CN104513688A - Composite calcium-zirconium-based hexa-polyurea lubricating grease and preparation method thereof - Google Patents
Composite calcium-zirconium-based hexa-polyurea lubricating grease and preparation method thereof Download PDFInfo
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- CN104513688A CN104513688A CN201310461756.1A CN201310461756A CN104513688A CN 104513688 A CN104513688 A CN 104513688A CN 201310461756 A CN201310461756 A CN 201310461756A CN 104513688 A CN104513688 A CN 104513688A
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- 0 CC1CC*CC1 Chemical compound CC1CC*CC1 0.000 description 3
- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 1
- AFZZYIJIWUTJFO-UHFFFAOYSA-N CCc1cccc(CC)c1 Chemical compound CCc1cccc(CC)c1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 1
- GWHJZXXIDMPWGX-UHFFFAOYSA-N Cc1ccc(C)c(C)c1 Chemical compound Cc1ccc(C)c(C)c1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 1
- HZAWPPRBCALFRN-UHFFFAOYSA-N Cc1ccc(Cc2ccc(C)cc2)cc1 Chemical compound Cc1ccc(Cc2ccc(C)cc2)cc1 HZAWPPRBCALFRN-UHFFFAOYSA-N 0.000 description 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N Cc1cccc(C)c1C Chemical compound Cc1cccc(C)c1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses composite calcium-zirconium-based hexa-polyurea lubricating grease which comprises following components, on the basis of the weight of the lubricating grease, by weight, 1-59% of a composite calcium-zirconium-based thickening agent, 1-59% of a polyurea compound, and 40-95% of basic oil, wherein the composite calcium-zirconium-based thickening agent is a calcium-zirconium soap generated through a reaction among a component A, a component B and a component C. The component A is a mixture composed of a higher fatty acid and an aromatic acid. The component B is an oxide and/or a hydroxide of calcium. The component C is at least one of an oxide of zirconium, a hydroxide of zirconium and alkoxyl zirconium. The polyurea compound is a hexa-polyurea compound. The invention also discloses a preparation method of the composite calcium-zirconium-based hexa-polyurea lubricating grease and the composite calcium-zirconium-based hexa-polyurea lubricating grease prepared through the method. The composite calcium-zirconium-based hexa-polyurea lubricating grease is better in high-temperature resistance, mechanical stability, water resistance, adhesivity, salt fog resistance, colloid stability and extreme-pressure wear resistance.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of composite calcium zirconium base six 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, extreme pressure anti-wear all better, cost is low, preparation technology's simple composite calcium zirconium base six polyurea grease and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the composite 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 composite 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 aromatic 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; Described polyurea compound is six polyurea compounds.This lubricating grease has good high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, 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 composite calcium zirconium base six polyurea grease, with lubricating grease weight for benchmark, comprise following component: the composite 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 composite 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 aromatic 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; Described polyurea compound is six polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the composite calcium zirconium base viscosifying agent of 3-40 % by weight; Six polyurea compounds of 2-40 % by weight; The base oil of 50-93 % by weight.
Preferably, in described composite 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 composite calcium zirconium base six polyurea grease as above, the method comprises: composite calcium zirconium base viscosifying agent, six 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 composite calcium zirconium base six 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 aromatic 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 monoamine, diamines and vulcabond 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 composite calcium zirconium base six polyurea grease obtained by method as above.
Composite calcium zirconium base six polyurea grease of the present invention, compare zirconium base six polyurea grease, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, 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 composite 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 mechanical stability of composite calcium zirconium base six polyurea grease, 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 composite calcium zirconium base six polyurea grease, this lubricating grease contains six polyurea compounds that composite 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 composite calcium zirconium base six polyurea grease, with lubricating grease weight for benchmark, comprise following component: the composite 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 composite 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 aromatic 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; Described polyurea compound is six polyurea compounds.
Preferably, with lubricating grease weight for benchmark, comprise following component: the composite calcium zirconium base viscosifying agent of 3-40 % by weight; Six 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 composite calcium zirconium base viscosifying agent of 5-30 % by weight; Six polyurea compounds of 2-30 % by weight; The base oil of 60-90 % by weight.
According to the present invention, although have composite calcium zirconium base six 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, extreme pressure anti-wear, but when in composite 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 mechanical stability of lubricating grease, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.Therefore, in composite 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 mechanical stability of lubricating grease, 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 mechanical stability of lubricating grease can be improved further, 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, aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, and aromatic acid can be replace or unsubstituted aromatic acid, and its substituting group can be at least one in the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, fluoro or perfluoro etc.Aromatic acid is preferably binary aromatic acid, such as, can be selected from least one in substituted or unsubstituted phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid and santowax dioctyl phthalate.
In the present invention, the mol ratio of higher fatty acid and aromatic acid is preferably 1:0.5-7, is more preferably 1:1-4.
In the present invention, H contained by higher fatty acid and aromatic 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 aromatic 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 six 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
with-CH
26-at least one.
Above-mentioned six 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 CN103060067A 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 composite calcium zirconium base six polyurea grease as above, the method comprises: composite calcium zirconium base viscosifying agent, six 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 composite calcium zirconium base viscosifying agent, six 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 composite 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 aromatic 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 composite calcium zirconium base six polyurea grease, the method comprises:
(1) component A, B component and component C are mixed in base oil, intensification draining saponification, wherein, component A is the mixture of higher fatty acid and aromatic 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;
(2) in step (1) gained mixture, add base oil and vulcabond, then add monoamine, diamines and vulcabond 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 composite calcium zirconium base polyurea grease according to the method described above, object of the present invention can be realized, namely the composite 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, 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 mechanical stability of obtained lubricating grease, 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 aromatic 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 mechanical stability of obtained lubricating grease, 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 aromatic acid and the weight ratio of base oil are preferably 1:0.5-5.
In step of the present invention (1), the mol ratio of higher fatty acid and aromatic acid is preferably 1:0.5-7, is more preferably 1:1-4.
The oxide compound of higher fatty acid, aromatic 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 aromatic 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), in step (1) gained mixture, adding base oil and vulcabond, then add monoamine, diamines and vulcabond successively and react, is namely prepare six polyurea compounds in step (1) gained mixture.
Prepare the method for six 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 monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, add the vulcabond be dissolved in base oil again, stir 2-8 minute, the mol ratio of vulcabond, monoamine, diamines and vulcabond added by each time is 2:2:2:1.
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, composite calcium zirconium base six polyurea grease that the preparation method that present invention also offers is provided by third aspect present invention obtains.
Compared with composite calcium zirconium base six polyurea grease obtained with the preparation method provided by second aspect, composite calcium zirconium base six polyurea grease that the preparation method that the third aspect provides obtains has better 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
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(0.36kg); ZrO (OH)
2(1.36kg); Ethanol zirconium (2.60kg); 12-oxystearic acid (4.8kg); Phthalic acid (2.6kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 10mm to HVI500SN lubricating base oil
2/ s, 40kg); Right, right '-di-iso-octyldiphenylamine (0.1kg).
A volume be 110L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add 4.8kg12-oxystearic acid, 2.6kg phthalic acid and 15kg HVI500SN lubricating base oil, stir, heat to 60 DEG C, successively add 1.36kg ZrO (OH)
2, 0.36kg Ca (OH)
2with the reaction of 2.60kg ethanol zirconium, the mol ratio of calcium and zirconium is 1:4, in zirconium, and ZrO (OH)
2be 1:1 with the mol ratio of ethanol zirconium, be warmed up to 120 DEG C of draining saponification; Add 5kg HVI500SN lubricating base oil and 0.78kgMDI, stir 4 minutes, add 0.84kg stearylamine, stir 4 minutes, add 0.19kg quadrol under rapid stirring, stir 4 minutes, add the 0.39kgMDI be dissolved in 2kg HVI500SN lubricating base oil, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, be then warmed up to 200 DEG C, constant temperature is after 10 minutes, add remaining HVI500SN lubricating base oil, cool; Treat that temperature is cooled to 110 DEG C, add 0.1kg couple, right '-di-iso-octyldiphenylamine, stir after 10 minutes, 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 2
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(0.36kg); ZrO (OH)
2(1.36kg); Ethanol zirconium (2.60kg); 12-oxystearic acid (4.8kg); Phthalic acid (2.6kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); (100 DEG C of kinematic viscosity are 10mm to HVI500SN lubricating base oil
2/ s, 40kg); Right, right '-di-iso-octyldiphenylamine (0.1kg).
A volume be 110L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add 4.8kg12-oxystearic acid, 2.6kg phthalic acid and 15kg HVI500SN lubricating base oil, stir, heat to 60 DEG C, successively add 1.36kg ZrO (OH)
2, 0.36kg Ca (OH)
2with the reaction of 2.60kg ethanol zirconium, the mol ratio of calcium and zirconium is 1:4, in zirconium, and ZrO (OH)
2be 1:1 with the mol ratio of ethanol zirconium, be warmed up to 120 DEG C of draining saponification.
Another volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add 5kg HVI500SN lubricating base oil and 0.78kg MDI, be warming up to 120 DEG C, stir 4 minutes, add 0.84kg stearylamine, stir 4 minutes, 0.19kg quadrol is added under rapid stirring, stir 4 minutes, add the 0.39kg MDI be dissolved in 2kg HVI500SN lubricating base oil, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.
All squeezed in a upper still by gained six polyureas, stir, be finally warmed up to 200 DEG C, constant temperature, after 10 minutes, adds remaining HVI500SN lubricating base oil, cools; Treat that temperature is cooled to 110 DEG C, add 0.1kg couple, right '-di-iso-octyldiphenylamine, stir after 10 minutes, 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
The six polyureas molecular structural formulas contained in component are:
Embodiment 3
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(0.71kg); Zr (OH)
4(0.38kg); Zirconium-n-propylate (3.94kg); Stearic acid (4.55kg); Terephthalic acid (2.66kg); Stearylamine (0.84kg); Quadrol (0.19kg); MDI(1.17kg); Synthetic oil poly & Alpha ,-olefin oil PAO10(100 DEG C of kinematic viscosity is 10mm
2/ s, 110kg); N-phenyl-a-naphthylamine (0.12kg).
A volume be 150L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add 4.55kg stearic acid, 2.66kg terephthalic acid and 40kg full synthetic oil poly & Alpha ,-olefin oil PAO10, stir, heat to 90 DEG C, order adds 3.94kg zirconium-n-propylate, 0.71kgCa (OH)
2with 0.38kgZr (OH)
4reaction, the mol ratio of calcium and zirconium is 1:1.5, in zirconium, Zr (OH)
4be 1:5 with the mol ratio of zirconium-n-propylate, be warming up to 105 DEG C of draining saponification; Add 20kg full synthetic oil poly & Alpha ,-olefin oil PAO10 and 0.78kg MDI, stir 8 minutes, 0.84kg stearylamine is added under rapid stirring, stir 8 minutes, under rapid stirring, add 0.19kg quadrol, stir 8 minutes, add the 0.39kg MDI be dissolved in 10kg full synthetic oil poly & Alpha ,-olefin oil, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1, and 100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, be cooled to 160 DEG C, add remaining full synthetic oil and gather
α-alkene oil PAO10; Treat that temperature is cooled to 100 DEG C, add 0.12kg N-phenyl-a-naphthylamine, stir after 10 minutes, 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: composite calcium zirconium base viscosifying agent 7.7 % by weight; Six polyureas 1.8 % by weight; Lubricating base oil 90.4 % by weight; N-phenyl-a-naphthylamine 0.1 % by weight.
Embodiment 4
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(2.5kg); ZrOCl
28H
2o(3.24kg); NaOH(0.81kg); Ethanol zirconium (2.73kg); 12-oxystearic acid (4.8kg); M-phthalic acid (8kg); Amino dodecane (0.66kg); Quadrol (0.21kg); MDI(1.33kg); Full synthetic oil poly & Alpha ,-olefin oil PAO6(100 DEG C of kinematic viscosity is 5.8mm
2/ s, 50kg).
By 3.24kg ZrOCl
28H
2o is dissolved in 20kg water, 4kg is contained the aqueous solution of 0.81kg 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.
Composite calcium zirconium base six polyurea grease is prepared according to the method for embodiment 1, unlike, replace ZrO (OH) by above-mentioned precipitation
2phthalic acid is replaced with m-phthalic acid, stearylamine is replaced with amino dodecane, HVI500SN lubricating base oil is replaced with full synthetic oil poly & Alpha ,-olefin oil PAO6, the ratio of four lubricating base oils used with embodiment 1, and treats that temperature is cooled to 110 DEG C, does not add the right of 2g, right '-di-iso-octyldiphenylamine, direct circulation filtration, homogenizing, degassedly obtains 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: composite calcium zirconium base viscosifying agent 23.9 % by weight; Six polyureas 3.2 % by weight; Lubricating base oil 72.9 % by weight.Wherein, the mol ratio of calcium and zirconium is 1:0.67.
Embodiment 5
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: Ca (OH)
2(0.21kg); Zr (OH)
4(0.06kg); Ethanol zirconium (0.09kg); 12-oxystearic acid (0.3kg); 4,4 '-biphenyl dicarboxylic acid (0.7kg); Stearylamine (1.43kg); Para-totuidine (0.57kg); 1,6-hexanediamine (1.23kg); TDI(2.77kg); (100 DEG C of kinematic viscosity are 30mm to HVI150BS lubricating base oil
2/ s, 23kg).
Composite calcium zirconium base six polyurea grease is prepared according to the method for embodiment 1, unlike, with Zr (OH)
4replace ZrO (OH)
2, replace phthalic acid with 4,4 '-biphenyl dicarboxylic acid, when adding stearylamine, also add para-totuidine, with 1,6-hexanediamine replaces quadrol, replace MDI with TDI, replace HVI500SN lubricating base oil with HVI150BS lubricating base oil, the ratio of four lubricating base oils used is with embodiment 1, and treat that temperature is cooled to 110 DEG C, do not add the right of 2g, right '-di-iso-octyldiphenylamine, direct circulation 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: composite calcium zirconium base viscosifying agent 3.9 % by weight; Six polyureas 20 % by weight; Lubricating base oil 76.1 % by weight.Wherein, the mol ratio of calcium and zirconium is 1:0.25.
Embodiment 6
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium zirconium base six polyurea grease is prepared according to the method for embodiment 1, unlike, at Ca (OH)
2, ZrO (OH)
2constant with the gross weight of ethanol zirconium, when the mol ratio of calcium and zirconium is constant, adjustment ZrO (OH)
2be 1:0.1 with the mol ratio of 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 7
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium zirconium base six polyurea grease is prepared according to the method for embodiment 1, unlike, at Ca (OH)
2, ZrO (OH)
2constant with the gross weight of ethanol zirconium, when the mol ratio of calcium and zirconium is constant, adjustment ZrO (OH)
2be 1:10 with the mol ratio of 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 8
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium zirconium base six 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 ZrO (OH)
2.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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 9
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium zirconium base six 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, by ZrO (OH)
2replace 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 10
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Prepare composite calcium zirconium base six polyurea grease according to the method for embodiment 1, keep mol ratio, the ZrO (OH) of 12-oxystearic acid and phthalic acid
2constant with the mol ratio of ethanol zirconium, 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 11
Composite calcium zirconium base six polyurea grease that the present embodiment is prepared for illustration of the present invention.
Prepare composite calcium zirconium base six polyurea grease according to the method for embodiment 1, keep mol ratio, the ZrO (OH) of 12-oxystearic acid and phthalic acid
2constant with the mol ratio of ethanol zirconium, 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: composite calcium zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Comparative example 1
Prepare compound zirconium base six polyurea grease according to the method for embodiment 1, keep mol ratio, the ZrO (OH) of 12-oxystearic acid and phthalic acid
2constant with the mol ratio of ethanol zirconium, unlike, by Ca (OH)
2replace with ZrO (OH)
2with ethanol zirconium, 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: compound zirconium base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Comparative example 2
Prepare composite calcium-base six polyurea grease according to the method for embodiment 1, keep the mol ratio of 12-oxystearic acid and phthalic acid constant, unlike, by ZrO (OH)
2ca (OH) is replaced with ethanol zirconium
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: composite calcium-base viscosifying agent 18.6 % by weight; Six polyureas 4.2 % by weight; Lubricating base oil 77 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 1 is compared can find out with comparative example 1 and comparative example 2 respectively, the dropping point of composite calcium zirconium base six polyurea grease of the present invention is higher than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, extend the difference of Drawing cone in-degree and Drawing cone in-degree much smaller than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, water drenches number of dropouts much smaller than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, salt-fog test is better than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, Stencil oil-dividing value is much smaller than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, tetra-ball machine test P
b, P
dvalue is greater than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, tetra-ball machine test D
40 60value is less than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, ball bearing lubricating life is greater than compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, illustrates that the high thermal resistance of composite calcium zirconium base six polyurea grease of the present invention, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, lubricating life are all better than compound zirconium
Base six polyurea grease and composite calcium-base six polyurea grease.
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: SH/T0202; Tetra-ball machine test (D
40 60): SH/T0204; Ball bearing lubricating life: ASTM D3336.
Embodiment 1 and embodiment 2 are compared and can find out, composite calcium zirconium base six polyurea grease prepared by original position, there is better 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 6 and embodiment 7 respectively, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5, composite calcium zirconium base six polyurea grease of preparation, there is better 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 raw material preparing the zirconium of composite calcium zirconium base viscosifying agent is the oxide compound of zirconium and/or the mixture of oxyhydroxide and zirconium alkoxide, composite calcium zirconium base six polyurea grease of preparation, there is better 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 mol ratio of calcium and zirconium is 1:0.25-4, composite calcium zirconium base six polyurea grease of preparation, there is better mechanical stability, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, there is longer lubricating life.
Composite calcium zirconium base six polyurea grease of the present invention, compare compound zirconium base six polyurea grease and composite calcium-base six polyurea grease, there is better high thermal resistance, mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, 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 composite 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 mechanical stability of composite calcium zirconium base six polyurea grease, 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 (34)
1. composite calcium zirconium base six polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the composite 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 composite 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 aromatic 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; Described polyurea compound is six polyurea compounds.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the composite calcium zirconium base viscosifying agent of 3-40 % by weight; Six 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 composite 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 composite 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 aromatic acid is binary aromatic acid.
10. lubricating grease according to claim 9, wherein, described aromatic acid is selected from least one in substituted or unsubstituted phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid and santowax dioctyl phthalate.
11. lubricating grease according to claim 1 and 2, wherein, the mol ratio of higher fatty acid and aromatic acid is 1:0.5-7.
12. 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.
13. 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.
14. lubricating grease according to claim 13, 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.
15. lubricating grease according to claim 1 and 2, wherein, described six polyurea compounds have following structure:
Wherein, R
1alkyl, cycloalkyl or aryl, R
2alkylidene group or arylidene, R
3arylidene, alkylidene group or cycloalkylidene.
16. lubricating grease according to claim 15, 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.
17. lubricating grease according to claim 16, 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
with-CH
26-at least one.
18. 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 composite calcium zirconium base six polyurea grease in 19. claim 1-18 described in any one, it is characterized in that, the method comprises: composite calcium zirconium base viscosifying agent, six 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 20. 1 kinds of composite calcium zirconium base six 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 aromatic 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 monoamine, diamines and vulcabond 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.
21. methods according to claim 20, wherein, in step (1), the mol ratio of calcium and zirconium is 1:0.1-10.
22. methods according to claim 21, wherein, in step (1), the mol ratio of calcium and zirconium is 1:0.25-4.
23. according to the method in claim 20-22 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.
24. methods according to claim 23, wherein, in zirconium, the mol ratio of the oxide compound of zirconium and/or oxyhydroxide and zirconium alkoxide is 1:0.5-5.
25. according to the method in claim 20-22 described in any one, and wherein, the mol ratio of higher fatty acid and aromatic acid is 1:0.5-7.
26. according to the method in claim 20-22 described in any one, wherein, in step (2), in step (1) gained mixture, add base oil and vulcabond, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, then add the vulcabond be dissolved in base oil, stir 2-8 minute, the mol ratio of vulcabond, monoamine, diamines and vulcabond added by each time is 2:2:2:1.
27. according to the method in claim 20-22 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.
28. according to the method in claim 20-22 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.
29. methods according to claim 28, 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.
30. according to the method in claim 20-22 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.
31. methods according to claim 30, 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.
32. according to the method in claim 20-22 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.
33. methods according to claim 32, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
34. composite calcium zirconium base six polyurea greases obtained by the method in claim 20-33 described in any one.
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