art that in step of the present invention (a), purer in order to obtainIntermediate M, also need reacted system to carry out post processing, the mode of post processing can comprise and subtractingPress except desolventizing, then through solvent dilution, washing, dry, decompression again except desolventizing, for example, will be anti-Should after system at 0.01-0.05MPa, 40-60 DEG C except desolventizing, then pour 1-10 times of volume intoIn ethyl acetate (or carrene), use respectively distilled water and saturated common salt water washing, then at 15-30 DEG CUnder add the drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keep 10-60min. Remove by filter dryAfter agent, at 0.01-0.05MPa, 40-60 DEG C, remove desolventizing, to obtain intermediate M.
In step of the present invention (a), 2,6-DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction of condensation reactionAs shown in Figure 1, in Fig. 1, what the first solvent adopted is methyl alcohol to equation, and what the first catalyst adopted isAcetic acid, only for purposes of illustration, is not construed as limiting scope of the present invention.
In step of the present invention (b), the condition of bromo-reaction preferably includes: under inert atmosphere,In two solvents, under the existence of the second catalyst, under lucifuge condition, during step (a) is obtainedMesosome M reacts 1-2h with bromide reagent at 15-30 DEG C, then uses quencher cancellation.
" inert atmosphere " as previously mentioned, do not repeat them here.
To it will be understood by those skilled in the art that in order reacting more stably and to carry out, preferably to intermediateIn M, slowly add brominated reagent.
In the present invention, the second solvent is preferably selected from oxolane, carrene, chloroform and ether extremelyFew a kind of, more preferably oxolane.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azoAt least one in bis-isobutyronitrile (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, more excellentElect NBS as.
In step of the present invention (b), carry out cancellation with quencher, quencher can be conventional for this areaQuencher can be for example saturated aqueous common salt.
In step of the present invention (b), the consumption of intermediate M and bromide reagent is essentially equimolar amounts,But bromide reagent generally can be suitably excessive, reach 1.1-3 times of equivalent of reaction substrate. Intermediate M withBromide reagent mol ratio is preferably 0.9-1.2:0.9-3.0.
In step of the present invention (b), the consumption of the second catalyst can be catalytic amount, with intermediate M'sMolal quantity is benchmark, and the consumption of the second catalyst is preferably 10-100 % by mole, and more preferably 40-60 rubsYou are %.
In the inventive method step (b), intermediate M contacts with bromide reagent and carries out the anti-of bromo-reactionAnswer equation as shown in Figure 2, in Fig. 2, that bromide reagent adopts is NBS, is only illustrational order, scope of the present invention is not construed as limiting.
In step of the present invention (b), except the bromination product shown in production (III), also has traceThe bromination product at ortho position generates, and between not having, the bromination product of position generates, but the amount of the bromination product at ortho position veryPettiness, does not have materially affect to subsequent reactions, negligible.
It will be understood by those skilled in the art that in step of the present invention (b), purer in order to obtainBromination product, also need the system after cancellation to carry out post processing, the mode of post processing can comprise waterWash, be dried, removal of solvent under reduced pressure, for example, the system after cancellation is washed with distilled water, then existAt 15-30 DEG C, add the drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keep 10-60min. FilterRemove after drier, at 0.01-0.05MPa, 40-60 DEG C, remove desolventizing, to obtain bromination product.
In step of the present invention (c), the condition of coupling reaction preferably includes: under inert atmosphere,In three solvents, under the existence of the 3rd catalyst, the bromination product that step (b) is obtained and formula (IV)Shown compound reacts 4-8h at 80-100 DEG C.
" inert atmosphere " as previously mentioned, do not repeat them here.
In the present invention, for stable reaction is carried out, be preferably warming up to gradually 80-100 DEG C, then existAt 80-100 DEG C, react 4-8h.
In the present invention, the 3rd solvent is preferably selected from carrene, chloroform, toluene and oxolane extremelyFew a kind of, more preferably carrene.
In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali. Palladium salt is preferably selected from palladiumAnd/or palladium-dibenzalacetone complex compound [Pd2(dba)3]; Part is preferably selected from tri-tert phosphorus, dinaphthol(BINAP) at least one and in two (diphenylphosphino) ferrocene (dppf); Alkali is preferably selected from uncleAt least one in sodium butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate.
In step of the present invention (c), the chemical combination shown in the bromination product that step (b) obtains and formula (IV)The consumption of thing is essentially equimolar amounts, but the compound shown in formula (IV) can be suitably excessive. Step(b) mol ratio of the compound shown in the bromination product obtaining and formula (IV) is preferably 0.9-1.5:0.9-2.5.
In step of the present invention (c), the consumption of catalyst can be catalytic amount, with bromination product moleNumber is benchmark, and the consumption of palladium salt is preferably 5-50 % by mole, and more preferably 5-20 % by mole more enters oneStep is preferably 5-10 % by mole; The consumption of part is preferably 5-50 % by mole, more preferably 10-30 % by mole;The consumption of alkali is preferably 5-50 % by mole, more preferably 10-30 % by mole.
In step of the present invention (c), the chemical combination shown in the bromination product that step (b) obtains and formula (IV)As shown in Figure 3, in Fig. 3, what palladium salt adopted is acetic acid to the reaction equation that coupling reaction is carried out in thing contactPalladium, only for purposes of illustration, is not construed as limiting scope of the present invention.
It will be understood by those skilled in the art that in order to obtain purer end product i.e. formula (I)Shown antioxidant, the inventive method preferably also comprises reacted system is carried out to post processing, post processingMode can comprise filtration, solvent dilution, washing, dry, removal of solvent under reduced pressure, for example, will be anti-Should after system filter after filtrate pour in the ethyl acetate (or carrene) of 1-10 times of volume,Then with distilled water washing, then at 15-30 DEG C, add anhydrous calcium chloride or anhydrous sodium sulfate etc. dryDrying prescription, keeps 10-60min. Remove by filter after drier, at 0.01-0.05MPa, 40-60 DEG C, removeDesolventizing, to obtain the antioxidant shown in formula (I).
Each step of the method for the compound of structure shown in preparation formula in the present invention (I) preferably under agitationCarrying out, without particular/special requirement, can be the mixing speed of this area routine for mixing speed, for example, stirsThe speed of mixing can be 100-800rpm.
Shown in preparation formula of the present invention (I) in the method for the compound of structure, for the first solvent, secondThe amount of solvent and the 3rd solvent, without particular/special requirement, can be the solvent load of this area routine, and this is abilityField technique personnel are known, do not repeat them here.
As mentioned above, the present invention is intended to contain formula (I) by the additive in sodium base grease compositionShown in structure compound and realize goal of the invention, good anti-oxidant etc. even if lubricant composition hasPerformance. Therefore, without particular/special requirement, can adopt this area routine for the preparation method of sodium base greaseThe method using, for example, second aspect, the present invention also provides a kind of sodium Ji Run of antioxygen property excellenceThe preparation method of consistent lubricant composition, the method comprises:
(1) by the lubricating base oil of 1/5-2/5 and higher fatty acids Hybrid Heating, be warming up to 70-90 DEG C,Add NaOH, carry out saponification, then optionally, add little molecule acid to carry out recombination reaction;
(2) be warming up to 100-120 DEG C, add the lubricating base oil of 1/5-2/5, be warming up to 180-220 DEG CRefine;
(3) add residue lubricating base oil, be cooled to 80-100 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 sodium base thickening agent of being prepared by higher fatty acids, optional little molecule acid and NaOHFor 4-30 % by weight, the consumption of additive is 0.1-15 % by weight, and additive contains knot shown in formula (I)The compound of structure:
In the inventive method, preferably, taking the weight of lubricant composition as benchmark, lubricating base oilThe sodium that consumption is 70-90 % by weight, prepared by higher fatty acids, optional little molecule acid and NaOHThe consumption of base thickening agent is 4-28 % by weight, and the consumption of additive is 1-10 % by weight.
In the inventive method, the total amount of higher fatty acids and optional little molecule acid and NaOH moleThan being preferably stoichiometric proportion, NaOH also can excessive 1-10 % by weight. Higher fatty acids is with optionalThe mol ratio of little molecule acid be preferably 1:0.1-1. It will be understood by those skilled in the art that according to byThe consumption of sodium base thickening agent prepared by higher fatty acids, optional little molecule acid and NaOH, can be anti-The consumption of releasing higher fatty acids, little molecule acid and NaOH, this is conventionally known to one of skill in the art,Do not repeat them here.
In the present invention, as previously mentioned, " optionally " refers to can be had also and can not have. In step (1)," then optionally, add little molecule acid to carry out recombination reaction " to refer to and " add little molecule acid to answerClose reaction " be an optional step, can comprise this step, also can not comprise this step; " appointThe little molecule acid of choosing " refer to that little molecule acid is a kind of optional component, can comprise this component, also canNot comprise this component; " total amount of higher fatty acids and optional little molecule acid and NaOH moleThan for stoichiometric proportion " refer in the time not containing little molecule acid the rubbing of higher fatty acids and NaOHYou are than being preferably stoichiometric proportion, when containing little molecule when sour, the total amount of higher fatty acids and little molecule acidBe preferably stoichiometric proportion with the mol ratio of NaOH. " higher fatty acids and optional little molecule acidMol ratio is 1:0.1-1 " refer in the time containing the acid of little molecule, higher fatty acids and little molecule acid moleThan being preferably 1:0.1-1. In a word, it will be understood by those skilled in the art that sodium base of the present invention multiviscosistyAgent can be reacted by higher fatty acids generation with NaOH, also can be by higher fatty acids and little molecule acidReact generation with NaOH.
In the inventive method, taking the weight of lubricant composition as benchmark, the change of structure shown in formula (I)The consumption of compound is preferably 0.1-3 % by weight, more preferably 0.2-1 % by weight.
In the inventive method, the lubricating base oil of 1/5-2/5 refers to the 1/5-2/5 that accounts for lubricating base oil total amount.
In the inventive method step (1), saponification temperature is preferably 100-110 DEG C, when saponificationBetween be preferably 1-3h, optional complex reaction time is preferably 1-3h. " optional complex reaction time is excellentElect 1-3h as " refer to that complex reaction time is preferably 1-3h in the time comprising recombination reaction step.
In the inventive method step (2), the time of refining is preferably 5-20min.
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, additive as previously mentioned, 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 physico-chemical analysis method of product: by inductively coupled plasma emission of ions spectrographic determination elementContent.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen spectrum,13C carbon spectrum), high resolution mass spectrum.
Preparation example
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), being filled with nitrogen protectsProtect, add the methyl alcohol of 150ml and the acetic acid of 0.01mol, fully cooling in ice-water bath after, then divideDo not add 2 of 0.1mol, 6-DI-tert-butylphenol compounds, the formaldehyde of 0.2mol and the benzene of 0.3mol. Reaction 1After hour, remove ice-water bath, be heated to 75 DEG C after rising to 25 DEG C and stop reaction after continuing to reflux 2 hours,Reacted system is steamed to solvent at 0.03MPa, 50 DEG C, then adds 250ml ethyl acetate,And proceed in separatory funnel, use respectively 100ml distilled water (twice) and the water washing of 50ml saturated common salt,And adding 10g anhydrous calcium chloride dry 20min at 25 DEG C, the filtrate after filtration is at 40 DEG C, 0.03MPaLower steaming desolventizes, and obtains midbody product M1.
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), being filled with nitrogen protectsProtect, add the dry tetrahydrofuran of 150ml, then dissolve in midbody product M1, and add 0.05molAmmonium nitrate, under lucifuge condition, slowly add 0.1mol brominated reagent NBS. At 25 DEG C, stir anti-Answer 1.5h, then use saturated aqueous common salt cancellation, then use 100ml distilled water (twice) washing, and addEnter 10g anhydrous sodium sulfate dry 20min at 25 DEG C. Filtrate after filtration is at 40 DEG C, 0.03MPaLower steaming desolventizes, and obtains bromination product.
In the 500ml flask with electromagnetic agitation (mixing speed is 200rpm), being filled with nitrogen protectsProtect, add the carrene of 150ml as solvent, add respectively above-mentioned bromination product and 0.12mol124 Triazole compound, adds the tri-tert phosphorus of 0.02mol subsequently, the sodium tert-butoxide of 0.02mol andThe Pd (OAc) of 0.005mol2. Be warming up to gradually 90 DEG C, continue to stir 6h. Then by reacted bodyFiltrate after system filters adds 250ml ethyl acetate, and proceeds in separatory funnel, uses 100ml distilled water(twice) washing, and add 10g anhydrous sodium sulfate dry 20min at 25 DEG C. Filtrate after filtrationUnder 40 DEG C, 0.03MPa, steam and desolventize, obtain end product S1.
The physico-chemical analysis data of S1 are as follows: nitrogen content, 11.2%.
S1 is carried out to structural characterization, obtain respectively hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, respectivelySee Fig. 4, Fig. 5 and Fig. 6.
Can find out from physico-chemical analysis data, Fig. 4, Fig. 5 and Fig. 6 of above-mentioned preparation example, S1 has formula(I) structure shown in.
Embodiment 1
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by 120 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, lower same) and 8.96Gram 12-hydroxy stearic acid adds in fat still processed, and agitating heating under 180rpm, is warming up to 80 DEG C, addsEnter the aqueous solution (concentration is 8 % by weight) containing 2 grams of NaOH, be warming up to 100 DEG C, carry out saponification anti-Answer 3h;
(2) be warming up to 120 DEG C, add 120 grams of 150BS base oils, be warming up to 200 DEG C, refining5min；
(3) add 120 grams of 150BS base oils, stir be cooled to 100 DEG C, add 0.8 gram of S1,0.7 gram of barium mahogany sulfonate stirs under 180rpm;
(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 sodium 9.62 % by weight; Lubricating base oil 90 % by weight; S10.2 % by weight; Barium mahogany sulfonate 0.18% by weight.
Embodiment 2
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by 84 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, lower same) and 25.5 grams12-hydroxy stearic acid adds in fat still processed, and agitating heating under 200rpm, is warming up to 70 DEG C, adds and containsThe aqueous solution (concentration is 15 % by weight) of 3.6 grams of NaOH, is warming up to 95 DEG C, carries out saponification1h；
(2) be warming up to 100 DEG C, add 34 grams of 500SN base oils, be warming up to 180 DEG C of refining 10min;
(3) add 42 grams of 500SN base oils, stir and be cooled to 90 DEG C, add 1.1 grams of S1,3.8Gram barium mahogany sulfonate stirs under 200rpm;
(4) grind 3 times by three-roller and become fat. Properties of product are as shown in table 1.
In the lubricating grease that the present embodiment obtains, taking lubricating grease weight as benchmark, consist of: 12-hydroxyl is hardResin acid sodium 15 % by weight; Lubricating base oil 82.4 % by weight; S10.6 % by weight; Barium mahogany sulfonate 2 weightsAmount %.
Embodiment 3
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by 75 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, lower same) and 21.5Gram stearic acid adds in fat still processed, and agitating heating under 300rpm, is warming up to 90 DEG C, adds containing 3.1The aqueous solution (concentration is 18 % by weight) of gram NaOH, is warming up to 105 DEG C, carries out saponification 2h;
(2) be warming up to 110 DEG C, add 35 grams of PAO6 synthetic hydrocarbon oils, be warming up to 220 DEG C of refining 15min;
(3) add 25 grams of PAO6 synthetic hydrocarbon oils, stir be cooled to 80 DEG C, add 1.3 grams of S1,1.6 grams of barium mahogany sulfonates stir under 300rpm;
(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: odium stearate 15.2% by weight; Lubricating base oil 83 % by weight; S10.8 % by weight; Barium mahogany sulfonate 1 % by weight.
Embodiment 4
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by the miscella of 24.6 grams of 500SN and 150BS, (100 DEG C of viscosity are 13mm2/ s, underWith) and 14.85 grams of stearic acid add in fat still processed, agitating heating under 230rpm, is warming up to 85 DEG C,Add the aqueous solution (concentration is 30 % by weight) containing 2 grams of NaOH, be warming up to 100 DEG C, carry out soapChange reaction 3h;
(2) be warming up to 120 DEG C, add the miscella of 24.6 grams of 500SN and 150BS, be warming up to 210 DEG CRefining 20min;
(3) add the miscella of 32.8 grams of 500SN and 150BS, stir and be cooled to 85 DEG C, add 1Gram S1,1 gram of barium mahogany sulfonate stir 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: odium stearate 16% by weight; Lubricating base oil 82 % by weight; S11 % by weight; Barium mahogany sulfonate 1 % by weight.
Comparative example 1
Method according to embodiment 4 is prepared sodium base grease, different, and S1 is replaced with to equivalentDiphenylamines. Properties of product are as shown in table 1.
In the lubricating grease that this comparative example obtains, taking lubricating grease weight as benchmark, consist of: odium stearate 16% by weight; Lubricating base oil 82 % by weight; Diphenylamines 1 % by weight; Barium mahogany sulfonate 1 % by weight.
Embodiment 5
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by 275 grams of 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, lower same) and 128.02Gram stearic acid adds in fat still processed, and agitating heating under 180rpm, is warming up to 80 DEG C, adds containing 32.4The aqueous solution (concentration is 22 % by weight) of gram NaOH, is warming up to 100 DEG C, carries out saponification 3h,In system, add 43.96 grams of benzoic acid again, carry out recombination reaction 3h;
(2) be warming up to 120 DEG C, add 265 grams of 500SN base oils, be warming up to 200 DEG C, refining5min；
(3) add 257 grams of 500SN base oils, stir and be cooled to 100 DEG C, add 10 grams of S1,7Gram barium mahogany sulfonate stirs under 180rpm;
(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: odium stearate 13.8% by weight; Sodium Benzoate 5.2 % by weight; Lubricating base oil 79.3 % by weight; S11 % by weight; OilBarium sulfonate 0.7 % by weight.
Embodiment 6
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by 270 grams of 150BS base oils, (100 DEG C of viscosity are 31mm2/ s, lower same) and 142.24Gram stearic acid adds in fat still processed, and agitating heating under 200rpm, is warming up to 70 DEG C, adds containing 32The aqueous solution (concentration is 15 % by weight) of gram NaOH, is warming up to 110 DEG C, carries out saponification 1h,In system, add 36.64 grams of benzoic acid again, carry out recombination reaction 1h;
(2) be warming up to 100 DEG C, add 260 grams of 150BS base oils, be warming up to 180 DEG C, refining10min；
(3) add 259 grams of 150BS base oils, stir and be cooled to 90 DEG C, add 4 grams of S1,7 gramsBarium mahogany sulfonate stirs under 200rpm;
(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: odium stearate 15.4% by weight; Sodium Benzoate 4.4 % by weight; Lubricating base oil 79.1 % by weight; S10.4 % by weight; OilBarium sulfonate 0.7 % by weight.
Embodiment 7
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by 311 grams of PAO6 synthetic hydrocarbon oils, (100 DEG C of viscosity are 5.8mm2/ s, lower same) and 85.34Gram stearic acid adds in fat still processed, and agitating heating under 300rpm, is warming up to 90 DEG C, adds containing 10.26The aqueous solution (concentration is 18 % by weight) of gram NaOH, is warming up to 105 DEG C, carries out saponification 2h,In system, add 32.97 grams of benzoic acid again, carry out recombination reaction 2h;
(2) be warming up to 110 DEG C, add 292 grams of PAO6 synthetic hydrocarbon oils, be warming up to 220 DEG C, refining15min；
(3) add 266 grams of PAO6 synthetic hydrocarbon oils, stir and be cooled to 80 DEG C, add 8 grams of S1,7Gram barium mahogany sulfonate stirs under 300rpm;
(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: odium stearate 9.1% by weight; Sodium Benzoate 3.8 % by weight; Lubricating base oil 85.6 % by weight; S10.8 % by weight; OilBarium sulfonate 0.7 % by weight.
Embodiment 8
The present embodiment is used for illustrating sodium base grease composition and method of making the same of the present invention.
(1) by the miscella of 285 grams of 500SN and 150BS, (100 DEG C of viscosity are 14mm2/ s, underWith) and 113.79 grams of stearic acid add in fat still processed, agitating heating under 230rpm, is warming up to 85 DEG C,Add the aqueous solution (concentration is 12 % by weight) containing 32 grams of NaOH, be warming up to 100 DEG C, carry out soapChange reaction 3h, then add 48.85 grams of benzoic acid in system, carry out recombination reaction 3h;
(2) be warming up to 120 DEG C, add the miscella of 270 grams of 500SN and 150BS, be warming up to 210 DEG C,Refining 20min;
(3) add the miscella of 253 grams of 500SN and 150BS, stir and be cooled to 85 DEG C, add 6Gram S1,7 grams of barium mahogany sulfonates stir 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: odium stearate 12.2% by weight; Sodium Benzoate 5.8 % by weight; Lubricating base oil 80.7 % by weight; S10.6 % by weight; OilBarium sulfonate 0.7 % by weight.
Comparative example 2
Method according to embodiment 8 is prepared sodium base grease, different, and S1 is replaced with to equivalentDiphenylamines. Properties of product are as shown in table 2.
In the lubricating grease that this comparative example obtains, taking lubricating grease weight as benchmark, consist of: odium stearate 12.2% by weight; Sodium Benzoate 5.8 % by weight; Lubricating base oil 80.7 % by weight; Diphenylamines 0.6 % by weight;Barium mahogany sulfonate 0.7 % by weight.
Table 1
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Oxidation onset temperature: ASTMD5483; MachineryImpurity: acid decomposition; Copper corrosion: GB/T7326; Anticorrosive property: GB/T5018.
Table 2
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Oxidation stability: SH/T0325; Stencil oil-dividing:SH/T0324; Copper corrosion: GB/T7326; Anticorrosive property: GB/T5018.
It will be understood by those skilled in the art that Drawing cone in-degree is less, the multiviscosisty of grease thickenerPerformance is better; Oxidation onset temperature is higher, and the oxidation resistance of lubricating grease is better; Oxidation stability is less,The antioxygenic property 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 non-oxidizability.
Lubricant composition provided by the invention, has good colloid stability, more at antioxygenic propertyOn have obvious advantage, and have good compatibility with other lubricating grease. This fat can be competent in respectivelyPlant the profit of motor, generator, air blast, transportation, iron and steel enterprise and other various industrial equipmentsSliding, be specially adapted to the lubricated of the various ball bearings such as high speed, middling speed.
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 (17)
1. a sodium base grease composition for antioxygen property excellence, taking the weight of lubricant composition asBenchmark, described lubricant composition comprises following component: the lubricating base oil of 65-95 % by weight, 4-30The sodium 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 sodium base thickening agent of 4-28 % by weight and the additive of 1-10 % 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 0.1-3 % by weight.
4. lubricant composition according to claim 3, wherein, with the weight of lubricant compositionAmount is benchmark, and shown in formula (I), the content of the compound of structure is 0.2-1 % by weight.
5. lubricant composition according to claim 1 and 2, wherein, described lubricating base oilFor at least one in mineral oil, vegetable oil and artificial oil.
6. lubricant composition according to claim 1 and 2, wherein, described sodium base thickening agentReact generation with NaOH for acid, 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 C4-C11.
8. lubricant composition according to claim 7, wherein, described higher fatty acids is the moonAt least one in cinnamic acid, palmitic acid, stearic acid and 12-hydroxy stearic acid, be preferably stearic acid and/or12-hydroxy stearic acid, described little molecule acid is in benzoic acid, terephthalic acid (TPA), azelaic acid and decanedioic acidAt least one.
9. lubricant composition according to claim 1 and 2, wherein, described additive also containsThere is antirust agent.
10. lubricant composition according to claim 9, wherein, described antirust agent is oil sulphurAt least one in acid barium, dinonyl barium benzosulfonate and Lanolin Calcium Soap.
The preparation method of the sodium base grease composition of 11. 1 kinds of antioxygen property excellences, described method comprises:
(1) by the lubricating base oil of 1/5-2/5 and higher fatty acids Hybrid Heating, be warming up to 70-90 DEG C,Add NaOH, carry out saponification, then optionally, add little molecule acid to carry out recombination reaction;
(2) be warming up to 100-120 DEG C, add the lubricating base oil of 1/5-2/5, be warming up to 180-220 DEG CRefine;
(3) add residue lubricating base oil, be cooled to 80-100 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 sodium base thickening agent of being prepared by higher fatty acids, optional little molecule acid and NaOHFor 4-30 % by weight, the consumption of additive is 0.1-15 % by weight, it is characterized in that, described additive containsThere is the compound of structure shown in formula (I):
12. methods according to claim 11, 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 sodium base thickening agent prepared by NaOH is 4-28 % by weight, and the consumption of additive is that 1-10 is heavyAmount %.
13. according to the method described in claim 11 or 12, wherein, and with the weight of lubricant compositionFor benchmark, shown in formula (I), the consumption of the compound of structure is 0.1-3 % by weight.
14. methods according to claim 13, wherein, taking the weight of lubricant composition as baseStandard, shown in formula (I), the consumption of the compound of structure is 0.2-1 % by weight.
15. according to the method described in claim 11 or 12, wherein, and higher fatty acids and optional littleThe total amount of molecule acid and the mol ratio of NaOH are stoichiometric proportion; Higher fatty acids and optional little pointThe mol ratio of son acid is 1:0.1-1.
16. according to the method described in claim 11 or 12, and wherein, in step (1), saponification is anti-Answering temperature is 100-110 DEG C, and the saponification time is 1-3h, and optional complex reaction time is 1-3h.
17. according to the method described in claim 11 or 12, wherein, in step (2), described refiningThe time of system is 5-20min.
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| CN109679714A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Composite sodium-based lubricating grease and preparation method thereof |
| CN114672360A (en) * | 2022-04-26 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature high-speed flexible gyroscope motor bearing lubricating grease and preparation method thereof |
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| CN109679714A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Composite sodium-based lubricating grease and preparation method thereof |
| CN109679714B (en) * | 2017-10-18 | 2022-06-24 | 中国石油化工股份有限公司 | Composite sodium-based lubricating grease and preparation method thereof |
| CN114672360A (en) * | 2022-04-26 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature high-speed flexible gyroscope motor bearing lubricating grease and preparation method thereof |
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