CN104513696A - Calcium zirconium-base octapolyurea lubricating grease and preparation method thereof - Google Patents
Calcium zirconium-base octapolyurea lubricating grease and preparation method thereof Download PDFInfo
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- CN104513696A CN104513696A CN201310460241.XA CN201310460241A CN104513696A CN 104513696 A CN104513696 A CN 104513696A CN 201310460241 A CN201310460241 A CN 201310460241A CN 104513696 A CN104513696 A CN 104513696A
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Abstract
The present invention discloses a calcium zirconium-base octapolyurea lubricating grease, which is characterized by comprising, by weight, 1-59% of a calcium zirconium-base thickener, 1-59% of a polyurea compound, and 40-95% of base oil, wherein the composite calcium zirconium-base thickener is a calcium zirconium soap formed by carrying out a reaction of a component A, a component B and a component C, the component A is a mixture of a higher fatty acid and a small molecule inorganic acid and/or lower straight-chain fatty acid, the component B is an oxide and/or hydroxide of calcium, the component C is at least one selected from a zirconium oxide, a zirconium hydroxide and alkoxy zirconium, and the polyurea compound is a octapolyurea compound. The present invention further discloses a preparation method of the composite calcium zirconium-base octapolyurea lubricating grease, and the composite calcium zirconium-base octapolyurea lubricating grease prepared through the preparation method. The composite calcium zirconium-base octapolyurea lubricating grease of the present invention has characteristics of good high temperature resistance, good mechanical stability, good water resistance, good adhesion resistance, good salt spray resistance, good colloidal stability and good extreme pressure wear resistance.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of calcium zirconium base eight polyurea grease and preparation method thereof.
Background technology
Zirconium belongs to IVB race as a kind of transition metal, is positioned at for the 5th cycle.Zirconium-containing compound has excellent lubrication, is often used as slip additive, as the oxide compound of zirconium is improved abradability as lubricant additive by CN101113382 and JP1973038444; WO2007143414 and US20060063682 describes zirconium tetrafluoride and can be used as one of wear reducing additive component becoming lubricant; US20060254823 finds that the lubricant containing 2 ethyl hexanoic acid zirconates shows good resistance to heavy loading and abrasion resistance; US20050043189 finds that fluozirconate is used in the lubricant as fluorine zirconic acid aluminium can be used as oxidation retarder; DE102004021812 finds the inorganic salt such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate to join inside lubricating grease and can improve abrasion resistance.
The patent preparing zirconium base grease using zirconates as viscosifying agent has US4189387, viscosifying agent reacts obtained by organic Hypophosporous Acid, 50 or monocarboxylic acid and zirconium hydroxide, obtained lubricating grease has good extreme pressure anti-wear, but other performances of lubricating grease still await further raising.
Summary of the invention
The object of this invention is to provide a kind of high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear all better, cost is low, preparation technology's simple calcium zirconium base eight polyurea grease and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the calcium zirconium base viscosifying agent of 1-59 % by weight; The polyurea compound of 1-59 % by weight; The base oil of 40-95 % by weight, wherein, described calcium zirconium base viscosifying agent reacts by component A, B component and component C the calcium zirconium soap generated, wherein, described component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, described B component is oxide compound and/or the oxyhydroxide of calcium, and described component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide, and described polyurea compound is eight polyurea compounds.This lubricating grease has good high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, and cost is low, and preparation technology is simple.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of calcium zirconium base eight polyurea grease, with lubricating grease weight for benchmark, comprise following component: the calcium zirconium base viscosifying agent of 1-59 % by weight; The polyurea compound of 1-59 % by weight; The base oil of 40-95 % by weight, wherein, described calcium zirconium base viscosifying agent reacts by component A, B component and component C the calcium zirconium soap generated, wherein, described component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, described B component is oxide compound and/or the oxyhydroxide of calcium, and described component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide, and described polyurea compound is eight polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the calcium zirconium base viscosifying agent of 3-40 % by weight; Eight polyurea compounds of 2-40 % by weight; The base oil of 50-93 % by weight.
Preferably, in described calcium zirconium base viscosifying agent, the mol ratio of calcium and zirconium is 1:0.1-10; Be more preferably 1:0.25-4.
Preferably, described component C is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10; Be more preferably 1:0.5-5.
Second aspect, the invention provides the preparation method of calcium zirconium base eight polyurea grease as above, the method comprises: calcium zirconium base viscosifying agent, eight polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of preparation method of calcium zirconium base eight polyurea grease, the method comprises:
(1) component A, B component and component C are mixed in base oil, intensification draining saponification, wherein, described component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, described B component is oxide compound and/or the oxyhydroxide of calcium, and described component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;
(2) in step (1) gained mixture, add base oil and vulcabond, then add diamines, diamines and monoamine successively and react;
(3) step (2) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
Preferably, in step (1), the mol ratio of calcium and zirconium is 1:0.1-10, is more preferably 1:0.25-4.
Preferably, in step (1), by described component A and base oil Hybrid Heating to 60-90 DEG C, add B component and component C, 90-120 DEG C of draining saponification, wherein, component C is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10, is more preferably 1:0.5-5.
Fourth aspect, the invention provides calcium zirconium base eight polyurea grease obtained by method as above.
Calcium zirconium base eight polyurea grease of the present invention, compare zirconium base eight polyurea grease, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, especially when the mol ratio of calcium in lubricating grease and zirconium is 1:0.25-4; The raw material preparing the zirconium of calcium zirconium base viscosifying agent is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide; In zirconium, when the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5, the high thermal resistance of calcium zirconium base eight polyurea grease, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure and antiwear behavior access very big raising.Preparation of greases technique of the present invention is simple, cost is low, constant product quality.Lubricating grease of the present invention can be widely used in the bearing lubrication such as high speed, heavy loading running, oil drilling.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of calcium zirconium base eight polyurea grease, this lubricating grease contains eight polyurea compounds that calcium zirconium base viscosifying agent and isocyanic ester and amine reaction produce simultaneously.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides calcium zirconium base eight polyurea grease, with lubricating grease weight for benchmark, comprise following component: the calcium zirconium base viscosifying agent of 1-59 % by weight; The polyurea compound of 1-59 % by weight; The base oil of 40-95 % by weight, wherein, calcium zirconium base viscosifying agent reacts by component A, B component and component C the calcium zirconium soap generated, wherein, component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, B component is oxide compound and/or the oxyhydroxide of calcium, and component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide, and described polyurea compound is eight polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the calcium zirconium base viscosifying agent of 3-40 % by weight; Eight polyurea compounds of 2-40 % by weight; The base oil of 50-93 % by weight; More preferably, with lubricating grease weight for benchmark, comprise following component: the calcium zirconium base viscosifying agent of 5-30 % by weight; The polyurea compound of 2-30 % by weight; The base oil of 60-90 % by weight.
According to the present invention, although have calcium zirconium base eight polyurea grease of said components, object of the present invention can be realized, namely lubricating grease has good high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, but when in calcium zirconium base viscosifying agent, the mol ratio of calcium and zirconium is 1:0.1-10, when being more preferably 1:0.25-4, can further improve the high thermal resistance of lubricating grease, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.Therefore, in calcium zirconium base viscosifying agent of the present invention, the mol ratio of calcium and zirconium is preferably 1:0.1-10, is more preferably 1:0.25-4.
The present inventor surprisingly finds under study for action, when component C is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, namely when the raw material of zirconium is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, can further improve the high thermal resistance of lubricating grease, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, therefore, component C is preferably the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, be more preferably 1:0.2-8, further be preferably 1:0.5-5, when the preferred molar ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, the high thermal resistance of lubricating grease can be improved further, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.
In the present invention, higher fatty acid can be 8-24 for carbon number, the straight chain fatty acid of preferred 10-20 or hydroxy fatty acid, such as, at least one in lauric acid, oleic acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, is more preferably 12-oxystearic acid.
In the present invention, small molecules mineral acid is preferably boric acid and/or phosphoric acid, lower straight lipid acid can be monoprotic acid or diprotic acid, such as, at least one in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid and bay diacid can be selected from.
In the present invention, the mol ratio of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid is preferably 1:0.2-10, is more preferably 1:0.4-5.
In the present invention, H contained by higher fatty acid and small molecules mineral acid and/or lower straight lipid acid
+mole number sum equal all and the oxide compound of calcium, the oxyhydroxide of calcium, the oxide compound of zirconium, the oxyhydroxide of zirconium and the H needed for zirconium alkoxide
+mole number, but the oxide compound of the oxyhydroxide of the oxide compound of calcium, calcium, zirconium, the oxyhydroxide of zirconium and zirconium alkoxide can excessive 1-10% relative to higher fatty acid and small molecules mineral acid and/or lower straight lipid acid.
In the present invention, the oxide compound of calcium and/or oxyhydroxide can be CaO, Ca (OH)
2; Oxide compound and/or the oxyhydroxide of zirconium are preferably selected from ZrO
2, ZrO (OH)
2, Zr (OH)
4and at least one in their hydrate.ZrO (OH)
2hydrate can be the wet hydrogen zirconium white of brand-new, it can pass through ZrOX
28H
2o(X is F, Cl, Br or I) or ZrO (NO
3)
22H
2o etc. obtain with alkali reaction, and wherein, alkali can be NaOH, KOH, strong aqua etc., preferred ZrOCl
28H
2o and NaOH reacts.
In the present invention, the general formula of zirconium alkoxide can be Zr (OR
1)
4, R
1can be the alkyl of C1-C10, be preferably the alkyl of C2-C6; More preferably, zirconium alkoxide is selected from least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and Pentyl alcohol zirconium.
In the present invention, described eight polyurea compounds preferably have following structure:
Wherein, R
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R
3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R
3be more preferably
in at least one.
Above-mentioned eight polyurea compounds can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060068A prepares.
In the present invention, base oil 100 DEG C of kinematic viscosity are preferably 2-150mm
2/ s, is more preferably 4-60mm
2/ s, base oil can be at least one in mineral oil, synthetic oil and vegetables oil, and synthetic oil can be poly & Alpha ,-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of calcium zirconium base eight polyurea grease as above, the method comprises: calcium zirconium base viscosifying agent, eight polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, described above for calcium zirconium base viscosifying agent, eight polyurea compounds, base oil and additive, do not repeat them here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are the total amount of base oil used, in the present invention, part basis oil is preferably 1:0.5-5 with the weight ratio of surplus base oil.
For calcium zirconium base viscosifying agent, can be obtained by reacting in base oil by component A, B component and component C, wherein, component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, B component is oxide compound and/or the oxyhydroxide of calcium, and component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide.Such as, by component A and part basis oil Hybrid Heating to 60-90 DEG C, add B component and component C, 90-120 DEG C of draining saponification, wherein, component C is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, is more preferably 1:0.2-8, is further preferably 1:0.5-5.
The third aspect, the invention provides a kind of preparation method of calcium zirconium base eight polyurea grease, the method comprises:
(1) component A, B component and component C are mixed in base oil, intensification draining saponification, wherein, described component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, described B component is oxide compound and/or the oxyhydroxide of calcium, and described component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;
(2) in step (1) gained mixture, add base oil and vulcabond, then add diamines, diamines and monoamine successively and react;
(3) step (2) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
According to the present invention, although prepare calcium zirconium base polyurea grease according to the method described above, object of the present invention can be realized, namely the calcium zirconium base polyurea grease prepared has good high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, but in step (1), when the mol ratio of calcium and zirconium is 1:0.1-10, when being more preferably 1:0.25-4, can further improve the high thermal resistance of obtained lubricating grease, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.Therefore, in step of the present invention (1), the mol ratio of calcium and zirconium is preferably 1:0.1-10, is more preferably 1:0.25-4.
In step of the present invention (1), base oil can be made first to mix with component A, base oil also can be made first to mix with B component and component C; Higher fatty acid and small molecules mineral acid and/or lower straight lipid acid can react with B component and component C simultaneously dewater in base oil, also can react dehydration respectively.Preferably by base oil and component A Hybrid Heating to 60-90 DEG C, add B component and component C, intensification draining saponification.
As previously mentioned, the present inventor surprisingly finds under study for action, in step (1), when component C is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, namely when the raw material of zirconium is the mixture of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide, can further improve the high thermal resistance of obtained lubricating grease, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, therefore, preferably, in step (1), by component A and base oil Hybrid Heating to 60-90 DEG C, add B component and component C, 90-120 DEG C of draining saponification, wherein, component C is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is preferably 1:0.1-10, be more preferably 1:0.2-8, further be preferably 1:0.5-5.
In step of the present invention (1), the total amount of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid and the weight ratio of base oil are preferably 1:5-50.
In step of the present invention (1), the mol ratio of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid is preferably 1:0.2-10, is more preferably 1:0.4-5.
The oxide compound of higher fatty acid, small molecules mineral acid and/or lower straight lipid acid, calcium, the oxyhydroxide of calcium, the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide as previously mentioned, do not repeat them here.
The mol ratio of the oxide compound of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid and calcium, the oxyhydroxide of calcium, the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide as previously mentioned, does not repeat them here.
In step of the present invention (2), base oil and vulcabond in step (1) gained mixture, then add diamines, diamines and monoamine successively and react, and is namely prepare eight polyurea compounds in step (1) gained mixture.
Prepare the method for eight polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, base oil and vulcabond can be added in step (2) gained mixture, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, add monoamine again, stir 2-8 minute, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2.
Described vulcabond structure is OCN-R
3-NCO, R
3can be carbon number be 6-30, the arylidene of preferred 6-20, alkylidene group or cycloalkylidene, be preferably
deng.Such as, described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexylmethyl vulcabond (HMDI) and an xylylene diisocyanate (XDI) etc.
Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R
1 '-NH
2, R wherein
1, R
1 'can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.Preferred monoamine can be the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Described diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
In step of the present invention (3), first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 80-130 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
Base oil and additive as previously mentioned, do not repeat them here.
In the present invention, in step (1), in the total amount of base oil used and step (2), in the total amount of base oil used and step (3), the weight ratio of the total amount of base oil used is preferably 1:0.5-5:0.5-5.
Fourth aspect, calcium zirconium base eight polyurea grease that the preparation method that present invention also offers is provided by third aspect present invention obtains.
Compared with calcium zirconium base eight polyurea grease obtained with the preparation method provided by second aspect, calcium zirconium base eight polyurea grease that the preparation method that the third aspect provides obtains has better high thermal resistance, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
Embodiment 1
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: ZrOCl
28H
2o(22.5g); NaOH(6g); Ethanol zirconium (19g); Ca (OH)
2(2.6g); 12-oxystearic acid (50g); Sebacic acid (18g); Stearylamine (6.9g); Quadrol (2.3g); MDI(12.8g); (100 DEG C of kinematic viscosity are 10mm to HVI500SN lubricating base oil
2/ s, 400g).
By 22.5gZrOCl
28H
2o is dissolved in 140g water, 80g is contained the aqueous solution of 6g NaOH, slowly adds above-mentioned ZrOCl
2the aqueous solution in, rapid stirring obtains white precipitate, and filtration is precipitated, and precipitation massive laundering is washed rear for subsequent use.
150g HVI500SN lubricating base oil, 50g12-oxystearic acid and 18g sebacic acid are added in normal oleosterin still, stir, be heated to 90 DEG C, by the precipitation of 19g ethanol zirconium, above-mentioned brand-new and 2.6gCa (OH)
2add wherein, the mol ratio of calcium and zirconium is 1:4, and in zirconium, the precipitation of brand-new and the mol ratio of ethanol zirconium are 1:1, are warming up to 105 DEG C of draining saponification, are warming up to 120 DEG C; Add 50g HVI500SN lubricating base oil and 12.8g MDI, stir 4 minutes, add 1.5g quadrol under rapid stirring, stir 4 minutes, under rapid stirring, again add 0.8g quadrol, stir 4 minutes, add 6.9g stearylamine, stir 4 minutes, the mol ratio of added successively MDI, quadrol, quadrol and stearylamine is 4:2:1:2,120 DEG C of constant temperature 20 minutes, is then warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium soap viscosifying agent 16.7 % by weight, eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Embodiment 2
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: ZrOCl
28H
2o(22.5g); NaOH(6g); Ethanol zirconium (19g); Ca (OH)
2(2.6g); 12-oxystearic acid (50g); Sebacic acid (18g); Stearylamine (6.9g); Quadrol (2.3g); MDI(12.8g); (100 DEG C of kinematic viscosity are 10mm to HVI500SN lubricating base oil
2/ s, 400g).
By 22.5gZrOCl
28H
2o is dissolved in 140g water, 80g is contained the aqueous solution of 6g NaOH, slowly adds above-mentioned ZrOCl
2the aqueous solution in, rapid stirring obtains white precipitate, and filtration is precipitated, and precipitation massive laundering is washed rear for subsequent use.
150g HVI500SN lubricating base oil, 50g12-oxystearic acid and 18g sebacic acid are added in normal oleosterin still, stir, be heated to 90 DEG C, by the precipitation of 19g ethanol zirconium, above-mentioned brand-new and 2.6gCa (OH)
2add wherein, the mol ratio of calcium and zirconium is 1:4, and in zirconium, the precipitation of brand-new and the mol ratio of ethanol zirconium are 1:1, are warming up to 105 DEG C of draining saponification.
50gHVI500SN lubricating base oil and 12.8g MDI is added in another is with the normal-pressure reaction kettle heating, stir, circulate, cool, be warming up to 120 DEG C, stir 4 minutes, under rapid stirring, add 1.5g quadrol, stir 4 minutes, again add 0.8g quadrol under rapid stirring, stir 4 minutes, add 6.9g stearylamine, stir 4 minutes, the mol ratio of added successively MDI, quadrol, quadrol and stearylamine is 4:2:1:2, and 120 DEG C of constant temperature 20 minutes, obtains eight polyureas.
Gained eight polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium soap viscosifying agent 16.7 % by weight, eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
The eight polyureas molecular structural formulas contained in component are:
Embodiment 3
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(5.8g); Zirconium-n-propylate (31.7g); Zr (OH)
4(3.1g); Stearic acid (61.1g); Nonane diacid (16.2g); Stearylamine (6.9g); Quadrol (2.3g); MDI(12.8g); Full synthetic oil poly & Alpha ,-olefin oil PAO10(100 DEG C of kinematic viscosity is 10mm
2/ s, 1100g).
400g full synthetic oil poly & Alpha ,-olefin oil PAO10,61.1g stearic acid and 16.2g nonane diacid are added in normal oleosterin still, stir, be heated to 60 DEG C, by 31.7g zirconium-n-propylate, 5.8g Ca (OH)
2with 3.1g Zr (OH)
4add wherein, the mol ratio of calcium and zirconium is 1:1.5, in zirconium, and Zr (OH)
4be 1:5 with the mol ratio of zirconium-n-propylate, be warming up to 120 DEG C of draining saponification; Add 200g full synthetic oil poly & Alpha ,-olefin oil PAO10 and 12.8g MDI, stir 8 minutes, add 1.5g quadrol under rapid stirring, stir 8 minutes, under rapid stirring, again add 0.8g quadrol, stir 8 minutes, add 6.9g stearylamine, stir 8 minutes, the mol ratio of added successively MDI, quadrol, quadrol and stearylamine is 4:2:1:2,100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, remaining full synthetic oil poly & Alpha ,-olefin oil PAO10 is added; Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium base viscosifying agent 7.8 % by weight, eight polyureas 1.8 % by weight; Lubricating base oil 90.4 % by weight.
Embodiment 4
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(16.8g); ZrO (OH)
2(10.7g); Ethanol zirconium (20.6g); Stearic acid (107.8g); Sebacic acid (38.3g); Amino dodecane (5.2g); Quadrol (2.6g); MDI(14.2g); Full synthetic oil poly & Alpha ,-olefin oil PAO6(100 DEG C of kinematic viscosity is 5.8mm
2/ s, 500g); Right, right '-di-iso-octyldiphenylamine (2g).
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, with ZrO (OH)
2replace the precipitation of brand-new, 12-oxystearic acid is replaced with stearic acid, stearylamine is replaced with amino dodecane, replace HVI500SN lubricating base oil with full synthetic oil poly & Alpha ,-olefin oil PAO6, the ratio of three lubricating base oils used with embodiment 1, and treats that temperature is cooled to 110 DEG C, add the right of 2g, right '-di-iso-octyldiphenylamine, stirs 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; As above, assay is in table 1 for the consumption of each raw material.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium base viscosifying agent 24.5 % by weight; Eight polyureas 3.2 % by weight; Lubricating base oil 72.0 % by weight; Right, right '-di-iso-octyldiphenylamine 0.3 % by weight.Wherein, the mol ratio of calcium and zirconium is 1:0.67.
Embodiment 5
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(1.6g); Zr (OH)
4(0.5g); Ethanol zirconium (0.8g); 12-oxystearic acid (1.8g); Sebacic acid (4.9g); Stearylamine (11.4g); Para-totuidine (4.5g); 1,6-hexanediamine (14.7g); TDI(29.4g); (100 DEG C of kinematic viscosity are 10mm to HVI500SN lubricating base oil
2/ s, 160g).
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, with Zr (OH)
4replace the precipitation of brand-new, when adding stearylamine, also add para-totuidine, replace quadrol with 1,6-hexanediamine, replace MDI with TDI, the ratio of three lubricating base oils used is with embodiment 1, and as above, assay is in table 1 for the consumption of each raw material.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium base viscosifying agent 3.6 % by weight, eight polyureas 26.3 % by weight; Lubricating base oil 70.1 % by weight.Wherein, the mol ratio of calcium and zirconium is 1:0.25.
Embodiment 6
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(1g); ZrO (OH)
2(1.0g); Ethanol zirconium (1.8g); 12-oxystearic acid (2.7g); Acetic acid (2.7g); Stearylamine (5.7g); 1,6-hexanediamine (3.7g); TDI(7.4g); (100 DEG C of kinematic viscosity are 10mm to HVI500SN lubricating base oil
2/ s, 100g).
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, with ZrO (OH)
2replace the precipitation of brand-new, replace sebacic acid with acetic acid, replace quadrol with 1,6-hexanediamine, replace MDI with TDI, the ratio of three lubricating base oils used is with embodiment 1, and as above, assay is in table 1 for the consumption of each raw material.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: consist of: zirconium calcium base viscosifying agent 6.5 % by weight, eight polyureas 5.3 % by weight; Lubricating base oil 88.2 % by weight.Wherein, the mol ratio of calcium and zirconium is 1:1.
Embodiment 7
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(0.68g); Zr (OH)
4(0.73g); Ethanol zirconium (1.23g); 12-oxystearic acid (2.7g); Boric acid (1.7g); Stearylamine (5.7g); 1,6-hexanediamine (3.7g); TDI(7.4g); Full synthetic oil poly & Alpha ,-olefin oil PAO40(100 DEG C of kinematic viscosity is 40mm
2/ s, 160g).
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, with Zr (OH)
4replace the precipitation of brand-new, sebacic acid is replaced with boric acid, with 1,6-hexanediamine replaces quadrol, replace MDI with TDI, replace HVI500SN lubricating base oil with full synthetic oil poly & Alpha ,-olefin oil PAO40, the ratio of three lubricating base oils used is with embodiment 1, as above, assay is in table 1 for the consumption of each raw material.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium base viscosifying agent 3.1 % by weight, eight polyureas 4.0 % by weight; Lubricating base oil 92.9 % by weight.Wherein, the mol ratio of calcium and zirconium is 1:1.
Embodiment 8
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, at Ca (OH)
2, brand-new precipitation and the gross weight of ethanol zirconium constant, when the mol ratio of calcium and zirconium is constant, the mol ratio of adjustment brand-new precipitation and ethanol zirconium is 1:0.1.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium soap viscosifying agent 16.7 % by weight, eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Embodiment 9
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, at Ca (OH)
2, brand-new precipitation and the gross weight of ethanol zirconium constant, when the mol ratio of calcium and zirconium is constant, the mol ratio of adjustment brand-new precipitation and ethanol zirconium is 1:10.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium soap viscosifying agent 16.7 % by weight, eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Embodiment 10
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, constant at total consumption of calcium and zirconium raw material, when the mol ratio of calcium and zirconium is constant, ethanol zirconium is replaced with the precipitation of brand-new.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium soap viscosifying agent 16.7 % by weight, eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Embodiment 11
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, unlike, constant at total consumption of calcium and zirconium raw material, when the mol ratio of calcium and zirconium is constant, the precipitation of brand-new is replaced with ethanol zirconium.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: zirconium calcium soap viscosifying agent 16.7 % by weight, eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Embodiment 12
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, keep the mol ratio of 12-oxystearic acid and the mol ratio of sebacic acid, the precipitation of brand-new and ethanol zirconium constant, unlike, the mol ratio of adjustment calcium and zirconium is 1:0.1, and each consumption is adjusted accordingly to keep viscosifying agent proportion constant.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: calcium zirconium base viscosifying agent 16.7 % by weight; Eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Embodiment 13
Calcium zirconium base eight polyurea grease that the present embodiment is prepared for illustration of the present invention.
Calcium zirconium base eight polyurea grease is prepared according to the method for embodiment 1, keep the mol ratio of 12-oxystearic acid and the mol ratio of sebacic acid, the precipitation of brand-new and ethanol zirconium constant, unlike, the mol ratio of adjustment calcium and zirconium is 1:10, and each consumption is adjusted accordingly to keep viscosifying agent proportion constant.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: calcium zirconium base viscosifying agent 16.7 % by weight; Eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Comparative example 1
Prepare zirconium base eight polyurea grease according to the method for embodiment 1, keep the mol ratio of 12-oxystearic acid and the mol ratio of sebacic acid, the precipitation of brand-new and ethanol zirconium constant, unlike, by Ca (OH)
2replace with precipitation and the ethanol zirconium of brand-new, each consumption is adjusted accordingly to keep viscosifying agent proportion constant.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: zirconium base viscosifying agent 16.7 % by weight; Eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Comparative example 2
Prepare calcium base eight polyurea grease according to the method for embodiment 1, keep the mol ratio of 12-oxystearic acid and sebacic acid constant, unlike, the precipitation of brand-new and ethanol zirconium are replaced with Ca (OH)
2, each consumption is adjusted accordingly to keep viscosifying agent proportion constant.Each physicochemical property of gained fat is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: calcium base viscosifying agent 16.7 % by weight; Eight polyureas 4.3 % by weight; Lubricating base oil 79.0 % by weight.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Stencil oil-dividing: SH/T0324; Tetra-ball machine test (P
b, P
d): SH/T0202; Tetra-ball machine test (D
40 60): SH/T0204; Ball bearing lubricating life: ASTM D3336.
Table 1(continues) each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Stencil oil-dividing: SH/T0324; Tetra-ball machine test (P
b, P
d): SH/T0202; Tetra-ball machine test (D
40 60): SH/T0204; Ball bearing lubricating life: ASTM D3336.
Embodiment 1 is compared can find out with comparative example 1 and comparative example 2 respectively, the dropping point of calcium zirconium base eight polyurea grease of the present invention is far above zirconium base eight polyurea grease and calcium base eight polyurea grease, extend the difference of Drawing cone in-degree and Drawing cone in-degree much smaller than zirconium base eight polyurea grease and calcium base eight polyurea grease, water drenches number of dropouts much smaller than zirconium base eight polyurea grease and calcium base eight polyurea grease, salt-fog test is better than zirconium base eight polyurea grease and calcium base eight polyurea grease, Stencil oil-dividing value is much smaller than zirconium base eight polyurea grease and calcium base eight polyurea grease, tetra-ball machine test P
b, P
dvalue is greater than zirconium base eight polyurea grease and calcium base eight polyurea grease, tetra-ball machine test D
40 60value is less than zirconium base eight polyurea grease and calcium base eight polyurea grease, ball bearing lubricating life is greater than zirconium base eight polyurea grease and calcium base eight polyurea grease, illustrates that the high thermal resistance of calcium zirconium base eight polyurea grease of the present invention, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear and lubricating life are all better than zirconium base eight polyurea grease and calcium base eight polyurea grease.
Embodiment 1 and embodiment 2 are compared and can find out, calcium zirconium base six polyurea grease prepared by original position, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, there is longer lubricating life; Embodiment 1 is compared can find out with embodiment 8 and embodiment 9 respectively, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5, calcium zirconium base eight polyurea grease of preparation, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, there is longer lubricating life; Embodiment 1 is compared can find out with embodiment 10 and embodiment 11 respectively, the raw material preparing the zirconium of calcium zirconium base viscosifying agent is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, calcium zirconium base eight polyurea grease of preparation, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, there is longer lubricating life; Embodiment 1 is compared can find out with embodiment 12 and embodiment 13 respectively, the mol ratio of calcium and zirconium is 1:0.25-4, calcium zirconium base eight polyurea grease of preparation, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, there is longer lubricating life.
Calcium zirconium base eight polyurea grease of the present invention, compare zirconium base eight polyurea grease and calcium base eight polyurea grease, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability and extreme pressure anti-wear, there is longer lubricating life, especially when the mol ratio of calcium in lubricating grease and zirconium is 1:0.25-4; The raw material preparing the zirconium of calcium zirconium base viscosifying agent is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide; In zirconium, when the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5, the high thermal resistance of calcium zirconium base eight polyurea grease, mechanical stability, water resisting property and adhesivity, colloid stability, extreme pressure anti-wear and lubricating life can be greatly improved.Preparation of greases technique of the present invention is simple, cost is low, constant product quality.Lubricating grease of the present invention can be widely used in the bearing lubrication such as high speed, heavy loading running, oil drilling.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (33)
1. calcium zirconium base eight polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the calcium zirconium base viscosifying agent of 1-59 % by weight; The polyurea compound of 1-59 % by weight; The base oil of 40-95 % by weight, wherein, described calcium zirconium base viscosifying agent reacts by component A, B component and component C the calcium zirconium soap generated, wherein, described component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, described B component is oxide compound and/or the oxyhydroxide of calcium, and described component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide, and described polyurea compound is eight polyurea compounds.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the calcium zirconium base viscosifying agent of 3-40 % by weight; Eight polyurea compounds of 2-40 % by weight; The base oil of 50-93 % by weight.
3. lubricating grease according to claim 1 and 2, wherein, in described calcium zirconium base viscosifying agent, the mol ratio of calcium and zirconium is 1:0.1-10.
4. lubricating grease according to claim 3, wherein, in described calcium zirconium base viscosifying agent, the mol ratio of calcium and zirconium is 1:0.25-4.
5. lubricating grease according to claim 1 and 2, wherein, described component C is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10.
6. lubricating grease according to claim 5, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.
7. lubricating grease according to claim 1 and 2, wherein, straight chain fatty acid or the hydroxy fatty acid of described higher fatty acid to be carbon number be 8-24.
8. lubricating grease according to claim 7, wherein, described higher fatty acid is selected from least one in lauric acid, oleic acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
9. lubricating grease according to claim 1 and 2, wherein, described small molecules mineral acid is boric acid and/or phosphoric acid, and described lower straight lipid acid is selected from least one in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid and bay diacid.
10. lubricating grease according to claim 1 and 2, wherein, the mol ratio of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid is 1:0.2-10.
11. lubricating grease according to claim 1 and 2, wherein, oxide compound and/or the oxyhydroxide of zirconium are selected from ZrO
2, ZrO (OH)
2, Zr (OH)
4and at least one in their hydrate.
12. lubricating grease according to claim 1 and 2, wherein, the general formula of described zirconium alkoxide is Zr (OR
1)
4, R
1for the alkyl of C1-C10.
13. lubricating grease according to claim 12, wherein, described zirconium alkoxide is selected from least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and Pentyl alcohol zirconium.
14. lubricating grease according to claim 1 and 2, wherein, described eight polyurea compounds have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
15. lubricating grease according to claim 14, wherein, R
1be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R
2be phenylene or biphenylene or carbon number be the alkylidene group of 2-12; R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
16. lubricating grease according to claim 15, wherein, R
1be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18, R
2be phenylene or biphenylene, or carbon number is the alkylidene group of 2-8; R
3be selected from
in at least one.
17. lubricating grease according to claim 1 and 2, wherein, described base oil is selected from least one in mineral oil, synthetic oil and vegetables oil, and described base oil 100 DEG C of kinematic viscosity are 2-150mm
2/ s.
The preparation method of calcium zirconium base eight polyurea grease in 18. claim 1-17 described in any one, it is characterized in that, the method comprises: calcium zirconium base viscosifying agent, eight polyurea compounds and part basis oil are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The preparation method of 19. 1 kinds of calcium zirconium base eight polyurea greases, it is characterized in that, the method comprises:
(1) component A, B component and component C are mixed in base oil, intensification draining saponification, wherein, described component A is the mixture of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid, described B component is oxide compound and/or the oxyhydroxide of calcium, and described component C is at least one in the oxide compound of zirconium, the oxyhydroxide of zirconium and zirconium alkoxide;
(2) in step (1) gained mixture, add base oil and vulcabond, then add diamines, diamines and monoamine successively and react;
(3) step (2) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
20. methods according to claim 19, wherein, in step (1), the mol ratio of calcium and zirconium is 1:0.1-10.
21. methods according to claim 20, wherein, in step (1), the mol ratio of calcium and zirconium is 1:0.25-4.
22. according to the method in claim 19-21 described in any one, wherein, in step (1), by described component A and base oil Hybrid Heating to 60-90 DEG C, add B component and component C, 90-120 DEG C of draining saponification, wherein, component C is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, and in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.1-10.
23. methods according to claim 22, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.
24. according to the method in claim 19-21 described in any one, and wherein, the mol ratio of higher fatty acid and small molecules mineral acid and/or lower straight lipid acid is 1:0.2-10.
25. according to the method in claim 19-21 described in any one, wherein, in step (2), in step (1) gained mixture, add base oil and vulcabond, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, then add monoamine, stir 2-8 minute, the mol ratio of vulcabond, diamines, diamines and monoamine added by each time is 4:2:1:2.
26. according to the method in claim 19-21 described in any one, wherein, in step (3), first at 100-120 DEG C of constant temperature 10-20 minute, is finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 80-130 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
27. according to the method in claim 19-21 described in any one, and wherein, the structural formula of described monoamine is R
1-NH
2, R
1 '-NH
2, wherein, R
1, R
1 'be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.
28. methods according to claim 27, wherein, described monoamine is the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
29. according to the method in claim 19-21 described in any one, and wherein, the structural formula of described diamines is NH
2-R
2-NH
2, wherein, R
2the alkylidene group of to be carbon number be 2-8, or phenylene or biphenylene.
30. methods according to claim 29, wherein, described diamines be selected from Ursol D, O-Phenylene Diamine, 4,4-benzidines aromatic amine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
31. according to the method in claim 19-21 described in any one, and wherein, the structure of described vulcabond is OCN-R
3-NCO, R
3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
32. methods according to claim 31, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
33. calcium zirconium base eight polyurea greases obtained by the method in claim 19-32 described in any one.
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| CN1208442C (en) * | 2002-10-30 | 2005-06-29 | 中国石油化工股份有限公司 | Preparation method of polyurea-composite calcium lubricating grease |
| CN1922295A (en) * | 2004-02-23 | 2007-02-28 | 日本精工株式会社 | Lubricating grease composition and rotating device |
| CN103031182B (en) * | 2011-09-29 | 2015-01-14 | 中国石油化工股份有限公司 | Composite zirconium-based octaurea lubrication grease and its preparation method |
| CN103060068B (en) * | 2011-10-20 | 2014-10-29 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
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| CN111100730A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Metal soap-based lubricating grease and preparation method thereof |
| CN111100730B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Metal soap-based lubricating grease and preparation method thereof |
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